CN108130603A - A kind of preparation method and application for the polymer fiber for adding tourmaline nano particle - Google Patents

Abstract

The invention discloses a preparation method and application of a polymer fiber added with tourmaline nanoparticles. The preparation method comprises the following steps: (1) dissolving the polymer as a solute in a solvent to configure a polymer solution; (2) mixing the same solvent with a volume of 10-20% of the solvent in step 1) with tourmaline nanoparticles Mix evenly under magnetic stirring to obtain a tourmaline suspension; (3) add the tourmaline suspension obtained in step 2) dropwise to the polymer solution obtained in step 1), and ultrasonicate at a frequency of 15kHz to 25kHz Disperse for 10min to 200min to obtain a homogeneously mixed electrospinning solution; (4) place the needle tube containing the electrospinning solution obtained in step 3) on a single-channel syringe pump, and obtain tourmaline nanoparticles by electrospinning. polymer fibers. In the method, an external electric field is applied to prevent tourmaline nanoparticles from agglomerating during the preparation process and uniformly disperse them inside the polymer fiber.

Description

A kind of preparation method and application of polymer fiber adding tourmaline nanoparticles

technical field

The invention belongs to the field of composite fiber preparation, in particular to a preparation method and application of a polymer fiber added with tourmaline nanoparticles.

Background technique

Tourmaline is the general name of tourmaline group minerals, and it is a natural silicate mineral with ring structure characterized by multi-element and boron content. Tourmaline belongs to the trigonal crystal system, the single crystal shape is mostly columnar, 3m symmetrical structure, and the general structural formula is XY ₃ Z ₆ [Si ₆ O ₁₈ ][BO ₃ ] ₃ W ₄ (wherein X=Ca ²⁺ , Na ⁺ , K ⁺ , Y=Mg ²⁺ , Fe ²⁺ , Li ⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Z=Al ³⁺ , V ³⁺ , Cr ³⁺ , Mg ²⁺ , W= OH ^- , F ^- , O ^2- ). Because of its special components and microstructure, tourmaline has piezoelectricity and pyroelectricity. Its piezoelectricity is that when the temperature and pressure change, the potential difference of the tourmaline crystal will also change. The air is ionized, and the hit electrons attached to neighboring oxygen molecules become air negative ions. Negative air ions can move freely in the air, thus sending their own negative charges to tiny particles in the air, so that the air will be purified. Its pyroelectricity is manifested in the fact that when the temperature changes, voltage will be generated at both ends of the crystal, polar particles will vibrate at the equilibrium position, the dipole moment will change, and far-infrared waves will be generated. This infrared radiation can be absorbed by the human body and produce beneficial effects. Tourmaline with special properties is widely used in water treatment, medical care, cosmetics, textiles, building profiles and many other fields. And the above properties of tourmaline are related to its particle size and distribution. Under a certain temperature and pressure, the smaller the particles of tourmaline, the more regular its internal structure, and the stronger its piezoelectric and thermoelectric properties. At present, a single tourmaline material can no longer To meet the needs of scientific and economic development, the dispersion of tourmaline nanoparticles and their composite preparation and application with other materials have become the focus of scientific research.

Polymer materials have the advantages of low density (about 1/10 of metal), low cost, and easy processing and molding, so they are widely valued by material developers; some polymer materials also have good biocompatibility. It has been widely used in tissue engineering and other fields. Electrospinning technology is a technology that sprays and stretches a polymer solution or melt using a high-voltage electrostatic method to obtain fibers. The diameter of fibers produced by electrospinning generally ranges from tens of nanometers to several microns, which is 1-2 orders of magnitude smaller than that of traditional spinning methods. Therefore, the fibers prepared by electrospinning have the advantages of large specific surface area, high porosity, and good air and moisture permeability. Due to the unique advantages of electrospinning, this technology has been widely studied in the fields of biomedicine, such as controlled drug release, tissue engineering, catalytic materials, and filter materials. Aiming at the research hotspot of inorganic nanoparticles/polymer composites, this new composite material not only has the morphology and advantages of polymer fibers, but also can uniformly disperse inorganic nanoparticles to exert its unique properties.

Application No. 03125213.3 discloses a composite material of cellulose and tourmaline nanocrystals and its preparation method and its use. The preparation method of the composite material containing tourmaline nanocrystals is relatively complicated, and it is only applicable to one kind of cellulose, which needs to be passed through The fibers can only be obtained by coagulation of calcium chloride aqueous solution and regeneration of hydrochloric acid aqueous solution. The monotony of the matrix material and the complexity of the processing process will affect the application field of tourmaline nanocrystals.

Contents of the invention

Aiming at the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a preparation method and application of a polymer fiber added with tourmaline nanoparticles.

The technical scheme that the present invention solves described technical problem is to provide a kind of preparation method of the polymer fiber that adds tourmaline nanoparticle, it is characterized in that the method comprises the following steps:

(1) Preparation of polymer solution: dissolving the polymer as a solute in a solvent to form a polymer solution;

(2) Preparation of tourmaline suspension: the volume is the same solvent of 10-20% of the solvent in step 1) and tourmaline nanoparticles are mixed uniformly under magnetic stirring to obtain tourmaline suspension; The quality of the stone nanoparticles accounts for 1% to 20% of the total mass of the tourmaline nanoparticles and the polymer;

(3) Preparation of electrospinning solution: Add the tourmaline suspension obtained in step 2) dropwise to the polymer solution obtained in step 1), and ultrasonically disperse at a frequency of 15 kHz to 25 kHz for 10 min to 200 min to obtain a mixed Uniform electrospinning solution;

(4) Preparation of polymer fibers: Place the needle tube containing the electrospinning solution obtained in step 3) on a single-channel syringe pump, set the flow rate to 0.1mL/h～3.0mL/h, and the spinning voltage to 10kV～ 30kV, the distance from the needle to the receiver is 10cm to 30cm, and the polymer fiber with tourmaline nanoparticles is obtained by electrospinning.

Compared with the prior art, the present invention has the beneficial effects of:

(1) Tourmaline nanoparticles have spontaneous polarization properties, so they are easier to agglomerate than other inorganic non-metallic nanoparticles, so tourmaline particles are not easy to be uniformly dispersed in polymer matrix materials as additives. The present invention avoids the agglomeration of tourmaline nanoparticles in the fiber preparation process through the applied electric field of electrospinning technology, and makes them evenly dispersed inside the polymer fiber, so as to improve the phenomenon that tourmaline particles are small and easy to agglomerate, and promote The combination of tourmaline and polymer realizes the synergistic effect of different properties.

(2) The electrospinning liquid suspension which can be stored stably for more than 5 hours can be obtained by adding dropwise and high-frequency ultrasonic dispersion.

(3) The method can select a variety of polymers as substrates to prepare tourmaline nanoparticle/polymer composite fibers, and has simple preparation process, strong applicability and easy operation.

(4) The fiber prepared by the method can be applied in the fields of human health care, tissue engineering, water treatment and the like, especially in small-diameter artificial blood vessels. Applied to small-diameter artificial blood vessels to prevent thrombosis. It can enhance or activate vascular endothelial cells, promote endothelial cell growth, promote blood circulation, slow down calcium salt ion deposition, prevent thrombosis after small-caliber blood vessel transplantation, improve the antithrombotic performance of small-caliber artificial blood vessels, and can be applied to tissue engineering In the field of stents, it can be especially applied to the replacement of small-diameter blood vessels such as carotid arteries or coronary arteries and peripheral blood vessels.

Description of drawings

Fig. 1 is the scanning electron micrograph of the tourmaline/polyurethane composite fiber membrane that the preparation method embodiment 1 of the polymer fiber that adds tourmaline nanoparticle of the present invention obtains;

Fig. 2 is the scanning electron micrograph of the tourmaline/polycaprolactone composite fiber film that the preparation method embodiment 2 of the polymer fiber that adds tourmaline nanoparticle of the present invention obtains;

3 is a scanning electron micrograph of the tourmaline/gelatin copolymer composite fiber membrane obtained in Example 3 of the preparation method of polymer fibers with tourmaline nanoparticles added in the present invention.

Detailed ways

Specific examples of the present invention are given below. The specific embodiments are only used to further describe the present invention in detail, and do not limit the protection scope of the claims of the present application.

The invention provides a kind of preparation method (abbreviation method) of the polymer fiber that adds tourmaline nanoparticle, it is characterized in that the method comprises the following steps:

(1) Preparation of the polymer solution: the polymer is dissolved in a solvent as a solute to configure a polymer solution; the polymer is polyurethane, polycaprolactone, polycaprolactone copolymer, polylactide, polylactide Ester copolymer, collagen or gelatin, etc.;

(2) Preparation of tourmaline suspension: the volume is the same solvent of 10-20% of the solvent in step 1) and tourmaline nanoparticles are mixed uniformly under magnetic stirring to obtain tourmaline suspension; The quality of the stone nanoparticles accounts for 1% to 20% of the total mass of the tourmaline nanoparticles and the polymer, preferably 5% to 18%;

(3) Preparation of electrospinning solution: Add the tourmaline suspension obtained in step 2) dropwise to the polymer solution obtained in step 1), and ultrasonically disperse at a frequency of 15 kHz to 25 kHz for 10 min to 200 min to obtain a mixed Uniform tourmaline/polymer suspension, that is, electrospinning solution;

(4) Preparation of polymer fibers: Place the needle tube containing the electrospinning solution obtained in step 3) on a single-channel syringe pump, set the flow rate to 0.1mL/h～3.0mL/h, and the spinning voltage to 10kV～ 30kV, the distance from the needle to the receiver is 10cm to 30cm, and the uniform, bead-free polymer fibers added with tourmaline nanoparticles with a diameter of 100nm to 1000nm are obtained by electrospinning.

Preferably, the receiver in step 4) is a grounded metal rod (2-6 mm in diameter) that can rotate at a constant speed, and uniform fibers with a diameter of 100 nm to 1000 nm are obtained by electrospinning, collected on the metal rod, collected After the completion, withdraw the metal rod, cut both ends neatly, remove the residual solvent and sterilize under vacuum at room temperature for 12 hours, and then obtain a tubular polymer fiber membrane with a length of 4-6 cm and added tourmaline nanoparticles.

The tubular polymer fiber membrane added with tourmaline nanoparticles is used as a small-diameter artificial blood vessel. The specific operation steps are as follows: clamp the two ends of the blood vessel of the original lesion with a hemostatic clip to temporarily stop the blood flow; cut it off and take it out. For the damaged section, replace it with a tourmaline nanoparticle/polyurethane composite material of corresponding length, and suture the two ends of the composite material corresponding to the cutting opening; then slowly release the hemostatic clips at the lower and upper ends respectively, restore blood flow, and check the suture There is no blood spillage, and the operation is completed.

Example 1

(1) Preparation of polymer solution: Weigh 1.50 g of polyurethane, measure 9.0 mL of N,N-dimethylformamide and 9.0 mL of butanone to completely dissolve the polyurethane to obtain a polyurethane solution;

(2) Preparation of tourmaline suspension: Measure 1.0 mL of N,N-dimethylformamide and 1.0 mL of butanone, and mix with 0.10 g of tourmaline nanoparticles;

(3) Preparation of electrospinning solution: the mixed solution containing tourmaline nanoparticles obtained in step 2) was added to the polyurethane solution, and ultrasonically dispersed at a frequency of 20 kHz for 30 minutes to obtain a uniform electrospinning solution.

(4) Preparation of polymer fiber membrane: use a needle tube to take the electrospinning solution, place it on a single-channel syringe pump, set the flow rate to 0.5mL/h, and the spinning voltage to 12kV. A rod (2 mm in diameter) was used as a fiber receiver, and the distance from the needle to the receiver was 15 cm, and homogeneous fibers were obtained by electrospinning. Collect on the metal rod for 30 minutes, withdraw the metal rod after the collection is completed, cut both ends neatly, remove the residual solvent and sterilize under vacuum at room temperature for 12 hours, and then the tubular polyurethane composite fiber membrane with tourmaline nanoparticles added can be obtained.

The tubular polyurethane composite fiber membrane added with tourmaline nanoparticles was applied to replace the damaged carotid artery in rabbits. Main operation steps: Clamp both ends of the blood vessel of the original lesion with a hemostatic clip to temporarily stop the blood flow; cut off and take out the lesion, and replace it with a corresponding length of tourmaline nanoparticle/polyurethane composite material, the composite material The two ends of the needle are sutured corresponding to the cutting openings; then slowly release the hemostatic clips at the lower and upper ends respectively to restore blood flow, check that there is no blood spillage at the sutures, and complete the operation.

Performance test: In the blood compatibility test, the thrombin time (TT) of the tourmaline nanoparticle/polyurethane composite sample was 15.8s, the prothrombin time (PT) was 13.2s, and the activated partial thromboplastin time ( APTT) was 32.5s, all of which were higher than the comparison samples without tourmaline nanoparticles (TT was 12.1s, PT was 11.6s, APTT was 26.1s), indicating that tourmaline nanoparticles can slow down blood coagulation, which is beneficial to the blood phase of artificial blood vessels. Capacitance improvement; in the cell test, the tourmaline nanoparticle/polyurethane small-diameter artificial blood vessel sample can promote the proliferation of endothelial cells 50% higher than the contrast sample without tourmaline nanoparticle; in the animal test, the neck of the rabbit was selected The common artery (diameter 2mm, replacement length 2.5cm) was used as a model. After 6 months of transplantation, it was observed that there was no obvious thrombus inside the tourmaline nanoparticle/polyurethane small-caliber artificial blood vessel sample, and the effect was significantly better than that of the comparison sample without tourmaline nanoparticle . Cell tests and animal tests show that the tourmaline nanoparticle/polyurethane small-diameter artificial blood vessel not only has good biocompatibility, but also has good antithrombotic ability.

Example 2

(1) Preparation of polymer solution: weigh 3.0 g of polycaprolactone, measure 5.4 mL of N,N-dimethylformamide and 12.6 mL of dichloromethane to completely dissolve the polycaprolactone;

(2) Preparation of tourmaline suspension: Measure 0.6mL of N,N-dimethylformamide and 1.4mL of dichloromethane, mix with 0.3g of tourmaline nanoparticles;

(3) Preparation of electrospinning solution: add tourmaline suspension dropwise into polycaprolactone solution, disperse with 20kHz high-frequency ultrasonic for 50min, and obtain uniform electrospinning solution;

(4) Preparation of polymer fiber: Take the electrospinning solution with a needle tube, place it on a single-channel syringe pump, set the spinning parameters: the voltage is 15kV, the flow rate is 0.5mL/h, and the grounded spinning machine that can rotate at a constant speed A metal rod (2 mm in diameter) was used as a fiber receiver, and the distance from the needle to the receiver was 15 cm. Uniform fibers were obtained by electrospinning. Collect on the metal rod for 30 minutes, withdraw the metal rod after the collection is completed, cut both ends neatly, remove the residual solvent and sterilize under vacuum at room temperature for 12 hours, and then obtain a tubular polycaprolactone fiber with a length of 2.5 cm and added tourmaline nanoparticles membrane.

Application of tourmaline nanoparticles/polycaprolactone composites in replacement of damaged carotid arteries in rabbits. Main operation steps: Clamp both ends of the blood vessel of the original lesion with a hemostatic clip to temporarily stop the blood flow; cut off and take out the lesion, and replace it with a corresponding length of tourmaline nanoparticle/polycaprolactone composite material , the two ends of the composite material are sutured corresponding to the cutting openings; then slowly release the hemostatic clips at the lower and upper ends respectively to restore blood flow, check that there is no blood spillage at the sutures, and complete the operation.

Performance test: In the blood compatibility test, the thrombin time (TT) of the tourmaline nanoparticle/polycaprolactone composite sample was 16.4s, the prothrombin time (PT) was 14.6s, and the activated partial thromboplastin The measurement time (APTT) was 33.1s, all of which were higher than the comparison samples without tourmaline nanoparticles (TT was 12.2s, PT was 11.9s, APTT was 26.2s), indicating that tourmaline nanoparticles can slow down blood coagulation, which is beneficial to artificial Improvement of vascular blood compatibility; in cell experiments, the ability of tourmaline nanoparticles/polycaprolactone small-caliber artificial blood vessel samples to promote endothelial cell proliferation was 45% higher than that of control samples without tourmaline nanoparticles; in animal experiments Among them, the rabbit's common carotid artery (diameter 2mm, replacement length 2.5cm) was selected as the model, and it was observed after 6 months of transplantation that there was no obvious thrombus inside the tourmaline nanoparticle/polycaprolactone small-caliber artificial blood vessel sample, and the effect was significantly better than Comparative sample without tourmaline nanoparticles. Cell experiments and animal experiments show that the tourmaline nanoparticle/polycaprolactone small-diameter artificial blood vessel not only has good biocompatibility, but also has good antithrombotic ability.

Example 3

(1) Preparation of polymer solution: weigh 5.00 g of gelatin, measure 2.50 mL of acetic acid and 9.50 mL of deionized water to completely dissolve the gelatin to obtain a gelatin solution;

(2) Preparation of tourmaline suspension: measure 1.0 mL of deionized water and mix with 1.00 g of tourmaline nanoparticles;

(3) Preparation of electrospinning solution: add tourmaline suspension into gelatin solution, and ultrasonically disperse for 25 minutes at a frequency of 15kHz-25kHz to obtain a uniform electrospinning solution.

(4) Preparation of polymer fibers: Take the electrospinning solution with a needle tube, place it on a single-channel syringe pump, set the spinning parameters: the voltage is 17kV, the flow rate is 1.0mL/h, the distance between the needle and the receiver Electrospinning was performed to obtain gelatin fibers added with tourmaline nanoparticles. After collecting for 30 minutes, the gelatin fiber membrane with tourmaline nanoparticles can be obtained by accumulating on the receiver.

What is not mentioned in the present invention is applicable to the prior art.

Claims (7)

1. A preparation method for adding tourmaline nanoparticles to polymer fibers, characterized in that the method may further comprise the steps: (1) Preparation of polymer solution: dissolve the polymer as a solute in a solvent to form a polymer solution; (2) Preparation of tourmaline suspension: Mix the same solvent with a volume of 10-20% of the solvent in step 1) and tourmaline nanoparticles evenly under magnetic stirring to obtain tourmaline suspension; The mass of stone nanoparticles accounts for 1%~20% of the total mass of tourmaline nanoparticles and polymer; (3) Preparation of electrospinning solution: Add the tourmaline suspension obtained in step 2) dropwise to the polymer solution obtained in step 1), and ultrasonically disperse at a frequency of 15kHz~25kHz for 10min~200min to obtain a mixed Uniform electrospinning solution; (4) Preparation of polymer fibers: Place the needle containing the electrospinning solution obtained in step 3) on a single-channel syringe pump, set the flow rate to 0.1mL/h~3.0mL/h, and the spinning voltage to 10kV~ 30kV, the distance from the needle to the receiver is 10cm~30cm, and the polymer fiber with tourmaline nanoparticles is obtained by electrospinning. 2. the preparation method of the polymer fiber that adds tourmaline nanoparticle according to claim 1 is characterized in that described polymer is polyurethane, polycaprolactone, polycaprolactone copolymer, polylactide, polylactide Ester copolymer, collagen or gelatin. 3. the preparation method of the polymer fiber that adds tourmaline nanoparticle according to claim 1, it is characterized in that the quality of tourmaline nanoparticle accounts for 5%～18% of tourmaline nanoparticle and polymer gross mass. 4. the preparation method of the polymer fiber that adds tourmaline nanoparticle according to claim 1, it is characterized in that the diameter of the polymer fiber that adds tourmaline nano particle that makes is 100nm～1000nm. 5. The preparation method of polymer fiber adding tourmaline nanoparticles according to claim 1, characterized in that the receiver in step 4) is a grounded metal rod that can rotate at a constant speed, and obtains a uniform fiber through electrospinning. The fibers are collected on the metal rod, and after the collection is completed, the metal rod is withdrawn, the two ends are trimmed neatly, and after the residual solvent is removed and sterilized, the tubular polymer fiber membrane added with tourmaline nanoparticles can be obtained. 6. a tubular polymer fiber membrane adding tourmaline nanoparticles obtained by the preparation method of adding tourmaline nanoparticles as claimed in claim 5. 7. An application of the tubular polymer fiber membrane adding tourmaline nanoparticles as claimed in claim 6, characterized in that the tubular polymer fiber membrane adding tourmaline nanoparticles is used as a small-diameter artificial blood vessel.