CN101440208B - Preparation of functionalized carbon nano-tube modification polyurethane elastomer - Google Patents
Preparation of functionalized carbon nano-tube modification polyurethane elastomer Download PDFInfo
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- CN101440208B CN101440208B CN2008102041941A CN200810204194A CN101440208B CN 101440208 B CN101440208 B CN 101440208B CN 2008102041941 A CN2008102041941 A CN 2008102041941A CN 200810204194 A CN200810204194 A CN 200810204194A CN 101440208 B CN101440208 B CN 101440208B
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention relates to a method for preparing a functional carbon nanotube modified polyurethane, which comprises: firstly, preparation of the functional carbon nanotube, namely, dissolving a carbon nanotube into a mixed solution of concentrated sulfuric acid and concentrated nitric acid the volume ratio of which is 3:1, performing ultrasonic vibration for 1 to 2 hours, heating the mixed solution in water bath, refluxing the mixed solution for 3 to 4 hours, taking out the mixed solution, and obtaining CNT-COOH after dilution, centrifugation, filtration and drying of the mixed solution by deionized water; and dispersing the CNT-COOH into an organic solvent, adding isocyanate into the organic solvent, performing heating in water bath, and obtaining the functional carbon nanotube; and secondly, preparation of a functional carbon nanotube/polyurethane composite system, namely, dissolving the functional carbon nanotube into a thermoplastic polyurethane solution by a solution mixing method, and processing the functional carbon nanotube to form the functional carbon nanotube/polyurethane composite system; or directly mixing the functional carbon nanotube and polyurethane by means of fusing and processing, and extruding the functional carbon nanotube to form the functional carbon nanotube/polyurethane composite system. The method is easy, simple and convenient, has simple equipment, and is suitable for mass production and used in the fields of material reinforcement, electrical conductance, heat conduction and so on; and the elasticity, the mechanical property and the thermal stability of the material obtained are changed correspondingly.
Description
Technical field
The invention belongs to the preparation field of modification polyurethane elastomer, particularly relate to a kind of preparation method of functionalized carbon nano-tube modification polyurethane elastomer.
Background technology
Urethane (PU) is as a kind of common macromolecular material, has snappiness, good flexibility, higher modulus of elasticity and good wear resisting property.The cruel elastomerics of thermoplastic poly ammonia (TPU) in numerous polyurethane products, be a kind of by soft section linear block copolymers that constitutes with the hard section of the cruel chainextender of two isocyanic acids of oligomer polyol, its output accounts for 25% of polyurethane elastomer total amount, be mainly used in trolley part and machine parts, sports shoes at the bottom of, rubber roll, electric wire, flexible pipe, film and thin plate, fabric (coating and high-elastic clothing socks etc.), tape tackiness agent, textile coating, tackiness agent etc.Similar to other thermoplasticss, thermoplastic polyurethane at room temperature has caoutchouc elasticity or plastic properties, and fusion at high temperature becomes rheid and also can process according to the thermoplastics processing mode.Thermoplastic polyurethane is a block polymer, forms physical crosslinking by intermolecular hydrogen bond, has higher physical strength.
Carbon nanotube has high intensity, toughness and Young's modulus.Its Elastic Modulus can reach 1Tpa, with adamantine Young's modulus much at one, be about firm 5 times; Its recoverable strain is about 5%, reaches as high as 12%, is about firm 60 times.No matter CNTs is intensity or toughness, all is to be far superior to other nano-filled particles.CNTs as composite material reinforcement body, can be shown good slight, elasticity, fatigue resistance and isotropy, and this is the development that helps matrix material.
Application number is that CN200410017699.9 discloses a kind of surface and has functionalized carbon nano-tube of isocyanate groups and preparation method thereof.The surface is had modified carbon nano-tube and the binary or the multicomponent isocyanate reaction of amino or hydroxyl, obtain the functionalized carbon nano-tube that the surface has isocyanate groups, and with other material (as polyureas, urethane etc.) be connected the outside surface of carbon nanotube by chemical reaction, realize the design of new nano material, preparation and application.Application number is preparation method and the device that CN20051022117.0 discloses a kind of carbon nano-tube filled high-density conduction rigid urethane foam, this method is to adopt strong oxidation that carbon nanotube is carried out surface treatment, be dispersed in the polyether glycol, water in the system is all volatilized, obtain the mixing solutions of carbon nanotube and polyether glycol, with the dissipation hydramine, organotin, silicone oil, water mixes with mechanical stirring device according to certain proportioning, again with the certain amount of isocyanate thorough mixing, be poured in the mould, close membrane cover, carry out maturation process at last and obtain goods.JP20060175371 has introduced a kind of preparation method that the carbon nanotube dispersion soln prepares sheet of polyurethane that sneaks in urethane, obtain containing the carbon nanotube dispersion soln of tensio-active agent, softening agent with supersound process, mixes film forming with urethane at last.
But existing carbon nanotube dispersed bad in polymer materials, and owing to shortcomings such as the strong change polymer materials impact of performance that causes of bonding force between carbon nanotube and the polymkeric substance are not remarkable.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of functionalized carbon nano-tube modification polyurethane elastomer, and this method technology is simple, easy to control, and cost is low.
The preparation method of a kind of functionalized carbon nano-tube modification polyurethane elastomer of the present invention comprises:
(1) preparation of functionalized carbon nano-tube: it is in 3: 1 the vitriol oil and concentrated nitric acid mixed solution that carbon nanotube is dissolved in volume ratio, ultrasonic concussion 1h-2h, 60-80 ℃ of heating in water bath then, backflow 3h-4h takes out, with deionized water dilution, centrifugal, filtration, drying, obtain acidifying carbon nanotube (CNT-COOH); The carbon nanotube that acidifying is good is dispersed in the organic solvent, adds isocyanic ester, and the mass ratio of carbon nanotube and isocyanic ester is 0.05: 1～1: 1,60-70 ℃ of heating in water bath, and reaction 4h-6h, promptly;
(2) preparation of functionalized carbon nano-tube/urethane compound system: adopt solution blending process functionalized carbon nano-tube to be dissolved in thermoplastic polyurethane (TPU) solution machine-shaping; Perhaps adopt method for melt processing, direct and polyurethane comixing extrusion moulding with functionalized carbon nano-tube.
Carbon nanotube in the described step (1) is one or both in multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube.
Organic solvent in the described step (1) is N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAC) or N, N '-dimethyl sulfoxide (DMSO) (DMSO).
Isocyanic ester is 2 in the described step (1), 4-dimethyl vulcabond (TDI), MDI (MDI), poly-methyl polyphenyl isocyanic ester (PAPI), isophorone diisocyanate (IPDI) or octadecylisocyanate (ODI).
Compound system in the described step (2), the part by weight of functionalized carbon nano-tube in this compound system is 0.1%～5%.
Utilize the strong acid oxide treatment, make carbon nano tube surface connect the carboxylic group of some amount, and then the grafting isocyanate groups is as particle filled composite, and then evenly spread in the urethane by solution blending or method for melt processing etc., strengthened the consistency of carbon nanotube and polyurethane matrix, improve the interaction in carbon nanotube and the polymeric matrix effectively, finally reached the effect of modification polyurethane elastomer.
Beneficial effect
(1) preparation technology of the present invention is simple, and is easy to control, and cost is low, is convenient to large-scale industrial production;
(2) isocyanic ester and the urethane of carbon nano tube surface has good consistency in the prepared material, thereby strengthened the interaction force between carbon nanotube and polyurethane matrix, carbon nanotube has effectively changed the elasticity of urethane, mechanical property to urethane is significantly improved, and can be used for fields such as material enhancing, conduction, heat conduction.
Description of drawings
Fig. 1 is the scanning electron microscope diagram sheet in the cross section of 1%CNT-TDI/TPU matrix material;
Fig. 2 is the infrared spectrogram of the carbon nanotube of grafting TDI, the multi-walled carbon nano-tubes of a acidification, the multi-walled carbon nano-tubes of b grafting TDI.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's claims institute restricted portion equally.
(1) with 2g multi-walled carbon nano-tubes (MWNT), put into the single port flask, vitriol oil mixed solution (the 100ml that adds 70% concentrated nitric acid and 95%, volume ratio 1: 3) ultrasonic 1h, 80 ℃ of heating in water bath condensing reflux 3h then, centrifugal, add deionized water wash and repeatedly be about neutrality until the pH of mixed value, the MWNT of washes clean is put into the dry 48h of vacuum drying oven, obtain the multi-walled carbon nano-tubes MWNT-COOH of oxidation, be placed in the moisture eliminator and preserve.
(2) MWNT that gets exsiccant 0.05g oxidation is dissolved in ultrasonic concussion 1h among the 10ml DMAC, and carbon nanotube is scatter in DMAC fully, and heating in water bath to 70 ℃ adds 0.8mlTDI then, and reaction 4h obtains the carbon nanotube that surface grafting has the TDI group.
(3) the 10g thermoplastic polyurethane particle is dissolved in the 30ml DMAc solvent, and swelling is 4 hours under the room temperature, does not stop to stir to obtain thermoplastic polyurethane solution.The carbon nanotube of grafting TDI in (2) is sneaked in the polyurethane solution for preparing.
(4) with the carbon nano-tube/poly ammonia ester solution for preparing in (3), preparing the MWNT-TDI mass percent by casting film-forming is 0.5% carbon nano-tube/poly ammonia ester matrix material.The tensile strength that records matrix material is 16MPa, and elongation at break is 501%.
Fig. 1 is the cross section pattern SEM photo of 1% compound polyurethane material for the MWNT-TDI mass percent.As can be seen, dark zone is a polyurethane matrix from electromicroscopic photograph, and brighter Points And lines is the carbon pipe, and part carbon pipe can be good at being dispersed in the polyurethane matrix, and this will help changing elasticity and the mechanical property and the thermal characteristics of urethane.
Fig. 2 is the infrared spectrogram of oxide/carbon nanometer tube, and wherein spectrogram (a) is acidifying MWNT (MWNT-COOH), (b) is the MWNT of grafting TDI.On the infrared spectra of MWNT-COOH at 3450cm
-1The place is for the hydroxyl absorption peak, at 1705cm
-1The place is the carboxyl absorption peak, and these all are because the result of strong acid oxide treatment.And scheme (b) at 1580cm
-1Carbamate absorption peak, 2920cm appear in the place
-1Be methyl vibration peak, 1340cm
-1Be the phenyl ring characteristic peak.These all illustrate TDI with carbon nanotube on carboxyl reaction has taken place, and the success be grafted on the carbon nanotube.
Embodiment 2
(1), multi-walled carbon nano-tubes is changed into Single Walled Carbon Nanotube (SWNT) with embodiment 1.
(2) SWNT that gets exsiccant 0.15g oxidation is dissolved in ultrasonic concussion 1h among the 10ml DMF, and carbon nanotube is scatter in DMF fully, and heating in water bath to 70 ℃ adds 2.5mlTDI then, and reaction 4h obtains the carbon nanotube that surface grafting has the TDI group.
(3), the carbon nanotube of grafting TDI in (2) is sneaked in the polyurethane solution for preparing with embodiment 1.
(4), can obtain the SWNT-TDI mass percent by casting film-forming and be about 1.5% carbon nano-tube/poly ammonia ester matrix material with the carbon nano-tube/poly ammonia ester solution for preparing in (3).The tensile strength that records matrix material is 21MPa, and elongation at break is 426%.
Embodiment 3
(1) with embodiment 1.
(2) MWNT that gets exsiccant 0.3g oxidation is dissolved in ultrasonic concussion 1h among the 10ml DMSO, and carbon nanotube is scatter in DMSO fully, and heating in water bath to 70 ℃ adds 5mlMDI then, and reaction 4h obtains the carbon nanotube that surface grafting has the MDI group.
(3), the carbon nanotube of grafting MDI in (2) is sneaked in the polyurethane solution for preparing with embodiment 1.
(4), can obtain the MWNT-MDI mass percent by casting film-forming and be about 3% carbon nano-tube/poly ammonia ester matrix material with the carbon nano-tube/poly ammonia ester solution for preparing in (3).
Embodiment 4
(1) with embodiment 1.
(2) MWNT that gets exsiccant 0.18g oxidation is dissolved in ultrasonic concussion 1h among the 10ml DMAC, and carbon nanotube is scatter in DMAC fully, and heating in water bath to 70 ℃ adds 2.5mlIPDI then, and reaction 6h obtains the carbon nanotube that surface grafting has the IPDI group.
(3), the carbon nanotube of grafting IPDI in (2) is sneaked in the polyurethane solution for preparing with embodiment 1.
(4), can obtain the MWNT-IPDI mass percent by casting film-forming and be about 1.8% carbon nano-tube/poly ammonia ester matrix material with the carbon nano-tube/poly ammonia ester solution for preparing in (3).
Claims (4)
1. the preparation method of a functionalized carbon nano-tube modification polyurethane elastomer comprises:
(1) preparation of functionalized carbon nano-tube: it is in 3: 1 the vitriol oil and concentrated nitric acid mixed solution that carbon nanotube is dissolved in volume ratio, ultrasonic concussion 1h-2h, 60-80 ℃ of heating in water bath then, backflow 3h-4h takes out, with deionized water dilution, centrifugal, filtration, drying, obtain acidifying carbon nanotube CNT-COOH; The carbon nanotube that acidifying is good is dispersed in the organic solvent, and adding and carbon nanotube mass ratio are 1: 0.05～1: 1 isocyanic ester, 60-70 ℃ of heating in water bath, and reaction 4h-6h, promptly;
(2) preparation of functionalized carbon nano-tube/urethane compound system: adopt solution blending process that functionalized carbon nano-tube is dissolved in the thermoplastic polyurethane TPU solution, wherein the part by weight of functionalized carbon nano-tube in this compound system is 0.1%～5%, machine-shaping; Perhaps adopt method for melt processing, the direct and polyurethane comixing extrusion moulding with functionalized carbon nano-tube, the part by weight of functionalized carbon nano-tube in this compound system is 0.1%～5%.。
2. the preparation method of a kind of functionalized carbon nano-tube modification polyurethane elastomer according to claim 1, it is characterized in that: the carbon nanotube in the described step (1) is one or both in multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube.
3. the preparation method of a kind of functionalized carbon nano-tube modification polyurethane elastomer according to claim 1, it is characterized in that: the organic solvent in the described step (1) is N, N '-dimethyl formamide DMF, N, N '-N,N-DIMETHYLACETAMIDE DMAC or N, N '-dimethyl sulfoxide (DMSO) DMSO.
4. the preparation method of a kind of functionalized carbon nano-tube modification polyurethane elastomer according to claim 1, it is characterized in that: isocyanic ester is 2 in the described step (1), 4-dimethyl vulcabond TDI, MDI MDI, poly-methyl polyphenyl isocyanic ester PAPI, isophorone diisocyanate IPDI or octadecylisocyanate ODI.
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| CN112778777A (en) * | 2020-12-30 | 2021-05-11 | 长安大学 | Carbon nano tube and rubber powder composite modified asphalt and preparation method thereof |
| CN113337102B (en) * | 2021-07-27 | 2022-05-17 | 浙江德斯泰新材料股份有限公司 | TPU film with good cohesiveness and preparation method thereof |
| CN115418097A (en) * | 2022-09-16 | 2022-12-02 | 广州美村橡胶科技股份有限公司 | High-strength modified nano composite rubber material and preparation method thereof |
| CN116355393A (en) * | 2023-04-14 | 2023-06-30 | 东莞市奥能工程塑料有限公司 | Thermoplastic polyurethane elastomer material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
| CN1884373A (en) * | 2006-06-28 | 2006-12-27 | 四川大学 | Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube |
-
2008
- 2008-12-09 CN CN2008102041941A patent/CN101440208B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562738A (en) * | 2004-04-15 | 2005-01-12 | 上海交通大学 | Functional nano carbon tubes possessing isocyanate radical on its surface and preparation method |
| CN1884373A (en) * | 2006-06-28 | 2006-12-27 | 四川大学 | Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube |
Non-Patent Citations (2)
| Title |
|---|
| 吴素霞.聚氨酯/ 碳纳米管复合材料的制备与表征.聚氨酯工业.2007,22(3),9-12. * |
| 杨正龙等.一种碳纳米管掺杂改性聚氨酯水性分散体的制备与性能研究.动能材料.2008,(6),1030-1033. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419302A (en) * | 2015-12-22 | 2016-03-23 | 合肥仲农生物科技有限公司 | Polyurethane composite material |
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