CN100551965C - A kind of carbon nano tube reinforced polyvinyl alcohol composite material and preparation method thereof - Google Patents
A kind of carbon nano tube reinforced polyvinyl alcohol composite material and preparation method thereof Download PDFInfo
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- CN100551965C CN100551965C CNB2006100522223A CN200610052222A CN100551965C CN 100551965 C CN100551965 C CN 100551965C CN B2006100522223 A CNB2006100522223 A CN B2006100522223A CN 200610052222 A CN200610052222 A CN 200610052222A CN 100551965 C CN100551965 C CN 100551965C
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- Prior art keywords
- polyvinyl alcohol
- carbon nanotube
- composite material
- cholate
- room temperature
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 66
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 66
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 56
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229940099352 cholate Drugs 0.000 claims abstract description 11
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 229960003964 deoxycholic acid Drugs 0.000 description 8
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940045946 sodium taurodeoxycholate Drugs 0.000 description 1
- AWDRATDZQPNJFN-VAYUFCLWSA-N taurodeoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 AWDRATDZQPNJFN-VAYUFCLWSA-N 0.000 description 1
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Abstract
Carbon nano tube reinforced polyvinyl alcohol composite material disclosed by the invention contains weight percent and is 1~9% carbon nanotube, 91~99% polyvinyl alcohol.Its preparation method is as follows: under the room temperature cholate and carbon nanotube are mixed formation suspension in water, the aqueous solution that adds polyvinyl alcohol then, obtain the carbon nanotube polyvinyl alcohol water solution after fully stirring, this aqueous solution is poured in the mould into evaporation obtains matrix material under the room temperature.Matrix material of the present invention is matrix with the polyvinyl alcohol, the carbon nanotube that cholate is modified is an additive, because the carbon nanotube that cholate is modified can be evenly dispersed in the polyvinyl alcohol, improve the mechanical property of polyvinyl alcohol composite material greatly, can be used for preparing the polyvinyl alcohol fiber product of high-strength and high-modulus.Composite material by adopting solution stirring method preparation simultaneously of the present invention, technology is simple, and is easy to operate, and good reproducibility is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of carbon nano tube reinforced polyvinyl alcohol composite material and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is a kind of water-soluble high polymers, and performance is between plastics and rubber, and purposes is quite extensive.Except making vinylon fibre, also be used to produce products such as coating, tackiness agent, fibre stuff, paper product machining agent, emulsifying agent, dispersion agent, film in a large number.The polyvinyl alcohol fiber product of high-strength and high-modulus receives much concern in recent years, and it is asbestos, and glass fibre ideal substitute also can partly replace the aramid fiber target plate as bullet resistant material.
Carbon nanotube is typical case's representative of one dimension novel nano-material, finds the beginning of the nineties in last century.It is to be rolled by certain mode by graphite linings to form, and can be divided into Single Walled Carbon Nanotube and multi-walled carbon nano-tubes by the number of plies of its formation.Carbon nanotube has excellent mechanical property, and its Young's modulus is up to 1Tpa, and tensile strength reaches 60Gpa, is polymkeric substance enhanced ideal filler.Yet dispersion, interface combination and the directed problem of carbon nanotube in polymeric matrix is not well solved as yet, causes carbon nanotube to fail to bring into play well its excellent mechanical property and unique conductivity in polymkeric substance.Therefore even carbon nanotube being dispersed in the matrix, and improving the bonding state etc. of carbon nanotube and polymkeric substance, is the key of the superior carbon nanotube polymer matrix material of processability.
Summary of the invention
The objective of the invention is provides carbon nano tube reinforced polyvinyl alcohol composite material of a kind of good mechanical performance and preparation method thereof for the polyvinyl alcohol fiber product of preparation high-strength and high-modulus.
Carbon nano tube reinforced polyvinyl alcohol composite material of the present invention, its component and weight percent content thereof are as follows: carbon nanotube 1~9%, polyvinyl alcohol 91~99%.
Carbon nano tube reinforced polyvinyl alcohol composite material of the present invention adopts the solution stirring preparation method, its step is as follows: under the room temperature cholate and carbon nanotube are mixed formation suspension in water, the weight percent 0.1%~10% of cholate and carbon nanotube, weight percent adding weight concentration by carbon nanotube in the claim 1 and polyvinyl alcohol is the polyvinyl alcohol water solution of 50mg/ml then, obtain the carbon nanotube polyvinyl alcohol water solution after fully stirring, this aqueous solution is poured in the mould into evaporation obtains matrix material under the room temperature.
Used cholate can be sodium deoxycholate or Taurodeoxycholate sodium among the present invention.
For polyvinyl alcohol is dissolved in preparation process in the water better, using molecular weight usually is 124~1750 polyvinyl alcohol.The diameter of carbon nanotube with 30nm~90nm for well.
For shortening preparation time, can adopt before the evaporation of carbon nanotube polyvinyl alcohol water solution room temperature, remove most water 120-160 ℃ of evaporation earlier.
Beneficial effect of the present invention is:
Matrix material of the present invention is matrix with the polyvinyl alcohol, the carbon nanotube that cholate is modified is an additive, because the carbon nanotube that cholate is modified can be evenly dispersed in the polyvinyl alcohol, improve the mechanical property of polyvinyl alcohol composite material greatly, can be used for preparing the polyvinyl alcohol fiber product of high-strength and high-modulus.Composite material by adopting solution stirring method preparation simultaneously of the present invention, technology is simple, and is easy to operate, and good reproducibility is suitable for large-scale industrial production.
Description of drawings
Fig. 1 is a carbon nanotube scanning electron microscope picture (SEM);
The carbon nanotube scanning electron microscope picture (SEM) that Fig. 2 modifies for sodium deoxycholate;
Fig. 3 is the scanning electron microscope picture (SEM) of carbon nano tube reinforced polyvinyl alcohol composite material stretching section;
Fig. 4 curve 1 is the stress-strain(ed) curve of polyvinyl alcohol, and curve 2 is the stress-strain(ed) curve of carbon nano tube reinforced polyvinyl alcohol composite material.
Embodiment
Embodiment 1:
The 0.5mg sodium deoxycholate and the 50mg carbon nanotube of inciting somebody to action under the room temperature mix formation suspension in 10ml water, adding weight concentration then is the polyvinyl alcohol water solution 99ml of 50mg/ml, at room temperature mix, forming content of carbon nanotubes is the carbon nanotube polyvinyl alcohol composite solution of 1wt%, slowly evaporate most water at 160 ℃ then, at last this carbon nanotube polyvinyl alcohol solution is poured into room temperature evaporation film forming in the mould.
Embodiment 2:
The 0.5mg sodium deoxycholate and the 50mg carbon nanotube of inciting somebody to action under the room temperature mix formation suspension in 10ml water, adding weight concentration then is the polyvinyl alcohol water solution 47ml of 50mg/ml, at room temperature mix, forming content of carbon nanotubes is the carbon nanotube polyvinyl alcohol composite solution of 5wt%, slowly evaporate most water at 160 ℃ then, at last this carbon nanotube polyvinyl alcohol solution is poured into room temperature evaporation film forming in the mould.Fig. 1 is a carbon nanotube scanning electron microscope picture (SEM), and the carbon nanotube entanglement is more serious as can be seen, is unfavorable for that carbon nanotube disperses in polyvinyl alcohol.The carbon nanotube scanning electron microscope picture (SEM) that Fig. 2 modifies for sodium deoxycholate, as can be seen sodium deoxycholate carbon nano-tube modified after, the carbon nanotube tube wall is by the sodium deoxycholate burden, the carbon pipe tangles and greatly reduces, this not only helps carbon nanotube and disperses in polyvinyl alcohol, also strengthened carbon nanotube and contacted, thereby strengthened the mechanical property of carbon nanotube polyvinyl alcohol composite material with interface between polyvinyl alcohol.Fig. 3 is the scanning electron microscope picture (SEM) of carbon nano tube reinforced polyvinyl alcohol composite material stretching section, and carbon nanotube is uniformly dispersed at polyvinyl alcohol as can be seen.Curve 1 is the stress-strain(ed) curve of polyvinyl alcohol among Fig. 4, and curve 2 is the stress-strain(ed) curve of carbon nano tube reinforced polyvinyl alcohol composite material, and when the carbon nanotube addition was 5wt% as seen from the figure, the tensile strength of matrix material had improved 67%.
Embodiment 3:
Sodium deoxycholate and 50mg carbon nanotube with 1.0mg under the room temperature mix formation suspension in 10ml water, adding weight concentration then is the polyvinyl alcohol water solution 9ml of 50mg/ml, at room temperature mix, forming content of carbon nanotubes is the carbon nanotube polyvinyl alcohol composite solution of 9wt%, slowly evaporate most water at 160 ℃ then, at last this carbon nanotube polyvinyl alcohol solution is poured into room temperature evaporation film forming in the mould.
Claims (2)
1. the preparation method of carbon nano tube reinforced polyvinyl alcohol composite material, its step is as follows:
Under the room temperature cholate and carbon nanotube are mixed formation suspension in water, the weight percent 0.1%~10% of cholate and carbon nanotube, suspension adding weight concentration with cholate and carbon nanotube is in the polyvinyl alcohol water solution of 50mg/ml then, obtain the carbon nanotube polyvinyl alcohol water solution after fully stirring, this aqueous solution poured in the mould into evaporation obtains the carbon nanotube polyvinyl alcohol composite material under the room temperature, the carbon nanotube weight percentage is 1%~9% in this matrix material, and the polyvinyl alcohol weight percentage is 91%~99%.
2. the preparation method of carbon nano tube reinforced polyvinyl alcohol composite material according to claim 1 is characterized in that removing most water 120-160 ℃ of evaporation earlier before with the evaporation of carbon nanotube polyvinyl alcohol water solution room temperature.
Priority Applications (1)
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CNB2006100522223A CN100551965C (en) | 2006-06-30 | 2006-06-30 | A kind of carbon nano tube reinforced polyvinyl alcohol composite material and preparation method thereof |
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CNB2006100522223A CN100551965C (en) | 2006-06-30 | 2006-06-30 | A kind of carbon nano tube reinforced polyvinyl alcohol composite material and preparation method thereof |
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CN1900155A CN1900155A (en) | 2007-01-24 |
CN100551965C true CN100551965C (en) | 2009-10-21 |
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Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101586259B (en) * | 2009-06-23 | 2011-06-22 | 东华大学 | Method for preparing polyvinyl alcohol spin dope added with carbon nano-tube |
CN101624462B (en) * | 2009-07-14 | 2010-12-01 | 蔡芳昌 | High-conductivity composition and preparation method thereof and preparation method of molding part |
CN102660097B (en) * | 2012-04-11 | 2013-07-10 | 上海交通大学 | Preparation method of reinforced polyvinyl alcohol compound |
CN103665389B (en) * | 2013-12-10 | 2016-02-03 | 苏州大学张家港工业技术研究院 | A kind of modified carbon nano-tube and preparation method thereof |
CN109721911A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Conductive polyvinyl alcohol film and combinations thereof and preparation method |
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2006
- 2006-06-30 CN CNB2006100522223A patent/CN100551965C/en not_active Expired - Fee Related
Non-Patent Citations (5)
Title |
---|
Fabrication and characterization of carbonnanotube/poly(vinyl alcohol) composites. Milo S. P. Shaffer and Alan H . Windle.Advanced Materials (Weinheim, Germany),Vol.11 No.11. 1999 |
Fabrication and characterization of carbonnanotube/poly(vinyl alcohol) composites. Milo S.P.Shaffer and Alan H.Windle.Advanced Materials(Weinheim,Germany),Vol.11 No.11. 1999 * |
poly(vinyl alcohol)/SWNT Composite Film. xiefei zhang, et al.ano letters,Vol.3 No.9. 2003 |
poly(vinyl alcohol)/SWNT Composite Film. xiefei zhang,et al.ano letters,Vol.3 No.9. 2003 * |
多壁碳纳米管/聚乙烯醇复合材料膜的制备与表征. 张娟玲等.《纳米材料与技术应用进展——第四届全国纳米材料会议论文集》. 2005 |
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Granted publication date: 20091021 Termination date: 20120630 |