CN104032403A - Rare-earth metal oxide/polyacrylonitrile (PAN) composite fiber and preparation method thereof - Google Patents
Rare-earth metal oxide/polyacrylonitrile (PAN) composite fiber and preparation method thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 97
- 239000000835 fiber Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 62
- 238000009987 spinning Methods 0.000 claims abstract description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 rare earth lanthanum oxide Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 22
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002166 wet spinning Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002114 nanocomposite Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 75
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 239000002121 nanofiber Substances 0.000 claims description 6
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 238000007791 dehumidification Methods 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 3
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 3
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229940075616 europium oxide Drugs 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 2
- 229940075624 ytterbium oxide Drugs 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 15
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 abstract description 9
- 239000004753 textile Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
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- 230000036541 health Effects 0.000 abstract description 5
- 238000001523 electrospinning Methods 0.000 abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 description 3
- 201000010099 disease Diseases 0.000 description 3
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 3
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
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- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- 201000009030 Carcinoma Diseases 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- HEQHIXXLFUMNDC-UHFFFAOYSA-N O.O.O.O.O.O.O.[Tb].[Tb].[Tb].[Tb] Chemical compound O.O.O.O.O.O.O.[Tb].[Tb].[Tb].[Tb] HEQHIXXLFUMNDC-UHFFFAOYSA-N 0.000 description 1
- 206010035226 Plasma cell myeloma Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LBFPNEPAKHGVSJ-UHFFFAOYSA-N acetic acid;praseodymium Chemical compound [Pr].CC(O)=O LBFPNEPAKHGVSJ-UHFFFAOYSA-N 0.000 description 1
- DGVVPRHPLWDELQ-UHFFFAOYSA-N acetic acid;samarium Chemical compound [Sm].CC(O)=O.CC(O)=O.CC(O)=O DGVVPRHPLWDELQ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
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- Artificial Filaments (AREA)
Abstract
The invention relates to a rare-earth metal oxide/polyacrylonitrile (PAN) composite fiber and a preparation method thereof. The preparation method comprises the steps of (1) dissolving nanoscale rare earth lanthanum oxide into anhydrous acetic acid, and dissolving PAN powder into N,N-dimethylacetamide (DMAc) solvent to form a homogeneous solution, wherein a small amount of lithium chloride is fed into the N,N-DMAc solvent; (2) mixing the prepared lanthanum acetate solution and the PAN solution according to a certain volume ratio for dissolving to obtain homogeneous mixed spinning dope; (3) defoaming, filtering and balancing the spinning dope, and spinning by an electrospinning technique to obtain nano-composite fiber felt loaded with rare earth lanthanum, wherein the nano-composite fiber felt has the advantages of being light in weight, large in specific surface area, and the like; and (4) defoaming, filtering and balancing the spinning dope, and spinning by a wet spinning technique to obtain the PAN composite fiber loaded with rare earth lanthanum. Compared with a traditional radiation shielding material, the composite fiber material prepared by the method has the advantages of being light in weight, high in yield and the like, can be further spun and processed to obtain a fabric, is made into a textile fabric loaded with rare earth, and integrates comfort, protective property and health care property.
Description
technical field:
The present invention relates to a kind of polyacrylonitrile composite fiber and preparation method thereof, a kind of especially rare-earth oxide/polyacrylonitrile composite fiber and preparation method thereof.
background technology:
Synthetic fiber have experienced semicentennial fast development, the reality that simultaneous petroleum resources are in short supply and environmental protection pressure increases.At the end of the seventies, polyacrylonitrile (PAN) fiber production accounts for 20% of synthetic fiber total amount.Just there is afterwards the day by day fierce situation of market saturation, excess production capacity, market competition.Developed country, in order to enhance one's market competitiveness, obtains higher economic benefit, and production and research emphasis have been turned to fibre in differentiation, utilizes the method production of physics or chemical modification to have high value-added product, and wherein, blending and modifying is one of important means.Polyacrylonitrile (PAN) fiber is carried out to a lot [the Bui NN of report of blending and modifying, Kim BH, Yang KS, Dela Cruz ME, Ferraris JP. Activated carbon fibers from electrospinning of polyacrylonitrile/pitch blends[J]. Carbon, 2009, 47 (10): 2538-2539. Zhang ZH, Sun RJ, Ma HF, Xu J.. Study on the graft modification of collagen and blending with polyacrylonitrile in wet spinning[J]. Proceedings of the 2007 International Conference on Advanced Fibers and Polymer Materials Vols. 1 and 2, 2007, 774-776. Wang LY, Xie J, Gu LX, Sun G. Preparation of antimicrobial polyacrylonitrile fibers:Blending with polyacrylonitrile-co-3-allyl-5, 5-dimethylhydantoin[J]. Polymer Bulletin, 2006, 56 (2-3): 247-256. Pan W., Yang SL., Li G., Jiang JM.. Electrical and structural analysis of conductive polyaniline/polyacrylonitrile composites[J]. European Polymer Journal, 2005, 41 (9): 2127-2133.], the people such as Diao CH use the polyvinyl alcohol (PEG) and polyacrylonitrile (PAN) blend of different molecular weight, prepared a kind of polyacrylonitrile (PAN) blending and modifying fiber [Diao CH of good hygroscopicity by wet spinning technology, Xiao CF, Hu XY, Hu XM. Study on Polyacrylonitrile Fibers Modified by Blending with Polyethylene Glycol[J]. Fibers and Polymers, 2010, 11 (7): 947-951.], Korean Patent [publication number KR759102-B1] has provided a kind of method of preparing compound Nano carbon fiber with polyacrylonitrile/pitch two component blend solutions by method of electrostatic spinning, and point out that this fiber has electric conductivity [Kim C., Kim Y M.. Method for manufacturing two-component carbon nanofibers and activated carbon nanofibers by electrospinning from polyacrylonitrile/pitch blending solution[P] .].Chinese patent [publication number CN101250764-A] discloses the one of preparing by wet spinning technology and has carried nano-grade medicine and can treat dermopathic (PAN) blending and modifying fiber [Zhu L., Yu D., Shen X., Han J.. Nanometer drug-loading polyacrylonitrile fiber for treating skin disease comprises polyacrylonitrile as matrix via wet spinning for blending spinning original solution including drug-loading nanometer particle[P] .], they first have bioactive ingredients nano particle with including, degradable high polymer is miscible in spinning solution system, adopt wet spinning to prepare drug-loading fibre.This fibrid further textile process becomes fabric, and finally can make medicine carrying textiles, as underwear, socks, shoes, bady's diaper etc., active constituents of medicine is slowly discharged from cloth fibers, people just can be by skin in daily wearing process the medication process that contacted with dress material, thereby meet medicament contact comprehensively and the trouble of exempting patient's medication every day; With Electrospinning Method obtain drug-loading fibre be more suitable for local application, wound clad material etc.
Along with the development of national defence scientific research, radioactivity medical science and Application of Nuclear Technology, various radioactive rays are widely used, the injury of ray to human body and the destruction of environment is also familiar with by the mankind gradually; In addition, after noise pollution, air pollution, water pollute, Contamination of Electromagnetic Wave has become to threaten the fourth-largest public hazards of human survival, the protection of electromagnetic radiation is more and more caused to people's attention.For the protection of daily electromagnetic pollution, obtain design and prepare absorbing material and solve electromagnetic pollution harm.Often the people of contact radioactive ray there will be skin burn, trichomadesis, ophthalmodynia, white blood cell to reduce even symptom [Liu Xiankun, Liu Ying, the Tang Jie such as myeloma, Dai Junlong, Hu Chunming, the progress of radiation shielding material, material Leader, 2006,20 (6): 32.]。For reduce and eliminate various rays to human body as far as possible, especially the harm to industries concerned staff, extensively carry out research work [the Gupta R. P. of radiation protection fabric and protective clothing both at home and abroad, Sen S. K.. Sternheimer shielding-antishielding-rare-earth ions, Physical Review A, 1973, 7 (3): 850. Chen G.. Cross-linked polyethylene insulation high voltage cable for rare earth aluminum sheath, has conductor shielding layer, insulation layer, insulation shielding layer, and rare earth aluminum sleeve provided between buffer layer and sheath, 2010, PN:CN2904221-Y. Hu S., Liu L., Wei Z., et al. X-ray shielding plastic composite material for e.g. medical diagnosis x-ray machine, has rare earth organic composition provided as unsaturated carboxylic acid rare earth salt, and base material made of plastic, 2010, PN:CN101572129-A. Hu S., Liu L., Wei Z., et al. Lead-free X-ray shielding rubber composite material comprises rubber, rare earth organic complex, inorganic rare earth compound, useful for protecting workers from radiating of X-ray in the fields where X-ray is generated, 2010, PN:CN101570606-A. Oyaizu E.. Radiation shielding sheet used for X-ray apparatus, consists of preset amount of organic macromolecular material, rare earth oxide as shielding material powder, and has preset porosity, 2007, PN:JP2007085865-A.].For example, to the shielding of high energy X ray, present popular with resin/nanometer lead composite material and resin/nano-sulfur lead plumbate composite [Yang C., Liu L., et al.. Study on X-ray shielding property and mechanical property of Gd (AA) 3/NR composites. China Synthetic Rubber Indusry, 2004,27 (1): 49.].
Conventionally, only have and reach 10-10 when the ratio resistance of fiber
-3when (Omega * centimetre), just there is ELECTROMAGNETIC RADIATION SHIELDING effect.Various undoubtedly metal fibres are best electromagnetic radiation shielding fibres, but be not take fiber.Carry out again for this reason metal fibre and conventional fibre have been carried out to blending to prepare easily the method for ELECTROMAGNETIC RADIATION SHIELDING fabric, but contain the textile process of metal fibre on traditional Weaving device time, must take special measure, otherwise can not normally carry out.Compound and the electrostatic spinning technique of rare earth and macromolecule can change these traditional ideas just.
Taking macromolecular material as matrix, the rare earth high polymer material that doping obtains affects because it is not subject to matrix the characteristic that demonstrates rare earth ion, and in use constantly demonstrate the incomparable advantage of other materials, just becoming the new material of showing up prominently, his development and application is also more and more subject to people's concern [He Lei, the research of the preparation of novel rare-earth/rubber composite and shielding property thereof and magnetic property, Beijing University of Chemical Technology's master thesis, 2005.]。The main purpose of mixing rare earth in macromolecular material is to utilize the ins and outs of rare earth ion, as utilizes the spectral quality of rare earth, doping type rare earth high polymer can make various fluorescent materials, laser material, selection absorption luminescent material, radiological protection material etc.; Utilize its magnetic can make magnetic element, plastic magnet and magnetic pipe recording material and utilize its chemical property polymer to be carried out to [the He Lei such as modification, the research of the preparation of novel rare-earth/rubber composite and shielding property thereof and magnetic property, Beijing University of Chemical Technology's master thesis, 2005.]。Rear-earth-doped polymer is mainly to be dissolved and realized by mechanical blending, melt blending, solvent or solvent.Visible is a kind of easy, method that applicability is wide and practical preparing on rare earth high polymer material doping.For this reason, the research of doping type rare earth high polymer is paid attention to by people very so far always from the sixties.The research range expanding day of doping type rare earth high polymer now, the rare earth of doping is no longer limited to rare earth compounding, and comprises that rare earth alloy, rare earth oxide, rare-earth hydroxide, inorganic salt of rare earth, rare earth organic salt, rare earth alkoxide etc. almost relate to all thermoplasticity and thermosetting resin.Rare earth doped macromolecular material also starts to go on from experimental exploring practical, starts to play a role in every field, and this just can find out from a large amount of articles and the patent of emerging in large numbers therebetween.But, in doping type rare earth high polymer, because of most of rare earth compounds especially rare earth inorganic matter and resin compatibility little, rare earth compound is difficult to be evenly dispersed in resin, this not only makes the transparent deformation of material poor, also make the strength of materials reduce, therefore this simple doping way can not get the high transparent rare earth high polymer material of high rare-earth content, thereby limit greatly their application [He Lei, the research of the preparation of novel rare-earth/rubber composite and shielding property thereof and magnetic property, Beijing University of Chemical Technology's master thesis, 2005.Dong Zhihua, preparation and the research of rare earth/macromolecule alpha ray shield composite, Beijing University of Chemical Technology's master thesis, 2009.]。Electrostatic spinning technique and wet spinning technology have powerful potentiality to make their Application Areas more extensive.
Make a general survey of document, in the data of having reported, polyacrylonitrile (PAN) blending and modifying fiber had to many types, but report transdermal delivery system fiber and few, and do not see from the modified fibre that therapeutic type proceeds to protection type.
From domestic polyacrylonitrile (PAN) fiber product market, China's polyacrylonitrile (PAN) fiberoptic fiber kind is very dull now, it is mostly conventional PAN fiber, as short cellucotton type 1.67dtex, wool type 3.33dtex, 6.77dtex, these conventional PAN fiber production account for the more than 97% of domestic PAN fiber total output.Under the prerequisite that current concept of health upgrades, spectrum of disease changes, aging society arrives, medical model also by simple treatment disease to prevention, health care future development, and along with the transition of China's economy, the exploitation of the protection type polyacrylonitrile (PAN) functional fibre new varieties of blending and modifying is imperative.
summary of the invention:
The present invention is to provide a kind of rare-earth oxide/polyacrylonitrile composite fiber and preparation method thereof, it has the blending and modifying composite fibre of protection type, health care, after adopting even spinning solution blend, carry out electrostatic spinning and wet spinning, can be effectively written into respectively nano-composite fiber felt and the polyacrylonitrile composite fiber of rare earth ion.Compared with traditional protection type fiber, fiber prepared by this method has that specific area is large, quality is light etc.
The preparation method of a kind of rare-earth oxide/polyacrylonitrile composite fiber of the present invention, comprises the steps:
1) homogeneous phase solution of preparation lithium chloride, DMA and polyacrylonitrile;
2) rare-earth oxide and anhydrous acetic acid are formulated as to rare earth metal acetate solution;
3) by 1) homogeneous phase solution and 2 of step polyacrylonitrile) step rare earth metal acetate solution fully mixes, and forms homogeneous phase solution mixed system, through deaeration, filter to obtain spinning solution;
4) spinning solution is spun into composite fibre or the nano-composite fiber felt of rare-earth oxide, and is placed on desiccant dehumidification in baking oven and makes rare-earth oxide/polyacrylonitrile composite fiber.
The preparation method of rare-earth oxide/polyacrylonitrile composite fiber of the present invention, the method step of preferably pressing is as follows:
1) at 40-60 DEG C of temperature, the homogeneous phase solution of preparation lithium chloride, DMA and polyacrylonitrile;
2), under room temperature, rare-earth oxide and anhydrous acetic acid are formulated as to rare earth metal acetate solution;
3) by 1) homogeneous phase solution and 2 of step polyacrylonitrile) step rare earth metal acetate solution fully mixes, form homogeneous phase solution mixed system, control 2) step rare earth metal acetate solution and 1) volume ratio of homogeneous phase solution of step polyacrylonitrile is 0.01%-33.35%, through deaeration, filter to obtain spinning solution;
4) under room temperature, adopt electrostatic spinning technique or wet spinning technology spinning solution to be spun into composite fibre or the nano-composite fiber felt of rare-earth oxide, and be placed on desiccant dehumidification in baking oven and make rare-earth oxide/polyacrylonitrile composite fiber.
Described control 1) mass concentration of lithium chloride in solvent DMA is 0.01%-20.00% in step.
Control 1 of the present invention) mean molecule quantity of step polyacrylonitrile is 60000-80000, and the solution temperature of polyacrylonitrile is at 40 DEG C-60 DEG C, and the mass concentration of controlling polyacrylonitrile in the homogeneous phase solution of polyacrylonitrile is 8.00%-20.00%.
Rare-earth oxide of the present invention and rare earth metal acetate are respectively any one in lanthana, neodymia, cerium oxide, praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide, luteium oxide, yittrium oxide, and make corresponding rare earth metal acetate with anhydrous acetic acid.That is to say that described rare earth metal acetic acid is the corresponding rare earth metal acetate that above-mentioned any one rare-earth oxide and anhydrous acetic acid salt are prepared from.
The preparation method of rare-earth oxide/polyacrylonitrile composite fiber of the present invention, described in it, electrostatic spinning condition is: controlling spinning solution flow velocity in syringe is 0.8-1.3 mL/h, the voltage applying is 10-12 kV, and two interpolar screen needle gages are 16-19 cm; The baking temperature of the nanofiber mats of spinning is between 40 DEG C-60 DEG C, and be 5-8 hour drying time.
Wet spinning condition of the present invention is: control the about 1.0-2.0 hour of time of sealing and standing deaeration in material-storage jar, the pressure in material-storage jar is 1.5 × 10
5pa; Coagulating bath is 1%-70%N, N-dimethylacetylamide-aqueous solution; Coagulation bath temperature is 20
oc-40
oc; The predraft bath temperature of solvent DMA is 40
oc-100
oc.
The inventive method, the temperature that further desolvation DMA boiling water bath stretches is 90
oc-100
oc; After reeling, the compacting by drying temperature of fiber is 90
oc-120
oc; The fibre single thread fiber number of spinning is that 2.0dtex-4.8dtex, intensity are 1.9 cN/dtex-3.5cN/dtex.
A kind of rare-earth oxide/polyacrylonitrile composite fiber adopts above-mentioned method to prepare.
Beneficial effect of the present invention:
Product prepared by the present invention and existing popular protective materials are compared with resin/nano-sulfur lead plumbate composite as resin/nanometer lead composite material, electrostatic spinning technique spins out rare earth lanthanum oxide/polyacrylonitrile composite nano fiber and has the advantages such as quality is light, specific area is large, and it is comfortable, convenient to dress;
Adopt the production of wet spinning technology, be conducive to improve spinning speed, improve product mechanical property and production efficiency; Spin out rare earth lanthanum oxide/polyacrylonitrile composite fiber and protection type textiles thereof, can effectively prevent that pathology from occurring, complied with current treatment medical science and turned to prevention and the development trend of physical-fitness medicine;
Above two classes of the present invention are carried rare earth fiber or textiles and are applicable to colony and prevent the generation of the diseases such as cutaneum carcinoma, are a kind of novel rare earth oxide carrier model fiber and a kind of grade textiles of containing, as safety goggles, Protection helmet, protective clothing etc.;
Dress ornament that the present invention has improved product is comfortable, health, improves fibre property, has increased added value of product, in improving people's living standard, increases huge economic benefit.
detailed description of the invention:
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that, after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
The method of the invention, comprises the following steps:
(1) DMA (DMAc) solution of preparation lithium chloride, dissolves polyacrylonitrile (PAN) powder in above-mentioned dicyandiamide solution and forms homogeneous phase solution;
(2) under room temperature, take a certain amount of rare earth lanthanum oxide and anhydrous acetic acid, preparation lanthanum acetate solution;
(3) under room temperature, above-mentioned solution is mixed lanthanum acetate solution according to certain volume ratio with polyacrylonitrile (PAN) homogeneous phase solution, form homogeneous phase solution mixed system, obtain spinning solution through deaeration, filtration;
(4) under room temperature, adopt electrostatic spinning technique spinning to carry the nano-composite fiber felt of Rare Earth Lanthanum, the nanofiber mats of spinning is placed in to vacuum drying oven desiccant dehumidification;
(5) under room temperature, adopt wet spinning technology spinning to carry the composite fibre of Rare Earth Lanthanum, the fiber of spinning is placed in to vacuum drying oven desiccant dehumidification.
In described step (1), the mass percent of lithium chloride in solvent DMA (DMAc) is between 0.01%-20.00%; The mean molecule quantity of polyacrylonitrile (PAN) powder is between 60000-80000, and polyacrylonitrile (PAN) powder solution temperature is between 40 DEG C-60 DEG C, and polyacrylonitrile in solution system (PAN) mass percent is 8.00%-20.00%.
Described step (2) rare earth oxide or anhydrous acetic acid salt comprise following one:
Lanthana (La
2o
3), neodymia (Nd
2o
3), cerium oxide (Ce0
2), praseodymium oxide (Pr
6o
11), samarium oxide (Sm
2o
3), europium oxide (Eu
2o
3), gadolinium oxide (Gd
2o
3), terbium oxide (Tb
4o
7), dysprosia (Dy
2o
3), holimium oxide (Ho
2o
3), erbium oxide (Er
2o
3), thulium oxide (Yb
2o
3), ytterbium oxide (Yb
2o
3), luteium oxide (Lu
2o
3), yittrium oxide (Y
2o
3); Or anhydrous rare earth acetate is any of anhydrous acetic acid salt of lanthanum acetate, acetic acid praseodymium, neodymium acetate, other rare earth element of acetic acid samarium.
The mixed volume ratio of (3) two kinds of homogeneous phase solutions of described step, lanthanum acetate solution/polyacrylonitrile (PAN) solution, V/V, is greater than 0.01% and is less than or equal to 33.33%.
Described step (4) electrostatic spinning condition is: in syringe, spinning solution flow velocity is 0.8-1.3 mL/h, and the voltage applying is 10-12 kV, and two interpolar screen needle gages are 16-19 cm; The baking temperature of the nanofiber mats of spinning is between 40 DEG C-60 DEG C, and be 5-8 hour drying time.
Described step (5) wet spinning condition is: approximately 1.0～2.0 hours time of sealing and standing deaeration in material-storage jar; Open air compressor, the constant pressure keeping in material-storage jar is 1.5 × 10
5pa; Coagulating bath is the 1%-70%DMAc-aqueous solution; Coagulation bath temperature is 20
oc-40
oc; The predraft bath temperature that can remove partial solvent is 40
oc-80
oc; The temperature approximately 90 that further desolvation boiling water bath stretches
oc-100
oc; After reeling, the compacting by drying temperature of fiber is 90
oc-120
oc; The fibre single thread fiber number of spinning is that 2.0dtex-4.8dtex, intensity are 1.9 cN/dtex-3.5cN/dtex.
embodiment 1
Raw material: rare earth lanthanum oxide (La
2o
3), purity is more than or equal to 99.99%; Polyacrylonitrile (PAN) powder, mean molecule quantity is 68,000, and molecular weight ranges is between 60000～80000, and glass transition temperature is 90 DEG C; DMA (DMAc), anhydrous acetic acid and anhydrous Lithium chloride are all to analyze pure rank.
Get 5 25mL conical flasks, configure the polyacrylonitrile solution of 5 parts of quality percentage compositions approximately 8.00%, concrete composition in table 1:
After contrast, find, No. 1 ratio sample is best with the compatibility of lanthanum acetate solution, all prepares polyacrylonitrile solution according to the ratio of No. 1 sample later.
Extract in the PAN solution that 1 mL lanthanum acetate solution is added drop-wise to rapidly 15mL (No. 1 sample), can observe white floccule mass aggressiveness, good seal is placed in 40
oin the air bath shaking table of C, after 8 hours, can dissolve completely, final, solution system becomes faint yellow and transparent viscosity solution by clarification, with this sample preparation spinning solution.
Table 1: the fine solution of polypropylene that mass concentration is 8%
The spinning solution of No. 1 sample preparation in above-mentioned table 1 is respectively charged into the syringe of 5 mL, with tack injection needle internal diameter be 0.45 mm, connect the positive pole of high pressure generator, aluminium foil receiving screen connects negative pole, for receiving electrostatic spinning fiber.By as follows each spinning process setting parameter: solution is 1.3 mL/h at the flow velocity at spinning nozzle place, the voltage applying is 12 kV, and two interpolar screen needle gages are 18 cm, under room temperature, operate.Under high voltage electric field effect, spinning solution sprays the final fiber laydown that forms on receiving screen, forms tunica fibrosa.Tunica fibrosa is placed in to 40
oCdried overnight in vacuum drying chamber, removes residual solvent and moisture, obtains rare earth lanthanum oxide/polyacrylonitrile composite nano fiber product.
embodiment 2
Raw material: rare earth lanthanum oxide (La
2o
3), purity is more than or equal to 99.99%; Polyacrylonitrile (PAN) powder, mean molecule quantity is 68,000, and molecular weight ranges is between 60000-80000, and glass transition temperature is 90 DEG C; DMA (DMAc), anhydrous acetic acid and anhydrous Lithium chloride are all to analyze pure rank.
Get 2 250 mL three-necked bottles, according to the polyacrylonitrile solution of embodiment 1 configuration quality percentage composition approximately 8.00% and 4.74% lanthanum acetate solution, the volume ratio preparation spinning solution that equals 1/15 and 2/15 according to lanthanum acetate/polyacrylonitrile.
Spinning solution is poured in the material-storage jar of spinning machine into sealing and standing deaeration approximately 1.5 hours; Open air compressor, make to keep in material-storage jar constant pressure (1.5 × 10
5pa), its objective is in order to allow measuring pump have stable pre-front pressure, thereby make measuring pump accurate measurement; Open successively each transmission device, be respectively: power supply, measuring pump, a roller, two rollers and take up roll.At this moment, spinning solution, is clamp-oned coagulating bath from spinnerets from material-storage jar after measuring pump metering supercharging, and coagulating bath is that mass concentration is 50% the DMAc-aqueous solution, and temperature is 20
oc; The tow being shaped after solidifying is walked around the first deflector roll and is entered temperature and be about 70
othe predraft water-bath of C also removes partial solvent, walks around the second deflector roll and carries out predraft; Tow enters boiling water bath and carries out the stretch one-step removal solvent of going forward side by side of boiling water bath afterwards, by coiling, drafting multiple is wherein set and equals 9; Winding speed is 70 ms/min; The fiber that collection has spinned is with after water rinse 3 times, in 100
ounder C, carry out preserving after compacting by drying.Sample (a) filament number finally obtaining is 3.9dtex, intensity 2.0cN/dtex, sample (b) filament number is 3.8dtex, intensity 2.2cN/dtex, sample (a) and (b) be the rare earth lanthanum oxide/polyacrylonitrile composite fiber of different fiber numbers.
Claims (8)
1. a preparation method for rare-earth oxide/polyacrylonitrile composite fiber, comprises the steps:
1) homogeneous phase solution of preparation lithium chloride, DMA and polyacrylonitrile;
2) rare-earth oxide and anhydrous acetic acid are formulated as to rare earth metal acetate solution;
3) by 1) homogeneous phase solution and 2 of step polyacrylonitrile) step rare earth metal acetate solution fully mixes, and forms homogeneous phase solution mixed system, through deaeration, filter to obtain spinning solution;
4) spinning solution is spun into composite fibre or the nano-composite fiber felt of rare-earth oxide, and is placed on desiccant dehumidification in baking oven and makes rare-earth oxide/polyacrylonitrile composite fiber.
2. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1, it is characterized in that its method step is as follows:
1) at 40-60 DEG C of temperature, the homogeneous phase solution of preparation lithium chloride, DMA and polyacrylonitrile;
2), under room temperature, rare-earth oxide and anhydrous acetic acid are formulated as to rare earth metal acetate solution;
3) by 1) homogeneous phase solution and 2 of step polyacrylonitrile) step rare earth metal acetate solution fully mixes, form homogeneous phase solution mixed system, control 2) step rare earth metal acetate solution and 1) volume ratio of homogeneous phase solution of step polyacrylonitrile is 0.01%-33.35%, through deaeration, filter to obtain spinning solution;
4) under room temperature, adopt electrostatic spinning technique or wet spinning technology, spinning solution is spun into composite fibre or the nano-composite fiber felt of rare-earth oxide, and is placed in baking oven, rare-earth oxide/polyacrylonitrile composite fiber is made in dry, dehumidifying.
3. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1 or 2, it is characterized in that controlling 1) mass concentration of lithium chloride in solvent DMA is 0.01%-20.00% in step.
4. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1 or 2, it is characterized in that controlling 1) mean molecule quantity of step polyacrylonitrile is 60000-80000, the solution temperature of polyacrylonitrile is at 40 DEG C-60 DEG C, and in the homogeneous phase solution of control polyacrylonitrile, the mass concentration of polyacrylonitrile is 8.00%-20.00%.
5. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1 or 2, it is characterized in that described rare-earth oxide and rare earth metal acetate are respectively any one in lanthana, neodymia, cerium oxide, praseodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosia, holimium oxide, erbium oxide, thulium oxide, ytterbium oxide, luteium oxide, yittrium oxide, and make corresponding rare earth metal acetate with anhydrous acetic acid.
6. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1 or 2, it is characterized in that described electrostatic spinning condition is: controlling spinning solution flow velocity in syringe is 0.8-1.3 mL/h, the voltage applying is 10-12 kV, and two interpolar screen needle gages are 16-19 cm; The baking temperature of the nanofiber mats of spinning is 40 DEG C-60 DEG C, and be 5-8 hour drying time.
7. according to the preparation method of the rare-earth oxide/polyacrylonitrile composite fiber described in claim 1 or 2, it is characterized in that described wet spinning condition is: the time of controlling sealing and standing deaeration in material-storage jar is 1.0-2.0 hour, and the pressure in material-storage jar is 1.5 × 10
5pa; Coagulating bath is that mass concentration is DMA-aqueous solution of 1%-70%; Coagulation bath temperature is 20
oc-40
oc; The predraft bath temperature of solvent DMA is 40
oc-100
oc.
8. a rare-earth oxide/polyacrylonitrile composite fiber prepares according to the method described in claim 1 or 2.
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