CN101407947B - Montmorillonite / polypropylene / polylactic acid composite fiber material and preparing method thereof - Google Patents
Montmorillonite / polypropylene / polylactic acid composite fiber material and preparing method thereof Download PDFInfo
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- CN101407947B CN101407947B CN2008102031719A CN200810203171A CN101407947B CN 101407947 B CN101407947 B CN 101407947B CN 2008102031719 A CN2008102031719 A CN 2008102031719A CN 200810203171 A CN200810203171 A CN 200810203171A CN 101407947 B CN101407947 B CN 101407947B
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Abstract
The invention relates to a montmorillonite/polypropylene/polylactic acid composite fiber material; the components thereof comprise montmorillonite, polypropylene and polylactic acid, with the weight percentage of 0.1 to 20: 80 to 99.9; and the preparation thereof comprises the following steps: (1) nano powder of the montmorillonite is arranged in a special transmission device of a plasma treatment device for carrying out modification treatment to the nano powder of the montmorillonite; (2) the montmorillonite prepared by plasma treatment is mixed with polypropylene/polylactic acid powder or polypropylene/polylactic acid slices, a double screw extruder or a single screw extruder is used for mixing the materials, and melting mixing is carried out at 180 to 260 DEG C to obtain nano montmorillonite/polypropylene/ polylactic acid composite slices; and (3) the slices obtained in the step (2) are treated with spinning according to a conventional melt-spinning method to obtain the montmorillonite/polypropylene/polylactic acid composite fiber material. The composite fibers produced by the method have good spinnability and high fiber-forming strength, and is characterized by controlled conductivity, heat conduction, antistatic and biodegradation.
Description
Technical field
The invention belongs to composite fibre and preparation field thereof, particularly relate to a kind of imvite/polypropylene composite fibre and preparation method thereof.
Background technology
Imvite (Montmorillonite) is the mineral that belong to imvite family; Imvite family mineral are found 11 altogether; They be sliding between bentonite, shellfish get native, lithium soap is native, soil, bentonite, zinc soap soil, this bentonite, lithium montmorillonite, chromium imvite and copper imvite etc. are taken off in imvite, sodium, but structure can be divided into imvite subtribe (dioctahedron) and bentonite subtribe (trioctahedron) internally.Imvite is one of typical layer silicate mineral, but and other layer silicate mineral dissimilarities be the layer with the layer between the space big especially, so just can layer and layer in contain the not hydrone and the exchangeable cation of determined number.
Imvite is to push up the tetrahedral si-o film folder one deck that connects altogether by two layers to be total to aluminium (magnesium) oxygen (hydrogen-oxygen) octahedral sheet that rib connects, and formation 2:1 type contains the silicate mineral of the crystallization water.Al3+ is by the isomorphous substitution of Mg3+, Fe3+, Fe2+ etc. in the octahedron of its structural posts; Cause octahedra distortion; And then force tetrahedral sheet to make rotation, elongation, form such as twisted is aligned; Until scission of link occurring, make polyhedron core CATION exposed, and produce strong and weak different permanent negative electrical charges at interlayer.For balancing charge, imvite just has the absorption CATION to the characteristic of interlayer, and needs only the cationic concentration that CATION (no matter organic cation or inorganic cation) concentration in the medium of living in is higher than its interlayer, and the ion in the interlamination region will be exchanged.This also is an imvite negative electricity characterization of adsorption.
Montmorillonite particle is superfine; Very big incomplete surface and scission of link are arranged; The surface is strong polarity; Have very high surface energy and chemism, certain adsorption capacity is arranged for multiple gases, liquid, organic molecule. thereby bentonite is widely used in industrial circles such as papermaking, drilling mud, wastewater treatment.Because tetrahedron or octahedral ion exchange in the imvite mineral elementary layer structure cause positive charge not enough. and compensate by interlayer cation.The existence of interlayer cation and hydrability make imvite have very strong cation exchange capacity (CEC) and water imbibition. a little less than the adhesion, be prone to peel off between cheating engaging layer. and behind the splitting, water imbibition obviously descends with the ability of absorption organic molecule.This just requires bentonite adding man-hour through suitably surface treatment, and its surface property is changed, and water imbibition and dilatancy reduce, and close organic matter performance strengthens, thereby widens its application.
The big paper of at first being delivered relevant Nano composite material of montmorillonite about 1985 by Japanese Toyota Company is through the development of recent two decades, the considerable progress that the preparation of imvite and application study all obtain.Before organo montmorillonite can commercialization large-scale production; Normally laboratory oneself prepares organo montmorillonite; Application to imvite conducts a research; Can find out that from a large amount of research documents organo montmorillonite can effectively improve each item performance of resin really, but in a very long time since the technical problem of the large-scale commercial applications production of organo montmorillonite do not solve; Therefore Nano composite material of montmorillonite does not drop into veritably and uses, and this situation just changes up to about calendar year 2001 to some extent.
Use in the nano composite material of organo montmorillonite production at present; Have only the nano-nylon 6 that adopts polymerisation to produce to realize peeling off completely; As add the organo montmorillonite of 2% (weight ratio), indexs such as most mechanical performances, thermal property, hygroscopicity and barrier property all have significantly raising, particularly some indexs; Like hygroscopicity and rejection rate, can't improve through adding other material at present.Nano-nylon 6 is used fewer at present for various reasons.
Using dual-screw-stem machine to produce Nano composite material of montmorillonite is the main at present method that adopts, and the resin that adopts dual-screw-stem machine to produce Nano composite material of montmorillonite has polyolefin, various elastomer and rubber etc.The front said because the organo montmorillonite production technology, used dual-screw-stem machine to add can't to realize montmorillonite layer in resin, to peel off completely, can only realize that intercalation and part peel off.When using the Nano composite material of montmorillonite of dual-screw-stem machine production; The amplitude that the addition of organo montmorillonite more (6% weight ratios), material property improve is smaller; But compare with conventional additive, Nano composite material of montmorillonite still has remarkable advantages.Based on the situation of present organo montmorillonite, each company all launches deep research to the process of nano composite material, through improving processing method, also can produce the pretty good product of cost performance
Currently, Nano composite material of montmorillonite has been represented the developing direction of composite from now on, promptly have addition few, comprehensively improve performance, density of material low, keep advantages such as the original processing characteristics of material basically.When imvite has good dispersive property; Can extensive use macromolecular material industry as the additive of nanometer polymer macromolecular material; Improve fire-retardant, shock resistance, antifatigue, DIMENSIONAL STABILITY and gas barrier property etc.; Thereby play the effect that strengthens the comprehensive physical property of polymer, improve the material processing characteristics simultaneously.Application in polymer can be added when polymer, also can when fusion, blend add (adopting the screw rod blend usually).
The limellar stripping of imvite is a kind of ideal structure in the polymeric matrix, also is simultaneously the key of Nano composite material of montmorillonite research.Imvite is dispersed in the polymeric matrix with the nanometer sheet form; Can significantly improve the mechanical property and the thermal stability of material; The intercalation lift-off structure makes material that outstanding barrier and anti-flammability arranged, and has broad application prospects in automobile, field of aerospace.The inventor of patent CN1740221 adopts imidazole salt modifier to improve the compatibility of polarity imvite and non-polar polyolefinic, and gives composite better hot-working stability, but imidazole salt modifier synthetic yield is undesirable.And alkyl triphenyl halo phosphorus modifier has heat endurance and synthesis yield preferably, and composite has better hot-working stability, and composite still keeps dispersed phase size and distribution (CN1789318) preferably after Overheating Treatment.
PLA (PLA) is a kind of green material, is that base stock makes by agricultural economy crop (corn etc.) tunning lactic acid, has favorable biological degradability, can degrade fully after the use to generate carbon dioxide and water, and is free from environmental pollution.It is high that PLA also has good mechanical property, thermoplasticity, fibre forming property, transparency, is applicable to blowing, extrudes, multiple processing method such as injection moulding, easy to process, uses very extensively.But pure PLA is not shock-resistant and high temperature, has limited its purposes and result of use, and this just impels people that the modification of its performance is launched further investigation.
Polypropylene (PP) is a kind of thermoplastic of excellent performance; Have cheap, advantages such as technology is easy, nontoxic, easy processing, proportion is little, impact strength is good; Be widely used in every field such as packing, commodity, chemical industry, automobile, medical treatment, become one of present most widely used plastics.Thereby can be used as the blend of PLA, improve its performance.But, make its Application Areas receive very big restriction owing to polyacrylic poor toughness, poor dimensional stability, ABRASION RESISTANCE deficiency, the not high shortcoming of heat distortion temperature.Be further to improve the performance of polypropylene and polylactic acid blend, like mechanical property and high temperature resistant etc., also need carry out modification to it, imvite is represented as the typical case of novel nano-material, is one of important candidate material.
People are doing many work aspect the PLA blending and modifying. and adopt the polypropylene blend can reduce polyacrylic consumption and reduction environmental pollution; Can make product keep mechanical property preferably again. but the compatibility of the PLA of polarity and nonpolar PP is poor; Document [carboxylated PP and PLA blend] has been chosen carboxylated PP and PLA blend; Hope to improve both compatibilities, do not appear in the newspapers but can realize that industrialization polypropylene blended compound material and polypropylene blended compound material fiber must be studied with patent.
Summary of the invention
Technical problem to be solved by this invention provides a kind of imvite/polypropylene complex fiber material and preparation method thereof; The composite fibre good spinnability that this method is produced; Become fine intensity high, and have controllable conductivity, heat conduction, antistatic and biodegradable characteristic.
A kind of imvite of the present invention/polypropylene complex fiber material, its component comprises: imvite, polypropylene, its weight ratio are 0.1～20:80～99.9, and the percentage by weight of polypropylene and PLA can be regulated arbitrarily.
The preparation method of a kind of imvite of the present invention/polypropylene complex fiber material comprises:
(1) modification of imvite is handled
The montmorillonite-based nano powder is placed on the dedicated transmissions device of apparatus for processing plasma; At atmospheric pressure, under the open environment, directly plasma jet is arrived the montmorillonite-based nano powder surface; The montmorillonite-based nano powder is moved in plasma atmosphere; The power of handling the montmorillonite-based nano powder is 10W-5000W, and the time is 0.01s-6000s, produces the montmorillonite-based nano powder surface modification;
(2) the above-mentioned plasma treatment imvite that makes is mixed the back with polypropylene powder or polypropylene compound slice by 0.1～20% weight percent and use the twin screw or single screw extruder batch mixing, obtain nano imvite/polypropylene compound slice 180～260 ℃ of melting mixing;
(3) section that step (2) is made is carried out spinning by the melt spinning method of routine, promptly gets the imvite/polypropylene complex fiber material of plasma treatment.
Described plasma is selected from one or more in helium, argon gas or the functional gas, and wherein helium, argon gas mol ratio are 50%-99.99%, and functional gas is 0.001～30%, and the plasma of flowing through simultaneously forms the district and forms plasma atmosphere;
The purity of described helium or argon gas is 99.99%;
Described functional gas is SO
2, ammonia, oxygen, hydrogen, nitrogen, carbon tetrafluoride, carbon dioxide, methane CH4, ethane C2H6, propane C3H8, butane C4H10, pentane C5H12, hexane C6H14, heptane C7H16, octane C8H18, nonane C9H20, decane C10H22, hendecane C11H24, dodecane C12H26, tridecane C13H28, ethene (C2H4), propylene (C3H6), butylene (C4H8), amylene (C5H10), hexene (C6H12), allene (C3H4), butadiene (C4H6), isoprene (C5H8), hexatriene (C6H8), acetylene (C2H2), propine (C3H4), butine (C4H6), pentyne (C5H8), hexin (C6H10), heptyne (C7H12), octyne (C8H14), n-heptylacetylene (C9H16), decine (C10H18), undecyne (C11H20), tetrafluoroethylene and silane, various siloxane gas, acrylic acid, the steam of methacrylic acid or their composition gas;
Described under jet plasma atmosphere prerequisite with the montmorillonite-based nano surface by the demand of demands of different carry out that surface modification is under the atmospheric pressure, normal temperature, open processing technology.
Normal temperature of the present invention, standard atmosphere plasma modified processing improve in the system of montmorillonite-based nano powder surface performance; Under jet plasma atmosphere prerequisite, form free radical and cause the surperficial imvite surface modification that forms the free radical grafting reaction under certain condition with other materials and component and obtain of imvite that further free radical causes thus, and because the radical polymerization that the imvite surface free radical that plasma causes causes is plasma initiation ATRP (ATRP).
Use the nano imvite of this method modification to can be applicable to the synthetic fiber of macromolecule as carrier.
Beneficial effect:
(1) montmorillonite particle of handling through modification of the present invention evenly and particle size distribution range diminish, the inner phase structure of nano particle is constant, the dispersiveness of nano particle in respective material improves, improve with corresponding high molecular binding ability;
(2) this spinning technique adopts conventional fusion method spinning technique, the spinnability that has improved with become fine intensity, and have controllable conductivity, heat conduction, an antistatic and biodegradable characteristic.
Description of drawings
Fig. 1 is a montmorillonite-based nano powder surface plasma modification device sketch map;
Wherein, 1 plasma carrier gas (helium or argon gas), 2 functional gases, 3 plasma generation control systems, 4 plasma generators and shower nozzle, 5 nano-powder transports, 6 are the surface-treated nano-powder of surface treating nano powder, 7 not;
Fig. 2 is electron micrograph * 500 times of fiber sample precursor;
Fig. 3 is electron micrograph * 5000 times of fiber sample precursor;
Fig. 4 is a sample precursor one-off drawing mechanical curves.
The specific 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 the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do 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 appended claims institute restricted portion equally.
Helium plasma treatment imvite/polypropylene compound silk processing technology
(1) getting the commercialization montmorillonite-based nano powder (inorganic gel) that 50 gram Zhejiang Feng Hong clay chemical industry Co., Ltds produce is placed on the dedicated transmissions device of apparatus for processing plasma.Sketch map such as Fig. 1 passage of plasma nozzle (or install additional); This container or carrier place normal pressure 2 centimetres of the spout below specific ranges of normal-temperature plasma injection apparatus with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 5 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that the imvite powder obtains handling under helium plasma atmosphere, 40 watts of power and 5 second time.
(2) normal pressure that step (1) is made, normal-temperature plasma are handled imvite and polypropylene powder or section and are used the double screw extruder batch mixing in 0.1～20% ratio, obtain polypropylene chip 180～260 ℃ of melting mixing;
(3) imvite/polypropylene that step (2) is made is carried out spinning by the melt spinning method of routine, can obtain containing in the fiber imvite/polypropylene composite fibre of normal pressure, normal temperature helium plasma treatment.
The electron micrograph of this fiber sample precursor such as Fig. 2, sample precursor mechanical property is seen Fig. 3.
Oxygen plasma treatment imvite/polypropylene compound silk processing technology
(1) getting the commercialization montmorillonite-based nano powder (inorganic gel) that 50 gram Zhejiang Feng Hong clay chemical industry Co., Ltds produce is placed on the dedicated transmissions device of apparatus for processing plasma.Sketch map such as Fig. 1 passage of plasma nozzle (or install additional); This container or carrier place normal pressure 2 centimetres of the spout below specific ranges of normal-temperature plasma injection apparatus with interior (design of nozzle segment passage is by particular requirement); Nano-powder lay thickness is by 5 millimeters thickness laies; Under the prerequisite of opening normal pressure, room-temperature plasma, container or carrier are done the motion of specific speed. realize that the imvite powder obtains handling under oxygen gas plasma atmosphere, 40 watts of power and 5 second time.
(2) normal pressure that step (1) is made, normal-temperature plasma are handled imvite and polypropylene powder or section and are used the double screw extruder batch mixing in 0.1～20% ratio, obtain polypropylene chip 180～260 ℃ of melting mixing;
(3) imvite/polypropylene that step (2) is made is carried out spinning by the melt spinning method of routine, can obtain containing in the fiber imvite/polypropylene composite fibre of normal pressure, normal temperature oxygen plasma treatment.
Claims (2)
1. imvite/polypropylene complex fiber material, its component comprises: imvite, polypropylene, its weight ratio are 0.1～20: 80～99.9, wherein, imvite is handled through plasma modification and is made.
2. the preparation method of imvite/polypropylene complex fiber material comprises:
(1) modification of imvite is handled
The montmorillonite-based nano powder is placed on the dedicated transmissions device of apparatus for processing plasma; At atmospheric pressure, under the open environment, directly plasma jet is arrived the montmorillonite-based nano powder surface; The montmorillonite-based nano powder is moved in plasma atmosphere; The power of handling the montmorillonite-based nano powder is 10W-5000W, and the time is 0.01s-6000s, produces the montmorillonite-based nano powder surface modification;
(2) with the above-mentioned plasma treatment imvite that makes and polypropylene powder or polypropylene compound slice by weight 0.1～20: 80～99.9 use the twin screw or single screw extruder batch mixing, obtain nano imvite/polypropylene compound slice 180～260 ℃ of melting mixing;
(3) section that step (2) is made is carried out spinning by the melt spinning method of routine, promptly gets the imvite/polypropylene complex fiber material of plasma treatment.
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| CN105926076A (en) * | 2016-05-18 | 2016-09-07 | 南通市苏中纺织有限公司 | Collagen/polyvinyl alcohol/polylactic acid composite fiber |
| CN108587093A (en) * | 2018-05-10 | 2018-09-28 | 甘肃汇投治沙科技股份有限公司 | Concave convex rod filled polypropylene polylactic acid degradable composite material and preparation method |
| CN108824018A (en) * | 2018-06-22 | 2018-11-16 | 安徽快来防水防腐有限公司 | A kind of preparation method of fire-retardant and smoke-inhibiting type SBS modified asphalt waterproof coiled material |
| CN108976599A (en) * | 2018-07-24 | 2018-12-11 | 常州达奥新材料科技有限公司 | A kind of preparation method of PP/PLA composite degradable plastics bloom lubrication masterbatch |
| CN110295406A (en) * | 2019-06-18 | 2019-10-01 | 浙江理工大学 | Porous cellulose acetate composite micro/nano tunica fibrosa, centrifugal spinning preparation method and its application at heavy metal ion adsorbed aspect |
| CN113308170A (en) * | 2021-05-18 | 2021-08-27 | 柳元光 | Waterproof wear-resistant crease-resistant fiber coating and preparation method thereof |
| CN114621524A (en) * | 2022-04-01 | 2022-06-14 | 深圳市欣恒坤科技有限公司 | High-barrier film and preparation method thereof |
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| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| CN1693549A (en) * | 2005-06-03 | 2005-11-09 | 中化国际余杭高分子材料研发设计有限公司 | Polyether montmorillonite modified polyurethane heat resistant elastic fibre and its preparation method |
| KR20060060454A (en) * | 2004-11-30 | 2006-06-05 | 가람테크(주) | The processing method of nanocomposite fiber dispersed montmorillonite and nanocomposite fiber produced thereof |
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| CN1284890C (en) * | 2004-01-06 | 2006-11-15 | 中国石化仪征化纤股份有限公司 | Sea island type composite fiber and its manufacturing method and application |
| EP1860138A1 (en) * | 2006-05-25 | 2007-11-28 | Sabanci Universitesi | Biodegradable thermoplastic nanocomposite polymers |
| CN101158059A (en) * | 2007-11-08 | 2008-04-09 | 天津市赛远保健品有限公司 | Moisture absorbent soft polypropylene fibre and method for manufacturing same |
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| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| KR20060060454A (en) * | 2004-11-30 | 2006-06-05 | 가람테크(주) | The processing method of nanocomposite fiber dispersed montmorillonite and nanocomposite fiber produced thereof |
| CN1693549A (en) * | 2005-06-03 | 2005-11-09 | 中化国际余杭高分子材料研发设计有限公司 | Polyether montmorillonite modified polyurethane heat resistant elastic fibre and its preparation method |
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