CN105837849A - Preparation method of functionalized composite porous material - Google Patents

Preparation method of functionalized composite porous material Download PDF

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CN105837849A
CN105837849A CN201610300686.5A CN201610300686A CN105837849A CN 105837849 A CN105837849 A CN 105837849A CN 201610300686 A CN201610300686 A CN 201610300686A CN 105837849 A CN105837849 A CN 105837849A
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preparation
porous material
pore creating
plga
composite porous
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CN105837849B (en
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刘福娟
王萍
徐岚
何吉欢
张岩
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Suzhou University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • C08J9/0071Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/0076Nanofibres
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a preparation method of a functionalized composite porous material. The method comprises the following steps that 1, pore-forming agent suspension liquid is flatwise laid on the carrier surface, and after drying is conducted, a pore-forming agent template attached to the carrier surface is obtained; 2, a matrix solution is laid on the pore-forming agent template, and drying is conducted to obtain a composite casting film, wherein the matrix solution is prepared from a polylactic acid-glycolic acid copolymer, carbon nanotubes and a solvent; 3, the composite casting film is immersed into an acid solution, and the functionalized composite porous material is obtained. According to the preparation method, the porous scaffold material is prepared by combining a particle dissolution method with a casting film method, and the prepared porous material can simulate the extracellular matrix in the form and function and has the good biocompatibility and the good mechanical strength; experiment results show that the tensile break stress of the functionalized composite porous material prepared through the preparation method is 3.5-4.1 MPa, and the elongation at break of the functionalized composite porous material prepared through the preparation method is about 75.16%.

Description

A kind of preparation method of functionalization composite porous material
Technical field
The invention belongs to porous material technical field, particularly relate to the system of a kind of functionalization composite porous material Preparation Method.
Background technology
Biomedical applications mainly includes tissue engineering bracket, drug release, biosensor, medical plants Enter thing, affinity membrane and wound dressing etc..In recent years, human health side is being promoted due to organizational project Face shows unlimited potential, and therefore, the research to them also achieves significant progress.To organize work As a example by journey, tissue, the defect of organ or the dysfunction that disease and wound cause is that human health is faced One of main harm.How to overcome present in autologous or allosome tissue, organ transplantation " with repair in trauma Wound ", the defect such as donor source is not enough, fundamentally solve tissue, organ defect reparation and reconstruction Etc. problem, it has also become the international advanced subject of life science.Wherein there is the porous material of functionalization The preparation of material is one of key technology of histoorgan recovery project.
During as tissue engineering bracket, the porous material of functionalization can for the sticking of cell, grow, move Move and breed the template providing good.Therefore, by means of the development of modern science and technology, how to make impaired Histoorgan obtain regeneration completely or copy required tissue in vitro or organ carries out substituting controlling Treatment becomes as biology, preclinical medicine and clinical medicine focus of attention, not only has important scientific value, And the hugest application prospect.
Porous polymer film material is widely used in tissue engineering bracket, because these materials can be with mould Intend the physical characteristic of natural extracellular matrix (ECM).In organizational project, it is good that polymer support has connection Good loose structure, they provide interim physical template for cell, it is simple to cell adhesion, migrate, increase Grow, break up, neoblastic regeneration and three dimensional structure.Finally, support should be by the natural fine of emiocytosis Extracellular matrix is substituted.Biodegradable high polymer is a kind of candidate material having very much allure, because it Have structured integrity, last natural decomposition, leave the tissue being newly formed, tissue will be undertaken required The mechanical load wanted.Porous material is as stenter to implant animal or human body, it is necessary to possess two functions, its One is to have certain mechanical strength to keep former organized shape;It two is to have certain biological live Property induced cell growth and differentiation, thus guide the regeneration of damaged tissues, and timbering material finally can quilt Degraded and absorbed.
At present, preparing porous support materials has a lot of method, mainly have particle leaching, fibres bond, Gas foaming, lyophilization, 3 D-printing and be separated etc. preparation method.Though these preparation methoies respectively have Feature but still have weak point.Such as, particle leaching is to add soluble granule conduct in the base Pore creating material, such as Sal, sucrose, mannitol, sodium bicarbonate, sodium dihydrogen phosphate and sodium glutamate etc., treats Matrix solidification after be soaked in particular solution so that it is in pore creating material dissolution and leave hole.This method Simple, but, the porous support materials mechanical strength that the method prepares is the highest.
Summary of the invention
The invention provides the preparation method of a kind of functionalization composite porous material, the preparation side in the present invention The functionalization composite porous material that method obtains has higher mechanical strength.
The present invention provides the preparation method of a kind of functionalization composite porous material, comprises the following steps:
A) pore creating material suspension is laid in carrier surface, obtains being attached to the pore-creating of carrier surface after drying Agent template;
B) Matrix Solution is taped against in described pore creating material template, obtains compound casting films after drying;
Described Matrix Solution includes matrix material, CNT and solvent;
Described matrix material includes in PLGA, polylactic acid, fibroin albumen and chitosan One or more;
C) described compound casting films is immersed in acid solution, obtain functionalization composite porous material.
Preferably, described pore creating material suspension is selected from melamine resin microsphere suspension liquid.
Preferably, in described pore creating material suspension, the particle diameter of pore creating material is 100~10000nm.
Preferably, the mass concentration of described pore creating material suspension is 3~5%.
Preferably, in described Matrix Solution, the mass concentration of PLGA is (0.06~0.14) g/mL。
Preferably, described CNT is (0.1~1) with the mass ratio of PLGA: 100.
Preferably, described solvent is oxolane and the mixed solution of dimethylformamide, hexafluoroisopropanol Or chloroform;
Described oxolane and oxolane in the mixed solution of dimethylformamide and dimethylformamide Volume ratio is (1~5): 1.
Preferably, described PLGA with the volume ratio of pore creating material in pore creating material suspension is (2~3): 1.
Preferably, described step B) particularly as follows:
Matrix Solution is taped against in pore creating material template, obtains hygrometric state casting films, then described hygrometric state is cast Film vibrates, and obtains compound casting films after drying.
Preferably, the time of described vibration is 10~60min.
The invention provides the preparation method of a kind of functionalization composite porous material, comprise the following steps: A) Pore creating material suspension is laid in carrier surface, obtains being attached to the pore creating material template of carrier surface after drying; B) Matrix Solution is taped against in described pore creating material template, obtains compound casting films after drying;Described matrix is molten Liquid includes PLGA, CNT and solvent.C) described compound casting films is immersed acid In property solution, obtain functionalization composite porous material.Particle leaching is tied mutually by the present invention with curtain coating embrane method Porous material is prepared in conjunction, prepared porous material form and functionally can analog cell epimatrix, and And have good biocompatibility and good mechanical strength, test result indicate that, the preparation in the present invention The functionalization composite porous material tensile break stress that method prepares is 3.5~4.1MPa, and elongation at break exists About 75.16%.It addition, the preparation method preparation process in the present invention is simple, pore size is easily controlled There is the structural stability of good pattern.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to reality Execute the required accompanying drawing used in example or description of the prior art to be briefly described, it should be apparent that below, Accompanying drawing in description is only embodiments of the invention, for those of ordinary skill in the art, not On the premise of paying creative work, it is also possible to obtain other accompanying drawing according to the accompanying drawing provided.
Fig. 1 is the scanning of the PLGA/MWCNTs functionalization composite porous material that the embodiment of the present invention 1 obtains Electronic Speculum figure;
Fig. 2 is the scanning of the PLGA/MWCNTs functionalization composite porous material that the embodiment of the present invention 2 obtains Electronic Speculum figure;
Fig. 3 is that cell is compound porous in the PLGA/MWCNTs functionalization of the embodiment of the present invention 1, embodiment 2 Adhesive tendencies on material and blank slide;
Fig. 4 is that cell is compound porous in the PLGA/MWCNTs functionalization of the embodiment of the present invention 1, embodiment 2 Proliferative conditions on material and blank slide;
Fig. 5 is on cell PLGA/MWCNTs functionalization composite porous material in the embodiment of the present invention 2 Adhere to and the scanning electron microscope (SEM) photograph of propagation;
Fig. 6 is the scanning of the PLGA/SWCNTs functionalization composite porous material that the embodiment of the present invention 3 obtains Electronic Speculum figure.
Detailed description of the invention
The invention provides the preparation method of a kind of functionalization composite porous material, comprise the following steps:
A) pore creating material suspension is laid in carrier surface, obtains being attached to the pore-creating of carrier surface after drying Agent template;
B) Matrix Solution is taped against in described pore creating material template, obtains compound casting films after drying;
Described Matrix Solution includes PLGA, CNT and solvent.
C) described compound casting films is immersed in acid solution, obtain functionalization composite porous material.
The functionalization composite porous material that preparation method in the present invention obtains has higher mechanical strength.
Pore creating material suspension is laid in carrier surface by the present invention, obtains after drying being attached to carrier surface Pore creating material template, in the present invention, described pore creating material suspension is the unit for uniform suspension of pore creating material and water, Described pore creating material suspension preferably includes melamine resin microsphere suspension liquid;Described pore creating material suspends The mass concentration of liquid is preferably 3~5%, more preferably 3.5~4.5%, and most preferably 4%;Described pore creating material Particle diameter be preferably 100~10000nm, more preferably 1000~9000nm, concrete, the present invention's In embodiment, can be 2 μm or 7 μm, the particle diameter provided such as Berlin, Germany microgranule company limited be respectively It is 2 ± 0.06 μm, the melamine resin microsphere of 7 ± 0.15 μm.
The present invention does not has special restriction to the kind of described carrier, it is preferred to use smooth the consolidating of surfacing Body carrier, such as glass slide.In the present invention, described dry temperature preferably 20~40 DEG C, more preferably 25~35 DEG C;The described dry time is preferably 24~48 hours, more preferably 30~40 hours;Obtain Pore creating material template is substantially attached to pore creating material microsphere layer on glass slide, and described pore creating material template can be Monolayer, it is also possible to be multilamellar, depend on the needs.
After obtaining pore creating material template, Matrix Solution is taped against described pore creating material template surface by the present invention, is dried After obtain compound casting films, Matrix Solution is preferably taped against in pore creating material template by the present invention, obtains hygrometric state stream Prolong film, then described hygrometric state casting films is vibrated, obtain compound casting films after drying.To described hygrometric state stream Prolonging film and carrying out the purpose of slight oscillatory is the gap allowing Matrix Solution to be completely filled with described pore creating material template. The time of described vibration is preferably 10~60min, more preferably 20~50min, most preferably 30~40min; The frequency of described vibration is preferably 120~240 times/min, more preferably 150~200 times/min.
In the present invention, described Matrix Solution includes matrix material, CNT and solvent, described matrix Material includes that PLGA (PLGA), polylactic acid (PLA), fibroin albumen and shell are poly- One or more in sugar;Wherein, the molecular weight of PLGA is 81000g/mol;Viscosity is 0.61dL/g. Described CNT can be SWCN (SWCNTs), it is also possible to be multi-walled carbon nano-tubes (MWCNTs);The diameter of described CNT is preferably 30~70nm, more preferably 40~60nm, Most preferably 45~55nm;The length of described CNT is preferably 100~400nm, more preferably 150~350nm, most preferably 200~300nm.The matter of PLGA in described Matrix Solution Amount concentration is preferably (0.06~0.14) g/mL, and more preferably (0.08~0.12) g/mL, concrete, In embodiments of the invention, can be 0.06g/mL, 0.08g/mL, 0.10g/mL, 0.12g/mL or 0.14g/mL.Described CNT is preferably (0.1~1) with the mass ratio of PLGA: 100, more preferably (0.2~0.9): 100, concrete, in an embodiment of the present invention, can be 0.5:100. Described solvent is preferably the mixed solution of oxolane and dimethylformamide, described oxolane and diformazan The volume ratio of base Methanamide is preferably (1~5): 1, more preferably (2~4): 1, most preferably 3:1.
In the present invention, in described pore-creating and suspension, the volume ratio of pore creating material and described matrix material is preferred For 1:(2~3), more preferably 1:2.5.
The present invention preferably by PLGA when stirring, add oxolane and two In the mixed organic solvents of methylformamide, fully dissolve, form PLGA solution, the most again carbon is received Mitron, under conditions of stirring, is dispersed in PLGA solution, obtains Matrix Solution, i.e. PLGA/CNTs solution.
In the present invention, described being dried is preferably vacuum drying, and described vacuum drying vacuum is preferably 0.02MPa;The described vacuum drying time is preferably 24~48 hours;Described vacuum drying temperature is preferred It it is 20~40 DEG C.
After obtaining compound casting films, described compound casting films is preferably immersed in acid solution by the present invention, To functionalization composite porous material.Described acid solution preferably includes hydrochloric acid solution or sulfuric acid solution;Described The molar concentration of acid solution is preferably 0.5~2mol/L, more preferably 1mol/L, by described compound curtain coating After film immerses acid solution, after 0.5~2 hour, pore creating material dissolves, and carrier and compound casting films completely disengage from, Again the compound casting films of described disengaging is carried out and is vacuum dried, obtain functionalization composite porous material.
In the present invention, the concentration of acid solution and the dissolution time of pore creating material need to strictly be controlled, during dissolving Between long, easily cause porous material to deform, dissolution time is too short, make pore creating material dissolve insufficient, this Pore creating material dissolution time in invention is preferably 0.5~2 hour, more preferably 1~1.5 hour;Acid solution Concentration is excessive, can destroy porous material, and concentration is too small, can affect the dissolving of pore creating material.
According to above-mentioned preparation method prepare for circular, membranaceous functionalization composite porous material, its thickness It is preferably 0.001~0.1cm, more preferably 0.002~0.05cm.
Preparation method in the present invention has the advantage that
(1) curtain coating embrane method and particle leaching is utilized to prepare PLGA/CNTs functionalization composite porous material, Its mechanical performance is made to be significantly improved;Additionally material central hole structure be formed by microsphere dissolution and reality Existing, the most particularly suitable prepare the porous material that thickness is less;
(2) by using the microsphere of different-grain diameter, it is achieved the controlled preparation to aperture of porous material, hole shape Looks and structural stability are good, and porosity is 67%~about 70.1%;
(3) micro nano structure of PLGA/CNTs functionalization composite porous material has bigger specific surface Long-pending (0.2~0.5m2/ g), the three-dimensional porous structure of its uniqueness can promote adhesion and the propagation of cell.
In order to further illustrate the present invention, a kind of functionalization provided the present invention below in conjunction with embodiment is multiple Conjunction porous material is described in detail, but can not be understood as limiting the scope of the present invention.
In the examples below, PLGA is purchased from Jinan Dai Gang biologic material products company, melamino-formaldehyde Resin microsphere (MF) suspension provides for Berlin, Germany microgranule company limited, and microspherulite diameter is respectively 2 ± 0.06 μm, 7 ± 0.15 μm.
Porosity computing formula:
ρ a = m πr 2 h
ϵ = ( 1 - ρ a ρ b ) × 100 %
In formula, m, r and h represent the quality of perforated membrane, radius and thickness respectively.ρbBasis for polymer Body density, ε is porosity.
Embodiment 1
By the PLGA (PLGA) of 1g under stirring, join oxolane with Dimethylformamide volume ratio is in the mixed organic solvents of 3:1, fully dissolves, and is made into concentration and is The solution of 0.1g/mL;The MWCNTs of 0.005g is dispersed in PLGA solution, makes PLGA/MWCNTs mixed solution.Measure the melamine resin microsphere that 5 μ L particle diameters are 2 μm (MF) suspension, is laid on the circular slide fully cleaned, and is completely dispersed and is dried, is attached to MF microsphere template on slide.The PLGA/MWCNTs mixed solution measuring 10 μ L again is taped against MF On microsphere template, then by the hygrometric state casting films slight oscillatory 30 minutes of mixed solution/MF template, purpose It is the gap allowing mixed solution to be completely filled with MF colloid template, vacuum drying 48 hours subsequently;Finally, The slide of the compound PLGA/MWCNTs/MF casting films being dried immerses in the hydrochloric acid solution of 1mol/L, After 1 hour, MF microsphere dissolves, and slide and PLGA/MWCNTs casting films completely disengage from, the most clearly Wash casting films, be then vacuum dried, obtain the membranaceous PLGA/MWCNTs of circle that thickness is 0.003cm Functionalization composite porous material.
Porous material quality m that the present embodiment obtains is about 0.001g, radius r and is about 0.5cm, thickness h It is about 0.003cm, ρbFor 1.25g/cm3.Calculate according to above-mentioned formula, the porous material in the present embodiment Porosity is 67%.
PLGA/MWCNTs functionalization composite porous material pattern in the present embodiment is as it is shown in figure 1, scheme The scanning electron microscope of the PLGA/MWCNTs functionalization composite porous material that 1 obtains for the embodiment of the present invention 1 Figure.As seen from Figure 1, the hole of PLGA/MWCNTs functionalization composite porous material in the present embodiment Footpath is 2 μm.
Measuring (Bei Shide instrument) through specific surface instrument, in the present embodiment, PLGA/MWCNTs functionalization is multiple The specific surface area closing porous material is 0.2~0.5m2/g。
The present invention uses universal testing machine (INSTRON 3365) to test in the present embodiment The mechanical performance of PLGA/MWCNTs functionalization composite porous material, its tensile break stress is 3.5MPa, elongation at break is 60.5%.
Embodiment 2
By the PLGA (PLGA) of 1.2g under stirring, join oxolane with Dimethylformamide volume ratio is in the mixed organic solvents of 3:1, fully dissolves, and is made into concentration and is The solution of 0.12g/mL;The MWCNTs of 0.012g is dispersed in PLGA solution, makes PLGA/MWCNTs mixed solution;Measure the melamine resin microsphere that 5 μ L particle diameters are 7 μm (MF) suspension, is laid on the circular slide fully cleaned, and is completely dispersed and is dried, is attached to MF microsphere template on slide.The PLGA/MWCNTs mixed solution measuring 10 μ L again is taped against MF On microsphere template, then by the hygrometric state casting films slight oscillatory 20 minutes of mixed solution/MF template, purpose It is the gap allowing mixed solution to be completely filled with MF colloid template, vacuum drying 48 hours subsequently;Finally, The slide of the compound PLGA/MWCNTs/MF casting films being dried immerses in the hydrochloric acid solution of 1mol/L, After 1.5 hours, MF microsphere dissolves, and slide and PLGA/MWCNTs casting films completely disengage from, the most clearly Wash casting films, be then vacuum dried, obtain the membranaceous PLGA/MWCNTs of circle that thickness is 0.0039cm Functionalization composite porous material.
Porous material quality m that the present embodiment obtains is about 0.0012g, radius r and is about 0.5cm, thickness H is about 0.0039cm, ρbFor 1.25g/cm3.Calculate according to above-mentioned formula, the porous material in the present embodiment Material porosity is 69%.
PLGA/MWCNTs functionalization composite porous material pattern in the present embodiment is as in figure 2 it is shown, scheme The scanning electron microscope of the PLGA/MWCNTs functionalization composite porous material that 2 obtain for the embodiment of the present invention 2 Figure.As shown in Figure 2, in the present embodiment, the aperture of PLGA/MWCNTs functionalization composite porous material is 7μm。
Measuring (Bei Shide instrument) through specific surface instrument, in the present embodiment, PLGA/MWCNTs functionalization is multiple The specific surface area closing porous material is 0.05~0.1m2/g。
The present invention uses universal testing machine (INSTRON 3365) to test in the present embodiment The mechanical performance of PLGA/MWCNTs functionalization composite porous material, its tensile break stress is 4.1MPa, elongation at break is 75.16%.
The compound porous material of PLGA/MWCNTs functionalization that Example 1 and Example 2 of the present invention is obtained 24 well culture plates put into by material and blank slide, add 75% ethanol, soaking disinfection 4 hours, then Sucking-off ethanol, dries, with PBS solution soak rinsing 3 times, each 20 minutes.Then DMEM is used About culture medium soak-out material half an hour, then suck culture medium, put into CO2After incubator a few hours, Inoculate according to the cell density in 20000, every hole.The cell cultivating certain time is taken out from incubator, Liquid-transfering gun sops up original culture fluid, rinses 3 times by the PBS solution through preheating, and every hole adds preheating To 37 DEG C not added with 10% hyclone and dual anti-DMEM culture medium 360 μ L, add and be preheating to 37 DEG C MTT 40 μ L, cultivate 4 hours, will have purple precipitation produce, then culture medium is sucked, every hole adds Enter 400 μ L DMSO, dissolution precipitation 20 minutes, become purple solution, then pipette solution with liquid-transfering gun 100 μ L add in every hole of 96 well culture plates, detect wavelength 570nm in Multifunction fluorescent microplate reader The fluorescent value at place, what size can reflect living cells sticks trend.
As seen in figures 3-5, Fig. 3 is that cell is at the embodiment of the present invention 1, embodiment 2 and blank slide to result On adhesive tendencies, wherein, the adhesive tendencies that 1 is cell on blank slide, 2 is that cell is in the present invention The adhesive tendencies on PLGA/MWCNTs functionalization composite porous material in embodiment 1,3 is cell The adhesive tendencies on PLGA/MWCNTs functionalization composite porous material in the embodiment of the present invention 2. As seen from Figure 3, prolongation over time, compared with the blank slide, cell is on the porous material Stick more and more;Fig. 4 is that cell is at the embodiment of the present invention 1, the PLGA/MWCNTs of embodiment 2 Proliferative conditions on functionalization composite porous material and blank slide, wherein, 1 is that cell is on blank slide Proliferative conditions, 2 is that the PLGA/MWCNTs functionalization in the cell embodiment of the present invention 1 is compound porous Proliferative conditions on material, 3 is that the PLGA/MWCNTs functionalization in the cell embodiment of the present invention 2 is multiple Close the proliferative conditions on porous material.As seen from Figure 4, along with the increase of cultivated days, with blank Slide is compared, and cell proliferative conditions on the porous material is good.Fig. 5 is that cell is in the embodiment of the present invention 2 In PLGA/MWCNTs functionalization composite porous material on the scanning electron microscope (SEM) photograph that adheres to and breed.
Embodiment 3
By the PLGA (PLGA) of 1g under stirring, join oxolane and two Methylformamide volume ratio is in the mixed organic solvents of 3:1, fully dissolves, and being made into concentration is 0.1g/mL Solution;The SWCNTs of 0.01g is dispersed in PLGA solution, makes PLGA/SWCNTs Mixed solution;Measure melamine resin microsphere (MF) suspension that 5 μ L particle diameters are 7 μm, flat Being laid on the circular slide fully cleaned, be completely dispersed and be dried, the MF obtaining being attached on slide is micro- Ball template.The PLGA/SWCNTs mixed solution measuring 10 μ L again is taped against on MF microsphere template, so After by the hygrometric state casting films slight oscillatory 20 minutes of mixed solution/MF template, it is therefore an objective to allow mixed solution It is completely filled with the gap of MF colloid template, subsequently vacuum drying 48 hours;Finally, be dried is compound The slide of PLGA/SWCNTs/MF casting films immerses in the hydrochloric acid solution of 1mol/L, after 1.5 hours, MF microsphere dissolves, and slide and PLGA/MWCNTs casting films completely disengage from, and fully clean casting films, Then it is vacuum dried, obtains the membranaceous PLGA/MWCNTs functionalization of circle that thickness is 0.0034cm multiple Close porous material.
Porous material quality m in the present embodiment is about 0.001g, radius r and is about 0.5cm, thickness h It is about 0.0034cm, ρbFor 1.25g/cm3.Being computed, the porosity of porous material in the present embodiment is 70.1%.
PLGA/SWCNTs functionalization composite porous material pattern in the present embodiment as shown in Figure 6, is schemed The scanning electron microscope of the PLGA/SWCNTs functionalization composite porous material that 6 obtain for the embodiment of the present invention 3 Figure.It will be appreciated from fig. 6 that the aperture of PLGA/SWCNTs functionalization composite porous material is in the present embodiment 7μm。
Measuring (Bei Shide instrument) through specific surface instrument, in the present embodiment, PLGA/SWCNTs functionalization is multiple The specific surface area closing porous material is 0.1~0.3m2/g。
The present invention uses universal testing machine (INSTRON 3365) to test in the present embodiment The mechanical performance of PLGA/SWCNTs functionalization composite porous material, its tensile break stress is 3.8MPa, Elongation at break is 69.3%.
The above is only the preferred embodiment of the present invention, it is noted that general for the art For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims (10)

1. a preparation method for functionalization composite porous material, comprises the following steps:
A) pore creating material suspension is laid in carrier surface, obtains being attached to the pore-creating of carrier surface after drying Agent template;
B) Matrix Solution is taped against in described pore creating material template, obtains compound casting films after drying;
Described Matrix Solution includes matrix material, CNT and solvent;
Described matrix material includes in PLGA, polylactic acid, fibroin albumen and chitosan One or more;
C) described compound casting films is immersed in acid solution, obtain functionalization composite porous material.
Preparation method the most according to claim 1, it is characterised in that described pore creating material suspension selects From melamine resin microsphere suspension liquid.
Preparation method the most according to claim 2, it is characterised in that in described pore creating material suspension The particle diameter of pore creating material is 100~10000nm.
Preparation method the most according to claim 1, it is characterised in that described pore creating material suspension Mass concentration is 3~5%.
Preparation method the most according to claim 1, it is characterised in that poly-breast in described Matrix Solution The mass concentration of acid ethanol copolymer is (0.06~0.14) g/mL.
Preparation method the most according to claim 4, it is characterised in that described CNT and poly-breast The mass ratio of acid ethanol copolymer is (0.1~1): 100.
Preparation method the most according to claim 1, it is characterised in that described solvent is oxolane Mixed solution, hexafluoroisopropanol or chloroform with dimethylformamide;
Described oxolane and oxolane in the mixed solution of dimethylformamide and dimethylformamide Volume ratio is (1~5): 1.
Preparation method the most according to claim 1, it is characterised in that described poly (lactic acid-glycolic acid) is altogether Polymers is (2~3) with the volume ratio of pore creating material in pore creating material suspension: 1.
9. according to the preparation method described in claim 1~8 any one, it is characterised in that described step B) particularly as follows:
Matrix Solution is taped against in pore creating material template, obtains hygrometric state casting films, then described hygrometric state is cast Film vibrates, and obtains compound casting films after drying.
Preparation method the most according to claim 9, it is characterised in that the time of described vibration is 10~60min.
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