CN104109254B - I-type collagen-sodium alginate-polyvinyl alcohol composite film and preparation method thereof - Google Patents

I-type collagen-sodium alginate-polyvinyl alcohol composite film and preparation method thereof Download PDF

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CN104109254B
CN104109254B CN201410325153.3A CN201410325153A CN104109254B CN 104109254 B CN104109254 B CN 104109254B CN 201410325153 A CN201410325153 A CN 201410325153A CN 104109254 B CN104109254 B CN 104109254B
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sodium alginate
collagen
polyvinyl alcohol
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composite film
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CN104109254A (en
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但卫华
刘婷
刘郁倩
但年华
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Sichuan University
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Sichuan University
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Abstract

The invention provides an I-type collagen-sodium alginate-polyvinyl alcohol composite film which comprises the following components by weight percent: 20% to 60% of I-type collagen, 20% to 60% of sodium alginate and 20% to 60% of polyvinyl alcohol. A preparation method of the composite film comprises the following steps: firstly, respectively dissolving the I-type collagen, the sodium alginate and the polyvinyl alcohol in different reaction kettles and regulating the pH of the I-type collagen to be within 5 to 8; then, successively adding a sodium alginate liquid and a polyvinyl alcohol liquid in proportion into an I-type collagen liquid and stirring for 4 to 10 hours; adding a defoaming agent to a mixed liquid and stirring for 20 to 60 minutes; then, pumping the mixed liquid into a storage tank and standing for defoaming; after the defoaming is checked to reach a requirement, pumping the mixed liquid into a film casting machine so as to obtain a film in a casting manner, drying and soaking the film in a cross-linking agent liquid or standing under a cross-linking condition for cross-linking for 4 to 24 hours, cleaning and drying; finally, shaping the film, packaging and irradiating, thereby obtaining the I-type collagen-sodium alginate-polyvinyl alcohol composite film. The composite film material is good in mechanical property, hydrophilcity and biocompatibility, moderate in degradation velocity and simple in preparation process. Thus, the composite film material can be widely applied to wound dressing, hemostatic materials, tissue engineering scaffold materials and the like.

Description

Type i collagen-sodium alginate-polyvinyl alcohol composite membrane and preparation method thereof
Technical field
The present invention relates to type i collagen-sodium alginate-polyvinyl alcohol composite membrane and preparation method thereof, belong to bio-medical material Material field.
Background technology
The special construction that 3 polypeptide chains of type i collagen form three spirals determines some of particular characteristic, its tensile strength Very high, there is outstanding one-tenth fibre property, cell proliferation, growth, degradable, histocompatbility, hemostatic and collagen can be promoted Multiple good characteristics such as self-association, therefore type i collagen is widely used in field of tissue engineering technology.Sodium alginate is due to good Biological degradability and biocompatibility, have been widely used in the fields such as chemistry, biology, medicine, food, and good with it Film forming and be widely used in multiple use membrane material preparation.PVA has good solvent resistance and excellent film forming, Smooth surface, the very powerful, film of solvent resistant, tear-proof can be formed, and due to having excellent biodegradability, to human body Have no toxic side effect, be also a kind of good bio-medical material.
At present, generally select in membrane material preparation be shitosan, sodium alginate, polyvinyl alcohol, collagen, PLA, PLGA etc., such as patent CN102978740A report using vinylon high-strength and high-modulus technique by collagen with PVA mixed Close spinning and produce a kind of protein composite fibre；Patent 200510020902.2 adopts metal ion-modified collagen-poly- second Enol composite fibre is to improve the stability of spinning solution and the intensity of composite fibre；For simulation collagen and elastin laminin in natural blood Ratio in pipe, has researcher to select 45% collagen and 15% elastin laminin, add respectively 40% biodegradable polymers PLGA, PLA, PCL, PLLA or PLA-caprolactone electrospinning prepare compound rest（Heydarkhan-Hagvall S, Schenke-Layland K, Dhanasopon AP,et al. Three-dimensional electrospun ECM- based hybrid scaffolds for cardiovascular tissue engineering[J].Biomaterials, 2008, 29(19): 2907-2914.）；Jiang Jianming et al. by plural gel approach be prepared for collagen- Sodium alginate-hydroxyapatite scaffold material（Jiang Jianming, Wang Xiaoliang, Wang Xiaomin, etc. plural gel approach prepares collagen-marine alga Sour sodium-hydroxyapatite scaffold material [J]. chemical research and application, 2007,19 (6): 695-697.）.In said method, Have the following disadvantages：（1）Most of collagen raw material（Collagen）It is the hydrolysate of collagen, lost collagen and kept three strands Distinctive biologically active during spiral；（2）Artificial macromolecular material compound tense need to be dissolved collagen with organic solvent with PLA, PLGA etc., The stronger solvent of the toxicity such as such as hexafluoroisopropanol or oxolane, makes the 26S Proteasome Structure and Function of collagen be affected after dissolving, and The organic solvent of residual will directly affect the biocompatibility of material；（3）Collagen is not having crosslinking with the membrane material of sodium alginate Under conditions of, bad mechanical property, structure is easily caved in, and is not suitable as timbering material.
Content of the invention
The purpose of the present invention is that have suitable hydrophily, permeable gas, power for field of biomedical materials offer is a kind of Learn functional, good biocompatibility type i collagen-sodium alginate-polyvinyl alcohol composite membrane and preparation method thereof.
The purpose of the present invention to be realized by following technical measures, wherein said Material Percentage unless otherwise indicated, All it is weight percentage：
（1）Type i collagen is dissolved in the reactor containing inorganic acid or organic acid soln, stirs at 4～10 DEG C and be allowed to It is completely dissolved, be configured to the type i collagen solution that mass fraction is 0.5%～1%；
（2）Sodium alginate powder is dissolved in the reactor containing distilled water and is heated to 40～60 DEG C of stirrings and is allowed to completely molten Solution, is configured to the sodium alginate soln that mass fraction is 1%～5%, is cooled to room temperature stand-by；
（3）Dissolve polyvinyl alcohol in and be heated to 50～90 DEG C in the reactor containing distilled water and be allowed to be completely dissolved, prepare The poly-vinyl alcohol solution becoming mass fraction to be 4%～10%, is cooled to room temperature stand-by；
（4）It is 5～8 that the gained type i collagen NaOH of 0.2～0.5mol/L in step (1) is neutralized to pH, then According to mass percent shared by each raw material：Type i collagen 20%～60%, sodium alginate 20%～60%, polyvinyl alcohol 20%～60%, Mix three of the above solution in reactor, stir 4～10 hours at 4～10 DEG C；
（5）To in step (4) gained mixed solution, add defoamer, stir 20-60 minute, then blended liquid is pumped into Holding vessel, stands froth breaking；
（6）After checking that froth breaking reaches requirement, blended liquid is pumped into flow-casting film forming machine, casting film-forming, re-dry film forming；
（7）Dried film is immersed in cross-linking agent solution or is placed under cross linking conditions after crosslinked 4～24 hours, cleaning, Re-dry；
（8）After processing and forming, packaging, irradiation, that is, obtain type i collagen-sodium alginate-polyvinyl alcohol composite membrane.
The type i collagen being prepared by said method-sodium alginate-polyvinyl alcohol composite film material, white or micro- Huang Color is membranaceous, smooth, is visible by naked eyes impurity；Porosity：70%～85%；Tensile strength：30～45MPa；Elongation at break：30% ～40%；Water absorption rate：1500g/g～2000g/g；Water retention：300g/g～400g/g；Water vapor permeability：37 DEG C under dry conditions When, it is 2000 ~ 3000g/ (m2·24h).
The present invention has advantages below：
1. type i collagen used by the present invention be through acid-enzyme hydrolysis method extract, it is advantageous that mild condition, environmentally friendly, carry Take rate high, can preferably keep the triple helix structure of collagen and reduce the antigenicity of collagen, retain its biologically active, can improve The biocompatibility of material；
2. the present invention utilizes polyvinyl alcohol good physical mechanical performance and histocompatbility, and sodium alginate is good The advantages of hydrophily, biological degradability and film forming, to overcome collagen bad mechanical property, intolerant to enzymolysis the shortcomings of；
3. do not use organic solvent in the preparation process of the present invention, can the good biocompatibility of reserved materials itself；
4. preparation process is simple of the present invention is stable, low cost, gentle environmental protection, it is easy to accomplish industrialized production, and possessing The specific function of medical material, has the potentiality of popularization and application, wide market.
Specific embodiment
Below by implement the present invention is specifically described it is necessary to it is pointed out here that to be that the present embodiment is served only for right The present invention is further described, and it is not intended that limiting the scope of the invention, the person skilled in the art in this field Some nonessential improvement can be made according to the content of foregoing invention and adjust.
Embodiment 1
（1）Type i collagen is dissolved in the reactor containing acetum, stirring at 4 DEG C is allowed to be completely dissolved, and is configured to Mass fraction is 0.5% type i collagen solution；
（2）Sodium alginate powder is dissolved in the reactor containing distilled water and is heated to 45 DEG C of stirrings and is allowed to be completely dissolved, It is configured to the sodium alginate soln that mass fraction is 2%, be cooled to room temperature stand-by；
（3）Dissolve polyvinyl alcohol in and be heated to 80 DEG C in the reactor containing distilled water and be allowed to be completely dissolved, be configured to matter Amount fraction is 4%～10% poly-vinyl alcohol solution, is cooled to room temperature stand-by；
（4）It is 7 that the gained type i collagen NaOH of 0.2mol/L in step (1) is neutralized to pH, then according to each former Mass percent shared by material：Type i collagen 20%, sodium alginate 60%, polyvinyl alcohol 20%, mixing three of the above is molten in a kettle. Liquid, stirs 4 hours at 4 DEG C；
（5）To in step (4) gained mixed solution, add defoamer, stir 30 minutes, then blended liquid is pumped into storage Tank, stands froth breaking；
（6）After checking that froth breaking reaches requirement, blended liquid is pumped into flow-casting film forming machine, casting film-forming, is then dried；
（7）Dried composite membrane is immersed in cross-linking agent solution or is placed under cross linking conditions after crosslinked 12 hours, cleaning, Re-dry；
（8）After processing and forming, packaging, irradiation, that is, obtain type i collagen-sodium alginate-polyvinyl alcohol composite membrane.
Embodiment 2
（1）Type i collagen is dissolved in the reactor containing acetum, stirring at 4 DEG C is allowed to be completely dissolved, and is configured to Mass fraction is 0.8% type i collagen solution；
（2）Sodium alginate powder is dissolved in the reactor containing distilled water and is heated to 40 DEG C of stirrings and is allowed to be completely dissolved, It is configured to the sodium alginate soln that mass fraction is 2%, be cooled to room temperature stand-by；
（3）Dissolve polyvinyl alcohol in and be heated to 80 DEG C in the reactor containing distilled water and be allowed to be completely dissolved, be configured to matter Amount fraction is 8% poly-vinyl alcohol solution, is cooled to room temperature stand-by；
（4）It is 6.5 that the gained type i collagen NaOH of 0.3mol/L in step (1) is neutralized to pH, then according to respectively Mass percent shared by raw material：Type i collagen 20%, sodium alginate 20%, polyvinyl alcohol 60%, mix three of the above in a kettle. Solution, stirs 6 hours at 4 DEG C；
（5）To in step (4) gained mixed solution, add defoamer, stir 30 minutes, then blended liquid is pumped into storage Tank, stands froth breaking；
（6）After checking that froth breaking reaches requirement, blended liquid is pumped into flow-casting film forming machine, casting film-forming, is then dried；
（7）Dried composite membrane is immersed in cross-linking agent solution or is placed under cross linking conditions after crosslinked 12 hours, cleaning, Re-dry；
（8）After processing and forming, packaging, irradiation, that is, obtain type i collagen-sodium alginate-polyvinyl alcohol composite membrane.
Embodiment 3
（1）Type i collagen is dissolved in the reactor of saliferous acid solution, stirring at 10 DEG C is allowed to be completely dissolved, and prepares Become the type i collagen solution that mass fraction is 0.8%；
（2）Sodium alginate powder is dissolved in the reactor containing distilled water and is heated to 45 DEG C of stirrings and is allowed to be completely dissolved, It is configured to the sodium alginate soln that mass fraction is 2%, be cooled to room temperature stand-by；
（3）Dissolve polyvinyl alcohol in and be heated to 60 DEG C in the reactor containing distilled water and be allowed to be completely dissolved, be configured to matter Amount fraction is 8% poly-vinyl alcohol solution, is cooled to room temperature stand-by；
（4）It is 6.5 that the gained type i collagen NaOH of 0.5mol/L in step (1) is neutralized to pH, then according to respectively Mass percent shared by raw material：Type i collagen 33.3%, sodium alginate 33.3%, polyvinyl alcohol 33.3%, mix in a kettle. with Upper three kinds of solution, stir 4 hours at 4 DEG C；
（5）To in step (4) gained mixed solution, add defoamer, stir 60 minutes, then blended liquid is pumped into storage Tank, stands froth breaking；
（6）After checking that froth breaking reaches requirement, blended liquid is pumped into flow-casting film forming machine, casting film-forming, is then dried；
（7）Dried composite membrane is immersed in cross-linking agent solution or is placed under cross linking conditions after crosslinked 12 hours, cleaning, Re-dry；
（8）After processing and forming, packaging, irradiation, that is, obtain type i collagen-sodium alginate-polyvinyl alcohol composite membrane.

Claims (6)

  1. The preparation method of 1.I Collagen Type VI-sodium alginate-polyvinyl alcohol composite film material is it is characterised in that comprise the steps of：
    （1）Type i collagen is dissolved in the reactor containing inorganic acid or organic acid soln, stirring at 4～10 DEG C is allowed to complete Dissolving, is configured to the type i collagen solution that mass fraction is 0.5%～1%；
    （2）Sodium alginate powder is dissolved in the reactor containing distilled water and is heated to 40～60 DEG C of stirrings and is allowed to be completely dissolved, It is configured to the sodium alginate soln that mass fraction is 1%～5%, be cooled to room temperature stand-by；
    （3）Dissolve polyvinyl alcohol in and be heated to 50～90 DEG C in the reactor containing distilled water and be allowed to be completely dissolved, be configured to matter Amount fraction is 4%～10% poly-vinyl alcohol solution, is cooled to room temperature stand-by；
    （4）It is 5～8 that the gained type i collagen NaOH of 0.2～0.5mol/L in step (1) is neutralized to pH, then according to Mass percent shared by each raw material：Type i collagen 20%～60%, sodium alginate 20%～60%, polyvinyl alcohol 20%～60%, in reaction Mix three of the above solution in kettle, stir 4～10 hours at 4～10 DEG C；
    （5）To in step (4) gained mixed solution, add defoamer, stir 20-60 minute, then blended liquid is pumped into storage Tank, stands froth breaking；
    （6）After checking that froth breaking reaches requirement, blended liquid is pumped into flow-casting film forming machine, casting film-forming, re-dry film forming；
    （7）Dried film is immersed in cross-linking agent solution or is placed under cross linking conditions after crosslinked 4～24 hours, cleaning, then do Dry；
    （8）After processing and forming, packaging, irradiation, that is, obtain type i collagen-sodium alginate-polyvinyl alcohol composite membrane；This membrane material Key Performance Indicator as follows：
    Outward appearance：Membrane material is white or slightly yellow membranaceous, smooth, is visible by naked eyes impurity；
    Porosity：70%～85%；
    Tensile strength：30～45MPa；
    Elongation at break：30%～40%；
    Water absorption rate：1500g/g～2000g/g；
    Water retention：300g/g～400g/g；
    Water vapor permeability：Under dry conditions when 37 DEG C, it is 2000 ~ 3000g/ (m2·24h)；
    Cell compatibility：Cytotoxicity should be not more than 1 grade；
    Sterility test：Aseptic；
    Thermal source：No thermal source；
    Sensitization is tested：No delayed type hypersensitivity, DTH.
  2. 2. composite film material according to claim 1 preparation method it is characterised in that：Described type i collagen molecular weight 30 More than ten thousand dalton, there is complete triple helix structure, from pigskin, ox-hide, pig tendon or beef tendon, when dissolving type i collagen Acid solution used is acetum, analyzes pure, sulfuric acid solution, analyzes pure or hydrochloric acid solution, analyzes pure one kind.
  3. 3. composite film material according to claim 1 preparation method it is characterised in that：Described sodium alginate is analysis Pure；The degree of polymerization of polyvinyl alcohol is 1500～2600, and analysis is pure.
  4. 4. composite film material according to claim 1 preparation method it is characterised in that：Described defoamer be ethylene glycol, Any one in glycerine, ethanol.
  5. 5. according to claim 1 composite film material preparation method it is characterised in that：Described crosslinking agent or cross linking conditions are UV-crosslinked, heat cross-linking, 1- ethyl -3- (3- DimethylAminopropyl)-carbodiimides, DGEEG, glycerine Any one or two kinds of in glycidol ether, Geniposide, OPC, gallic acid.
  6. 6. composite film material according to claim 1 preparation method it is characterised in that：Drying mode is to air-dry, freeze It is dried or microwave low-temperature drying.
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CN104974384A (en) * 2015-06-25 2015-10-14 山东洁晶集团股份有限公司 Sodium alginate film and preparation method thereof
CN108530651A (en) * 2018-01-25 2018-09-14 四川大学 PH is sensitive, can self-healing, can cell adhesion medical aquogel and preparation method thereof
CN108578760A (en) * 2018-02-07 2018-09-28 苏州元禾医疗器械有限公司 A kind of preparation method of the medical dressing of promotion wound healing
CN108310451A (en) * 2018-02-07 2018-07-24 苏州元禾医疗器械有限公司 A kind of medical dressing promoting wound healing
CN109251352A (en) * 2018-08-30 2019-01-22 太原理工大学 A kind of polyvinyl alcohol/sodium alginate of structure-controllable/hydroxyapatite porous support preparation method
CN111607114B (en) 2020-06-16 2022-09-27 陕西科技大学 Preparation method of green degradable multifunctional collagen-based nano composite membrane

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524577A (en) * 2003-02-27 2004-09-01 珠海亿胜生物制药有限公司 Alkaline fibroblast growth factor pellicle and its production method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4460253B2 (en) * 2003-09-26 2010-05-12 積水化成品工業株式会社 Hydrophilic polymer gel adhesive

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1524577A (en) * 2003-02-27 2004-09-01 珠海亿胜生物制药有限公司 Alkaline fibroblast growth factor pellicle and its production method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
海藻酸-聚乙烯醇二元膜的结构表征与性能研究;王康健 等;《皮革科学与工程》;20090228;第19卷(第1期);第19页第1.2节 *
聚乙烯醇-胶原创伤敷料的研制;叶春婷 等;《生物医学工程学杂志》;20080615;第25卷(第3期);第605页第2.2.1节、第606页第4节 *

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