CN1230580C - Method for preparing nano particle reinforced, toughened ultrahigh realtive molecular mass polyethylene fiber - Google Patents
Method for preparing nano particle reinforced, toughened ultrahigh realtive molecular mass polyethylene fiber Download PDFInfo
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- CN1230580C CN1230580C CN 02148597 CN02148597A CN1230580C CN 1230580 C CN1230580 C CN 1230580C CN 02148597 CN02148597 CN 02148597 CN 02148597 A CN02148597 A CN 02148597A CN 1230580 C CN1230580 C CN 1230580C
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Abstract
The present invention relates to a preparation method for a nanometer particle reinforcing and toughening polyethylene fiber with superhigh relative molecular weight. The present invention is characterized by comprising the following procedures: (1) surface distributed processing is carried out to nanometer particles; (2) a spinning stock solution of nanometer particle modified polyethylene with superhigh relative molecular weight is prepared; (3) a nanometer particle modified polyethylene fiber with superhigh relative molecular weight is prepared from the spinning stock solution. The mechanical modulus of the fiber can be enhanced by 20% to 70% on the original basis, and the mechanical strength is enhanced to a certain extent.
Description
Technical field
The present invention relates to nano particle in superelevation average molecular weight northylen (the weight average relative molecular weight is 100～5,000,000) fiber preparation method.
Background technology
Ultra high molecular weight polyethylene (English UHMWPE) fiber is the third generation high-performance fiber that occurs after carbon fiber and aramid fiber, have other high-performance fiber incomparable mechanical property.In addition, the ultra high molecular weight polyethylene fiber also has excellent chemical resistance and weather resisteant, high-energy absorption, low electric conductivity, can see through x-ray and certain characteristics such as water proofing property, thereby in military affairs, space flight navigation engineering and fields such as high-performance, light composite material and sports apparatus wide application prospect is arranged.Particularly militarily, the ultra high molecular weight polyethylene fiber has progressively replaced aramid fiber, is used for the making of bulletproof jacket.But by the bulletproof jacket that the ultra high molecular weight polyethylene fiber is made, can only resist penetrating of pistol and low speed rifle bullet mostly, then not have resistance for the high speed rifle.Improve the impact resistance of bulletproof jacket, except that the preparation method that will improve bulletproof jacket, the mechanical moduli of the most basic mechanical property, particularly fiber that still will improve the ultra high molecular weight polyethylene fiber.
Many bibliographical informations make composite with nano-particles filled in polyethylene, can improve poly performance greatly.
As He Peng etc. at " Wear Resistance of nanometer particle-modified high density polyethylene (HDPE) " (plastics, 2001, the method of disperseing by ultrasonic dispersing or vibromill 1:39) adds nano-silicon dioxide particle in the high density polyethylene (HDPE), can make nano particle in high density polyethylene (HDPE), reach nanoscale and disperse, improve the mechanical property and the ABRASION RESISTANCE of material greatly; Huang Rui etc. disclose the preparation method of nm particles reinforced and toughened polyethylene composition in patent CN1283650A, be characterized in nano particle, solvent and surface dispersant add and have supersonic oscillations generator or vibration agitating device, in the presence of a small amount of solvent, utilize ball mill grinding that dispersant and nano particle are evenly disperseed, then surface treated nano particle is carried out drying back and polyethylene mixing preparation masterbatch on mill or double screw extruder, again masterbatch and polyethylene are strengthened toughened polyethylene composition through the preparation of double screw extruder extruding pelletization.But above-mentioned two methods institute modified polyethylene is relatively low high density polyethylene (HDPE) of molecular weight or low density polyethylene (LDPE), and the ultra high molecular weight polyethylene molecular weight is higher, viscosity is big especially, and the adding method of above-mentioned several nano particles all can not make nano particle reach the nanoscale dispersion in ultra high molecular weight polyethylene.
Wang Haibao etc. " nanometer Al2O3 is to polyethylene engineering material Effect on Performance " (University Of Chongqing's journal, 2002,4:26) in ultra high molecular weight polyethylene powder and nano-aluminium oxide (Al
2O
3) particle puts into mould, at high temperature (200 ± 5 ℃) and high pressure (150Mpa) sintering 2 hours down, cooling makes the polyethylene engineering plastics, can significantly improve the hardness and the ABRASION RESISTANCE of ultra high molecular weight polyethylene engineering plastics.But the method can't make nano particle reach nanoscale in ultra high molecular weight polyethylene disperses.
In order effectively to solve the even scattering problem of nano particle in the polymer body, people have proposed the compound new method of in-situ polymerization, promptly on the nano particle of polymolecularity, be written into component, and then on this nanoparticle surface, carry out polymerisation and prepare composite with catalytic activity.As disclosing a kind of preparation method of olefin polymerization nanometer composite material among the USP6465543, this composite is the dispersion thing of nano particle in polyolefin that is made by layered metal oxide or metal oxide salt.At first, remove water then and make the hydrophobicity organic clay that can in non-polar organic solvent, disperse untreated clay swelling in water.This organic clay is formed a kind of complex compound that causes alkene or styrene polymerization with catalyst treatment again with the alkyl aluminum compound processing.Alkene or styrene are directly carried out the nano composite material that in-situ polymerization can make polyolefin or polystyrene in nanoparticle surface under no shearing condition.CN1255510A and USP6444742 disclose the nanocomposite of a kind of polyolefin and clay, this composite is made up of 40～99.9% polyethylene and 0.1～60% fiber rod stone kind clay (weight proportion), transistion metal compound with the nanoscale clay is a catalyst, with the organo-aluminum compound is co-catalyst, carry out the in-situ polymerization of alkene, prepared composite has excellent mechanical property and hot property.This method can make nano particle be evenly dispersed in the ultra high molecular weight polyethylene, but situ aggregation method is comparatively loaded down with trivial details, the cost of gained composite is higher, and can gained ultra high molecular weight polyethylene composite be spun into high-performance fiber and yet there are no research report.
Summary of the invention
The object of the present invention is to provide a kind of nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method, its processing is simple, and production cost is low, and the mechanical property of fiber is good.
Technical scheme of the present invention is: a kind of nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method may further comprise the steps
(1) nanoparticle surface dispersion treatment;
With nano particle, nano particle solvent and surface dispersant, by the weight ratio of nano particle and nano particle solvent be 1: 1～5, the weight ratio of nano particle and surface dispersant is 1: 0.01～0.05, add in the device that has the supersonic oscillations stirring and stir, nano particle and surface dispersant are evenly disperseed;
(2) preparation of nanometer particle-modified ultra high molecular weight polyethylene spinning solution;
Nano particle through surperficial dispersion treatment is carried out drying, be to join the container that have supersonic generator in carry out high-speed stirred at 0.003～0.1: 100 more by weight with dried nano particle and ultra high molecular weight polyethylene solvent, make nano particle in the ultra high molecular weight polyethylene solvent, evenly disperse to form nano-particle solution, weight ratio by nano particle and ultra high molecular weight polyethylene powder is 0.1～1: 100 then, the weight ratio of ultra high molecular weight polyethylene powder and antioxidant is 100: 0.1～1 mixed nano-particle solution, the ultra high molecular weight polyethylene powder, antioxidant, under stirring, heat up, being warming up to the best swelling temperature of ultra high molecular weight polyethylene in this solvent earlier stopped 1 hour, make the abundant swelling of polyethylene powders, and then be warming up to about 185 ℃ and stopped 1 hour, polyethylene is fully dissolved, to prepare the homodisperse ultra high molecular weight polyethylene spinning solution of nano particle;
(3) prepare nanometer particle-modified ultra high molecular weight polyethylene fiber by spinning solution;
By the ultra high molecular weight polyethylene spinning solution of above-mentioned preparation,, make nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber through twin-screw spinning, extraction, stretching.
The present invention compared with prior art has following advantage:
The mechanical moduli of this fiber can improve 20～70% on the original basis, and mechanical strength also improves.
The specific embodiment
Nano particle silica 250 grams, nano particle solvent acetone 150 grams, surface dispersant γ-(methacryloxypropyl) propyl trimethoxy silicane 2 grams are added and have in the reaction vessel of supersonic oscillations, at room temperature handled 20 minutes, the nano silicon after the processing places 50 ℃ baking oven inner drying 2 hours.
With dried nano silicon (SiO
2) with the ultra high molecular weight polyethylene solvent---mineral oil joins by 0.018: 100 ratio and carries out high-speed stirred formation in 20 minutes nano-particle solution in the container that has supersonic generator, be that 0.18: 60 ratio is that 3,500,000 ultra high molecular weight polyethylene powder (being that the concentration of UHMWPE condensate in mineral oil is 6wt%) mixes mutually with nano-particle solution and weight average relative molecular weight in the nano particle and the weight ratio of ultra high molecular weight polyethylene then, in the ultra high molecular weight polyethylene powder and the ratio of antioxidant is that 60: 0.3 ratio is mixed both, under stirring, be warming up to 130 ℃ of swellings 1 hour, be warming up to 180 ℃ of dissolvings 1 hour again, make nascent gel spun fiber through twin-screw spinning (The hole diameter of spinneret is 0.8mm) then, put into fiber barrel and place a period of time and be separated fully.
Through the ultra high molecular weight polyethylene gel spun fiber after being separated, at room temperature carry out 3 times of predrafts, enter then and carry out ultrasonic tensioning extraction in the extraction bath, enter air dry oven and carry out room temperature tensioning drying, the one-level of ultra high molecular weight polyethylene dry freeze glue fiber being carried out 8 times under 100 ℃ stretches, under 110 ℃, carry out 1.4 times of secondary drawing, under 120 ℃, carry out 1.1 times of three grades of stretchings, the intensity of the nanometer particle-modified ultra high molecular weight polyethylene fiber of gained is 31.6cN/dtex, modulus is 1850cN/dtex, and extension at break is 3.61%.
Comparing embodiment:
Do not add nano particle, the additional proportion of ultra high molecular weight polyethylene powder, antioxidant and mineral oil and swelling, dissolving, spinning, extraction and the drawing process of ultra high molecular weight polyethylene are all identical with above-mentioned example, the intensity of prepared ultra high molecular weight polyethylene fiber is 30.2cN/dtex, modulus is 1130cN/dtex, extension at break is 3.97%, and its mechanical property is relatively poor.
Claims (8)
1, a kind of nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method, carry out the nanoparticle surface dispersion treatment earlier, be about to nano particle, nano particle solvent and surface dispersant, by the weight ratio of nano particle and nano particle solvent be 1: 1～5, the weight ratio of nano particle and surface dispersant is 1: 0.01～0.05, add in the device that has the supersonic oscillations stirring and stir, nano particle and surface dispersant are evenly disperseed;
It is characterized in that: carry out the preparation of nanometer particle-modified ultra high molecular weight polyethylene spinning solution again;
Promptly the nano particle through surperficial dispersion treatment is carried out drying, again with dried nano particle be to join the container that have supersonic generator in carry out high-speed stirred at 0.003～0.1: 100 by weight as the mineral oil of solvent, make nano particle in mineral oil, evenly disperse to form nano-particle solution, weight ratio by nano particle and ultra high molecular weight polyethylene powder is 0.1～1: 100 then, the weight ratio of ultra high molecular weight polyethylene powder and antioxidant is 100: 0.1～1 mixed nano-particle solution, the ultra high molecular weight polyethylene powder, antioxidant, under stirring, heat up, being warming up to the best swelling temperature of ultra high molecular weight polyethylene in this solvent earlier stopped 1 hour, make the abundant swelling of polyethylene powders, and then be warming up to about 185 ℃ and stopped 1 hour, polyethylene is fully dissolved, to prepare the homodisperse ultra high molecular weight polyethylene spinning solution of nano particle;
Prepare nanometer particle-modified ultra high molecular weight polyethylene fiber by spinning solution again;
By the ultra high molecular weight polyethylene spinning solution of above-mentioned preparation,, make nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber through twin-screw spinning, extraction, stretching.
2, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: described nano particle is silica or calcium carbonate or alundum (Al.
3, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: described ultra high molecular weight polyethylene weight average relative molecular weight is 100～5,000,000.
4, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: described nano particle solvent is isopropyl alcohol or ethanol or acetone.
5, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: described surface dispersant is titanate esters or aluminic acid ester or silane coupling agent.
6, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1, it is characterized in that: the weight ratio of described nano-particle solution and ultra high molecular weight polyethylene powder is 0.1～0.7: 100.
7, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: when the nanoparticle surface dispersion treatment, stirred under the ultrasonic wave condition 10～30 minutes.
8, nano particle reinforced tenacity increased ultra high molecular weight polyethylene fiber preparation method according to claim 1 is characterized in that: described is under the condition of 40～80 ℃ of temperature dry 2～5 hours to the drying through the nano particle of surperficial dispersion treatment.
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| CN 02148597 CN1230580C (en) | 2002-12-18 | 2002-12-18 | Method for preparing nano particle reinforced, toughened ultrahigh realtive molecular mass polyethylene fiber |
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| CN 02148597 CN1230580C (en) | 2002-12-18 | 2002-12-18 | Method for preparing nano particle reinforced, toughened ultrahigh realtive molecular mass polyethylene fiber |
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| CN1230580C true CN1230580C (en) | 2005-12-07 |
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| CN100390335C (en) * | 2005-03-10 | 2008-05-28 | 中国科学院化学研究所 | Polymer compounding fiber composed by surface-modified, inorganic filler and polymer |
| CN101886298B (en) * | 2010-06-23 | 2013-05-08 | 东华大学 | Preparation method of ultra-high molecular weight polyethylene monofilaments |
| CN102586927B (en) * | 2012-03-01 | 2013-11-27 | 中国人民解放军总后勤部军需装备研究所 | Ultrahigh molecular weight polyethylene/nano tungsten disulfide composite fiber and preparation method and application thereof |
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| CN103147150B (en) * | 2012-11-09 | 2014-12-10 | 中国水产科学研究院东海水产研究所 | Preparation method of monofilament for net cage body and trawl fishing gear |
| CN103147151B (en) * | 2012-11-09 | 2014-12-10 | 中国水产科学研究院东海水产研究所 | Processing method of composite filament for netting gear manufacture |
| CN103147149B (en) * | 2012-11-09 | 2014-12-10 | 中国水产科学研究院东海水产研究所 | Preparation method of composite monofilament for netting gear manufacture |
| CN103132171B (en) * | 2013-03-19 | 2014-08-27 | 中国水产科学研究院东海水产研究所 | Method for manufacturing polyethylene fiber for fishing |
| CN103572396B (en) * | 2013-10-11 | 2015-04-29 | 杭州翔盛高强纤维材料股份有限公司 | Preparation method of blended modified ultra-high molecular weight polyethylene fiber |
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| CN107759813A (en) * | 2017-11-14 | 2018-03-06 | 东莞市鑫益电子科技有限公司 | A kind of preparation method of modified ultra-high molecular weight polyethylene |
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| CN113529199B (en) * | 2021-08-10 | 2023-06-20 | 瑞安市博安防刺穿材料科技有限公司 | Flame-retardant nano SiO 2 Synthesis method of super-molecular weight polyethylene puncture-proof fiber |
| CN115216856A (en) * | 2022-06-09 | 2022-10-21 | 青岛信泰科技有限公司 | Lightweight antistatic ultra-high molecular weight polyethylene short fiber and preparation method thereof |
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Assignee: Changshu Super Fibers Co., Ltd. Assignor: Donghua University Contract fulfillment period: 2008.1.1 to 2012.12.31 contract change Contract record no.: 2009320000311 Denomination of invention: Method for preparing nano particle reinforced, toughened ultrahigh realtive molecular mass polyethylene fiber Granted publication date: 20051207 License type: Exclusive license Record date: 2009.3.10 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.1.1 TO 2012.12.31; CHANGE OF CONTRACT Name of requester: CHANGSHU XIUBO FIBER CO., LTD. Effective date: 20090310 |
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Granted publication date: 20051207 Termination date: 20161218 |