阅读说明：本技术 一种高强度医用纤维复合材料的制备方法 (Preparation method of high-strength medical fiber composite material ) 是由 赵彻 刘嵩雪 冯春 武之炜 张祎伟 姜文彪 李晓贞 于 2020-06-19 设计创作，主要内容包括：本发明涉及医用复合材料技术领域,尤其涉及一种高强度医用纤维复合材料的制备方法。海藻酸钠水凝胶的机械性能较差,刚度和强度较低,外力作用下容易碎裂,所以在单独使用时往往难以满足实际应用要求。为了解决上述问题,本发明提供一种高强度医用纤维复合材料,包括海藻酸钠水凝胶基质和纤维骨架,所述纤维骨架完全嵌入海藻酸钠水凝胶基质中,所述纤维骨架由支撑层纤维和增强层纤维复合而成,增强层纤维位于支撑层纤维的上方,增强层纤维与支撑层纤维相互正交。本发明所制备的高强度医用纤维复合材料的刚度提高了3-4个数量级,拉伸强度提高了2-3个数量级,具备良好的生物相容性和安全性,具有良好的应用前景。(The invention relates to the technical field of medical composite materials, in particular to a preparation method of a high-strength medical fiber composite material. The sodium alginate hydrogel has poor mechanical properties, low rigidity and strength and is easy to crack under the action of external force, so that the sodium alginate hydrogel is difficult to meet the requirements of practical application when used alone. In order to solve the problems, the invention provides a high-strength medical fiber composite material which comprises a sodium alginate gel matrix and a fiber skeleton, wherein the fiber skeleton is completely embedded into the sodium alginate gel matrix, the fiber skeleton is formed by compounding supporting layer fibers and reinforcing layer fibers, the reinforcing layer fibers are positioned above the supporting layer fibers, and the reinforcing layer fibers and the supporting layer fibers are mutually orthogonal. The rigidity of the high-strength medical fiber composite material prepared by the invention is improved by 3-4 orders of magnitude, the tensile strength is improved by 2-3 orders of magnitude, and the high-strength medical fiber composite material has good biocompatibility and safety and good application prospect.)

1. The preparation method of the high-strength medical fiber composite material is characterized by comprising the following steps of:

(1) heating and softening the fibers of the reinforcing layer and the fibers of the supporting layer, stretching the diameter of the fibers to 0.1-0.3mm, and then cooling the obtained fibers to obtain standby fibers;

(2) performing plasma etching on the standby fiber obtained in the step (1) by using a plasma cleaning machine, wherein etching gas is oxygen;

(3) soaking the fiber subjected to plasma etching in a KH550 aqueous solution with the mass concentration of 2.5%, performing silanization treatment for 3h, cleaning the reinforcing layer fiber and the supporting layer fiber with deionized water and ethanol, and drying for later use;

(4) orienting, fixing and locking the reinforced layer fibers and the supporting layer fibers processed in the step (3) through a combined die to obtain a fiber framework formed by mutually orthogonally compounding the reinforced layer fibers and the supporting layer fibers;

(5) soaking the fiber framework obtained in the step (4) and the combined die into a surface treatment solution to realize chemical grafting chemical anchoring points on the surface of the fiber framework, taking out the fiber framework and the combined die together, cleaning the fiber framework with deionized water, and drying the fiber framework for later use;

(6) preparing sodium alginate into sodium alginate aqueous solution, heating the solution to 50-60 ℃, uniformly stirring, performing ultrasonic treatment at 60kHz until the solution is clear, and standing for 12h to obtain sodium alginate hydrogel;

(7) injecting the sodium alginate hydrogel obtained in the step (6) into the die 2 of the combined die dried in the step (5), repeatedly smearing the sodium alginate hydrogel along the upper surface of the die 2 by using a scraper, and then leveling the sodium alginate hydrogel so as to enable the sodium alginate hydrogel to be fully contacted with the fiber framework, and standing the die for 12 hours after smearing is finished to obtain a preformed material;

(8) and (3) soaking the preformed material obtained in the step (7) and the combined die in a calcium chloride aqueous solution, curing for 4 hours, repeatedly washing away residual calcium chloride on the surface of the material by using deionized water, drying, cutting the material cured in the combined die according to the required size, and stripping from the die to obtain the high-strength medical fiber composite material.

2. The method for preparing the high-strength medical fiber composite material according to claim 1, wherein the method comprises the following steps: the plasma etching power in the step (2) is 30W-40W, and the etching time is 5min-10 min.

3. The method for preparing the high-strength medical fiber composite material according to claim 1, wherein the method comprises the following steps: and (3) soaking the fiber subjected to plasma etching in the surface treatment liquid for 18-24 h.

4. The method for preparing the high-strength medical fiber composite material according to claim 1, wherein the method comprises the following steps: the mass concentration of the sodium alginate aqueous solution in the step (6) is 3-4%.

5. The method for preparing the high-strength medical fiber composite material according to claim 1, wherein the method comprises the following steps: the mass concentration of the calcium chloride aqueous solution in the step (8) is 1-3%.

Technical Field

The invention relates to the technical field of medical composite materials, in particular to a preparation method of a high-strength medical fiber composite material.

Background

The natural hydrogel is a three-dimensional network high molecular polymer prepared from natural raw materials, can absorb a large amount of water, is bound in a hydrogel three-dimensional network structure, and has strong water absorption and moisture retention properties, wherein the sodium alginate hydrogel has good biocompatibility and low toxicity, and has been widely applied to the fields of food, medicines, biomedicine and the like. However, compared with artificially synthesized high molecular polymers, the sodium alginate hydrogel has poor mechanical properties (low rigidity and strength) and is easy to break under the action of external force, so that the sodium alginate hydrogel is difficult to meet the requirements of practical application when used alone, and can only be applied to products with low requirements on mechanical properties, such as dressings, water-absorbing fillers, medicament-carrying agents and the like.

With the development of medical technology, the clinical requirements on tissue repair materials such as artificial skin, artificial muscle, artificial tendon and the like are increasing day by day, so how to remarkably enhance the mechanical properties of the sodium alginate hydrogel and improve the practicability of the sodium alginate hydrogel while maintaining excellent biocompatibility and water absorption and moisture retention is a key problem to be solved urgently.

At present, scientific researchers generally improve the mechanical properties of natural hydrogel by a polymer compounding method, namely two polymers are combined by an interpenetrating network technology to generate complementary and synergistic effects between the two polymers, so that the defect of single hydrogel is overcome, for example, Chinese invention patent CN 104311841A discloses a preparation method of high-strength covalent/ionic interpenetrating network easily-shaped gel, and further discloses that the tensile strength of the prepared material can reach 1.8 MPa. The interpenetrating network technology only improves the three-dimensional network structure of the high molecular polymer at the molecular level, has limited improvement on the overall mechanical properties of the material, particularly the strength and the rigidity, generally does not exceed 2 orders of magnitude, and still cannot achieve the load capacity required by artificial muscles, artificial tendons and the like.

Therefore, it is necessary to find a method for improving the rigidity and strength of the sodium alginate hydrogel by 2 to 3 orders of magnitude.

Disclosure of Invention

Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: the sodium alginate hydrogel has poor mechanical properties, low rigidity and strength and is easy to crack under the action of external force, so that the sodium alginate hydrogel is difficult to meet the requirements of practical application when used alone.

The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides a high-strength medical fiber composite material which comprises sodium alginate hydrogel and a fiber framework, wherein the fiber framework is completely embedded into the sodium alginate hydrogel, and a chemical anchoring point is grafted on the surface of the fiber framework and is chemically bonded with the sodium alginate hydrogel.

Specifically, the fiber framework is formed by compounding a plurality of supporting layer fibers and a plurality of reinforcing layer fibers, the reinforcing layer fibers are positioned above the supporting layer fibers, and the reinforcing layer fibers and the supporting layer fibers are orthogonal to each other.

Specifically, the plurality of reinforcing layer fibers are arranged at equal intervals, and the plurality of supporting layer fibers are arranged at equal intervals.

Specifically, the distance between two adjacent fibers of the reinforcing layer fibers is 0.4-0.8mm, and the distance between two adjacent fibers of the supporting layer fibers is 1.2-1.6 mm.

Specifically, the fiber of the reinforced layer is polyester fiber, nylon fiber or polyether-ether-ketone resin fiber, and the diameter of the fiber of the reinforced layer is 0.1-0.3 mm.

Specifically, the supporting layer fiber is polyester fiber, nylon fiber or polyether-ether-ketone resin fiber, and the diameter of the supporting layer fiber is 0.1-0.3 mm.

Specifically, the chemical anchoring point is an aminosilane functional group on the surface of the fiber skeleton after being soaked in the surface treatment solution.

Specifically, the surface treatment solution is prepared by dissolving 1g of sodium alginate, 241mg of Solfo-NHS and 178mg of EDC in 100mL of MES hydrate.

Specifically, the molecular weight of the sodium alginate is 26000 and 28000.

Specifically, the preparation method of the high-strength medical fiber composite material comprises the following steps:

(1) heating and softening the fibers of the reinforcing layer and the fibers of the supporting layer, stretching the diameter of the fibers to 0.1-0.3mm, and then cooling the obtained fibers to obtain standby fibers;

(2) performing plasma etching on the standby fiber obtained in the step (1) by using a plasma cleaning machine, wherein the etching gas is oxygen, the etching power is 30W-40W, and the etching time is 5min-10 min;

(3) soaking the fiber subjected to plasma etching in a KH550 aqueous solution with the mass concentration of 2.5%, performing silanization treatment for 3h, cleaning the reinforcing layer fiber and the supporting layer fiber with deionized water and ethanol, and drying for later use;

(4) orienting, fixing and locking the reinforced layer fibers and the supporting layer fibers processed in the step (3) through a combined die to obtain a fiber framework formed by mutually orthogonally compounding the reinforced layer fibers and the supporting layer fibers;

(5) soaking the fiber framework obtained in the step (4) and the combined die in a surface treatment solution for 18-24h to realize chemical grafting of chemical anchoring points on the surface of the fiber framework, taking out the fiber framework and the combined die together, cleaning the fiber framework by deionized water, and drying the fiber framework for later use;

(6) preparing sodium alginate into 3-4% sodium alginate aqueous solution, heating the solution to 50-60 deg.C, stirring, performing ultrasonic treatment at 60kHz until the solution is clear, and standing for 12 hr to obtain sodium alginate hydrogel;

(7) injecting the sodium alginate hydrogel obtained in the step (6) into the die 2 of the combined die dried in the step (5), repeatedly smearing the sodium alginate hydrogel along the upper surface of the die 2 by using a scraper, and then leveling the sodium alginate hydrogel so as to enable the sodium alginate hydrogel to be fully contacted with the fiber framework, and standing the die for 12 hours after smearing is finished to obtain a preformed material;

(8) and (3) soaking the preformed material obtained in the step (7) and the combined die in a calcium chloride aqueous solution with the mass fraction of 1-3%, curing for 4h, repeatedly washing away residual calcium chloride on the surface of the material by using deionized water, drying, cutting the material cured in the combined die according to the required size, and stripping from the die to obtain the high-strength medical fiber composite material.

The invention has the beneficial effects that:

(1) the medical fiber reinforced composite material provided by the invention is characterized in that a fiber framework formed by high-strength medical fibers such as nylon, terylene and polyether ketone resin is embedded into the sodium alginate hydrogel matrix, so that the overall mechanical performance of the medical composite material is effectively improved, the rigidity can be improved by 3-4 orders of magnitude, the tensile strength can be improved by 2-3 orders of magnitude, and the medical fiber reinforced composite material has good biocompatibility and safety;

(2) the medical fiber reinforced composite material provided by the invention has good designability and adjustability, the mechanical property of the whole material can be adjusted and controlled by adjusting the density degree of the fibers of the reinforcing layer according to specific application requirements, if the distance between the fibers is reduced and the arrangement is tight, the rigidity and the strength of the whole composite material are increased, the flexibility is reduced, if the distance between the fibers is ever large and the arrangement is sparse, the rigidity and the strength of the whole material are reduced, and the flexibility is increased;

(3) the preparation method of the medical fiber reinforced composite material provided by the invention can realize the functions of fiber orientation, weaving, density adjustment, fixation, locking, injection molding and the like by using a simple mould structure without complex and expensive machine equipment, and has the characteristics of low cost, high efficiency, simple operation and batch production;

(4) the method has universality and can be suitable for medical fibers with different physical and chemical properties such as nylon, terylene, polyether ketone resin and the like.

Drawings

FIG. 1: the preparation process of the high-strength medical fiber composite material is shown in the schematic diagram.

FIG. 2: the invention discloses a structural schematic diagram of a high-strength medical fiber composite material.

FIG. 3: the structure of the mould 1 is schematically shown.

FIG. 4: and the structure schematic diagram of the combined die.

FIG. 5: the process of manufacturing the fiber framework by using the mold 1 is shown schematically.

In the figure: 1. supporting layer fiber, 2 reinforcing layer fiber, 3, chemical anchoring point, 4, sodium alginate hydrogel, 5, dies 1 and 6, dies 2 and 7, fixing base plate, 8 and screw holes.

Detailed Description

The present invention will now be described in further detail with reference to the accompanying drawings.

The preparation process of the high-strength medical fiber composite material in the following examples of the invention is shown in fig. 1, and fig. 2 is a schematic structural view of the high-strength medical fiber composite material prepared in examples 1 to 7.

The combined molds used in the following examples and comparative examples of the present invention are shown in fig. 4 and consist of a mold 1 and a mold 2. As shown in fig. 3, the die 1 is a stainless steel plate with two rows of circular holes at equal intervals respectively arranged on the periphery, the thickness of the stainless steel plate is 1-3mm, the interval between two rows of circular holes transversely adjacent to the stainless steel plate is 6mm, the interval between two rows of circular holes longitudinally adjacent to the stainless steel plate is 5mm, the diameter of the holes is 0.2-0.4mm, the center distance of any row of circular holes transversely distributed on the stainless steel plate is 1.2-1.6mm, the center distance of any row of circular holes longitudinally distributed on the stainless steel plate is 0.4-0.8mm, the stainless steel plate is transversely provided with 2-1, 2-2, 2-3, 2-4, and longitudinally provided with 1-1, 1-2, 1-3, 1-4, wherein 1-2 corresponds to 1-3 and 2-2 corresponds to 2-3; the thickness of the mould 2 is 0.25-0.5mm, the length and width of the inner frame are 29mm and 68mm, the width of the frame is 3-4mm, when in use, the fibers of the supporting layer sequentially penetrate through the one-to-one corresponding round holes arranged on the die 1 at 2-1, 2-2, 2-3 and 2-4 and are locked, the fibers of the reinforcing layer sequentially penetrate through the one-to-one corresponding round holes arranged on the die 1 at 1-1, 1-2, 1-3 and 1-4 and are locked, then, the four frames of the mould 2 are just fallen on the non-porous area between the two rows of corresponding round holes on the periphery of the mould 1, and the mold 1 and the mold 2 are fixed on the substrate together by using a threaded connection method (the fiber skeleton manufactured on the combined mold is shown in fig. 5), and then sodium alginate hydrogel is injected into the mold 2 for subsequent operation.

The surface-treating liquids used in the following examples and comparative examples of the present invention were prepared by dissolving 1g of sodium alginate (molecular weight: 26000-28000), 241mg of N-hydroxythiosuccinimide (Solfo-NHS, CAS:106627-54-7), 178mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC, CAS:25952-53-8) in 100mL of morpholine ethanesulfonic acid hydrate (MES hydrate, CAS: 1266615-59-1).

The molecular weight of sodium alginate used in the following examples and comparative examples of the present invention is 26000-28000.