CN102181145A - PluronicF127-micro-porous polyurethane (PU) film as well as preparation method and application thereof - Google Patents

PluronicF127-micro-porous polyurethane (PU) film as well as preparation method and application thereof Download PDF

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Publication number
CN102181145A
CN102181145A CN 201110043876 CN201110043876A CN102181145A CN 102181145 A CN102181145 A CN 102181145A CN 201110043876 CN201110043876 CN 201110043876 CN 201110043876 A CN201110043876 A CN 201110043876A CN 102181145 A CN102181145 A CN 102181145A
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urethane
pluronic
dmso
film
porous membrane
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沈健
毛春
陈晓寒
侯小妹
王晓波
孙冲
黄晓华
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Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention discloses a PluronicF127-micro-porous polyurethane (PU) film as well as a preparation method and an application thereof. The preparation method comprises the following steps: taking dimethyl sulfoxide (DMSO) as a solvent, mixing PU with PluronicF127 for dissolution, adding water so that the obtained mixture is subjected to phase separation, adding NaC1 crystal particles, evenly stirring and leading the mixture into a die; and cooling, taking the mixed solution of water and ethanol as a medium, removing the NaC1 and the DMSO, and drying to obtain the PU film. The preparation method has the advantages of simple operation process route, less energy consumption and no pollution, thus providing an idea for preparing a novel PU composite material. The prepared PluronicF127-micro-porous PU film has the advantages of good biocompatibility and no adhesion behavior found in experiments for contact between the film as well as platelets and hemocytes, thus the PluronicF127-micro-porous PU film can be applied to preparing biological medical materials.

Description

Little porous membrane of a kind of PluronicF127-urethane and its production and application
Technical field
The present invention relates to prepare the method for the little porous membrane of Pluronic F127-urethane in different apertures with salting-out process and phase separation method, with and in the application of biomedical sector.
Technical background
From the 1950's the urethane first Application since biomedicine, medical polyurethane material is because have ideal histocompatibility and blood compatibility, good toughness, solvent resistance, hydrolytic resistance, anti-microorganism property, nontoxicity, and it is wear-resistant, cohesiveness, anti-excellent properties such as deflect, and easy forming process, thereby promoted urethane at medically extensive use, as the fracture repair material, vascular operation is sewed up with replenishing coating etc., to the eighties, succeed with polyurethane elastomer manufacture of intraocular heart transplant operation, make the application of polyurethane material on biomedicine obtain further development, in recent years, along with the progress of science and technology and the raising of research level, new medical polyurethane material continues to bring out, and the performance of goods is also constantly perfect.
Pluronic is the trade(brand)name of polyoxyethylene-polyoxygenated third rare-polyoxyethylene (PEO-PPO-PEO) triblock copolymer, and it is typical amphipathic multipolymer.In recent years, Pluronic is because have good albumen resistance and biocompatibility and a lower synthetic cost thereof, so aspect bio-medical materials such as organizational project, medical device many application is arranged all.Pluronic F127 is that molecular weight is 12600 PEO-PPO-PEO triblock copolymer among the Pluronic.
The present invention has prepared a kind of novel little porous film material of Pluronic F127-urethane by simple high polymer material composite hybridization approach.The participation hydridization of Pluronic F127, make the physiologically acceptable performance of matrix material be better than former composition material and satisfy higher bio-medical requirement, though it is existing at present with Pluronic F127 and polyurethane hybrid research together, but only limit to the film of surfacing, but not little vesicular structure hybrid film material that the present invention proposes.The meaning of the little porous form of film is to provide the diffusion of film both sides material to exchange.For example, when being prepared into artificial blood vessel,, can form the exchange of the inside and outside physiological solution of this artificial blood vessel in the human body planted agent time spent with this little vesicular structure hybrid film.Thereby expanded the biomedical applications scope of Pluronic F127 and urethane.
Summary of the invention
Necessity and importance at little porous film material preparation of Pluronic F127-urethane mentioned in the above-mentioned technical background and application, the object of the invention is to provide the preparation of the little porous film material of a kind of advantages of simplicity and high efficiency Pluronic F127-urethane, and applies it among the fields such as biomedicine.Technical scheme of the present invention is as follows:
To saltout and the little porous film material of Pluronic F127-urethane in the synthetic different apertures of phase separation process method.
Concrete technology approach is: with dimethyl sulfoxide (DMSO) (Dimethyl sulfoxide, DMSO) be solvent, in 30 ~ 80 ℃ of temperature ranges with urethane and Pluronic F127(mass ratio from 99:1 in the 90:10 scope) fully dissolving, adding quality then is the water of above-mentioned system (DMSO-urethane-Pluronic F127) 1-5%, make said mixture be separated, (quality is 4-8 a times of urethane quality to add sodium-chlor (NaCl) crystal fine particle again, in advance through grinding, high temperature drying), through stirring, mould is inserted in guiding.After the cooling, be medium, remove NaCl and DMSO, after the drying, can obtain the little porous membrane of Pluronic F127-urethane in different apertures (100-200 μ m) with water and alcohol mixed solution.
The little porous membrane of Pluronic F127-urethane of the present invention has excellent biological compatibility, contacts experiment with thrombocyte, hemocyte, finds no adhesion behavior, can be applicable to prepare bio-medical material.
Description of drawings
Fig. 1 is the little porous membrane scanning electron microscope of Pluronic F127-urethane (SEM) figure.
Fig. 2 is the infrared figure of the little porous membrane of Pluronic F127-urethane.
Fig. 3 is Pluronic F127-urethane little porous membrane platelet adhesion reaction experimental result scanning electron microscope of the present invention (SEM) figure, and wherein B is the partial enlarged drawing of A.
Fig. 4 is platelet adhesion reaction experimental result scanning electron microscope (SEM) figure of urethane flat film.
Fig. 5 is that the little porous membrane whole blood of Pluronic F127-urethane of the present invention sticks experimental result scanning electron microscope (SEM) figure, and wherein B is the partial enlarged drawing of A.
Fig. 6 is that the whole blood of urethane flat film sticks experimental result scanning electron microscope (SEM) figure.
Specific implementation method
Following examples are in order to explanation the present invention, and non-limiting its scope.
Embodiment 1, the little porous membrane of Pluronic F127-urethane stop platelet adhesion reaction
The DMSO and the 0.1 gram Pluronic F127 that in reaction flask, add 15 milliliters, 9.9 gram urethane, under 30 degrees centigrade, mechanical stirring to urethane becomes homogeneous phase (both mass ratioes are 99:1) with Pluronic F127.Adding quality then is the water of above-mentioned system (DMSO-urethane-Pluronic F127) 1%, stir after 3 hours, (quality is 4 times of urethane quality to add sodium-chlor (NaCl) crystal fine particle, in advance through grinding, high temperature drying), stop when continuing to be stirred to system, reactant is poured out, make desired shape than thickness.Be medium with water and alcohol mixed solution again, remove NaCl and DMSO, promptly obtaining the aperture after the drying is the little porous membrane of Pluronic F127-urethane of 100 μ m, its surface topography as shown in Figure 1, Fig. 2 is its infrared spectrum.This film is placed on 37 ℃ to be rich in the hematoblastic blood plasma and to soak 3 hours, after sample usefulness physiological saline rinsing 3 times, in 2.5% glutaraldehyde solution, soaked 24 hours, fixedly be attached on the thrombocyte on the sample, take out sample, be 55%, 70%, 80% in volume fraction successively, 90%, soaked 30 minutes in 95%, 100% ethanolic soln, dewater step by step.By scanning electron microscope observation, film surface does not have platelet adhesion reaction phenomenon (Fig. 3).
As blank reference sample, carry out same platelet adhesion reaction experiment with the urethane flat film of not adding Pluronic F127, the result shows that there is a large amount of platelet adhesion reaction (Fig. 4) on blank reference sample surface.The effect of Pluronic F127 as additive has been described thus, can have effectively improved the blood compatibility of urethane.
Embodiment 2, the little porous membrane of Pluronic F127-urethane stop hemocyte to stick
The DMSO and the 1 gram Pluronic F127 that add 15 milliliters in reaction flask, 9 gram urethane, under 80 degrees centigrade, mechanical stirring to urethane is 90:10 with Pluronic F127(mass ratio) become homogeneous phase.Adding quality again is the water of above-mentioned system (DMSO-urethane-Pluronic F127) 5%, stir and add sodium-chlor (NaCl) crystal fine particle after 3 hours (quality is 8 times of urethane quality, in advance through grinding, high temperature drying), system stops when fading to than thickness, reactant is poured out made desired shape.Be medium with water and alcohol mixed solution again, remove NaCl and DMSO, promptly obtaining the aperture after the drying is the little porous membrane of Pluronic F127-urethane of 200 μ m.This film is placed in 37 ℃ the whole blood and soaked 30 minutes, after sample usefulness physiological saline rinsing 3 times, in 2.5% glutaraldehyde solution, soaked 24 hours, fixedly be attached on the hemocyte on the sample, take out sample, be 55%, 70%, 80% in volume fraction successively, 90%, soaked 30 minutes in 95%, 100% ethanolic soln, dewater step by step.By scanning electron microscope observation, the film surface achroacyte sticks phenomenon (Fig. 5).
, carry out same whole blood and stick experiment as blank reference sample with the urethane flat film of not adding Pluronic F127, the result shows that blank reference sample surface has a large amount of hemocytes to stick (Fig. 6).The effect of Pluronic F127 as additive has been described thus, can have effectively improved the blood compatibility of urethane.
Embodiment 3, the little porous membrane of Pluronic F127-urethane prepare artificial blood vessel
The DMSO and the 1 gram Pluronic F127 that in reaction flask, add 15 milliliters, 10 gram urethane, mechanical stirring to Pluronic F127 urethane becomes homogeneous phase.Add 0.75 gram water then, stir the sieve that adds 78 ground gram NaCl(90 microns after 3 hours), system stops when fading to than thickness, pours reactant into rider and becomes conduit with Mold Making.Be medium with water and alcohol mixed solution again, remove NaCl and DMSO, promptly obtain the little porous artificial blood vessel of Pluronic F127-urethane in required aperture after the drying.

Claims (4)

1. little porous membrane of Pluronic F127-urethane, it is characterized by by the following method and make: be solvent with the dimethyl sulfoxide (DMSO), with urethane and Pluronic F127 mixed dissolution, add entry then, make said mixture be separated, add the NaCl crystal fine particle again, through stirring, mould is inserted in guiding; After the cooling, be medium, remove NaCl and dimethyl sulfoxide (DMSO), after the drying, can obtain the little porous membrane of Pluronic F127-urethane in 100-200 μ m aperture with water and alcohol mixed solution.
2. the little porous membrane of Pluronic F127-urethane according to claim 1, it is characterized in that specifically: be solvent with the dimethyl sulfoxide (DMSO), in 30 ~ 80 ℃ of temperature ranges being 99:1 with mass ratio fully dissolves to urethane and the Pluronic F127 of 90:10, adding quality then is the water of above-mentioned dimethyl sulfoxide (DMSO)-urethane-Pluronic F127 system 1-5%, make mixture be separated, the 4-8 sodium chloride crystal particulate doubly that adds the urethane quality again, through stirring, mould is inserted in guiding; After the cooling, be medium with water and alcohol mixed solution, remove sodium-chlor and dimethyl sulfoxide (DMSO), after the drying, can obtain different apertures is the little porous membrane of Pluronic F127-urethane of 100-200 μ m.
3. the little porous membrane of Pluronic F127-urethane according to claim 1 is as the purposes of bio-medical material.
4. the application of the little porous membrane of Pluronic F127-urethane according to claim 1 in the preparation artificial blood vessel.
CN 201110043876 2011-02-24 2011-02-24 PluronicF127-micro-porous polyurethane (PU) film as well as preparation method and application thereof Pending CN102181145A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103349796A (en) * 2013-01-29 2013-10-16 吉林大学 Degradable bone regeneration guidance biomembrane, preparation method and application thereof
CN103524734A (en) * 2013-10-11 2014-01-22 南京师范大学 Polypyrrole-F127 nano composite and application thereof in preparation of electrochemical sensor for whole blood detection
CN106079497A (en) * 2016-08-19 2016-11-09 昆山华富新材料股份有限公司 Salting out method prepares the method for microporous polyurethane thin film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429287A (en) * 2008-11-28 2009-05-13 南京大学 Highly blood coagulation resistant cellulose membrane material and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101429287A (en) * 2008-11-28 2009-05-13 南京大学 Highly blood coagulation resistant cellulose membrane material and preparation method thereof

Non-Patent Citations (2)

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Title
《2010年海峡两岸功能性复合材料论坛论文集》 20101117 梁存霞 等 生物医用形状记忆聚氨酯材料的制备及其血液相容性研究 第1-4 1-4 , *
《化学进展》 20090831 姚响 等 可降解聚氨酯型组织工程多孔支架材料的制备 第1547-1551页 1-4 第21卷, 第7/8期 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103349796A (en) * 2013-01-29 2013-10-16 吉林大学 Degradable bone regeneration guidance biomembrane, preparation method and application thereof
CN103349796B (en) * 2013-01-29 2016-03-23 吉林大学 A kind of degradable Guided Bone Regeneration biomembrane and its preparation method and application
CN103524734A (en) * 2013-10-11 2014-01-22 南京师范大学 Polypyrrole-F127 nano composite and application thereof in preparation of electrochemical sensor for whole blood detection
CN106079497A (en) * 2016-08-19 2016-11-09 昆山华富新材料股份有限公司 Salting out method prepares the method for microporous polyurethane thin film
CN106079497B (en) * 2016-08-19 2018-06-19 昆山华富新材料股份有限公司 The method that salting out method prepares microporous polyurethane film

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Application publication date: 20110914