CN103122583B - Preparation method of novel amphiphilic nano fiber having core-shell structure - Google Patents

Preparation method of novel amphiphilic nano fiber having core-shell structure Download PDF

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CN103122583B
CN103122583B CN201310037534.7A CN201310037534A CN103122583B CN 103122583 B CN103122583 B CN 103122583B CN 201310037534 A CN201310037534 A CN 201310037534A CN 103122583 B CN103122583 B CN 103122583B
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solution
preparation
electrospun
spinning
nano
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CN103122583A (en
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马贵平
余云英
聂俊
方大为
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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Abstract

The invention combines an electrostatic spinning technology and a photocuring technology. A nano fiber of which the surface is provided with a photosensitive initiator is prepared through an electrospinning method, a hydrophilic monomer is coated on the nano fiber, and polymerization is performed to prepare a nano composite fiber having a core/shell structure, wherein the inner layer of the nano composite fiber is oleophilic, and the outer layer of the nano composite fiber is hydrophilic. The preparation method comprises the following specific steps: blending a 7-20wt% polymer solution and a fluorine-containing initiator accounting for 5-10wt% of the polymer, performing electrospinning to prepare a nano fiber film of which the surface is provided with the photosensitive initiator, soaking the fiber film in a 50-80% monomer solution, curing to form a film under the irradiation of ultraviolet light, washing with water to remove the excessive monomer, and drying to form a film. The nano fiber can enhance the property of the electrospinning nano fiber and widen the application area.

Description

A kind of preparation of nanofiber of amphipathic nucleocapsid structure
Technical field
The present invention relates to a kind of preparation method of functionalized macromolecular nanofiber, belong to functionalized nano-fiber preparation field.
Technical background
Electrostatic spinning technique is one of most important basic skills preparing continuous nano-fibre at present.Electrospun appears at 1934 the earliest, and Formalas introduces a kind of electrostatic spinning apparatus utilizing electrostatic force to produce polymer fiber first in its patent, from then on opens electrostatic spinning technique field.When electrostatic spinning technique is mainly carried between spinning nozzle and receiving system by high-tension electricity, the polymer drop surface being suspended on spinning head will be induced charged, under the effect of the Coulomb force that the electrostatic repulsion forces between surface charge and external electrical field apply, drop will become conical.When voltage increases above critical value gradually, electrostatic force overcomes the capillary constraint of polymer solution, and liquid jet sprays continuously from spinning nozzle.Liquid jet is in the electric field by the stretching continued, and diameter is reduced to hundreds of nanometer even tens nanometers from hundreds of micron, and meanwhile solvent volatilizees fast, and finally, dry nanofiber drops on the contrary receiving system of electric charge.Electricity spinning fibre film, due to its high-specific surface area, good bionic performance, carries at bioengineered tissue support, medicine and releases, has higher using value in wound reparation etc.In order to widen the range of application of Electrospun nano-fibers, people study and have prepared the nanofiber with special construction, as the nanofiber etc. of the nanofiber of porous structure, hollow Nano fiber in use pipe, nucleocapsid structure.
Under photo-polymerization process refers to the radiation of liquid monomer or prepolymer light (ultraviolet or visible ray), rapid polymerization is cross-linked to form covalent cross-linking and is converted into the process of solid-state material.Light polymerization technique is the industrial technology with " 5E " feature a: efficient (efficiently); Enabling (wide adaptability); Economical (economy); Energy saving (energy-conservation); Environmental friendly (environmental friendliness).Photocuring technology, owing to having above advantage, has been widely used in all trades and professions such as printing, packaging, advertisement, building materials, decoration, electronics, communication, computer, household electrical appliances, automobile, Aeronautics and Astronautics, instrument and meter, physical culture, health.Along with environmental consciousness strengthens day by day, photocuring technology as a green technology, its development potentiality and the market space huger.
The nanofiber of nucleocapsid structure can at internal layer load some drugs and bioactie agent, as slow releasing carrier of medication and tissue engineering bracket, if any people by bovine serum albumin(BSA) FITC.BSA load in internal layer spinning liquid, with hydrophobicity polycaprolactone (PCL) for skin, nuclear shell structure micro-nano rice fiber PCL-r-FITC.BSA/PEG significantly can be alleviated FITC.BSA and release phenomenon release the prominent of initial stage.The nano-composite fiber of nucleocapsid structure comprises two parts usually: polymer or inorganic material form core structure, and another kind of polymer forms Shell Materials.The nano-composite fiber of usual core/shell structure has chemistry coating, surface chemistry combination, blended electrostatic spinning, coaxial electrostatic spinning four kinds of methods.Electrostatic spinning and photocuring technology combine by the present invention, the nanofiber that surface has photosensitive initiator is prepared with electrical spinning method, painting is covered with to be had hydrophilic monomer and is polymerized, and preparation has internal layer oleophylic, the nano-composite fiber of outer hydrophilic core/shell structure.This kind of nanofiber can improve the performance of Electrospun nano-fibers, widens its Application Areas.
Summary of the invention
Fluorine-containing light trigger and oleophilic polymer solution blending Electrospun have been prepared the photosensitive type nanofiber with photoreceptor activity by the present invention, by photocuring technology at the coated one deck hydrophilic polymer of fibrous outer, the nuclear shell structure nano fiber of preparation functionalization.
Concrete operation step of the present invention is as follows:
1) preparation of Electrospun solution: compound concentration is the polymer solution of 7wt% ~ 20wt%, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator of polymer content 5wt% ~ 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 10 ~ 20kV, and spinning mouth is 15 ~ 25cm to the distance of receiver, and spinning mouth diameter is 0.7mm.Be there is by Electrospun preparation the nanofiber of light trigger;
3) preparation of nuclear shell structure nano: compound concentration is the solution of the hydrophilic monomer of 50% ~ 80%, after it dissolves completely, by 2) in preparation tunica fibrosa soak wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Above-mentioned steps 1) in polymer be polyacrylonitrile (PAN);
Above-mentioned steps 1) in fluorine-containing initator be 2959-F;
Above-mentioned steps 3) in monomer be 2-acrylamide-2-methylpro panesulfonic acid (AMPS), NIPA, dimethylamino-propyl Methacrylamide (DMAPMA)
Innovative point of the present invention is:
1) utilize method of electrostatic spinning and photocuring technology to combine to have prepared the core-shell nano fiber that internal layer oleophylic, top layer are hydrophilic.
Accompanying drawing explanation
Fig. 1 the present invention is by the nanofiber scanning electron microscope (SEM) photograph of the PAN/AMPS nucleocapsid structure prepared by embodiment 1;
Specific embodiment
Embodiment 1
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) preparation process of electrospinning cortina: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 10kV, and spinning mouth is 10cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) of 50%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film is Fig. 1 through its structure chart of transmission electron microscope observing.
Embodiment 2
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 15kV, and spinning mouth is 15cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) of 60%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 3
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) preparation process of electrospinning cortina: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 20kV, and spinning mouth is 20cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) of 80%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, be solidified into through ultraviolet lighting, wash away unnecessary monomer, drying and forming-film.
Embodiment 4
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 10kV, and spinning mouth is 10cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer NIPA of 50%, after it dissolves completely, by 2) in preparation tunica fibrosa soak wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 5
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 15kV, and spinning mouth is 15cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the NIPA of 60%, after it dissolves completely, by 2) in preparation tunica fibrosa soak wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 6
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 20kV, and spinning mouth is 20cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the NIPA of 80%, after it dissolves completely, by 2) in preparation tunica fibrosa soak wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 7
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 10kV, and spinning mouth is 10cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer dimethylamino-propyl Methacrylamide (DMAPMA) of 50%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 8
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 15kV, and spinning mouth is 15cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer dimethylamino-propyl Methacrylamide (DMAPMA) of 60%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
Embodiment 9
1) preparation of Electrospun solution: compound concentration is the N of the polyacrylonitrile (PAN) of 10wt%, dinethylformamide (DMF) solution, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator 2959-F of polymer content 10wt% with in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 20kV, and spinning mouth is 20cm to the distance of receiver, and spinning mouth diameter is 0.7mm.The nano fibrous membrane of light trigger is worn by Electrospun preparation table;
3) preparation of nuclear shell structure nano: compound concentration is the DMF solution of the monomer dimethylamino-propyl Methacrylamide (DMAPMA) of 80%, after it dissolves completely, by 2) the middle tunica fibrosa immersion prepared is wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.

Claims (2)

1. a preparation for the nanofiber of amphipathic nucleocapsid structure, is characterized in that following steps:
1) preparation of Electrospun solution: compound concentration is polyacrylonitrile (PAN) solution of 7wt% ~ 20wt%, after it dissolves completely, to add in solution, for Electrospun after it dissolves completely relative to the fluorine-containing initator of polymer content 5wt% ~ 10wt% in darkroom;
2) electro-spinning process: by step 1) prepared by Electrospun solution in darkroom, carry out Electrospun, arranging spinning voltage is 10 ~ 20kV, and spinning mouth is 15 ~ 25cm to the distance of receiver, and spinning mouth diameter is 0.7mm;
3) compound concentration is the solution of the hydrophilic monomer of 50% ~ 80%, after it dissolves completely, by 2) in preparation tunica fibrosa soak wherein, through ultraviolet lighting film-forming, wash away unnecessary monomer, drying and forming-film.
2. preparation method according to claim 1, it is characterized in that above-mentioned steps 3) in monomer be 2-acrylamide-2-methylpro panesulfonic acid (AMPS), DMF (DMF) solution of NIPA (NIPAM), dimethylamino-propyl Methacrylamide (DMAPMA).
CN201310037534.7A 2013-01-31 2013-01-31 Preparation method of novel amphiphilic nano fiber having core-shell structure Expired - Fee Related CN103122583B (en)

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CN103757742B (en) * 2014-01-03 2015-10-28 北京化工大学常州先进材料研究院 A kind of preparation method of nuclear shell structure nano fiber of fluorine-contained surface
CN104141173B (en) * 2014-06-25 2016-08-24 广西科技大学 The preparation method of photocurable cellulose esters nano fibrous membrane
CN104264248B (en) * 2014-09-16 2017-01-18 北京化工大学 Preparation method for controllable core-shell structure nanofiber
CN105220244B (en) * 2015-08-25 2018-04-17 青岛大学 A kind of method of the standby photo-curing material micro nanometer fiber of scale no-solvent electrically spinning
CN109537284A (en) * 2018-11-27 2019-03-29 五邑大学 Thermal sensitivity nanofiber and preparation method carry medicine thermal sensitivity nanofiber and preparation method
CN113430828B (en) * 2021-06-23 2023-04-07 清华大学 Fiber product and preparation method thereof
CN114411274B (en) * 2022-01-27 2023-02-28 青岛中科凯尔科技有限公司 Electrostatic spinning system based on multilayer tectorial membrane
CN114775279B (en) * 2022-06-20 2022-09-09 河南源宏高分子新材料有限公司 Antistatic flame-retardant polyester material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1847473A (en) * 2006-04-26 2006-10-18 北京化工大学 Electric spinning-in-situ photopolymerization apparatus and process for preparing nanometer fiber
CN102675490A (en) * 2012-05-13 2012-09-19 北京化工大学常州先进材料研究院 Preparation of photoinitiator for gradient polymerization and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1847473A (en) * 2006-04-26 2006-10-18 北京化工大学 Electric spinning-in-situ photopolymerization apparatus and process for preparing nanometer fiber
CN102675490A (en) * 2012-05-13 2012-09-19 北京化工大学常州先进材料研究院 Preparation of photoinitiator for gradient polymerization and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
原位聚合法制备PANI-TSA/PA6核壳纳米纤维;董宪君等;《化工新型材料》;20120615;第40卷(第6期);42-44 *

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