CN104480560A - Electrostatic spinning solution of polyvinylidene fluoride and preparation method of electrostatic spinning solution - Google Patents

Electrostatic spinning solution of polyvinylidene fluoride and preparation method of electrostatic spinning solution Download PDF

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Publication number
CN104480560A
CN104480560A CN201410669025.0A CN201410669025A CN104480560A CN 104480560 A CN104480560 A CN 104480560A CN 201410669025 A CN201410669025 A CN 201410669025A CN 104480560 A CN104480560 A CN 104480560A
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China
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pvdf
spinning solution
electrostatic spinning
polyvinylidene fluoride
spinning
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CN201410669025.0A
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Inventor
程博闻
厉宗洁
康卫民
焦晓宁
庄旭品
李磊
赵义侠
乔春梅
胡敏
李甫
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Abstract

The invention relates to an electrostatic spinning solution of polyvinylidene fluoride. The electrostatic spinning solution is characterized by being used for producing a dendritic polyvinylidene fluoride nanofiber membrane, and being prepared from polyvinylidene fluoride, an organic branched salt, a plasticizer and a solvent. The preparation method comprises dissolution of polyvinylidene fluoride and dispersion of the organic branched salt. The dendritic polyvinylidene fluoride nanofiber membrane prepared from the spinning solution disclosed by the invention has excellent blocking and adsorption properties; the filtering efficiencies of the dendritic polyvinylidene fluoride nanofiber membrane with the gram weight being 1g/m<2> on 0.26mu m of sodium chloride particles in air and 0.3mu m of polystyrene particles in a water solution both reach over 99%; and the preparation method has a wide application prospect in the fields of filtration and protection.

Description

A kind of electrostatic spinning liquid of Kynoar and compound method thereof
Technical field
The present invention relates to the electrostatic spinning liquid of a kind of Kynoar (PVDF), particularly provide a kind of can the electrostatic spinning liquid of production dendroid PVDF nano fibrous membrane, belong to textile technology field.
Technical background
Nanofiber reaches nanoscale due to its diameter, and the draw ratio of fiber, specific area are relative to the high several order of magnitude of traditional fibre.Along with the development in epoch, the nanofiber that increasing field needs diameter less, many researchers have carried out a large amount of research work.
PVDF has excellent mechanical property, and heat resistance, good corrosion resistance, mechanical strength is high, and also has the properties such as piezoelectricity, dielectricity and pyroelectricity.PVDF chemical stability is good, at room temperature not by the strong oxidizers such as acid, alkali and halogen corrode, very stable to organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohols and aldehydes, in hydrochloric acid, nitric acid, sulfuric acid and alkali lye and up at 1000 DEG C of temperature, its performance is substantially constant.PVDF has excellent anti-gamma-rays, ultraviolet radiation and ageing-resistant performance, and its film is placed in outdoor for a long time and does not become fragile, and does not chap.Owing to having above excellent properties, PVDF is widely used in every field.
Electrostatic spinning is received the current techique of minute yardstick tunica fibrosa as a kind of production and is subject to paying close attention to more and more widely, because nano fibrous membrane has larger specific area, and higher porosity and very extensive in filtration art application through filter.Also relevant report is had about Static Spinning PVDF nano fibrous membrane, as the people such as the Renuga Gopal PVDF nano fibrous membrane that adopted electrostatic spinning process to prepare, and adopting Technology for Heating Processing to increase the structural intergrity of tunica fibrosa, obtained fibre diameter is about 380nm.This tunica fibrosa is that the rejection of the ps particle of 1 μm is up to 98% (Gopal R to particle diameter, Kaur S, Ma Z, et al.Electrospunnanofibrous filtration membrane [J] .Journal of Membrane Science, 2006,281 (1): 581-586.), the people such as Zhe-Qin Dong prepare PVDF-PTFE nano fibrous membrane by electrospinning process, desalinized seawater by membrane distillation method, obtained nanofiber diameter is about 500nm (Dong Z Q, Ma X, Xu Z L, et al.Super hydrophobic PVDF-PTFE electrospun nanofibrous membranesfor desalination by vacuum membrane distillation [J] .Desalination, 2014,347:175-183.), the people such as behaviour's Jian Hua adopt Static Spinning technique to prepare PVDF and Kynoar-hexafluoropropylene copolymer blended nanofibre polymer electrolyte membrane, and obtained nanofiber diameter is distributed in 300-700nm (China Patent No.: CN 101805454A), PVDF is dissolved in N by the people such as Yuan Xiaoyan, in dinethylformamide and acetone mixed solvent, be made into spinning solution, through electrostatic spinning, the operations such as vacuumize and continuous heat seal process obtain the conventional superfine fibre film of PVDF of good mechanical performance, fibre diameter is 50-500nm (China Patent No.: CN 100450598C), they have also prepared a kind of PVDF/ Merlon (PC) superfine fibre of core-shell structure, three components (PMMA or BTEAC) is added particular by PVDF/PC electrospinning liquid, to the modification of PVDF/PC multicomponent polymeric electrolyte, enable modified PVDF/PC electrospinning liquid in electrospinning, form the superfine fibre having homogeneous fiber morphology and improve core/shell structure, obtained fibre diameter is 300-500nm (China Patent No.: CN 101586268A).Relate to electro-spinning to also have for PVDF and compound nano fibrous membrane patent thereof: Chinese patent 201310688683,200710056878,201110165813 etc.But the Static Spinning PVDF nanofiber of existing document and patent report is mostly distributed in tens of regular circular configuration nanofiber to hundreds of nanometer based on diameter, rarely has the report of dendritic structure.
Summary of the invention
The present invention relates to a kind of PVDF electrostatic spinning liquid, adopt spinning solution of the present invention, coordinate certain electrostatic spinning process can produce the PVDF nano fibrous membrane of dendritic structure, this dendroid nanofiber is made up of trunk fiber and branched fiber.Compared with conventional circular electrostatic spinning fiber, in dendroid nanofiber of the present invention, branched fiber diameter is superfine, reach Nano grade (below 100nm), give the more excellent obstruct of PVDF nano fibrous membrane, absorption property, in filtration, protection field, there is more wide application prospect.
The electrostatic spinning liquid of Kynoar of the present invention, is characterized in that can be used for production dendroid polyvinylidene fluoride nanometer tunica fibrosa, by PVDF, organic branching salt, plasticizer and solvent composition.
Described organic branching molecules of salt weight range is between 200-400, and accounting for described spinning solution mass percent is 2%-5%; It is 0.5%-2% that described plasticizer accounts for described spinning solution mass percent.
PVDF of the present invention is spinning-grade, with existing document and patent report general, without particular/special requirement, its solvent is the mixed solvent of acetone and DMF, and ratio of solvent is preferably 1: 3, and described spinning solution PVDF concentration is preferably 10%-20%.
Provided by the present invention a kind of can the compound method of electrostatic spinning liquid of production dendroid PVDF nano fibrous membrane, comprise the steps:
(1) PVDF dissolves: it is in the mixed solvent of 1: 3 acetone and DMF that a certain amount of PVDF and a small amount of plasticizer are joined ratio of solvent, is constantly stirred to and dissolves completely, makes finite concentration PVDF solution;
(2) organic branching salt dispersion: add a certain amount of organic branching salt in above-mentioned solution, control mixing time between 10min to 30min.
In spinning solution of the present invention, the use of organic branching salt is the fibroplastic key factor of dendroid.Organic branching salt feature is in its structure with relatively long alkane chain, under suitable mixing time, its dispersion to a certain extent in spinning solution can be controlled uneven, form the spinning solution in organic less region of branching salt content (calling rich in polymers district 1 in the following text) and the higher region (calling Fu Yan district 2 in the following text) of organic branching salt content as shown in schematic diagram 1, this spinning solution is under electrostatic spinning effect, Fu Yan district makes that it is subject to larger electric field force and splitting becomes branch part due to its larger electrical conductivity, i.e. branched fiber, the branch trunk that rich in polymers district is formed after being subject to electric field force drawing-off refinement, i.e. trunk fiber, the nanofiber of a kind of dendritic structure of general performance.On spinning effect impact significantly, molecular weight excessive or too small being all difficult to obtains dendroid nanofiber to organic branching molecules of salt amount size.Organic branching molecules of salt weight range of the present invention preferably controls between 200-400, is preferably any one in N, N, N-tributyl-1-fourth ammonium bromide, four n-pro-pyl ammonium chlorides, N, N, N-tributyl-1-fourth ammonium chloride, four pentyl ammonium chloride.
Plasticizer can reduce the large intermolecular force of PVDF in the present invention, promotes the slenderizing of fiber, makes component fibre diameter reach nanoscale.Plasticizer of the present invention is the one in dibutyl phthalate, sulfolane, glyceryl triacetate, propene carbonate.
It should be noted that the mixing time of organic branching salt in spinning solution in preparation of spinning solution process of the present invention, mixing time is too short, and large-area skewness appears in branching salt, is unfavorable for spinning; Mixing time is long, and branching salt distribution is too even, cannot form rich in polymers district and Fu Yan district spinning solution.
Utilize spinning solution of the present invention, adopt the dendroid nano fibrous membrane that electrospinning process is produced, wherein trunk distribution of fiber diameters is between 100-500nm, and branched fiber diameter is distributed between 5-50nm.This nano fibrous membrane grammes per square metre is only 1g/m 2time, to the filter efficiency of 0.3 μm of ps particle in 0.26 μm of sodium chloride particle in air and the aqueous solution all more than 99%, show excellent solid-gas and solid-liquid strainability.
Picture and text simply describe
Fig. 1 is spinning solution of the present invention organic branching salt distribution schematic diagram
Fig. 2 is the ESEM schematic diagram of the dendroid PVDF nanofiber utilizing the embodiment of the present invention 1 spinning solution to prepare.
Fig. 3 is the ESEM schematic diagram of the PVDF nanofiber utilizing the embodiment of the present invention 5 spinning solution to prepare.
Detailed description of the invention
Embodiment 1
It is in the mixed solvent of 1: 3 acetone and DMF that PVDF and the 0.06g dibutyl phthalate getting 1.2g molecular weight 500,000 joins ratio of solvent, is constantly stirred to it and dissolves completely, make the PVDF spinning solution that concentration is 10%; Then in above-mentioned solution, add 0.25g tetra-n-pro-pyl ammonium chloride, stir 10min, obtained spinning solution.
Join in electrostatic spinning apparatus by above-mentioned spinning solution, at spinning voltage 25kV, under the technological parameter of receiving range 15cm, rate of extrusion 1mL/h, it is 1g/m that spinning certain hour prepares surface density 2dendroid PVDF nano fibrous membrane, its structure and morphology is see Fig. 2.
Recording trunk fibre diameter by SEM electromicroscopic photograph is 100-300nm, and branched fiber diameter is 10-50nm; Utilize TSI8130 to filter testboard, under air velocity 32L/min, testing this dendroid tunica fibrosa to 0.26 μm of sodium chloride particle filtration efficiency is 99.6%; Under 0.05MPa pressure, this nano fibrous membrane is 99.2% to the rejection of 0.3 μm of polystyrene particle in the aqueous solution.
Embodiment 2
It is in the mixed solvent of 1: 3 acetone and DMF that PVDF and the 1.2g glyceryl triacetate getting 1.8g molecular weight 300,000 joins ratio of solvent, is constantly stirred to it and dissolves completely, make the PVDF spinning solution that concentration is 15%; In above-mentioned solution, add 0.38gN, N, N-tributyl-1-fourth ammonium chloride, stir 20min, obtained spinning solution.
Join in electrostatic spinning apparatus by above-mentioned spinning solution, spinning technology parameter is: spinning voltage 25kV, receiving range 15cm, rate of extrusion 1mL/h, and it is 1g/m that spinning certain hour prepares surface density 2dendroid PVDF nanofiber.
Recording trunk fibre diameter by SEM electromicroscopic photograph is 100-380nm, and branched fiber diameter is 5-50nm; Utilize TSI8130 to filter testboard, under air velocity 32L/min, testing this dendroid tunica fibrosa to 0.26 μm of sodium chloride particle filtration efficiency is 99.9%; Under 0.05MPa pressure, this nano fibrous membrane is 99.7% to the rejection of 0.3 μm of polystyrene particle in the aqueous solution.
Embodiment 3
It is in the mixed solvent of 1: 3 acetone and DMF that PVDF and the 2g propene carbonate getting 2.4g molecular weight 350,000 joins ratio of solvent, is constantly stirred to it and dissolves completely, make the PVDF spinning solution that concentration is 20%; In above-mentioned solution, add 0.5g four pentyl ammonium chloride, stir 25min, obtained spinning solution.
Join in electrostatic spinning apparatus by above-mentioned spinning solution, spinning technology parameter is: spinning voltage 30kV, receiving range 15cm, rate of extrusion 1.2mL/h, and it is 1g/m that spinning certain hour prepares surface density 2dendroid PVDF nanofiber.
Recording trunk fibre diameter by SEM electromicroscopic photograph is 100-500nm, and branched fiber diameter is 5-50nm; Utilize TSI8130 to filter testboard, under air velocity 32L/min, testing this dendroid tunica fibrosa to 0.26 μm of sodium chloride particle filtration efficiency is 99.7%, air velocity 32L/min; Under 0.05MPa pressure, this nano fibrous membrane is 99.3% to the rejection of 0.3 μm of polystyrene particle in the aqueous solution.
Embodiment 4
It is in the mixed solvent of 1: 3 acetone and DMF that PVDF and the 2g sulfolane getting 2g molecular weight 400,000 joins ratio of solvent, is constantly stirred to it and dissolves completely, make the PVDF spinning solution that concentration is 17%; In above-mentioned solution, add 0.5g N, N, N-tributyl-1-fourth ammonium bromide, stir 30min, obtained spinning solution.
Join in electrostatic spinning apparatus by above-mentioned spinning solution, spinning technology parameter is: spinning voltage 30kV, receiving range 15cm, rate of extrusion 1.5mL/h, and it is 1g/m that spinning certain hour prepares surface density 2dendroid PVDF nanofiber.
Recording trunk fibre diameter by SEM electromicroscopic photograph is 100-500nm, and branched fiber diameter is 5-50nm; Utilize TSI8130 to filter testboard, under air velocity 32L/min, testing this dendroid tunica fibrosa to 0.26 μm of sodium chloride particle filtration efficiency is 99.5%, air velocity 32L/min; Under 0.05MPa pressure, this nano fibrous membrane is 99.0% to the rejection of 0.3 μm of polystyrene particle in the aqueous solution.
Embodiment 5
The PVDF spinning solution that concentration is 10% is made with reference to embodiment 1; Then in above-mentioned solution, add 0.25g tetra-n-pro-pyl ammonium chloride, stir 60min, obtained spinning solution.
Spin certain hour with reference to embodiment 1 and prepare 1g/m 2pVDF nano fibrous membrane, its appearance structure is see Fig. 3.
Record this nano fibrous membrane by SEM electromicroscopic photograph and do not occur dendritic structure, average fibre diameter is 250nm; Utilize TSI8130 to filter testboard, under air velocity 32L/min, testing this dendroid tunica fibrosa to 0.26 μm of sodium chloride particle filtration efficiency is 60.2%; Under 0.05MPa pressure, this nano fibrous membrane is 48.5% to the rejection of 0.3 μm of polystyrene particle in the aqueous solution.

Claims (2)

1. an electrostatic spinning liquid for Kynoar (PVDF), is characterized in that can be used for production dendroid PVDF nano fibrous membrane, by PVDF, organic branching salt, plasticizer and solvent composition;
Described organic branching molecules of salt weight range is between 200 ~ 400, and accounting for described spinning solution mass percent is 2% ~ 5%; It is 0.5% ~ 2% that described plasticizer accounts for described spinning solution mass percent.
2. a compound method for electrostatic spinning liquid according to claim 1, comprises the steps:
(1) a certain amount of PVDF and a small amount of plasticizer being joined ratio of solvent is in the mixed solvent of 1: 3 acetone and DMF, is constantly stirred to and dissolves completely, makes finite concentration PVDF solution;
(2) in above-mentioned solution, add a certain amount of organic branching salt, control mixing time between 10min to 30min.
CN201410669025.0A 2014-11-17 2014-11-17 Electrostatic spinning solution of polyvinylidene fluoride and preparation method of electrostatic spinning solution Pending CN104480560A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105803678A (en) * 2016-04-18 2016-07-27 生纳科技(上海)有限公司 Nanofiber membrane capable of filtering out impurities and preparation method and application thereof
CN107641898A (en) * 2016-05-27 2018-01-30 天津工业大学 A kind of modified polyvinilidene fluoride nanofiber smart membrane
CN107964736A (en) * 2016-10-19 2018-04-27 苏州汉力新材料有限公司 The preparation method of Kynoar/polystyrene composite superhydrophobic material
CN112481832A (en) * 2020-12-18 2021-03-12 四川大学 Preparation method of P (VDF-TrFE) tree-shaped micro-nano fiber piezoelectric film
CN113430719A (en) * 2021-07-14 2021-09-24 常州纺织服装职业技术学院 Preparation method of air filtration nanofiber membrane with dendritic multi-level structure

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105803678A (en) * 2016-04-18 2016-07-27 生纳科技(上海)有限公司 Nanofiber membrane capable of filtering out impurities and preparation method and application thereof
CN107641898A (en) * 2016-05-27 2018-01-30 天津工业大学 A kind of modified polyvinilidene fluoride nanofiber smart membrane
CN107964736A (en) * 2016-10-19 2018-04-27 苏州汉力新材料有限公司 The preparation method of Kynoar/polystyrene composite superhydrophobic material
CN112481832A (en) * 2020-12-18 2021-03-12 四川大学 Preparation method of P (VDF-TrFE) tree-shaped micro-nano fiber piezoelectric film
CN112481832B (en) * 2020-12-18 2022-07-19 四川大学 Preparation method of P (VDF-TrFE) tree-shaped micro-nano fiber piezoelectric film
CN113430719A (en) * 2021-07-14 2021-09-24 常州纺织服装职业技术学院 Preparation method of air filtration nanofiber membrane with dendritic multi-level structure
CN113430719B (en) * 2021-07-14 2022-05-20 常州纺织服装职业技术学院 Preparation method of air filtration nanofiber membrane with dendritic multi-level structure

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Application publication date: 20150401