CN102787448B - Preparation method of degradable polycarbonate butanediol ester electrospinning fiber films - Google Patents
Preparation method of degradable polycarbonate butanediol ester electrospinning fiber films Download PDFInfo
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- CN102787448B CN102787448B CN201210260780.4A CN201210260780A CN102787448B CN 102787448 B CN102787448 B CN 102787448B CN 201210260780 A CN201210260780 A CN 201210260780A CN 102787448 B CN102787448 B CN 102787448B
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Abstract
The invention relates to a preparation method of degradable polycarbonate butanediol ester electrospinning fiber membranes. The preparation method comprises the following steps that (1) polycarbonate butanediol ester is sheared into pieces to be added into solvents, modification components are added, the polycarbonate butanediol ester is dissolved through stirring, and in addition, the modification components are fully and uniformly dispersed; and (2) spinning liquid is obtained and is subjected to electrostatic spinning to obtain electrospinning fiber membrane materials. The electrospinning fiber membrane materials have the advantages that the mechanical strength is good, the fiber diameter is adjustable and controllable, the degradation period of the prepared materials is short, and the purpose is wide. The preparation method provided by the invention has the advantages that the operation is simple, and the cost is low.
Description
Technical field
The invention belongs to the preparation field of electrospun fiber membrane, particularly a kind of preparation method of degradable polytetramethylene carbonate diol electrospun fiber membrane.
Background technology
Electrostatic spinning is the common technology that nanofiber is prepared in a kind of processing, and method can prepare fibre diameter is thus the fiber of 2nm to some tens of pm, these fibers stacking, can form the nonwoven fabric that a specific area is very huge.The principles illustrated of this technical method is as follows: macromolecule preparation is become Polymer Solution or melt, this solution or melt is added in storage device, and slowly extruded by propulsion plant.On the other hand, apply a thousands of high voltage to tens thousand of volt at discharging opening, this high voltage has two effects: make Polymer Solution or bath surface with a large amount of electric charge, secondly, and produces an electric field between receiving system.Under high-tension effect, the Polymer Solution or the bath surface that gather a large amount of like charges define taylor cone in the electric field, and after the repulsive interaction of like charges is greater than surface tension of liquid, liquid surface ejects macromolecule jet.Subsequently, jet just moves along direction of an electric field to receiving system, and generation whip moves and stretches in the electric field, moves in process at whip, Polymer Solution solvent evaporates, if melt is as electrospinning stoste, then it obtains cooling (macromolecule electrospinning stoste can be melt or solution) in this course.Finally obtain macromolecular fibre fine in a large number on the reception device.These fibers constitute a macromolecule nonwoven fabric jointly.
Nowadays, because it is unique, the performance of excellence has received increasing concern to the macromolecule electrospun fiber membrane prepared of electrospinning, about the research work of this respect is also carried out more extensive.Have the correlative study paper about macromolecule electrospun fiber membrane also to have one in recent years to increase more fast.More external companies, as micro/nano fibrous membrane material has even been applied on their product by Finetex and Donaldson, but do not carry out open as trade secret.
In the last few years, and though be in environmental protection or use procedure more easily angle consider, degradation material receives the concern of people all day by day.Wherein particularly bio-medical material, in order to avoid second operation, needs as the object such as medicament slow release and zymophore, the research of degradable high polymer material is carried out more and more extensive.Wherein, degradable poly ester material is better with their biocompatibilities, mechanical strength is good, catabolite is nontoxic the feature such as is easy to excrete and the focus, particularly polycaprolactone (PCL) that become wherein have been a great concern especially.Can simultaneously, PCL also causes degradation time long because its hydrophily is not good and degree of crystallinity is too high.
Polytetramethylene carbonate diol (PBC) is a kind of in the degradable poly ester material of synthesis in 20 end of the centurys, backbone structure has similitude with PCL, simultaneously mechanical property and thermal property and PCL are very close, but because its slower crystallization rate causes its machine-shaping to have difficulty, therefore do not arouse enough attention.But when the shortcoming that PCL degradation cycle is long deeply and is more and more given prominence to along with research, how to utilize this material capable of being fast degraded of PBC to become the work being worth studying.
In electrostatic spinning process, the dynamic and stretching of the whip of jet makes these nano-scale fibers be easy to solidification and shaping, avoids the shortcoming of solution and melt-processed process in which materials not easy-formation.Therefore, the method for electrostatic spinning can be adopted to be processed by PBC material, prepare degradation speed fast, the micro/nano fibrous membrane material that mechanical strength is good.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of electrostatic spinning preparation method of degradable polyester material, the electrospun fiber membrane mechanics of materials intensity prepared is good, degradation time is short, and discarded object is substantially pollution-free to environment, and improves material hydrophilic performance by adding hydrophilic component; Electrospinning fibre membrane material of the present invention can be used for multiple different purposes, as: use as water filtration film; Be prepared into air filter screen for air filtration; Be prepared into the membrane material of bio-medical; In addition, electrospinning preparation manipulation is simple, and cost is low.
The electrostatic spinning preparation method of a kind of degradable polyester material of the present invention, comprising:
(1) polytetramethylene carbonate diol is shredded join in solvent, add modified component, stir and polytetramethylene carbonate diol is dissolved, and make modified component obtain full and uniform dispersion, obtain spinning solution;
(2) above-mentioned spinning solution is carried out electrostatic spinning and obtain electrospinning fibre membrane material.
Polytetramethylene carbonate diol number-average molecular weight in described step (1) is 40,000 ~ 250,000.
The solvent of the polytetramethylene carbonate diol in described step (1) comprises one or more in formic acid, acetic acid, hexafluoroisopropanol, trifluoroethanol, trifluoroacetic acid, carrene, dichloroethanes, chloroform, dimethyl formamide, dimethylacetylamide etc.
Modified component in described step (1) comprises biological material and the PGAs (PGA) such as starch, sodium alginate, Carboxymethyl Cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, carboxymethyl chitosan, gelatin, collagen, polylactide (PLA), poly (glycolide-lactide) (PGLA), polycaprolactone (PCL), the synthetic materials such as polyesteramide (PEA), polyphosphate, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene glycol oxide, polymine or PVP.
Modified component in described step (1) and the mass ratio of polytetramethylene carbonate diol are 0:100-5:100.
In solution in described step (2), the mass fraction of polytetramethylene carbonate diol is 8-40%.
Electrospinning receiving system in described step (2) can select as required aluminium foil flat receiver, orientation rotating cylinder receiver, space bar receiver, model receiver or thus a few class receiving system rationally promote the other types receiving system obtained.
Electrospinning parameters in described step (2) is: fltting speed (i.e. feeding speed) is 0.01 ~ 100mL/h, and voltage strength is 2 ~ 50kV, and fiber accepts distance is 1 ~ 50cm, and electrospinning preparation time is 0.01 ~ 100h.
The physical parameter of the electrospinning fibre membrane material in described step (2) is: its fibre diameter is 10nm ~ 50,000nm, and yield strength is 0.05 ~ 10MPa, and fracture strength is 0.1 ~ 20MPa, and elongation at break is 10% ~ 200%.
A series of degradable PBC electrospinning films prepared by the inventive method, can be used for the fields such as liquid filtering, gas purification and bio-medical.Polytetramethylene carbonate diol itself has degradation speed faster, and after being prepared into the electrospun fiber membrane of superhigh specific surface area, its discarded object can be degraded to carbon dioxide and water within a short period of time after abandoning, and does not substantially have what adverse effect to environment in addition.Meanwhile, shorter degradation cycle also can enable this material at bio-medical, is particularly applied to restore cycle shorter some field of tissue engineering technology, makes it palliating degradation degree and sick and wounded position resume speed matches.
beneficial effect
(1) the present invention can prepare the goods of different fibre diameter, thickness and difference in functionality according to the different electrospinning parameter of change, and the fiber film material mechanical strength made is good, and preparation process is simple to operate, and cost is low.
(2) a kind of degradable electrospinning fibre membrane material prepared by the present invention has very large practicality, can be used for multiple different purposes, as: a. uses as water filtration film; B. air filter screen is prepared into for air filtration; C. the membrane material of bio-medical is prepared into;
(3) a kind of degradable electrospun fiber membrane material degradation cycle prepared by the present invention is short, and discarded object is substantially pollution-free to environment.
Accompanying drawing explanation
Fig. 1 is the PBC electrospun fiber membrane stereoscan photograph (magnifying power 500 times) of embodiment 1;
Fig. 2 is photo captured after the PBC electrospun fiber membrane of embodiment 2 is received by tweezers;
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By number-average molecular weight be 80,000 PBC shred, be dissolved in hexafluoroisopropanol, be mixed with the solution that mass fraction is 8%, being joined by solution in barrel, extruded by propulsion plant, is 0.5mL/h for amount, electrospinning voltages is 25kV, distance 20cm, board joint receiving apparatus receives 10h continuously, the electrospun fiber membrane that obtained 0.4mm is thick, fiber diameter is 400nm, tunica fibrosa yield strength is 1.2MPa, and fracture strength is 7MPa, and elongation at break is 70%.Tunica fibrosa stereoscan photograph as shown in Figure 1.
Get this tunica fibrosa and make disc-shaped, through soak repeatedly determine residual without hexafluoroisopropanol after, can be used as last one deck microfiltration membranes use of water filtration, it can adsorbing metal ions and water sub-micron level particulate intercept bacterium effectively.
Embodiment 2
By number-average molecular weight be 150,000 PBC shred, the polyvinylpyrrolidone (PVP) of mixing sole mass 5% together heats and is dissolved in dimethyl formamide, be mixed with the solution that PBC mass fraction is 18%, solution is joined in the barrel of heat insulation function, keeping 45 DEG C, extruded by propulsion plant, is 1mL/h for amount, electrospinning voltages is 35kV, receiving range 30cm.Adopt pipeline system operation, the screen pack other parts loaded slowly moves past before electrospinning spout, filter screen receives tunica fibrosa 1h continuously, the final electrospun fiber membrane being covered with a layer thickness and being about 0.1mm on filter screen, fiber diameter is 400nm, again this composite screen is soaked in ethanol repeatedly to remove PVP contained on fiber, obtain the fiber film material that fiber surface has a large amount of regular pore structure, it is used for air cleaner, as last layer filter screen, the fine dust in air and microorganism can be removed efficiently.Accompanying drawing 2 adopts tweezers to carry out within 20 minutes, receiving rear captured photo to electrospun fiber membrane as receiving pole, and can be clear that from this picture, this formula productive rate is higher, can produce thicker one deck microporous fiber membranes within a short period of time.
Embodiment 3
By number-average molecular weight be 100,000 PBC shred, be dissolved in acetic acid, be mixed with the solution that PBC mass fraction is 18%, the cyanoacrylate Nano microsphere being coated with short nerve growth medicine to be joined in electrospinning material liquid and to carry out electrospinning after it being fully uniformly dispersed, solution is added in feeding cylinder, extruded by propulsion plant, for measuring as 0.75mL/h, electrospinning voltages is 20kV, receiving range 15cm, rotating cylinder receiver receives 20h continuously, rotating cylinder linear velocity 9m/s, the electrospun fiber membrane that obtained 0.7mm is thick, fiber diameter is 450nm, differently-oriented directivity tunica fibrosa yield strength is 3MPa, fracture strength is 12MPa, elongation at break is 120%.
Getting this tunica fibrosa soaks repeatedly to remove solvent acetic acid in ethanol, tubulose (namely differently-oriented directivity is identical with the cephlad-caudal of gained pipe) is made again along differently-oriented directivity winding, tubular material is used in repairing of neural injury, use as nerve trachea, plant in pipe into NSC, can help well and promote that nerve fiber is recovered.And in nerve fiber recovery process, conduit is degraded into Small molecular and excretes, and catabolite is nontoxic to health.Along with the degradation process of conduit, nerve fiber also recovers its function gradually.
Claims (5)
1. a preparation method for degradable polytetramethylene carbonate diol electrospun fiber membrane, comprising:
(1) polytetramethylene carbonate diol is shredded join in solvent, add modified component, stir and polytetramethylene carbonate diol is dissolved, and make modified component obtain full and uniform dispersion, obtain spinning solution; Wherein, modified component is biological material or synthetic material; Biological material is collagen; Synthetic material is PGA PGA, polylactide PLA, poly (glycolide-lactide) PGLA, polycaprolactone (PCL), polyesteramide PEA, polyphosphate or PVP;
(2) above-mentioned spinning solution is carried out electrostatic spinning and obtain electrospinning fibre membrane material.
2. the preparation method of a kind of degradable polytetramethylene carbonate diol electrospun fiber membrane according to claim 1, is characterized in that: the modified component in described step (1) and the mass ratio of polytetramethylene carbonate diol are 5:100.
3. the preparation method of a kind of degradable polytetramethylene carbonate diol electrospun fiber membrane according to claim 1, is characterized in that: the electrospinning receiving system in described step (2) comprises aluminium foil flat receiver, orientation rotating cylinder receiver or space bar receiver.
4. the preparation method of a kind of degradable polytetramethylene carbonate diol electrospun fiber membrane according to claim 1, it is characterized in that: the electrospinning parameters in described step (2) is: fltting speed is 0.01 ~ 100mL/h, voltage strength is 2 ~ 50kV, fiber accepts distance is 1 ~ 50cm, and electrospinning preparation time is 0.01 ~ 100h.
5. the preparation method of a kind of degradable polytetramethylene carbonate diol electrospun fiber membrane according to claim 1, it is characterized in that: the physical parameter of the electrospinning fibre membrane material in described step (2) is: its fibre diameter is 10nm ~ 50,000nm, yield strength is 0.05 ~ 10MPa, fracture strength is 0.1 ~ 20MPa, and elongation at break is 10% ~ 200%.
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| CN103739940B (en) * | 2013-12-08 | 2015-11-11 | 山东天蓝环保科技发展有限公司 | A kind of method of medical waste infusion bag of carrying out a biological disposal upon |
| CN106702598B (en) * | 2017-01-22 | 2018-11-09 | 齐齐哈尔大学 | A kind of preparation method of degradable graphene composite electrospun tunica fibrosa |
| CN112831917A (en) * | 2020-12-30 | 2021-05-25 | 淄博华士元环保科技有限公司 | Preparation method of PBC/PLA/TP composite antibacterial dressing |
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