CN106498539B - A kind of preparation method of polycaprolactone electrostatic spinning solution - Google Patents
A kind of preparation method of polycaprolactone electrostatic spinning solution Download PDFInfo
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- CN106498539B CN106498539B CN201610874028.7A CN201610874028A CN106498539B CN 106498539 B CN106498539 B CN 106498539B CN 201610874028 A CN201610874028 A CN 201610874028A CN 106498539 B CN106498539 B CN 106498539B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a kind of preparation methods of polycaprolactone electrostatic spinning solution.Polycaprolactone is added in a solvent, stirring to obtain concentration is the mixed solution of mass volume ratio 5% ~ 15%, adds the additive for accounting for solvent volume percentage 0.1% ~ 1%, stirs evenly, obtains polycaprolactone electrostatic spinning solution.The additive is one kind or mixture of oil soluble surfactant.The solvent is one of N,N-dimethylformamide and methanol and chloroform, methylene chloride, tetrahydrofuran these low boiling point good solvents or a variety of.Using the method for mixed solvent and addition surfactant, the surface tension of spinning solution is reduced, improves the electric conductivity of spinning solution, fiber bead structure disappears, and microscopic appearance gets a new look.So that tunica fibrosa even compact, and easily taken off from collection screen.Cost is relatively low for additive used in the present invention, and dosage is few, can increase substantially the practicability of polycaprolactone tunica fibrosa, promotes the fast development of polycaprolactone superfine fibre and promotes and applies.
Description
Technical field
The present invention relates to a kind of preparations for electrospun polymer stoste, in particular to polycaprolactone (PCL) electrostatic
Spinning solution belongs to high molecule nano material preparation technical field.
Background technique
Electrostatic spinning be a kind of pair of charged polymer solution increase piezoelectric field formed accelerate jet stream production diameter be 5 ~
The method of 500nm fiber, phase
Than the spinning of conventional method preparation, small 2 ~ 4 orders of magnitude of electrostatic spinning diameter.As made from electrostatic spinning technique
Nano fiber non-woven fabric has with extracellular matrix (ECM) similar design feature and biological function, thus in organizational project
Concern of the medical domain by more and more people.Its technical characterstic is not only in that the controllability and electrospun solution property of operating parameter
Easy modulability, while its high specific surface area and porosity is also beneficial to the adherency of cell and enters internal stent to grow.Mesh
Before, it is generally acknowledged excellent degradable high score that low-cost PCL, which has good tensile property and flexibility and degradability,
Sub- polymer is much successfully prepared into nano fibrous tissue engineering bracket, is applied to bone, cartilage, nerve, skin, tendon etc.
Various Tissues reparation and regeneration research.According to the literature, electrostatic spinning may be implemented in polycaprolactone solution, such as in publication number
In 101543645 Chinese invention patent " polycaprolactone (PCL) static spinning nerve conduit ", discloses and a kind of prepare polycaprolactone
(PCL) method of nanofiber, technical solution are that PCL is dissolved in volume ratio=5:1 ~ 2:1 chloroform/methanol solution
In, stirring obtains the mixed solution that PCL mass percent is 4% ~ 20%；The solution, voltage 10 are spinned using method of electrostatic spinning
~ 50kv, receiving distance is 10 ~ 30cm, and flow is 0.3 ~ 5ml/h.But since PCL polarity is lower, conductivity is low, surface tension compared with
Greatly, spinning fibre is easy to appear a beading, and easily sticks on collection screen, is not easy to remove, influences its service performance.This is largely
On affect the fast development of PCL superfine fibre and promote and apply.
Summary of the invention
A kind of low in cost the purpose of the invention is to overcome the deficiencies of the prior art and provide, can effectively improve PCL can
The property spun, the preparation method of tearable, the preferable PCL electrostatic spinning solution of microscopic appearance.
Specific steps are as follows:
Solvent is added in polycaprolactone (PCL), stirring to obtain concentration is the mixed solution of mass volume ratio 5% ~ 15%,
The additive for accounting for solvent volume percentage 0.1% ~ 1% is added, is stirred evenly, PCL electrostatic spinning solution is obtained.
The solvent is n,N-Dimethylformamide, methanol and cosolvent, and the cosolvent is chloroform, dichloromethane
One of alkane and tetrahydrofuran are a variety of, the volume ratio of n,N-Dimethylformamide, methanol and cosolvent are as follows:
VN,N-dimethylformamide/VMethanol/VCosolvent=0.5 ~ 1:1 ~ 4:1 ~ 8.
The additive be oil soluble surfactant be specially double ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums,
Three ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums, span 20 (Span20), span 40 (Span40), sorbester p18
(Span60), sorbester p17 (Span80), polysorbate85 (Tween85) it is one or more.
The chemical reagent is that analysis is pure.
Since PCL polarity is lower, conductivity is low, and surface tension is larger, and spinning fibre is easy to appear a beading, and easily sticks in
It collects on screen, is not easy to remove, influences its service performance.This largely affects the fast development of PCL superfine fibre and promotes
Using.Compared with prior art, the present invention has following obvious advantage:
1. being reduced due to using the method for adding methanol, n,N-Dimethylformamide and surfactant in PCL solution
The surface tension of spinning solution improves the electric conductivity of spinning solution, and fiber bead structure disappears, and microscopic appearance gets a new look.From
And make tunica fibrosa even compact, and easily take off from collection screen.
2. cost is relatively low for additive used in the present invention, dosage is few, can increase substantially polycaprolactone tunica fibrosa
Practicability promotes the fast development of PCL superfine fibre and promotes and applies.
Detailed description of the invention
Fig. 1 (a) be not added with surfactant concentration be mass volume ratio 7% PCL electrostatic spinning scanning electron microscope (SEM) photograph
(SEM)；Fig. 1 (b) is that the concentration of addition surfactant is the PCL electrostatic spinning scanning electron microscope (SEM) photograph of mass percent 7%
(SEM).
Fig. 2 (a) be not added with surfactant concentration be mass volume ratio 10% PCL electrostatic spinning SEM figure；2
(b) be add surfactant concentration be mass volume ratio 10% PCL electrostatic spinning SEM figure.
Fig. 3 is that the concentration of present invention addition surfactant is the PCL tunica fibrosa pictorial diagram that mass volume ratio 7% is taken off.
Specific embodiment
The present invention is described further with example with reference to the accompanying drawing, following chemical reagent are that analysis is pure.
Embodiment 1:
In the present embodiment, selecting additive is oil soluble surfactant Span80.
With molecular weight for 8 × 104 PCL be raw material, n,N-Dimethylformamide: methanol: the volume ratio of chloroform=
1:2:7 is solvent, stirs evenly the solution that configuration concentration is mass volume ratio 7%, is added accounts for solvent volume percentage wherein
0.5% Span80, stirs evenly, and obtains PCL electrostatic spinning solution.
Obtained PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, high pressure
The output voltage position 12kv of power supply, receiving screen is 10cm at a distance from spinning nozzle.Electrostatic spinning process is stablized, and collect has on screen
The white fiber film of even densification, and be easy to take off.
Using above-mentioned identical electrostatic spinning process, using n,N-Dimethylformamide: methanol: the volume ratio of chloroform
=1:2:7 is solvent, and configuration concentration is 7% homogeneous solution of mass volume ratio, regathers and obtains product on screen.
Referring to attached drawing 1 (a), 1 (b), 1 (a) be not added with surfactant concentration be mass volume ratio 7% PCL electricity
Spinning SEM figure；Fig. 1 (b) is that the concentration of addition surfactant is the PCL Electrospun SEM figure of mass volume ratio 7%.Figure acceptance of the bid
Ruler ratio is classified as 2 μm.Comparison diagram 1 (a), by Fig. 1 (b) it will be clear that the diameter without bead structure being collected into is to be distributed in
The ultra-fine polycaprolactone fiber of 500nm or so.
Embodiment 2:
In the present embodiment, selecting additive is the mixture of oil soluble surfactant Span80 and Tween85.
With molecular weight for 8 × 104 PCL be raw material, n,N-Dimethylformamide: methanol: chloroform=1:1:8 is
Solvent stirs evenly the solution that configuration concentration is mass volume ratio 10%, accounts for solvent volume percentage being wherein added as 0.5%
The mixture of Span80 and Tween85, Span80 and Tween85 volume ratio are 1:1, stir evenly, it is molten to obtain PCL electrostatic spinning
Liquid.
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, high voltage power supply
Output voltage position 10kv, receiving screen is 10cm at a distance from spinning nozzle.Electrostatic spinning process is stablized, and collecting on screen has even compact
White fiber film, and be easy to take off.
Using above-mentioned identical electrostatic spinning process, using n,N-Dimethylformamide: methanol: the volume ratio of chloroform
=1:1:8 is solvent, and configuration concentration is 10% homogeneous solution of mass volume ratio, regathers and obtains product on screen.
Referring to attached drawing 2 (a), 2 (b), 2 (a) to be not added with surfactant concentration be concentration is mass volume ratio 10%
Polycaprolactone SEM figure；Fig. 2 (b) is to add the SEM figure that surfactant concentration is the PCL that concentration is mass volume ratio 10%.
Scale ratio is classified as 10 μm in figure.Comparison diagram 2 (a), by Fig. 2 (b) it will be clear that the diameter without bead structure being collected into
For the PCL fiber for being distributed in 800nm or so.
Embodiment 3:
In the present embodiment, selecting additive is the double ethyl stearte base hydroxyethyl methyl sulfuric acid of oil soluble surfactant
The mixture of ammonium methyl, three ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums and Span20.
With molecular weight for 8 × 104 PCL be raw material, n,N-Dimethylformamide: methanol: the volume ratio of chloroform=
1:1:8 is solvent, stirs evenly the solution that configuration concentration is mass volume ratio 7%, is added accounts for solvent volume percentage wherein
Double ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums, three ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums for 0.8%
And the mixture of Span20, double ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums, three ethyl stearte Ji Qiangyijijia
The volume ratio of base sulfate methyl ammonium and Span20 are 1:1:1, stir evenly, obtain PCL electrostatic spinning solution.
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, high voltage power supply
Output voltage position 10kv, receiving screen is 10cm at a distance from spinning nozzle.Electrostatic spinning process is stablized, and collecting on screen has even compact
White fiber film, and be easy to take off.
It is the PCL tunica fibrosa pictorial diagram taken off referring to attached drawing 3.
Embodiment 4:
In the present embodiment, selecting additive is the mixture of oil soluble surfactant Span80 and Tween85.
With molecular weight for 8 × 104 PCL be raw material, n,N-Dimethylformamide: methanol: the volume ratio of methylene chloride=
1:1:8 is solvent, stirs evenly the solution that configuration concentration is 15 % of mass volume ratio, is added accounts for solvent volume percentage wherein
For the mixture of the mixture of the Span80 and Tween85 of 1 %, the volume ratio of the mixture of Span80 and Tween85 is 1:1,
It stirs evenly, obtains PCL electrostatic spinning solution.
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, high voltage power supply
Output voltage position 8kv, receiving screen is 13cm at a distance from spinning nozzle, and electrostatic spinning process is stablized, and collecting on screen has even compact
White fiber film, and be easy to take off.
Claims (1)
1. a kind of preparation method of polycaprolactone electrostatic spinning solution, it is characterised in that specific steps are as follows:
With molecular weight for 8 × 104PCL be raw material, n,N-Dimethylformamide: methanol: volume ratio=1:2:7 of chloroform
For solvent, the solution that configuration concentration is mass volume ratio 7% is stirred evenly, is added accounts for solvent volume percentage 0.5% wherein
Span80, stir evenly, obtain polycaprolactone electrostatic spinning solution；
Obtained PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, high voltage power supply
Output voltage position 12kv, receive screen with spinning nozzle at a distance from as 10cm；
Or with molecular weight for 8 × 104PCL be raw material, n,N-Dimethylformamide: methanol: chloroform=1:1:8 solvent stirs
The solution that uniform configuration concentration is mass volume ratio 10% is mixed, accounts for solvent volume percentage being wherein added as 0.5%
The mixture of Span80 and Tween85, Span80 and Tween85 volume ratio are 1:1, stir evenly, obtain polycaprolactone electrostatic
Spinning solution；
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, the output of high voltage power supply
Voltage position 10kv, receiving screen is 10cm at a distance from spinning nozzle；
Or with molecular weight for 8 × 104PCL be raw material, n,N-Dimethylformamide: methanol: volume ratio=1:1 of chloroform:
8 be solvent, stirs evenly the solution that configuration concentration is mass volume ratio 7%, and addition wherein accounts for solvent volume percentage and is
0.8% double ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums, three ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums
And the mixture of Span20, double ethyl stearte base hydroxyethyl methyl sulfate methyl ammoniums, three ethyl stearte Ji Qiangyijijia
The volume ratio of base sulfate methyl ammonium and Span20 are 1:1:1, stir evenly, obtain PCL electrostatic spinning solution；
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, the output of high voltage power supply
Voltage position 10kv, receiving screen is 10cm at a distance from spinning nozzle；
Or with molecular weight for 8 × 104PCL be raw material, n,N-Dimethylformamide: methanol: volume ratio=1:1 of methylene chloride:
8 be solvent, stirs evenly the solution that configuration concentration is mass volume ratio 15%, and addition wherein accounts for solvent volume percentage and is
The volume ratio of the mixture of the mixture of the mixture of 1% Span80 and Tween85, Span80 and Tween85 is 1:1, is stirred
It mixes uniformly, obtains PCL electrostatic spinning solution；
PCL electrostatic spinning solution is injected in self-control spinning solution stoste memory, spinning temperature is room temperature, the output of high voltage power supply
Voltage position 8kv, receiving screen is 13cm at a distance from spinning nozzle；
The chemical reagent is that analysis is pure.
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| CN115467092A (en) * | 2022-09-15 | 2022-12-13 | 大连医科大学附属第二医院 | Preparation method of supported dimethyloxalglycine nanofiber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543645A (en) * | 2009-05-04 | 2009-09-30 | 东华大学 | Polycaprolactone (PCL) static spinning nerve conduit and preparation and application thereof |
| CN102493009A (en) * | 2011-12-08 | 2012-06-13 | 东华大学 | Preparation method of porous nano fiber |
| CN102747453A (en) * | 2012-07-05 | 2012-10-24 | 四川大学 | Porous superfine polymer fiber and preparation method thereof |
| CN105239206A (en) * | 2015-11-03 | 2016-01-13 | 华侨大学 | Polycaprolactone / polyethylene glycol (PCL / PEG) composite beaded fiber and preparation method thereof |
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- 2016-10-05 CN CN201610874028.7A patent/CN106498539B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543645A (en) * | 2009-05-04 | 2009-09-30 | 东华大学 | Polycaprolactone (PCL) static spinning nerve conduit and preparation and application thereof |
| CN102493009A (en) * | 2011-12-08 | 2012-06-13 | 东华大学 | Preparation method of porous nano fiber |
| CN102747453A (en) * | 2012-07-05 | 2012-10-24 | 四川大学 | Porous superfine polymer fiber and preparation method thereof |
| CN105239206A (en) * | 2015-11-03 | 2016-01-13 | 华侨大学 | Polycaprolactone / polyethylene glycol (PCL / PEG) composite beaded fiber and preparation method thereof |
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