CN1194121C - Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation - Google Patents
Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation Download PDFInfo
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- CN1194121C CN1194121C CNB031152309A CN03115230A CN1194121C CN 1194121 C CN1194121 C CN 1194121C CN B031152309 A CNB031152309 A CN B031152309A CN 03115230 A CN03115230 A CN 03115230A CN 1194121 C CN1194121 C CN 1194121C
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Abstract
The present invention discloses gel spinning polyethylene / carbon nanometer tube composite fiber with super molecule mass and a preparation method. The gel spinning polyethylene / carbon nanometer tube composite fiber with super molecule mass of the present invention is composed of super molecule mass polyethylene (UHMWPE) and a carbon nanometer tube, wherein the carbon nanometer tube accounts for 0.01 to 5 wt% of the fiber. The preparation method of the present invention comprises purification and organification treatment of the carbon nanometer tube, gelation preparation and gel spinning. The present invention has the advantages that the carbon nanometer tube as a modifying agent has good performance, and compared with other modifying agents (such as inorganic filling agents and fiber), the carbon nanometer tube compounded with the UHMWPE performs good performance, especially in the aspects of heat resistance and creep resistance; the damage to the original good performance of the UHMWPE fiber is little. Compared with the high energy radiation modification method, the implementation method is simple, and the required equipment is simple. The original UHMWPE fiber production equipment can be slightly improved for direct production.
Description
Technical field
The present invention relates to a kind of gel-spun ultra-high molecular weight polyethylene/carbon nano tube composite fibre and preparation method thereof.This composite fibre is formed through the gel spinning processes by the blend solution of treated CNT and ultra high molecular weight polyethylene, belongs to the high-performance fiber technical field.
Background technology
As everyone knows, ultra high molecular weight polyethylene (UHWMPE) fiber is to be raw material with the ultra high molecular weight polyethylene, the special fibre of a kind of novelty that technical process such as process dissolution with solvents, gel fiber that quenching is spun, extraction, drying, the hot ultra-drawing of segmentation are made.This fiber has premium properties such as light weight, high-strength, Gao Mo, anti-ultraviolet, shock-resistant, seawater corrosion resistance, electric insulation, has a wide range of applications in fields such as military affairs, Aeronautics and Astronautics, navigation engineering and sports apparatus.Yet, form no any polar group on the strand by the methylene group because the macromolecular structure of UHWMPE is a linear structure, so its heat resistance poor (serviceability temperature generally is lower than 100), and its comprehensive mechanical intensity is also relatively poor, and creep is serious, has greatly limited the application of UHMWPE fiber.The heat resistance and the creep resistance that how to change the UHMWPE fiber have become the important topic that further develops the UHMWPE fiber.
At present, improve the heat resistance of UHMWPE fiber and the method for creep resistance and mainly contain following method: make the fiber self-crosslinking, to wherein adding inorganic filler and making methods such as itself and other fiber hybrid.Though this several method can be to a certain extent the heat resistance and the creep resistance of UHMWPE fiber is increased, the insufficient amplitude ideal that improves, and to a certain extent the original performance of UHMWPE fiber is damaged to some extent again.
Wherein, make the method for UHMWPE fiber self-crosslinking have two kinds: chemical crosslinking and crosslinking with radiation.For chemical crosslinking, be exactly after in UHMWPE, adding suitable crosslinking agent, in melting process, take place crosslinked, because the molecular mass of UHMWPE is very big, is difficult for fusion, and nonpolarity group on the strand, so chemical crosslinking is difficult for carrying out, the effect of modification is not clearly, and also degradation reaction can take place in cross-linking process, and the performance of UHMWPE is reduced.So main now method that adopts crosslinking with radiation, utilize high-energy radiation to make between strand to produce laterally crosslinked, this can improve the heat resistance and the creep resistance of UHMWPE fiber to a certain extent, but in crosslinked process, also inevitably produce chain-scission degradation, along with the increase of dosage of radiation, palliating degradation degree also increases, and the TENSILE STRENGTH of fiber and extension at break are decreased, in addition, this technical process is comparatively complicated.
Adopt fillers such as glass microballoon, mica, talcum powder, silica, alchlor, molybdenum bisuphide, carbon black to carry out filling-modified to UHMWPE, because UHMWPE is a kind of high tenacity material, the filler that adds forms the physical crosslinking point, limited the warm-up movement of molecule, can improve its heat resistance and creep resistance, but filler also becomes stress concentration point simultaneously, causes the impact strength of UHMWPE fiber to descend.
UHMWPE fiber and carbon fiber, glass fibre and Kevlar is fiber blended, also can improve its heat resistance and creep resistance, but owing to do not have polar group and smooth surface on the UHMWPE strand, can not and use with and form compatible interface between fiber, can not form good active force between two components, finally can not obtain the complex fiber material of function admirable.
In addition, nanomaterial science is a new scientific domain just having risen and be subjected to common concern in recent years.In general, nano composite material be meant have at least in the material phase material be nanoscale (in 1～100nm) scope, thus the material with property.The document introduction is arranged, the heat resistance and the creep resistance that can improve polymer by the melt or the solution intercalation technology of polymer, exemplary is exactly to utilize the nanometer composite polyamide-clay material of intercalation technique preparation, it strengthens effect and surpasses the prepared composite of traditional blending technology technology, especially heat resistance is greatly improved, and does not influence impact flexibility.But the composite of intercalation technique gained only keeps nanoscale on one dimension, therefore is mainly used in the preparation of plastics, film.For fibrous material, after the composite spinning of intercalation gained, nano particle may cause a lot of defectives therein, forms stress concentration point, makes the intensity decreases of fiber, even process can't be carried out smoothly.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of gel-spun ultra-high molecular weight polyethylene/carbon nano tube composite fibre and preparation method, to overcome the above-mentioned defective that prior art exists.
Technical conceive of the present invention is such:
CNT is the seamless hollow tube that is surrounded by the former sub-grid of hexagonal carbon, two ends are covered by hemispheric big fullerene molecule usually, diameter zero point several nanometers to tens nanometers, length then is several to a hundreds of micron, as a kind of new material, the strength ratio steel of CNT is high more than 100 times, and Young's modulus can be up to 1TPa, and proportion has only 1/6 of steel; CNT also has high toughness simultaneously, and is very soft, is considered to following " super fiber ", is reinforcement material fabulous in the composite.The present invention selects CNT to have suitable advantage as the modifier of the heat resistance of improving the UHMWPE fiber and creep resistance, its reason is that CNT is to present spiral helicine hollow tube, very high draw ratio is arranged,, can on the bidimensional yardstick, keep nanoscale generally greater than 1000.Because the acting in conjunction of hollow nano pipe and helicity has determined that it is a kind of perfect, the thinnest fibrous material, be better than current any fiber, the intrinsic property that had both had carbon fiber, the electrical and thermal conductivity that has metal material again, the heat-proof corrosion-resistant of ceramic material, the softness property compiled of textile fabric, and the slight workability of macromolecular material, be functional material and the structural material that an a kind of material multipotency and a material are used more, can estimate that the material known to its strength ratio a few days ago wants high two orders of magnitude, and by testing discovery CNT (carbon nano-tube) flintiness than carbon fiber height, but fragility is low, the composite that many walls nanotube and polymer backbone are made, the deformation rate before its fracture can reach 15%.And being easy to machine-shaping with the composite of made of carbon nanotubes, the density of CNT is low on the other hand, can make the composite of light weight.
Technical scheme of the present invention:
Gel-spun ultra-high molecular weight polyethylene/carbon nano tube composite fibre of the present invention is a kind of composition, constitute by ultra high molecular weight polyethylene (UHMWPE) and CNT, wherein, the content of CNT is 0.01～5% of total weight of fiber, preferred 0.1～3%.
In order on the basis of not damaging the original excellent properties of UHMWPE fiber, to improve the heat resistance and the creep resistance of UHMWPE fiber better, the invention provides a kind of UHWMPE/ carbon nano tube composite fibre and preparation method thereof, this method comprises the steps:
(1) pre-treatment of CNT, the key for preparing this kind composite fibre are CNT to be had comparatively uniformly disperse in matrix, and with matrix more excellent compatibility are arranged.Processing method comprises purification process and the processing that organises.
The purifying of CNT:
The CNT of being addressed be impregnated in the mixed solution of sulfuric acid and potassium permanganate, and under reflux temperature 1～5 hour, the impurity on CNT (carbon nano-tube) surface was removed in oxidation, obtained the carbon pipe behind the purifying.The concentration of potassium permanganate in sulfuric acid is 1～8g/100ml, and preferred treating capacity is 1～3g CNT/100ml;
The processing that organises of CNT;
Carbon pipe and titanate coupling agent behind the purifying were refluxed in solvent 1～3 hour, obtain the carbon pipe after the coupling agent grafting; Said solvent is conventional organic solvent, preferably ethanol, isopropyl alcohol or acetone etc.; Preferred titanate coupling agent is C
1～C
4Titanate esters, as butyl titanate or metatitanic acid methyl esters, the suitable concentration of titanate coupling agent is 0.01～0.04g/ml in the solvent, treating capacity is 1～4g CNT/ml.
(2) preparation of gel: utilize ultrasonic wave to be evenly dispersed in CNT and contain in the paraffin oil of UHMWPE, slowly be warming up to 150～190 ℃, programming rate is controlled at 1 ℃/minute, is incubated 1～4 hour, obtains gel.According to the present invention, preferably slowly heat up according to table 1 heating step:
Table 1
| Between heating zone (℃) | 0～100 | 100～110 | 110～120 | 120～130 | 130～180 |
| Temperature retention time (min) | 10 | 30 | 30 | 30～60 | 120 |
(3) gel spinning: to fully the UHMWPE/ CNT composite solution of dissolving adopt conventional gel spinning method to carry out spinning, can obtain fiber of the present invention.
The spinning temperature of said gel spinning method is 130 ℃～140 ℃, and the gelatine silk of preparation obtains fiber of the present invention through extraction, three hot drawing-offs etc.
Evidence, fiber of the present invention can overcome the shortcoming that prior art exists to a great extent, obtain the UHMWPE fiber of high comprehensive performance, can expand it in many-sided application.Through peroxidating and organise after handling CNT can and the UHMWPE matrix between compatibility is preferably arranged, can produce stronger active force between the two, the transfer of can loading well, and because CNT itself just can be regarded as a kind of high-quality fibrous material, in to the process of UHMWPE tensile fiber, form certain orientation, the performance of composite fibre is further enhanced.Because CNT has a lot of premium properties, it has good heat resistance, intensity and creep resistance, so according to the compatibility principle of composite, can reach the heat resistance of improving the UHMWPE fiber and the purpose of creep resistance theoretically.
Compared with prior art, advantage of the present invention is:
(1) modifier CNT itself has excellent performance, reveal more performance than other modifier (as inorganic filler and fiber) and UHMWPE composite table, especially aspect heat resistance and creep resistance, and very little to the damage of the original excellent properties of UHMWPE fiber.
(2) implementation method than high-energy radiation method of modifying is simple, and the equipment that requires is simple, can improve a little on the production equipment of original UHMWPE fiber and directly produce.
The specific embodiment
Embodiment 1
The 2g CNT be impregnated in the mixed solution of 100ml sulfuric acid and potassium permanganate, handled 1.5 hours under reflux temperature, the concentration of potassium permanganate in sulfuric acid is 5g/100ml; CNT behind the 2g purifying and butyl titanate coupling agent were refluxed in ethanol 2 hours, obtain the carbon pipe after the coupling agent grafting; The concentration of titanate coupling agent is 0.03g/ml in the ethanol;
Utilize ultrasonic wave to be evenly dispersed in CNT and contain in the paraffin oil of UHMWPE, slowly heat up 180 ℃ according to the following table heating step, programming rate is controlled at 1 ℃/minute, is incubated 2.5 hours, obtains gel;
| Between heating zone (℃) | 0～100 | 100～110 | 110～120 | 120～130 | 130～180 |
| Temperature retention time (min) | 10 | 30 | 30 | 30～60 | 120 |
(3) gel spinning: to fully the UHMWPE/ CNT composite solution of dissolving adopt conventional gel spinning method to carry out spinning, can obtain fiber of the present invention.
The spinning temperature of said gel spinning method is 130 ℃, and the gelatine silk of preparation obtains fiber of the present invention through extraction, three drawing-offs.The performance test results such as table 2.
Comparative example 1
Except not adding any CNT (carbon nano-tube), all by aforesaid preparation process, the preparation gel spun fiber.The performance test results such as table 2.
Comparative example 2
Except CNT (carbon nano-tube) is changed into the imvite, all prepare gel spun fiber by aforesaid preparation process.The performance test results such as table 2.
Table 2
| Test event | Young's modulus (GPa) | Intensity (GPa) | 80 ℃ of creep properties, 500Mpa, | Thermal degradation during 390 ℃ of heat resistances | Spinnability | |
| 10 1s | 10 4s | |||||
| Embodiment 1 | 108 | 2.2 | 3.2 | 3.7 | 9.4 | Good |
| Comparative example 2 | 91 | 1.4 | 3.6 | 4.6 | 12 | Difference |
| Comparative example 1 | 78 | 2.1 | 4.1 | 6.5 | 14.6 | Good |
By table 2 as seen, the frozen glue that comparative example 2 adds nano imvites spins the PE fiber, although the common frozen glue of modular ratio spins the high about 17% of PE fiber, creep also has improvement, and loss of strength is bigger, and spinnability is very poor, frequent fracture of wire during stretching.Because the intercalation imvite is a 1-dimention nano synusia shape, two-dimensional can reach 10～80% of fibre diameter in addition, is disadvantageous to spinning fibre therefore.
Spin the PE fiber and add treated CNT frozen glue, then because the external diameter of CNT is about 20～30 nanometers, and internal diameter is about 1～3 nanometer, length can reach 1 μ m, draw ratio 100～1000, it is fibrous to be two-dimensional nano, therefore can be evenly distributed in the frozen glue body, behind capillary spinning and ultra-drawing, CNT is along fiber axis direction orientation and play humidification, do not influence the carrying out of spinning process, and fiber modulus improves 40%, heat resistance raising about 50%.
Claims (6)
1. a gel-spun ultra-high molecular weight polyethylene/carbon nano tube composite fibre is characterized in that being made of ultra high molecular weight polyethylene and CNT.
2. fiber according to claim 1, the content that it is characterized in that CNT is 0.01～5% of total weight of fiber.
3. fiber preparation method according to claim 1 and 2 is characterized in that comprising the steps:
(1) CNT carries out purification process and the processing that organises;
(2) utilize ultrasonic wave to be evenly dispersed in CNT and contain in the paraffin oil of ultra high molecular weight polyethylene, be warming up to 150～190 ℃, obtain gel.
(3) adopt conventional gel spinning method to carry out spinning, promptly obtain fiber of the present invention.
4. method according to claim 3 is characterized in that the purification process of CNT comprises the steps:
The CNT of being addressed be impregnated in the mixed solution of sulfuric acid and potassium permanganate, handled under reflux temperature 1～5 hour, the impurity on CNT (carbon nano-tube) surface is removed in oxidation, obtains the carbon pipe behind the purifying; The concentration of potassium permanganate in sulfuric acid is 1～8g/100ml, and treating capacity is 1～3g CNT/100ml.
5. method according to claim 3 is characterized in that, organises to handle to comprise the steps:
Carbon pipe and titanate coupling agent behind the purifying were refluxed in solvent 1～3 hour, obtain the carbon pipe after the coupling agent grafting, the concentration of titanate coupling agent is 0.01～0.04g/ml in the solvent, and treating capacity is 1～4g CNT/ml.
6. method according to claim 3 is characterized in that, titanate coupling agent is C
1～C
4Titanate esters.
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| CNB031152309A CN1194121C (en) | 2003-01-28 | 2003-01-28 | Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation |
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