CN105602005A - Method for preparing high-abrasion-resistance functional carbon nano-tube and composite rubber material - Google Patents
Method for preparing high-abrasion-resistance functional carbon nano-tube and composite rubber material Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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Abstract
The invention discloses a method for preparing a high-abrasion-resistance functional carbon nano-tube and a composite rubber material, belongs to the field of functional carbon nano-tube modified rubber materials, and aims at improving the abrasion resistance and the like of an existing rubber material. The method comprises the steps of grafting a polyurethane molecular chain on the surface of the carbon wall of a carbon nano-tube, and cladding to form an inorganic-organic covalent bond structure. The rubber material is compounded with the functional carbon nano-tube. Large-molecular-weight polyurethane molecular chain is grafted to the surface of the high-abrasion-resistance functional carbon nano-tube, the surface free energy of the carbon nano-tube is reduced, the agglomeration phenomenon occurring when a matrix is filled with the carbon nano-tube can be effectively avoided, and the dispersibility and compatibility of the carbon nano-tube with a rubber matrix material are improved. The rubber material is compounded with the functional carbon nano-tube, can realize uniform dispersion of the carbon nano-tube in a rubber matrix, and can be used for remarkably enhancing the abrasion resistance of the composite rubber material.
Description
Technical field
The present invention relates to functionalized carbon nano-tube modification elastomeric material technical field, relate in particular to a kind of preparation method of high abrasion functionalized carbon nano-tube and the rubber composite of compound this functionalized carbon nano-tube.
Background technology
Natural rubber (NR) refers to the Heveatex gathering from rubber tree, the natural polymer elasticity decorating film of making through supersolidification, the manufacturing procedure such as dry, its rubber hydrocarbon (polyisoprene) content, more than 97%, is non-polar rubber. Though the common anti-wear performance of natural rubber can meet most of relative industrial products demand, but at some, the wearability of rubber is required to high equipment industry, such as vehicle tyre, mine conveyer belt and military industry equipment field, the anti-wear performance of existing rubber can not reach instructions for use. In addition, the raising of the anti-wear performance of rubber can not reduce or destroy the performance of other side, such as improving anti-wear performance but can not too much increasing hardness. Above-mentioned requirements has been brought great challenge to the development of elastomeric material.
CNT belongs to a kind of New Type of Carbon structural material, mainly be hybridized to master with SP2, in its space topological structure, there is again the chemical bond of SP2 and SP3 mixed hybridization, and these P tracks overlap each other in the time of carbon nano tube surface, the large π key of height of formation delocalization simultaneously. The unique texture of CNT makes it have many good performances, for example: high-wearing feature, specific area is large, intensity is high, good toughness. In rubber industry, become desirable blended compound material of research high-end rubber product one of to various rubber matrixs to improve the performance of rubber matrix by carbon nano-tube filled, but CNT self has very high surface free energy, easily there is agglomeration, so in the time of composite filled use, CNT is reunited in rubber matrix, with rubber matrix can not be well compatible, not only affected the performance of elastomeric material itself, and CNT is not brought into play its premium properties yet.
Summary of the invention
One object of the present invention is to propose that a kind of surface free energy is lower for the preparation of going out, the preparation method of dispersiveness and the better high abrasion functionalized carbon nano-tube of compatibility.
Another object of the present invention is to propose greatly to improve on a kind of basis not affecting the original performance of rubber the rubber composite of anti-wear performance.
For reaching this object, the present invention is by the following technical solutions on the one hand:
A preparation method for high abrasion functionalized carbon nano-tube, at the carbon wall surface grafted polyurethane strand of CNT, the coated inorganic-organic covalent bond structure that forms.
Further technical scheme is that described CNT is multi-walled carbon nano-tubes.
Further technical scheme is that the described carbon wall surface grafted polyurethane strand at CNT comprises:
Step 1: mix, stir carbon nanotube dust, butyl acetate, isocyanates and catalyst, reaction setting-up time, to carry out the Surface grafting reaction for the first time of CNT;
Step 2: add poly-dihydric alcohol in the reaction system in step 1, stir the mixture, to carry out the Surface grafting reaction for the second time of CNT;
Step 3: add small molecular alcohol and stir setting-up time in the reaction system in step 2, obtain the functionalized carbon nano-tube of surface grafting polyurethane molecular chain.
Further technical scheme is that described step 1 comprises:
Step 101: carbon nanotube dust, butyl acetate are mixed in reactor with isocyanates;
Step 102: pass into N2, it is 50-90 DEG C that reaction temperature is set, and after stirring setting-up time, obtains functionalized carbon nano-tube predispersion;
Step 103: add catalyst in the functionalized carbon nano-tube predispersion obtaining to step 102, reaction temperature is set is 50-90 DEG C, stir and make mixture reaction 1-3h.
Further technical scheme is that described step 2 is:
In setting-up time, add to the reaction system in step 1 poly-dihydric alcohol of setting metering, stir and make mixture reaction 1-3h.
Further technical scheme is that described step 3 comprises:
Step 301: add small molecular alcohol in the reaction system in step 2, be cooled to room temperature after stirring 1-2h;
Step 302: ultrasonic dispersion is less than or equal to 1h, prepares the functionalized carbon nano-tube dispersion of surface grafting polyurethane molecular chain;
Step 303: at the temperature of 80 DEG C, the functionalized carbon nano-tube dispersion in decompression, distillation, oven dry and grinding steps 302 is to obtain the functionalized carbon nano-tube nano-powder of surface grafting polyurethane molecular chain.
Further technical scheme is, described isocyanates is toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), 1, hexamethylene-diisocyanate (HDI), IPDI (IPDI), liquefied mdi, TDI dimer, dimeric one or more mixing of HDI, consumption is the 8-25% of described multi-walled carbon nano-tubes powder weight;
Catalyst used is N, N-dimethyl cyclohexyl amine, triethylamine, N, N-dimethyl benzylamine, triethanolamine, dibutyl tin laurate, stannous octoate, dibutyltin diacetate, N, N '-lutidines, N, N '-lutidines, N-methylmorpholine, N, one or more of N '-diethyl piperazine, addition is the 2-5% of described multi-walled carbon nano-tubes powder weight;
Described poly-dihydric alcohol is one or more of the PCDL, the pla-pcl glycol that distribute of different molecular weight, polytetrahydrofuran diol, polyethylene glycol, hydroxyl-terminated injecting two methyl siloxane, and addition is the 25-200% of described multi-walled carbon nano-tubes powder weight.
Further technical scheme is, described small molecular alcohol be in methyl alcohol, ethanol, butanols any one or several arbitrarily.
For reaching this object, the present invention is by the following technical solutions on the other hand:
A kind of rubber composite, is mixed with the high abrasion functionalized carbon nano-tube as described above of preset proportion in described rubber composite.
Further technical scheme is that the component of described rubber composite and each composition weight proportioning are:
Natural rubber: 100 parts;
Functionalization multi-walled carbon nano-tubes powder body material: 1 part or 3 parts or 5 parts;
Zinc oxide: 6 parts;
Sulphur IS-60:3.5 part;
Stearic acid S.A:0.5 part;
Vulcanization accelerator: 0.7 part.
Beneficial effect of the present invention is:
The functionalized carbon nano-tube of surface grafting polyurethane molecular chain prepared by the present invention, has reduced the surface free energy of CNT effectively, the agglomeration having occurred while effectively having avoided it to be filled into matrix, thus promote dispersiveness and the compatibility of CNT.
Elastomeric material of the present invention is compounded with above-mentioned high abrasion functionalized carbon nano-tube, realized dispersed in rubber matrix of CNT, significantly strengthened the anti-wear performance of rubber composite.
Brief description of the drawings
Fig. 1 is the preparation method's of the high abrasion functionalized carbon nano-tube that provides of the preferred embodiment of the present invention 1 simple and clear flow chart;
Fig. 2 is the preparation method's of the high abrasion functionalized carbon nano-tube that provides of the preferred embodiment of the present invention 2 flow chart;
Fig. 3 is the infrared spectrogram that the preferred embodiment of the present invention 2 provides;
Fig. 4 is the thermogravimetric curve figure that the preferred embodiment of the present invention 2 provides;
Fig. 5 is the scanning electron microscope (SEM) photograph that the preferred embodiment of the present invention 2 provides;
Fig. 6 is transmission electron microscope picture after the cryoultramicrotome that provides of the preferred embodiment of the present invention 3;
Fig. 7 is the NR/MWCNTs that provides of the preferred embodiment of the present invention 3 and the wearing and tearing comparison diagram of NR/F-MWCNTs composite.
Detailed description of the invention
Further illustrate technical scheme of the present invention below in conjunction with accompanying drawing and by detailed description of the invention.
Preferred embodiment 1
The present embodiment discloses the preparation method of a kind of high abrasion functionalized carbon nano-tube (F-MWCNTs). The preparation method of the present embodiment high abrasion functionalized carbon nano-tube is: at the carbon wall surface grafted polyurethane strand of CNT, and the coated inorganic-organic covalent bond structure that forms.
Preferably, described CNT is multi-walled carbon nano-tubes.
The functionalized carbon nano-tube of the surface grafting polyurethane molecular chain that the present embodiment is prepared, effectively reduce the surface free energy of CNT, the agglomeration having occurred while effectively having avoided it to be filled into matrix, thus dispersiveness and the compatibility of CNT promoted.
The concrete preparation method of the carbon wall surface grafted polyurethane strand of CNT does not limit. Concrete, the present embodiment provides a kind of preferred version, as shown in Figure 1, comprises the steps:
Step 1: mix, stir carbon nanotube dust, butyl acetate, isocyanates and catalyst, reaction setting-up time, to carry out the Surface grafting reaction for the first time of CNT. Concrete, step 1 comprises the steps:
Step 101: carbon nanotube dust, butyl acetate are mixed in reactor with isocyanates;
Step 102: pass into N2, it is 50-90 DEG C that reaction temperature is set, and after stirring setting-up time, obtains functionalized carbon nano-tube predispersion;
Step 103: add catalyst in the functionalized carbon nano-tube predispersion obtaining to step 102, reaction temperature is set is 50-90 DEG C, stir and make mixture reaction 1-3h.
Step 2: add poly-dihydric alcohol in the reaction system in step 1, stir the mixture to carry out the Surface grafting reaction for the second time of CNT. Concrete, in setting-up time, add to the reaction system in step 1 poly-dihydric alcohol of setting metering, stir and make mixture reaction 1-3h.
Step 3: add small molecular alcohol and stir setting-up time in the reaction system in step 2, obtain the functionalized carbon nano-tube of surface grafting polyurethane molecular chain. Small molecular alcohol is terminator, for cessation reaction.
Concrete, step 3 comprises the steps:
Step 301: add small molecular alcohol in the reaction system in step 2, be cooled to room temperature after stirring 1-2h;
Step 302: ultrasonic dispersion is less than or equal to 1h, prepares the functionalized carbon nano-tube dispersion of surface grafting polyurethane molecular chain;
Step 303: at the temperature of 80 DEG C, the functionalized carbon nano-tube dispersion in decompression distillation step 302, dries and grind to obtain the functionalized carbon nano-tube nano-powder of surface grafting polyurethane molecular chain after distillation.
Wherein: described isocyanates is toluene di-isocyanate(TDI) (TDI), 4,4'-methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), 1, hexamethylene-diisocyanate (HDI), IPDI (IPDI), liquefied mdi, TDI dimer, dimeric one or more mixing of HDI. Preferably, the consumption of described isocyanates is the 8-25% of described carbon nanotube powders weight.
Catalyst used is N, N-dimethyl cyclohexyl amine, triethylamine, N, N-dimethyl benzylamine, triethanolamine, dibutyl tin laurate, stannous octoate, dibutyltin diacetate, N, N '-lutidines, N, N '-lutidines, N-methylmorpholine, N, one or more of N '-diethyl piperazine. Preferably, the consumption of described catalyst is the 2-5% of described carbon nanotube powders weight.
Described poly-dihydric alcohol is one or more of the PCDL, the pla-pcl glycol that distribute of different molecular weight, polytetrahydrofuran diol, polyethylene glycol, hydroxyl-terminated injecting two methyl siloxane. Preferably, the consumption of described poly-dihydric alcohol is the 25-200% of described carbon nanotube powders weight.
Described terminator is one or more in methyl alcohol, ethanol, butanols.
The functionalized carbon nano-tube of surface grafting polyurethane molecular chain prepared by the present embodiment, has reduced the surface free energy of CNT effectively, the agglomeration having occurred while effectively having avoided it to be filled into matrix, thus promote dispersiveness and the compatibility of CNT.
Preferred embodiment 2
The present embodiment discloses a kind of preparation method of high abrasion functionalized carbon nano-tube, as shown in Figure 2, comprises the steps:
Steps A: multi-walled carbon nano-tubes powder 25g, butyl acetate 500g are mixed in reactor with IPDI 2g;
Step B: pass into N2, it is 50-90 DEG C that reaction temperature is set, and after stirring setting-up time, obtains functionalization multi-walled carbon nano-tubes predispersion;
Step C: add catalyst dibutyltin diacetate 0.5g in functionalization multi-walled carbon nano-tubes predispersion, reaction temperature is set is 50-90 DEG C, stir and make mixture reaction 1-3h.
Step D: add hydroxyl-terminated injecting two methyl siloxane (Mn=2000) 18g in above-mentioned reaction system in 15min, stir (mixing speed is made as 500～600rpm) and make mixture reaction 1-3h to carry out the Surface grafting reaction for the second time of multi-walled carbon nano-tubes.
Step e: add ethanol 0.80g in above-mentioned reaction system, be cooled to room temperature after stirring 1-2h;
Step F: ultrasonic dispersion is less than or equal to 1h, prepares the functionalization multi-walled carbon nano-tubes dispersion of surface grafting polyurethane molecular chain;
Step G: at the temperature of 80 DEG C, the functionalization multi-walled carbon nano-tubes dispersion in decompression distillation step 302, dries and grind to obtain the functionalization multi-walled carbon nano-tubes nano-powder of surface grafting polyurethane molecular chain after distillation. In order to characterize the material behavior of functionalized carbon nano-tube prepared by the present embodiment, carry out following test:
Choose the functionalized carbon nano-tube (F-MWCNTs powder body material) that the present embodiment prepares, carry out infrared, thermogravimetric and ESEM and characterize, specific as follows:
1) infrared spectrum characterization
As shown in Figure 3, Fig. 3 is infrared spectrum: original hydroxylating multi-walled carbon nano-tubes MWCNTs (a); Isophorone two isocyanic acid IPDI (b); F-MWCNTs (c) after butyl acetate solvent extraction carbon wall surface physics is coated.
From Fourier transform infrared spectroscopy figure, in Fig. 3 (a), 3500cm-1 peak is around that original MWCNTs surface-OH stretching vibration produces. And infrared spectrum Fig. 3 (c) of MWCNTs surface grafting polyurethane macromolecular chain can observe the characteristic infrared absworption peak of polyurethane structural: 2853-2964cm-1 place is the stretching vibration peak (ν CH2 and ν CH3) of methylene and methyl; The deformation vibration of C-N key can be seen by 1563cm-1 place; Within the scope of 1500-1719cm-1, large absworption peak is the stretching vibration of the C=O in amino-formate bond (NH-CO-O-) and the flexural vibrations absworption peak of N-H; 1258cm-1 place is the stretching vibration peak of C-O-C in urethano. In Fig. 3 (c), do not observe Fig. 3 (b) isophorone two isocyanic acids-NCO group characteristic absorption peak 2260cm-1, illustrate that isocyanates has participated in graft reaction completely. In addition, the strong vibration peak that 1105cm-1 left and right occurs is attributed to Si-O-Si stretching vibration, shows that hydroxyl-terminated injecting two methyl siloxane has further occurred to react with isocyano-NCO.
Above-mentioned F-MWCNTs powder body material analysis result is to be based upon it through fully centrifugal, washing, has got rid of the impact of physical absorption completely, show MWCNTs surface oneself through grafting polyurethane organic molecule chain, formed chemical bonding.
2) thermogravimetric analysis
As shown in Figure 4, Fig. 4 is thermogravimetric curve: original hydroxylating multi-walled carbon nano-tubes MWCNTs (a); F-MWCNTs (b) after butyl acetate solvent extraction carbon wall surface physics is coated.
Fig. 4 has shown the thermal stability of the F-WMCNTs after original hydroxylating MWCNTs and butyl acetate solvent extraction carbon wall surface physics are coated. Contrasting two curves can find out, though original hydroxylating MWCNTs at 550 DEG C, weight-loss ratio is only 1.50%, illustrates that it has good heat endurance. And modification F-WMCNTs is with the slowly thermal degradation of rising of temperature, in the time of temperature rise to 550 DEG C, weightlessness is 8.00%, and the difference of the two weight-loss ratio is 6.50%. The difference of these two curves is mainly because low than original hydroxylating MWCNTs of the heat endurance of surface chemistry grafted-organosilicon type polyurethane molecular chain. The proportion that meanwhile, can estimate the silicone based type polyurethane covering amount of original hydroxylating MWCNTs modification rear surface chemical graft is approximately 6.50%.
3) scanning electron microscope analysis
Fig. 5 is ESEM picture: original hydroxylating multi-walled carbon nano-tubes MWCNTs (a); F-MWCNTs (b) after butyl acetate solvent extraction carbon wall surface physics is coated
Fig. 5 has provided the stereoscan photograph of original hydroxylating MWCNTs and the butyl acetate solvent extraction surface physics F-WMCNTs after coated. Contrast scans Electronic Speculum picture can be found out, the about 50nm of original hydroxylating MWCNTs mean outside diameter, and surface is comparatively coarse. And modification F-WMCNTs mean outside diameter is increased to about 70nm, surface is Paint Gloss, shows the distinctive shape characteristic of fractionated polymer subchain. Owing to having become inorganic-organic covalent bond material after MWCNTs grafted-organosilicon type polyurethane molecular chain, be conducive to increase the interaction of itself and rubber matrix, improve the interfacial structure between rubber and multi-walled carbon nano-tubes.
Preferred embodiment 3
The present embodiment discloses a kind of rubber composite (NR/F-MWCNTs), is mixed with the high abrasion functionalized carbon nano-tube as disclosed in preferred embodiment 2 of preset proportion in described rubber composite.
Concrete, the component of described rubber composite and each composition weight proportioning are:
Natural rubber: 100 parts;
Functionalization multi-walled carbon nano-tubes powder body material: 1 part or 3 parts or 5 parts;
Zinc oxide: 6 parts;
Sulphur IS-60:3.5 part;
Stearic acid S.A:0.5 part;
Vulcanization accelerator: 0.7 part.
Said components is carried out to mixing, banburying and sulfidization molding and can be obtained the rubber composite (NR/F-MWCNTs) of complex function carbon nano tube.
In order to characterize the characteristic of rubber composite (NR/F-MWCNTs) of the present embodiment complex function carbon nano tube, carry out following test:
Choose the NR/F-WMCNTs composite preparing in the present embodiment, carry out transmission electron microscope, Akron abrasion sign, specific as follows:
1) transmission electron microscope analysis
Fig. 6 be transmission electron microscope picture: NR/F-MWCNTs after cryoultramicrotome (1 part) (a); NR/F-MWCNTs (3 parts) (b); NR/F-MWCNTs (5 parts) (c).
In order to characterize the true dispersity after the compound NR of F-MWCNTs, the NR/F-MWCNTs composite sulfuration sample of filling 1 part, 3 parts and 5 parts three kinds of Different adding amounts is carried out to cryoultramicrotome, then carry out transmission electron microscope observing. Fig. 6 has provided transmission electron microscope picture after NR/F-MWCNTs composite cryoultramicrotome, can find out, along with the increase of F-MWCNTs interpolation umber, the quantity of carbon nanotubes occurring in NR matrix also increases gradually, in the time adding 5 parts to, CNT in whole NR matrix can show certain contiguous network structure, contribute to composite to be subject to being carried out effectively transmitting and maybe the heat of conversion effectively being derived after extraneous effect of stress, thereby be conducive to improve the anti-wear performance of rubber composite under various motion states. Meanwhile, in three kinds of NR/F-MWCNTs sulfuration samples, all do not find obvious agglomeration, illustrate after original hydroxylating MWCNTs grafted-organosilicon type polyurethane molecular chain, can improve its mobility and dispersiveness, thereby reduce the reunion of MWCNTs powder body material.
2) anti-wear performance
Fig. 7 is the wearing and tearing contrast of NR/MWCNTs and NR/F-MWCNTs composite.
Akron abrasion is a kind of relatively slow and less loading process of deformation, and the rigidity network structure of multi-walled carbon nano-tubes has formed the three-dimensional " cage " of similar support, can protect the rubber molecular chain of " cage " the inside to be subject to the effect of less frictional force. Along with adding gradually of original MWCNTs, the anti-wear performance of NR/MWCNTs composite improves gradually, in the time joining 3-5 part, variation tendency is mild, and wearing and tearing are far smaller than NR/MWCNTs composite after F-MWCNTs composite natral rubber, while adding 5 parts, its Akron abrasion value is 0.9cm3/ 1.61km, also much smaller than the 2.96cm of NR rubber in professional standard NY/T1403-20073/ 1.61km, illustrates that the anti-wear performance of rubber is greatly improved after Complex Function carbon nanotube dust material. Therefore, compared with original MWCNTs, not only be conducive to reduce carbon nano tube surface energy at the silicone based type polyurethane strand of its surface grafting, can also reduce the frictional force of carbon wall and rubber molecular chain, and greatly bring into play the rigidity of multi-walled carbon nano-tubes, jointly resist the effect of external load, provide new method for manufacturing high wear-resistant rubber product.
Preferred embodiment 4
The present embodiment discloses a kind of preparation method of high abrasion functionalized carbon nano-tube, and its preparation method and preferred embodiment 2 are basic identical, and difference part is: choose different isocyanates and poly-dihydric alcohol, and corresponding proportioning difference.
The present embodiment is: functionalized carbon nano-tube powder 25g, butyl acetate 500g, 4,4 '-methyl diphenylene diisocyanate 5g, dibutyltin diacetate 0.5g, pla-pcl glycol (Mn=2000) 40g, ethanol are 1.80g.
The functionalized carbon nano-tube of surface grafting polyurethane molecular chain prepared by the present embodiment, has reduced the surface free energy of CNT effectively, the agglomeration having occurred while effectively having avoided it to be filled into matrix, thus promote dispersiveness and the compatibility of CNT.
Preferred embodiment 5
The present embodiment discloses a kind of preparation method of high abrasion functionalized carbon nano-tube, and its preparation method and preferred embodiment 2 are basic identical, and difference part is: choose different isocyanates and poly-dihydric alcohol, and corresponding proportioning difference.
The present embodiment is: functionalized carbon nano-tube powder 25g, butyl acetate 500g, 4,4 '-methyl diphenylene diisocyanate 3.0g, dibutyltin diacetate 0.5g, poly-second dihydroxylic alcohols (Mn=1000) 12g, ethanol are 1.10g.
The functionalized carbon nano-tube of surface grafting polyurethane molecular chain prepared by the present embodiment, has reduced the surface free energy of CNT effectively, the agglomeration having occurred while effectively having avoided it to be filled into matrix, thus promote dispersiveness and the compatibility of CNT.
Know-why of the present invention has below been described in conjunction with specific embodiments. These are described is in order to explain principle of the present invention, and can not be interpreted as by any way limiting the scope of the invention. Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other detailed description of the invention of the present invention, within these modes all will fall into protection scope of the present invention.
Claims (10)
1. a preparation method for high abrasion functionalized carbon nano-tube, is characterized in that,
At the carbon wall surface grafted polyurethane strand of CNT, polyurethane molecular chain is coated by CNTForm inorganic-organic covalent bond structure.
2. the preparation method of high abrasion functionalized carbon nano-tube according to claim 1, its feature existsIn, described CNT is multi-walled carbon nano-tubes.
3. the preparation method of high abrasion functionalized carbon nano-tube according to claim 1 and 2, its featureBe, the described carbon wall surface grafted polyurethane strand at CNT comprises:
Step 1: mix, stir carbon nanotube dust, butyl acetate, isocyanates and catalyst, reactionSetting-up time, to carry out the Surface grafting reaction for the first time of CNT;
Step 2: add poly-dihydric alcohol in the reaction system in step 1, stir the mixture, to carry out carbonThe Surface grafting reaction for the second time of nanotube;
Step 3: add small molecular alcohol and stir setting-up time in the reaction system in step 2, shownThe functionalized carbon nano-tube of face grafted polyurethane strand.
4. the preparation method of high abrasion functionalized carbon nano-tube according to claim 3, its feature existsIn, described step 1 comprises:
Step 101: carbon nanotube dust, butyl acetate are mixed in reactor with isocyanates;
Step 102: pass into N2, it is 50-90 DEG C that reaction temperature is set, and after stirring setting-up time, obtains functionalizationCNT predispersion;
Step 103: add catalyst in the functionalized carbon nano-tube predispersion obtaining to step 102, establishPut reaction temperature and be 50-90 DEG C, stir and make mixture reaction 1-3h.
5. the preparation method of high abrasion functionalized carbon nano-tube according to claim 3, its feature existsIn, described step 2 is:
In setting-up time, add to the reaction system in step 1 poly-dihydric alcohol of setting metering, stir and make to mixCompound reaction 1-3h.
6. the preparation method of high abrasion functionalized carbon nano-tube according to claim 3, its feature existsIn, described step 3 comprises:
Step 301: add small molecular alcohol in the reaction system in step 2, be cooled to chamber after stirring 1-2hTemperature;
Step 302: be not more than the ultrasonic dispersion of 1h, prepare the merit of surface grafting polyurethane molecular chainEnergy carbon nano tube dispersion;
Step 303: at the temperature of 80 DEG C, the function in decompression, distillation, oven dry and grinding steps 302Carbon nano tube dispersion is to obtain the functionalized carbon nano-tube nano-powder of surface grafting polyurethane molecular chain.
7. the preparation method of high abrasion functionalized carbon nano-tube according to claim 3, is characterized in that:
Described isocyanates is toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanate(MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), 1, hexamethylene-diisocyanate (HDI), different Fo ErKetone vulcabond (IPDI), liquefied mdi, TDI dimer, HDI are dimeric, and one or more are mixedClose, consumption is the 8-25% of described multi-walled carbon nano-tubes powder weight;
Catalyst used is N, N-dimethyl cyclohexyl amine, triethylamine, N, N-dimethyl benzylamine, three ethanolAmine, dibutyl tin laurate, stannous octoate, dibutyltin diacetate, N, N '-lutidines,N, N '-lutidines, N-methylmorpholine, N, one or more of N '-diethyl piperazine, addition isThe 2-5% of described multi-walled carbon nano-tubes powder weight;
Described poly-dihydric alcohol is PCDL, the pla-pcl glycol, poly-four that different molecular weight distributesOne or more of hydrogen furans glycol, polyethylene glycol, hydroxyl-terminated injecting two methyl siloxane, described in addition isThe 25-200% of multi-walled carbon nano-tubes powder weight.
8. the preparation method of high abrasion functionalized carbon nano-tube according to claim 3, its feature existsIn: described small molecular alcohol be in methyl alcohol, ethanol, butanols any one or several arbitrarily.
9. a rubber composite, is characterized in that: in described rubber composite, be mixed with and set ratioExample as arbitrary in claim 1-8 as described in high abrasion functionalized carbon nano-tube.
10. rubber composite according to claim 9, is characterized in that, described rubber combined materialComponent and each composition weight proportioning of material are:
Natural rubber: 100 parts;
Functionalization multi-walled carbon nano-tubes powder body material: 1 part or 3 parts or 5 parts;
Zinc oxide: 6 parts;
Sulphur IS-60:3.5 part;
Stearic acid S.A:0.5 part;
Vulcanization accelerator: 0.7 part.
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| CN113214638A (en) * | 2021-05-27 | 2021-08-06 | 湖南飞鸿达新材料有限公司 | Wave-absorbing heat-conducting flexible composite material and preparation method thereof |
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