阅读说明：本技术 一种基于反应性纺丝的水凝胶光导纤维的连续制备方法 (Continuous preparation method of hydrogel optical fiber based on reactive spinning ) 是由 朱美芳 陈国印 侯恺 成艳华 艾玉露 危培玲 姜耘蒙 于 2019-09-19 设计创作，主要内容包括：本发明涉及一种基于反应性纺丝的水凝胶光导纤维的连续制备方法,包括：皮层纺丝液、芯层纺丝液,利用横向同轴针头作为纺丝喷丝口,以CaCl<Sub>2</Sub>水溶液为凝固浴固化皮层海藻酸钠,加以紫外光源引发芯层纺丝液中PEGDA的自由基聚合反应；牵伸后最终得到具有良好的生物相容性的皮芯结构水凝胶光纤。本发明制备得到的皮芯结构水凝胶光纤具有连续、直径可控的特点,并且具有优异的生物相容性和光导特性。(The invention relates to a continuous preparation method of a hydrogel optical fiber based on reactive spinning, which comprises the following steps: using a transverse coaxial needle as a spinning nozzle, using a CaCl2 aqueous solution as a coagulating bath to solidify sodium alginate of the skin layer, and using an ultraviolet light source to initiate the free radical polymerization reaction of PEGDA in the spinning solution of the core layer; and finally obtaining the hydrogel optical fiber with the sheath-core structure and good biocompatibility after drafting. The hydrogel optical fiber with the sheath-core structure prepared by the invention has the characteristics of continuity and controllable diameter, and has excellent biocompatibility and photoconductive characteristics.)

1. A method for continuously preparing a hydrogel optical fiber, comprising:

(1) The sodium alginate aqueous solution with the mass fraction of 1-5% is a cortex spinning solution;

(2) adding a photoinitiator and anhydrous CaCl2 into a polyethylene glycol diacrylate PEGDA aqueous solution with the mass fraction of 10-90%, and uniformly stirring in a dark place to obtain a core layer spinning solution;

(3) extruding the skin layer spinning solution and the core layer spinning solution into a water bath of a coagulating bath through a coaxial needle, setting a wavelength at a position 1-10mm away from a spinning nozzle to be an ultraviolet point light source, solidifying the skin layer spinning solution due to the existence of Ca2+ in the water bath and the core layer, and solidifying and forming the core layer solution after entering an ultraviolet solidification area to obtain primary hydrogel fibers, and collecting the primary hydrogel fibers by winding to obtain the hydrogel fibers with the skin-core structure.

2. The preparation method as claimed in claim 1, wherein the molecular weight of the sodium alginate in the step (1) is Mw 4000-.

3. the method as claimed in claim 1, wherein the molecular weight of PEGDA in step (2) is Mw of 250-; the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone IRGACURE 2959.

4. the preparation method according to claim 1, wherein the mass of the photoinitiator in the step (2) is 0.2-1% of the mass of the PEGDA solution, and the mass of CaCl2 is 0.5-3 wt.% of the mass of the deionized water.

5. the preparation method according to claim 1, wherein the diameter of the outer layer spinning hole of the coaxial needle in the step (3) is 1.0-3.0mm, the diameter of the core layer is 0.2-1.0mm, and the coaxial needle is horizontally placed at a depth of 2-10cm below the liquid level; the coagulation bath is CaCl2 aqueous solution.

6. The method according to claim 1, wherein the extruding in the step (3) is: extruding the spinning solution through a coaxial needle head by a propelling pump; wherein the extrusion rate of the sheath spinning solution is 2-20 mL/h; the extrusion rate of the core layer spinning solution is 0.5-10 mL/h; the skin-core layer extrusion rate ratio is in the range of 0.01-20.

7. the method as claimed in claim 1, wherein the wavelength of the UV point light source in step (3) is 200-400 nm; the linear speed of winding in the winding collection is 1 to 150 m/h.

8. A hydrogel optical fiber prepared by the method of claim 1.

9. Use of the hydrogel optical fiber according to claim 8.

10. an apparatus for the continuous production of the hydrogel optical fiber according to claim 1.

Technical Field

The invention belongs to the field of preparation of hydrogel optical fibers, and particularly relates to a continuous preparation method of a hydrogel optical fiber based on reactive spinning.

Background

In recent years, the application of light to medical treatment has been increasing, and the light is widely used in the fields of photodynamic therapy, photothermal ablation, surgical treatment, body fluid monitoring sensors, and the like. However, when light is applied to in vivo treatment and signal sensing, the light can only penetrate 0.1-2cm below the tissue matrix due to poor penetrability of the light to the body tissue, and the treatment and sensing effects are greatly influenced. There is therefore a need for a material that can function to conduct light in vitro into the body with less light loss.

The optical fiber is a material which plays a role in light conduction by relying on the principle of total reflection of light, and has wide application in the fields of signal transmission, medical treatment, medical appliances and the like. However, the optical fiber material is generally prepared from silica and polymer, and is brittle and hard to withstand bending with a small radius of curvature, and once broken, it may cause damage to the matrix structure, even dangerous damage. And the traditional optical fiber material has poor cell compatibility, is incompatible with organisms and is difficult to adapt to the complex in vivo environment of organisms, so the traditional optical fiber material has great defects in realizing the application in the organisms. The hydrogel optical fiber with the skin-core structure is prepared by Seok-Hyun Yun et al through a template method, and the material not only has the characteristic of softness and wetness of hydrogel, but also has excellent light guide performance. However, the size and length of the material can be greatly limited by the template material, and large-scale continuous preparation is difficult to realize. CN106243296 discloses a method for improving mechanical properties of hydrogel fibers by secondary crosslinking, but this method is only suitable for preparing hydrogel fibers with a single-phase structure, and cannot prepare hydrogel fibers with a skin-core structure.

Disclosure of Invention

The invention aims to solve the technical problem of providing a continuous preparation method of hydrogel optical fiber based on reactive spinning, which overcomes the problem that the prior template method limits the large-scale preparation of the material; solidifying the cortex layer sodium alginate by using CaCl2 water solution as a coagulating bath, and initiating a free radical polymerization reaction of PEGDA in the core layer spinning solution by using an ultraviolet light source; and finally obtaining the hydrogel optical fiber with the sheath-core structure and good biocompatibility after drafting.

The invention discloses a continuous preparation method of a hydrogel optical fiber, which comprises the following steps:

(1) The sodium alginate aqueous solution with the mass fraction of 1-5% is a cortex spinning solution;

(2) Adding a photoinitiator and anhydrous CaCl2 into a polyethylene glycol diacrylate PEGDA aqueous solution with the mass fraction of 10-90%, and uniformly stirring in a dark place to obtain a core layer spinning solution;

(3) Extruding the skin layer spinning solution and the core layer spinning solution through a coaxial needle head into a water bath of a coagulating bath, setting a wavelength at a position 1-10mm away from a spinning nozzle as an ultraviolet point light source, solidifying the skin layer spinning solution due to the existence of Ca2+ in the water bath and the core layer, and solidifying and forming the core layer hydrogel fiber after the core layer solution enters an ultraviolet curing area to obtain primary hydrogel fiber, and winding and collecting to obtain the hydrogel fiber with a skin-core structure.

The preferred mode of the above preparation method is as follows:

The molecular weight of the sodium alginate in the step (1) is Mw 4000-.

The molecular weight of the PEGDA in the step (2) is Mw of 250-; the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone IRGACURE 2959.

In the step (2), the mass of the photoinitiator is 0.2-1% of the mass of the PEGDA solution, and the mass of the CaCl2 is 0.5-3 wt% of the mass of the aqueous solution.

The diameter of the outer layer spinning hole of the coaxial needle in the step (3) is 1.0-3.0mm, the diameter of the core layer is 0.2-1.0mm, and the coaxial needle is horizontally placed at the depth of 2-10cm below the liquid level; the coagulation bath is CaCl2 aqueous solution.

the extrusion in the step (3) is as follows: extruding the spinning solution through a coaxial needle head by a propelling pump; the extrusion rate of the skin layer spinning solution is 2-20 mL/h; the extrusion rate of the core layer spinning solution is 0.5-10 mL/h; the skin-core layer extrusion rate ratio is in the range of 0.01-20.

The wavelength of the ultraviolet point light source in the step (3) is 200-400 nm; the included angle range of the optical path direction and the extrusion direction of the spinning solution is 0-90 degrees; the linear speed of winding in the winding collection is 1 to 150 m/h.

And (4) winding and collecting in the step (3), and drafting the obtained primary hydrogel fiber by adjusting the rotating speed of the roller.

The hydrogel optical fiber prepared by the method is provided.

The invention provides an application of the hydrogel optical fiber.

The invention also provides equipment for preparing the hydrogel optical fiber, which sequentially comprises the following components: the spinning head is a coaxial needle head, the coaxial needle head is horizontally placed at a depth of 2-10cm below the liquid level, the ultraviolet point light source is arranged at a position 1-10mm away from the spinning head, a godet roller is arranged in the bath, and the winding device is arranged outside the bath and used for fiber drafting and collection. Wherein the winding device is outside the water bath near the wall of the bath tank.

Advantageous effects

(1) Aiming at the defects that the length and the diameter of the skin-core structure hydrogel fiber prepared by a template method are limited by a template, the method based on coaxial wet spinning is utilized, sodium alginate is used as a skin layer spinning solution, PEGDA is used as a core layer spinning solution, the core layer solution is stabilized by utilizing the solidified skin layer sodium alginate fiber after being extruded to a water bath, the PEGDA solution of the core layer is ensured to stably reach an ultraviolet curing area, and the skin-core structure hydrogel fiber is finally obtained by drafting after curing;

(2) The preparation method is a continuous preparation method of hydrogel optical fiber based on reactive spinning, which comprises the steps of respectively using sodium alginate and PEGDA monomers with good biocompatibility as skin layer and core layer spinning solutions, and using a transverse coaxial needle as a spinning nozzle; solidifying the cortex layer sodium alginate by using CaCl2 water solution as a coagulating bath, and initiating a free radical polymerization reaction of PEGDA in the core layer spinning solution by using an ultraviolet light source; the skin-core structure hydrogel fiber with good biocompatibility and good optical guide characteristic is finally obtained after drafting;

(3) The diameters of the inner layer and the outer layer of the hydrogel fiber with the skin-core structure can be controlled by the extrusion speed ratio, the winding speed, the concentration and the like of the skin-core layer, and the preparation method is carried out at room temperature.

Drawings

FIG. 1 is a photograph of a skin-core hydrogel fiber in example 1 in real and microscopic form (the core layer was dyed with methylene blue);

FIG. 2 is a graph showing the change of the diameter of the skin-core structure hydrogel skin-core layer according to the basal rate ratio, which is obtained in example 1;

FIG. 3 (a) is a photograph of an optical fiber light guide substance; (b) bending loss of optical fiber light intensity;

FIG. 4 is a schematic view of an apparatus for preparing hydrogel fiber according to the present invention and a photo of a fiber light guide material.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims. The device adopted in the embodiment is as follows: the spinning head is a coaxial needle head, the coaxial needle head is horizontally placed at a depth of 2-10cm below the liquid level, the ultraviolet point light source is arranged at a position 1-10mm away from the spinning head, a yarn guide roller is arranged in the bath tank, the winding device is arranged outside the bath tank and used for fiber drafting and collection, and the winding device is close to the wall of the bath tank outside the water bath.