CN102660794B - Method for single-spinning poly-(vinyl caprolactam-co-methacrylic acid) nanometer fiber through static spinning technology - Google Patents
Method for single-spinning poly-(vinyl caprolactam-co-methacrylic acid) nanometer fiber through static spinning technology Download PDFInfo
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- CN102660794B CN102660794B CN201210124731.8A CN201210124731A CN102660794B CN 102660794 B CN102660794 B CN 102660794B CN 201210124731 A CN201210124731 A CN 201210124731A CN 102660794 B CN102660794 B CN 102660794B
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Abstract
The invention relates to a method for single-spinning p poly-(vinyl caprolactam-co-methacrylic acid) nanometer fiber through the static spinning technology. The method includes: (1) adding solid poly-(vinyl caprolactam-co-methacrylic acid) into mixed solvents prepared by methanol and N', N'-dimethylacetamide, and dissolving to obtain uniform and thick spinning solution; and (2) performing static spinning on the spinning solution to obtain nanometer fiber, and finally vacuum drying the nanometer fiber to obtain the single-spinning p poly-(vinyl caprolactam-co-methacrylic acid) nanometer fiber. The method is simple in operation, less in time consumption and capable of obtaining nanometer materials with the diameter and aperture of nanometer level, and basic raw materials are cheap and accessible. The nanometer fiber itself has abundant carboxyl (-COOH) and can be used for affine adsorption, drug carrying and the like.
Description
Technical field
The invention belongs to the field that utilizes temperature sensitive copolymer electrostatic spinning nano fiber, particularly a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) (p (NVCL-co-MAA)) nanofiber.
Background technology
In recent years, electrostatic spinning technique had become the technology of preparing of popular polymeric biomaterial, and this technology is only used simple equipment can obtain form, the controlled nanofiber of porosity, and fiber diameter range is greatly to several microns, little of 2nm.In Static Spinning process, at the syringe needle that polymer solution is housed, add highfield, polymer solution flows out from syringe needle, enters electric field and forms taylor cone.When electric field force overcomes the surface tension of drop, polymer solution ejection.A series of processes such as charged jet is elongated under electric field influence, and process is unstable, dry finally form unordered nanofiber on receiving system.The nano-fiber for production of non-woven of preparation all causes the great interest of people as aspects such as medical dressing, tissue engineering bracket, drug carrier systems in biomedical engineering.
The polymer that can be used in Static Spinning technology is very many, and can make Sub-micro Fibers, applies also very extensive.At present the known polymer that can be used for preparing electrostatic spinning fiber has synthetic polymer, natural polymer, and comprise protein, and nucleic acid, even polysaccharide is at interior graft copolymer.Copolymer electrospinning can be strengthened the part of properties of polymeric material, such as heat endurance, and mechanical strength, isolation, therefore by copolymerisation, melt blending, and add the methods such as inorganic filler can realize the application in engineering structure.Utilize copolymer can obtain the new material of certain special properties, if suitably adjusted, the performance of copolymer material electrospinning fibre can have obvious lifting than homopolymers.Therefore in organizational project application aspect, people often utilize copolymer to carry out electrospinning for raw material, to improve the performance of material.
N-caprolactam (NVCL) is the important intermediate of synthetic poly N-vinyl caprolactam series high polymer.Monomer whose polymer---poly N-vinyl caprolactam (pNVCL) has Thermo-sensitive, useful as drug carrier.Meanwhile, the serial high polymer of poly N-vinyl caprolactam (pNVCL) has purposes extremely widely at biology, medical material and household chemicals and other field, and can become progress in Intelligent Hydrogel with polysaccharide material grafting.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber, the method is quick, easy, cheap, efficient, on fiber, contain a large amount of carboxyls (COOH), can be used for affine absorption, pharmaceutical carrier etc.
A kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) p (NVCL-co-MAA) nanofiber of the present invention, comprising:
(1) will gather (caprolactam-co-methacrylic acid) solid and be added to by methyl alcohol and N ', in the mixed solvent that N '-dimethylacetylamide (DMAc) is made into, after dissolving, obtain the spinning solution of homogeneous thickness;
(2) adopt above-mentioned spinning solution to carry out electrostatic spinning, obtain nanofiber, last vacuumize.
In spinning solution described in step (1), the concentration of poly-(caprolactam-co-methacrylic acid) is 0.05-0.15g/mL.
In mixed solvent described in step (1), the volume ratio of methyl alcohol (concentration >=99.5%) and DMAc (concentration >=99%) is 1: 1～6: 1.
Mixed solvent described in step (1) is 20～40 ℃ of preparations.
The concrete operations of the dissolving described in step (1) are ultrasonic concussion or magnetic agitation, and solution temperature is 20～40 ℃, and dissolution degree is the mixed solution of homogeneous thickness, without solid insoluble matter.
Specification of syringe described in step (2) in electrostatic spinning is 5mL, and syringe needle internal diameter is 0.9mm, and receiving system adopts the reception of aluminium foil ground connection.
Ejection flow velocity described in step (2) in electrostatic spinning is 0.5～1.5mL/h, and voltage is 13～16kV.
Described in step (2), in electrostatic spinning, the distance between syringe needle and receiving system is 20～26cm.
The present invention fully takes into account take the advantage of the electrostatic spinning that copolymer is raw material, take and be rich in the synthetic temperature sensitive copolymer of carboxyl (COOH)---poly-(caprolactam-co-methacrylic acid) (p (NVCL-co-MAA)) singly spins as raw material, by groping relevant spinning condition parameter, successfully prepared comparatively ideal p (NVCL-co-MAA) nanofiber.
Beneficial effect:
(1) method of the present invention is simple to operate, consuming time less, can obtain at short notice diameter and aperture at nano level fibrous material;
(2) basic raw material used in the present invention is cheap and easy to get, and prepared fiber itself contains abundant carboxyl (COOH), has a extensive future.
Accompanying drawing explanation
Fig. 1 is the SEM characterization result of electrospinning fibre, and in figure, in electrospinning liquid, p (NVCL-co-MAA) concentration (w/v) is followed successively by: (A) 6%, (B) 8%, (C) 10%, (D) 12%, (E) 14%;
Fig. 2 is the diameter distribution map of electrospinning fibre, and in figure, in electrospinning liquid, p (NVCL-co-MAA) concentration (w/v) is followed successively by: (A) 6%, (B) 8%, (C) 10%, (D) 12%, (E) 14%;
Fig. 3 is the FTIR collection of illustrative plates of electrospinning fibre, and in figure, in electrospinning liquid, p (NVCL-co-MAA) concentration (w/v) is followed successively by: (A) 6%, (B) 8%, (C) 10%, (D) 12%, (E) 14%;
Fig. 4 is the XRD collection of illustrative plates of electrospinning fibre, and in figure, in electrospinning liquid, p (NVCL-co-MAA) concentration (w/v) is followed successively by: (A) 6%, (B) 8%, (C) 10%, (D) 12%, (E) 14%.
The specific embodiment
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 those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Singly spin poly-(caprolactam-co-methacrylic acid) nanofiber
Within 85: 15 in proportion, (v/v) measures methyl alcohol, N ', and N '-dimethylacetylamide (DMAc) is placed in ground tool plug triangular flask, under the condition of 20-22 ℃, is made into mixed solvent; Taking a certain amount of synthetic product p (NVCL-co-MAA) solid is added in above-mentioned mixed solvent, under the condition of 25-28 ℃, ultrasonic concussion or magnetic agitation are to dissolving, form the viscous solution of homogeneous, in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.06g/mL; After solution preparation is good, with 5mL syringe, extract a certain amount of p (NVCL-co-MAA) spinning solution, be fixed on electrostatic spinning apparatus, spinning parameter is set, at flow velocity, be 0.5mL/h, voltage is 16kV, and the distance between syringe needle and receiving system is under 22cm condition, to carry out electrospinning; Finally the fiber of collecting is carried out after vacuumize standby.
Embodiment 2
Singly spin poly-(caprolactam-co-methacrylic acid) nanofiber
Within 3: 1 in proportion, (v/v) measures methyl alcohol, N ', and N '-dimethylacetylamide (DMAc) is placed in ground tool plug triangular flask, under the condition of 20-25 ℃, is made into mixed solvent; Taking a certain amount of synthetic product p (NVCL-co-MAA) solid is added in above-mentioned mixed solvent, ultrasonic concussion or magnetic agitation are to dissolving under not higher than the condition of 24-28 ℃, form the viscous solution of homogeneous, in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.08g/mL; After solution preparation is good, with 5mL syringe, extract a certain amount of p (NVCL-co-MAA) spinning solution, be fixed on electrostatic spinning apparatus, spinning parameter is set, at flow velocity, be 1.5mL/h, voltage is 14kV, and the distance between syringe needle and receiving system is under 22cm condition, to carry out electrospinning; Finally the fiber of collecting is carried out after vacuumize standby.
Embodiment 3
Singly spin poly-(caprolactam-co-methacrylic acid) nanofiber
Within 2: 1 in proportion, (v/v) measures methyl alcohol, N ', and N '-dimethylacetylamide (DMAc) is placed in ground tool plug triangular flask, under the condition of 28-30 ℃, is made into mixed solvent; Taking a certain amount of synthetic product p (NVCL-co-MAA) solid is added in above-mentioned mixed solvent, under the condition of 25-28 ℃, ultrasonic concussion or magnetic agitation are to dissolving, form the viscous solution of homogeneous, in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.10g/mL; After solution preparation is good, with 5mL syringe, extract a certain amount of p (NVCL-co-MAA) spinning solution, be fixed on electrostatic spinning apparatus, spinning parameter is set, at flow velocity, be 1.0mL/h, voltage is 13kV, and the distance between syringe needle and receiving system is under 22cm condition, to carry out electrospinning; Finally the fiber of collecting is carried out after vacuumize standby.
Embodiment 4
Singly spin poly-(caprolactam-co-methacrylic acid) nanofiber
Within 85: 15 in proportion, (v/v) measures methyl alcohol, N ', and N '-dimethylacetylamide (DMAc) is placed in ground tool plug triangular flask, under the condition of 20-22 ℃, is made into mixed solvent; Taking a certain amount of synthetic product p (NVCL-co-MAA) solid is added in above-mentioned mixed solvent, ultrasonic concussion or magnetic agitation are to dissolving under not higher than the condition of 22-25 ℃, form the viscous solution of homogeneous, in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.12g/mL; After solution preparation is good, with 5mL syringe, extract a certain amount of p (NVCL-co-MAA) spinning solution, be fixed on electrostatic spinning apparatus, spinning parameter is set, at flow velocity, be 0.8mL/h, voltage is 15kV, and the distance between syringe needle and receiving system is under 22cm condition, to carry out electrospinning; Finally the fiber of collecting is carried out after vacuumize standby.
Singly spin poly-(caprolactam-co-methacrylic acid) nanofiber
Within 85: 15 in proportion, (v/v) measures methyl alcohol, N ', and N '-dimethylacetylamide (DMAc) is placed in ground tool plug triangular flask, under the condition of 25-28 ℃, is made into mixed solvent; Taking a certain amount of synthetic product p (NVCL-co-MAA) solid is added in above-mentioned mixed solvent, ultrasonic concussion or magnetic agitation are to dissolving under not higher than the condition of 22-29 ℃, form the viscous solution of homogeneous, in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.14g/mL; After solution preparation is good, with 5mL syringe, extract a certain amount of p (NVCL-co-MAA) spinning solution, be fixed on electrostatic spinning apparatus, spinning parameter is set, at flow velocity, be 1.0mL/h, voltage is 16kV, and the distance between syringe needle and receiving system is under 22cm condition, to carry out electrospinning; Finally the fiber of collecting is carried out after vacuumize standby.
Embodiment 6
The fiber of preparation is characterized to (as Fig. 1) with SEM, and make corresponding fiber diameter distribution profile, as shown in Figure 2.Adopt the JSM-5600LV scanning electronic microscope (SEM) of Japanese JEOL company to observe the fiber of preparation, sample is processed through metal spraying, then with ImageJ software, from picture, extract immediately 100 fiber measurement diameters, excel makes corresponding fiber diameter distribution profile.
The fiber of preparation is characterized with FT-IR, as shown in Figure 3.Adopt the Nicolet Nexus 670 type Fourier infrared spectrographs of U.S. Thermo Fisher company to measure the infrared spectrum (FTIR) of fiber the fiber of preparation.
The fiber of preparation is characterized with XRD, as shown in Figure 4.Adopt the D/Max-2550PC type X-ray diffractometer (XRD) of Japanese RIGAKU company to measure the degree of crystallinity of fiber the fiber of preparation.
Embodiment 7
The preparation method of poly-(caprolactam-co-methacrylic acid)
(1) taking 1.0g caprolactam is dissolved in the tool plug ground round-bottomed flask that 25mL deionized water is housed, heating or sonic oscillation dissolve completely to it, add again 100 μ l methacrylic acids, shake up, with 1mol/l NaOH solution, regulating pH value is 7.0, vacuum outgas 10min, passes into a certain amount of nitrogen.
(2) in reaction system, add 0.04g ammonium persulfate (APS), vacuum nitrogen filling gas, after three times, vacuum outgas 10min, is incubated 3h in 65 ℃ of water-baths repeatedly.
(3) after reaction finishes, in reaction system, add 0.2mol/l sodium chloride (NaCl) aqueous solution, supernatant liquor is decanted.Add again 25ml deionized water will precipitate dissolving.Repeat to precipitate 3 times, after precipitation is dissolved completely, be placed in 65 ℃ of water bath with thermostatic control 30min, centrifugal collected polymer precipitation.
(4) polymer of gained is placed in vacuum drying chamber to 50 ℃ and is dried to constant weight, stand-by.
Claims (6)
1. utilize Static Spinning technology list to spin a method for poly-(caprolactam-co-methacrylic acid) nanofiber, comprising:
(1) will gather (caprolactam-co-methacrylic acid) solid and be added to by methyl alcohol and N', in the mixed solvent that N'-dimethylacetylamide is made into, after dissolving, obtain the spinning solution of homogeneous thickness; Wherein in spinning solution, the concentration of poly-(caprolactam-co-methacrylic acid) is 0.05-0.15g/mL; Methyl alcohol and N' in mixed solvent, the volume ratio of N'-dimethylacetylamide is 1:1～6:1;
(2) adopt above-mentioned spinning solution to carry out electrostatic spinning, obtain nanofiber, last vacuumize.
2. a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber according to claim 1, is characterized in that: the mixed solvent described in step (1) is 20～40 ℃ of preparations.
3. a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber according to claim 1, it is characterized in that: the concrete operations of the dissolving described in step (1) are ultrasonic concussion or magnetic agitation, solution temperature is 20～40 ℃.
4. a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber according to claim 1, it is characterized in that: the specification of syringe described in step (2) in electrostatic spinning is 5mL, syringe needle internal diameter is 0.9mm, and receiving system adopts the reception of aluminium foil ground connection.
5. a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber according to claim 1, it is characterized in that: the ejection flow velocity described in step (2) in electrostatic spinning is 0.5～1.5mL/h, voltage is 13～16kV.
6. a kind of method of utilizing Static Spinning technology list to spin poly-(caprolactam-co-methacrylic acid) nanofiber according to claim 1, is characterized in that: described in step (2), in electrostatic spinning, the distance between syringe needle and receiving system is 20～26cm.
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