阅读说明：本技术 一种皮肤用生物医用材料及其制备方法 (Biomedical material for skin and preparation method thereof ) 是由 范红霞 倪爱荣 范孝鹏 于 2020-03-25 设计创作，主要内容包括：本发明公开了一种皮肤用生物医用材料,其特征在于,由如下重量份的各原料制成：2,6-二氨基嘌呤核苷/2,5-呋喃二甲酸缩聚物12-17份、乙烯基磺酸二甲胺/蓖麻油酸/芦荟新甙D/3,4-环氧环己基甲基甲基丙烯酸酯共聚物6-10份、超支化咪唑盐型离子聚合物4-7份、鱼鳞蛋白肽1-2份、维生素C 0.2-0.5份。本发明还公开了所述皮肤用生物医用材料的制备方法。本发明公开的皮肤用生物医用材料兼具生物相容性、生物功能性及抗菌性能,能促进受损皮肤迅速恢复,且其透气性和消炎功能优异,机械力学性能良好。(The invention discloses a biomedical material for skin, which is characterized by being prepared from the following raw materials in parts by weight: 12-17 parts of 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate, 6-10 parts of vinyl sulfonic dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl methacrylate copolymer, 4-7 parts of hyperbranched imidazolium ionic polymer, 1-2 parts of fish scale protein peptide and 0.2-0.5 part of vitamin C. The invention also discloses a preparation method of the biomedical material for skin. The biomedical material for skin disclosed by the invention has biocompatibility, biological functionality and antibacterial performance, can promote the damaged skin to recover quickly, and has excellent air permeability, anti-inflammatory function and good mechanical property.)

1. The biomedical material for skin is characterized by being prepared from the following raw materials in parts by weight: 12-17 parts of 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate, 6-10 parts of vinyl sulfonic dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl methacrylate copolymer, 4-7 parts of hyperbranched imidazolium ionic polymer, 1-2 parts of fish scale protein peptide and 0.2-0.5 part of vitamin C.

2. The biomedical material for skin according to claim 1, wherein the preparation method of the copolymer of dimethylamine vinylsulfonate/ricinoleic acid/barbaloin D/3, 4-epoxycyclohexyl methacrylate comprises the following steps: adding vinylsulfonic acid dimethylamine, ricinoleic acid, barbaloin D, 3, 4-epoxy cyclohexyl methyl methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 4-6 hours at 60-80 ℃ under the atmosphere of nitrogen or inert gas, then precipitating in water, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the copolymer of vinylsulfonic acid dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl methacrylate.

3. The biomedical material for skin according to claim 2, wherein the mass ratio of the dimethylamine vinylsulfonate, the ricinoleic acid, the barbaloin D, the 3, 4-epoxycyclohexyl methyl methacrylate, the initiator and the high-boiling solvent is 1:1:2:1 (0.04-0.06) to (15-20).

4. The biomedical skin material of claim 2, wherein said initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.

5. The biomedical material for skin according to claim 2, wherein the high boiling point solvent is at least one of dimethylsulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.

6. The biomedical material for skin according to claim 1, characterized in that said polycondensate of 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid is prepared by a process comprising the following steps: dissolving 2, 6-diaminopurine nucleoside in N-methylpyrrolidone, adding 2, 5-furandicarboxylic acid and 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline after completely dissolving, stirring and reacting for 5-8 hours at 100-110 ℃ in nitrogen atmosphere, then removing N-methylpyrrolidone and byproducts by rotary evaporation, and placing in a vacuum drying oven for drying at 80-90 ℃ to constant weight.

7. The biomedical material for skin according to claim 6, wherein the molar ratio of the 2, 6-diaminopurine nucleoside, N-methylpyrrolidone, 2, 5-furandicarboxylic acid and 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline is 1 (5-8) to 1 (0.8-1.2).

8. The biomedical material for skin according to any one of claims 1 to 7, characterized in that the preparation method of the biomedical material for skin comprises the following steps: the raw materials are uniformly mixed according to a ratio to obtain a mixture, then the mixture is added into N-methyl pyrrolidone, stirred and reacted for 3 to 5 hours at the temperature of 100 ℃ and 110 ℃, and then the mixture is poured into a mold and is placed into an oven to be dried, so that the biomedical material for skin is obtained.

9. The biomedical skin material as claimed in claim 8, wherein the mass ratio of the mixed material to the N-methylpyrrolidone is 1 (3-5).

10. The biomedical material for skin as claimed in claim 8, wherein the drying time is 15-25 hours, and the drying temperature is 110-120 ℃.

Technical Field

The invention relates to the technical field of biomedical materials, in particular to a biomedical material for skin and a preparation method thereof.

Background

With the development of social economy and the improvement of living standard, people are focusing on their medical health career unprecedentedly. The skin is an important barrier of a human body, various operations, traumas, burns, dermatitis and the like can cause skin damage and defect to cause various traumas, and wound repair is an important field of medical development and has important significance for relieving pain of patients, recovering early and avoiding scars from being left after repair. One material essential in the process of wound repair is a biomedical material for skin, which can protect the wound surface, prevent the loss of body fluid and protein, prevent the invasion of bacteria, and provide spatial support and physiological stimulation for various cells related to repair.

The ideal biomedical material for skin should have good biocompatibility, no obvious rejection reaction and inflammation reaction, certain mechanical strength and certain tissue stress resistance so as to support local tissues. The biomedical materials for skin in the prior art can be classified into medical high polymer materials, medical metal materials, civil non-metal materials and the like according to different materials. The common skin biomedical materials in the market comprise autologous skin allogenic skin transplantation, artificial auxiliary materials and tissue engineering skin, and the products can not be applied to the treatment of various skin injuries on a large scale due to the defects of antigen reaction, high price, limited sources, easy secondary injury and the like, particularly the treatment of patients with serious skin defects. Other skin biomedical materials disclosed in the market often have the defects of tearing in the using process, or poor strength due to poor adhesion, too strong antigenicity, high irritation, or poor permeability, susceptibility to infection, or scar accumulation due to the inhibition of the growth of autogenous skin, or difficulty in raw material source, high cost, or complicated process, difficulty in manufacturing and storage, and the materials generally have single function and the biocompatibility and antibacterial property need to be further improved.

CN201310520955.5 discloses a functional dressing and a preparation method and application thereof, the dressing comprises bioactive glass, alginate, chitosan and other components, the bioactive glass needs to be subjected to high temperature calcination, grinding and other steps, the preparation process is complex, the dressing only has an antibacterial effect on the alginate and the chitosan, the antibacterial effect is not obvious, but if other antibacterial components such as antibiotics and antiseptics are used, the problems of drug resistance, secondary infection and the like are caused.

Therefore, the development of the biomedical material for skin, which has biocompatibility, biological functionality and antibacterial performance and can promote the damaged skin to recover quickly, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the biomedical material industry.

Disclosure of Invention

In view of the above, the invention aims to provide a biomedical material for skin and a preparation method thereof, wherein the preparation method is simple and easy to implement, has low requirements on equipment and reaction conditions, wide raw material sources and low price, is suitable for continuous large-scale production, and has high economic value, social value and ecological value; the prepared biomedical material for skin has biocompatibility, biological functionality and antibacterial performance, can promote damaged skin to recover quickly, and has excellent air permeability, anti-inflammatory function and good mechanical property.

In order to achieve the purpose, the invention adopts the technical scheme that:

the biomedical material for skin is characterized by being prepared from the following raw materials in parts by weight: 12-17 parts of 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate, 6-10 parts of vinyl sulfonic dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl methacrylate copolymer, 4-7 parts of hyperbranched imidazolium ionic polymer, 1-2 parts of fish scale protein peptide and 0.2-0.5 part of vitamin C.

Further, the preparation method of the copolymer of dimethylamine vinylsulfonate/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methacrylate comprises the following steps: adding vinylsulfonic acid dimethylamine, ricinoleic acid, barbaloin D, 3, 4-epoxy cyclohexyl methyl methacrylate and an initiator into a high boiling point solvent, stirring and reacting for 4-6 hours at 60-80 ℃ under the atmosphere of nitrogen or inert gas, then precipitating in water, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain the copolymer of vinylsulfonic acid dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl methacrylate.

Preferably, the mass ratio of the dimethylamine vinylsulfonate, the ricinoleic acid, the barbaloin D, the 3, 4-epoxy cyclohexyl methyl methacrylate to the initiator to the high-boiling-point solvent is 1:1:2:1 (0.04-0.06) to (15-20).

Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.

Preferably, the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.

Preferably, the inert gas is one of helium, neon and argon.

Further, the preparation method of the 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate comprises the following steps: dissolving 2, 6-diaminopurine nucleoside in N-methylpyrrolidone, adding 2, 5-furandicarboxylic acid and 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline after completely dissolving, stirring and reacting for 5-8 hours at 100-110 ℃ in nitrogen atmosphere, then removing N-methylpyrrolidone and byproducts by rotary evaporation, and placing in a vacuum drying oven for drying at 80-90 ℃ to constant weight.

Preferably, the molar ratio of the 2, 6-diaminopurine nucleoside, N-methylpyrrolidone, 2, 5-furandicarboxylic acid and 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline is 1 (5-8) to 1 (0.8-1.2).

Preferably, the hyperbranched imidazolium salt type ionic polymer is hyperbranched polyion liquid, and the preparation method is as follows: example 1 of chinese patent 201510944282.5.

Another object of the present invention is to provide a method for preparing the biomedical material for skin, comprising the following steps: the raw materials are uniformly mixed according to a ratio to obtain a mixture, then the mixture is added into N-methyl pyrrolidone, stirred and reacted for 3 to 5 hours at the temperature of 100 ℃ and 110 ℃, and then the mixture is poured into a mold and is placed into an oven to be dried, so that the biomedical material for skin is obtained.

Preferably, the mass ratio of the mixture to the N-methyl pyrrolidone is 1 (3-5).

Preferably, the drying time is 15-25 hours, and the drying temperature is 110-120 ℃.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the preparation method of the biomedical material for skin provided by the invention is simple and feasible, has low requirements on equipment and reaction conditions, has wide raw material sources and low price, is suitable for continuous large-scale production, and has higher economic value, social value and ecological value.

(2) The biomedical material for skin provided by the invention overcomes the defects of more or less antigen reaction, high price, limited source, easy secondary damage, often tearing, weak adhesion, poor strength, too strong antigenicity, high irritation, poor permeability, susceptibility to infection, inhibition of the growth of autogenous skin and scar accumulation, difficult raw material source, high cost, complex process, difficult manufacture and storage, single function and further improved biocompatibility and antibacterial property of the traditional biomedical material for skin, and has the advantages of excellent biocompatibility, biological functionality and antibacterial property, capability of promoting the quick recovery of damaged skin, good air permeability and anti-inflammatory function and good mechanical and mechanical properties.

(3) The invention provides a biomedical material for skin, which takes a 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate, a vinyl sulfonic acid dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl acrylate copolymer and a hyperbranched imidazolium salt type ionic polymer as base materials, hydroxyl on the 2, 6-diaminopurine nucleoside/2, 5-furandicarboxylic acid polycondensate reacts with epoxy on the vinyl sulfonic acid dimethylamine/ricinoleic acid/barbaloin D/3, 4-epoxy cyclohexyl methyl acrylate copolymer, an imidazolium salt on the hyperbranched imidazolium salt type ionic polymer reacts with the vinyl sulfonic acid dimethylamine/ricinoleic acid/barbaloin D/3, the carboxyl groups on the 4-epoxy cyclohexyl methyl methacrylate copolymer are connected by ionic bonds to form a three-dimensional network structure, so that the comprehensive performance of the material is effectively improved, and the mechanical property of the material is better; the base materials have good biocompatibility, do not stimulate and react with skin, contain more hydrophilic hydroxyl groups on molecular chains, and can effectively ensure the air permeability of the material.

(4) The biomedical material for skin provided by the invention has the advantages that the nucleoside, ricinoleic acid, barbaloin D and imidazole salt are introduced into the material, and the material has a synergistic effect, so that the biomedical material for skin can have excellent antibacterial, anti-infection and antiviral properties; the introduction of the barbaloin D can also play a role in resisting skin aging and moistening skin, so that the material has a better skin care function; due to the introduction of the hyperbranched structure, the hyperbranched imidazolium salt type ionic polymer has good compatibility with other components, and can effectively improve the air permeability of the material after being compatible with other components; the sulfonic dimethylamine structure, the aminopurine nucleoside and the furan have synergistic effect, so that the anti-inflammatory function of the material can be improved; the fish scale protein peptide and the vitamin C have synergistic effect, can provide nutrition for the growth of new skin, and can promote the healing of wounds, so that the damaged skin can be quickly recovered.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

In the embodiment of the invention, the raw materials are all purchased commercially; the hyperbranched imidazolium salt ionic polymer is hyperbranched polyion liquid, and the preparation method is as follows: example 1 of chinese patent 201510944282.5.