CN1221290C - Medical biomaterial and its preparing method - Google Patents
Medical biomaterial and its preparing method Download PDFInfo
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- CN1221290C CN1221290C CN 03112755 CN03112755A CN1221290C CN 1221290 C CN1221290 C CN 1221290C CN 03112755 CN03112755 CN 03112755 CN 03112755 A CN03112755 A CN 03112755A CN 1221290 C CN1221290 C CN 1221290C
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- fibroin
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- biomaterial
- prepolymer solution
- polyurethane
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Abstract
The present invention relates to a medical biomaterial and a preparation method of the medical biomaterial, particularly to a medical biomaterial prepared by the graft copolymerization of crosslinking type polyurethane and fibroin and a preparation method of the medical biomaterial. In the preparation method, isocyanate containing active-NCO functional groups is used as a prepolymer, and the prepolymer is under grafting reaction with base groups of-OH,-NH-,-NH2 in the fibroin macromolecules; the humidity of the reaction system is controlled to form a crosslinking type polyurethane-fibroin graft copolymerization structure. The medical biomaterial which has the advantages of favorable compatibility with biological tissue, enough flexibility and other mechanical properties and high stability is the ideal medical biomaterial.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose and preparation method thereof, biomaterial for medical purpose of particularly a kind of cross-linked type polyurethane and fibroin graft copolymerization and preparation method thereof.
Background technology
In recent years, the applied research of polyurethane (PU) material in biomedical sector receives much concern always.Extraordinary PU material with certain biocompatibility has been applied to the various artificial organs such as medical catheter, artificial lung, artificial heart and artificial cornea that contact with blood.Because common PU can form in various degree blood coagulation when contact with blood, therefore, the design of biocompatible polymeric material is become one of current biomaterial focus in studying with modifying.At present, the main method of polyurethane material being carried out finishing is that bulk copolymerization and interface connect the skill copolymerization, in the polyurethane molecular segment, introduce hydrophilic synthetic high polymer chain segment, after polysiloxanes, polyoxyethylene and polyethers blend, form PU by block copolymerization with isocyanates; Introduce anion groups such as polyacrylamide, polyacrylate, sulfonic group or sulfophenyl at the PU interface by connecing the skill copolymerization.Though said method can play certain effect to the blood compatibility that improves the PU interface, modification group is along with the prolongation in service time and storage time comes off easily, and the anticoagulation function that makes the PU interface reduces gradually and catabiosis occurs.Therefore, seek stable performance, have the novel PU compound interface of good biocompatibility, research and the application of biomaterial had positive meaning.
Fibroin is a kind of natural protein material, and is nontoxic to human body, have no stimulation, and therefore, the biomaterial of making as raw material with fibroin albumen has the favorable tissue compatibility, helps fibroblast propagation thereon.Before the present invention makes; notification number is the Chinese invention patent " a kind of Wound surface protection film and preparation method thereof " of CN1059125C; disclose and a kind of silkworm silk is come unstuck, dissolves, dialyses, purifies, made fibroin protein film, be used as the technology of wound surface cladding material.Owing to be in a kind of random rolled state under the structure routine of silk fibroin molecular, easily βization taking place and causes pure fibroin membrane hardening to become fragile, lack pliability, so, use it for biomaterial for medical purpose, in particular as being biological histoorgan such as materials such as trunnion, blood vessel, there is certain deficiency.
Summary of the invention
The object of the present invention is to provide a kind ofly can have the good compatibility with biological tissue, has enough mechanical properties such as pliability again, and the biomaterial for medical purpose of good stability and preparation method thereof.
Biomaterial for medical purpose of the present invention, it is the layer structure of oiliness cross-linked type polyurethane and fibroin graft copolymerization.
The preparation method of biomaterial for medical purpose of the present invention, earlier silkworm silk is come unstuck, dissolve, dialyse, purify make the fibroin film material after, carry out the processing of following steps again:
(1) be feedstock production prepolymer solution, wherein NCO: OH=1.35～2.31 (mol) with isocyanates, polyhydric alcohol, described prepolymer solution is a base polyurethane prepolymer for use as solution;
(2) prepolymer solution being placed the fibroin membrane surface, is 20～50 ℃ in temperature, and humidity is lower than in 5% the inert gas atmosphere graft reaction takes place, and makes fibroin-performed polymer graft;
(3) be 75～95% with above-mentioned fibroin-performed polymer graft in humidity, temperature is to react under 20～70 ℃ the condition, makes the layer structure material of polyurethane and fibroin graft copolymerization.
The polyhydric alcohol for preparing above-mentioned base polyurethane prepolymer for use as solution is one or more the mixture in the polyolefin diols of molecular weight Mn=1000～2500, PTMEG, polyether triol, polyester-diol, the polyester triol; Isocyanates is one or more the mixture in aromatic series, the aliphatic diisocyanate.
Technical solutions according to the invention owing to contain activated-NCO functional group in the prepolymer solution that adopts, it can with the fibroin macromole in-OH ,-NH-,-NH
2Graft reaction takes place between group, again by controlling the humidity of response system, form the cross-linked type polyurethane film, therefore, material after the shaping structurally is fibroin and polyurethane grafted copolymerization, has the advantage that the good histocompatibility of mechanical properties such as the pliability that polyurethane is good and fibroin organically combines, not only can be used as the wound surface cladding material of human body different parts, can also be processed into different biological tissue's organ such as trunnion, blood vessel etc., be with a wide range of applications at clinical medicine domain.
The specific embodiment
Polyurethane of the present invention and fibroin are connect skill copolymeric material and preparation method thereof, further illustrate in conjunction with following two embodiment:
Embodiment one:
First preparation fibroin membrane: with the domestic silkworm silk is primary raw material, after it is come unstuck in concentration is 0.05% aqueous sodium carbonate, presses CaCl
2: H
2O: C
2H
5OH=1: 8: 2 (mol) prepares mixed solvent, with the fibroin dissolving, obtains silk fibroin solution after dialysis, and solid content is 2-3%; With above-mentioned solution film-forming, be film forming in 50 ℃ the baking oven in temperature, its thickness is about 10 μ m.
Preparation prepolymer solution: get the polybutadiene diol that molecular weight Mn=2000 contains the two keys of reactivity, add proper amount of acetone and 1.0% dibutyl tin dilaurate, behind the mix homogeneously, 30 ℃ of constant temperature, under the electromagnetic agitation, slowly be added drop-wise in nitrogen atmosphere in the toluene di-isocyanate(TDI) (TDI), the NCO in control polybutadiene diol and the toluene di-isocyanate(TDI): OH is 1.55mol, fully reaction is about 1 hour, makes solid content and be 20% prepolymer solution.
Polyurethane-fibroin graft copolymerization: above-mentioned prepolymer solution is cast on the fibroin membrane of certain area, is placed on humidity and is 5%, temperature is reaction 24 hours in 35 ℃ the nitrogen atmosphere reactor; Adjust humidity to 75%, reaction temperature is 50 ℃, continues one week of reaction.In this reaction, water is used as chain extender, hydrone in the gas phase constantly is diffused into polybutadiene performed polymer liquid layer surface, and further spread to internal layer, the generation amido reacts after NCO and water are met, amido and excessive on every side NCO further react and form the urea key, have so just reached the effect and the final cross-linked type polyurethane film that forms of chain extension.
Take out this double-layered compound film, use 80%ZnCl
2Aqueous solution dissolving unreacted residual fibroin, the reuse distilled water wash makes polybutadiene polyurethane-fibroin graft copolymerization film behind the vacuum drying, and the thickness of film is 80 μ m, and surperficial fibroin content is 2.1mg/cm
2
The plain intermembranous performance of the polybutadiene polyurethane that makes with this method--fibroin graft copolymerization film and pure silk is relatively referring to table 1.
Embodiment two:
Prepare fibroin membrane as embodiment one described method.
The preparation prepolymer solution: with polyhydric alcohol is the polypropylene glycol of molecular weight Mn=1000, adding an amount of butanone and concentration is 0.5% tin octoate mix homogeneously, constant temperature under 30 ℃ temperature, slowly drip a kind of toluene di-isocyanate(TDI) (TDI) of aromatic isocyanate class in electromagnetic agitation, the nitrogen atmosphere, NCO in control polypropylene glycol and the toluene di-isocyanate(TDI): OH is 1.41mol, fully reacts after 1 hour to make prepolymer solution.
Polyurethane-fibroin graft copolymerization: it is 30% prepolymer solution that the fibroin membrane that will prepare gained places solid content, is placed on humidity and is lower than in 5% the reactor, 35 ℃ of reactions 24 hours down; Adjust humidity to 95% then, reaction temperature is 45 ℃, continues one week of reaction.
With the composite CaCl that makes
2: H
20: C
2H
5OH=1: (mol) mixed solvent dissolved unreacted fibroin in 8: 2, and reaction temperature is 60 ℃, and the time is 5 hours, use distilled water wash at last, obtain polypropylene glycol polyurethane-fibroin graft copolymerization composite membrane behind the vacuum drying, its thickness is about 85 μ m, and fibroin content is 2.4mg/cm
2
Polypropylene glycol polyurethane with the described technical scheme preparation of present embodiment--the plain intermembranous performance of fibroin graft copolymerization film and pure silk is relatively referring to table 2.
In the foregoing description one, embodiment two, employed polyhydric alcohol can be one or more the mixture in polyolefin diols, PTMEG, polyether triol, polyester-diol, the polyester triol, isocyanates can be one or more the mixture in aromatic series or the aliphatic, as 2 in the vulcabond, 4-toluene di-isocyanate(TDI), tetramethylene diisocyanate, hexamethylene diisocyanate and 1,4-cyclohexane diisocyanate etc.
Table 1:
Table 2:
Claims (4)
1. biomaterial for medical purpose is characterized in that: it is the layer structure of oiliness cross-linked type polyurethane and fibroin graft copolymerization.
2. the preparation method of a biomaterial for medical purpose, silkworm silk is made the fibroin film material after coming unstuck, dissolve, dialyse, purifying, it is characterized in that carrying out the processing of following steps again:
(1) be feedstock production prepolymer solution, wherein NCO: OH=1.35～2.31 (mol) with isocyanates, polyhydric alcohol, described prepolymer solution is a base polyurethane prepolymer for use as solution;
(2) prepolymer solution being placed the fibroin membrane surface, is 20～50 ℃ in temperature, and humidity is lower than in 5% the inert gas atmosphere graft reaction takes place, and reacts 24 hours, makes fibroin-performed polymer graft;
(3) be 75～95% with above-mentioned fibroin-performed polymer graft in humidity, temperature is one week of reaction under 20～70 ℃ the condition, makes the layer structure material of polyurethane and fibroin graft copolymerization.
3. the preparation method of a kind of biomaterial for medical purpose according to claim 2 is characterized in that: the polyhydric alcohol of preparation prepolymer solution is one or more the mixture in the polyolefin diols of molecular weight Mn=1000～2500, PTMEG, polyether triol, polyester-diol, the polyester triol.
4. the preparation method of a kind of biomaterial for medical purpose according to claim 2 is characterized in that: the isocyanates of preparation prepolymer solution is one or more the mixture in aromatic series, the aliphatic diisocyanate.
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|---|---|---|---|
| CN 03112755 CN1221290C (en) | 2003-01-23 | 2003-01-23 | Medical biomaterial and its preparing method |
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|---|---|---|---|
| CN 03112755 CN1221290C (en) | 2003-01-23 | 2003-01-23 | Medical biomaterial and its preparing method |
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| CN1221290C true CN1221290C (en) | 2005-10-05 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100346861C (en) * | 2006-06-02 | 2007-11-07 | 东华大学 | Blood filter material and process for preparing same |
| CN101905030B (en) * | 2010-06-02 | 2013-06-12 | 苏州大学 | Method for preparing fibroin-modified polyurethane biomedical material |
| CN102839497A (en) * | 2012-02-24 | 2012-12-26 | 武汉纺织大学 | Silk fibroin peptide chain-containing AlaGlyAlaGly polyurethane fiber film and preparation method thereof |
| CN104959042A (en) * | 2015-06-24 | 2015-10-07 | 苏州乔纳森新材料科技有限公司 | Dialysis membrane and preparation method thereof |
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