CN101942198B - Preparation method of porous silicon hydrogel interpenetrating network (IPN) membrane - Google Patents

Preparation method of porous silicon hydrogel interpenetrating network (IPN) membrane Download PDF

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CN101942198B
CN101942198B CN2010102732542A CN201010273254A CN101942198B CN 101942198 B CN101942198 B CN 101942198B CN 2010102732542 A CN2010102732542 A CN 2010102732542A CN 201010273254 A CN201010273254 A CN 201010273254A CN 101942198 B CN101942198 B CN 101942198B
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pdms
ipn
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membrane
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CN101942198A (en
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胡祖明
汤琦
于俊荣
陈蕾
诸静
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Donghua University
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Abstract

The invention relates to a preparation method of a porous silicon hydrogel interpenetrating network (IPN) membrane, which comprises the following steps: (1) respectively dissolving polyethylene glycol in CaCl2 solution and Na2CO3 solution, adding sodium lauryl sulfate to one solution, and adding the sodium lauryl sulfate to the other solution; (2) adding CaCO3 microspheric powder to aluminum-zirconium coupling agent aqueous solution; (3) dissolving dimethyl polysiloxane, tetraethyl orthosilicate and stannous octoate in isopropanol, and adding CaCO3 template particles to obtain a PDMS first network membrane; (4) adding isopropanol to a mixed liquor of hydroxyethyl methacrylate (HEMA), azoisobutyronitrile and N,N'-dimethylene diacrylamide; and soaking the first network membrane in the mixedliquor to obtain PDMS/PHEMA IPN; and (5) soaking the first network membrane in dilute hydrochloric acid, and carrying out oscillating with ultrasonic wave to obtain the porous silicon hydrogel IPN membrane. The method is simple and suitable for industrial production; and the IPN membrane has an interpenetrating porous structure, and has the advantages of favorable water-retaining property and high drug loading capacity.

Description

The preparation method of porous silicon hydrogel interpenetrating network (IPN) film
Technical field
The invention belongs to the preparation field of silicone hydrogel interpenetrating network (IPN) film, particularly relate to the preparation method of a kind of porous silicon hydrogel interpenetrating network (IPN) film.
Background technology
YSR 3286 (PDMS) material has good biocompatibility, stability and oxygen-permeable; Therefore; Have good application prospects as bio-medical material, but because the long-term embedded material of itself hydrophobic characteristic conduct can cause some detrimentally affects.Want to make PDMS to be applied even more extensively every field such as tissue filling, drug release, the introducing through hydrophilic component improves its surperficial wetting properties and is a kind of valid approach to the perviousness of water-soluble substances.
Through hydrogel PDMS being carried out modification can be realized by following several method: (1) makes the surface grafting of hydrogel at PDMS; (2) silicone-hydrogel copolymer systems; (3) the particle composites system of silicone-hydrogel; (4) interpenetrating(polymer)networks of silicone-hydrogel (IPN) system.Wherein, Silicone-hydrogel IPN is considered to obtain the valid approach the most of ideal silicone-hydrogel material at present; Its advantage concentrated area is embodied in through hydrogel component can effectively improve the surface hydrophilicity of PDMS and give its certain swelling behavior, and compares and have better stability with other each systems.
At present existingly the technology of preparing of silicone hydrogel interpenetrating network material is introduced hydrophilic hydrogel second through the mode of order IPN usually realize mutually in PDMS, and IPN a series of character relevant with wetting ability are all directly related with content with the character of hydrogel second network.But the hydrogel component content that this method can be introduced is very limited.From improving material water-retentivity and infiltrative angle, be easy to let us and expect another kind of material, just porous material.The special construction of porous material makes this type material in plurality of applications, demonstrate advantage.Especially in organizational project and drug release field, porousness has given this type material some special performances.After for example in the porous material implantable bioartificial body; Can be at material and organizational interface's place's healthy tissues through the hole growth that is interconnected; Thereby material and autologous tissue are integrally formed, avoid embedded material to be shifted over time, have very important significance in this orthopaedic surgical operations operation.In addition, the porousness of material makes it compare with non-porous material to have better water-retentivity and perviousness, more can adapt to the interior environmental facies of organism.Therefore, seeking a kind of preparation approach that obtains porous silicon hydrogel IPN is the challenge that we face.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of porous silicon hydrogel interpenetrating network (IPN) film, and this method is simple, is suitable for suitability for industrialized production; Gained PDMS/PHEMAIPN film has the vesicular structure of mutual perforation, well water-retentivity and stronger medicine carrying ability; Better biocompatibility.
The preparation method of a kind of porous silicon hydrogel interpenetrating network of the present invention (IPN) film comprises:
(1) CaCO 3The preparation of template
(PEG) is dissolved in CaCl with polyoxyethylene glycol 2In the solution, be designated as solution A; Polyoxyethylene glycol (PEG) is dissolved in Na 2CO 3In the solution, be designated as solution B; In said solution B, add sodium lauryl sulphate (SDS) thorough mixing, add fast said solution A afterwards, stir 1-2min and 20-30 ℃ still aging, promptly get CaCO 3The microballoon deposition, water washing and precipitating 4-6 time, drying;
(2) surface-treated of template particles
The preparation aluminum-zirconium coupling agent aqueous solution adds above-mentioned dried CaCO then 3The microballoon powder; Behind sonic oscillation, be warming up to 40-60 ℃ and continue constant temperature and stir 1-2h; Filtration, drying, grinding promptly obtain the CaCO through surface-treated 3Template particles;
(3) preparation of the PDMS first network film
YSR 3286 (PDMS), positive tetraethyl orthosilicate (TEOS) and stannous octoate are dissolved in Virahol, add the CaCO of step (2) gained 3Particle, and fully stirring is designated as mixture C; Petridish is adorned water to the 1/2-2/3 place; Mixture C slowly is poured on the water surface and with petridish seals; Room temperature condition reaction down obtained the PDMS first network film in 2-3 days; Adopt the Suo Shi extraction process to remove unreacted PDMS prepolymer monomer, then 40-60 ℃ of vacuum oven with normal hexane;
(4) formation of PDMS/PHEMA IPN
At methylacrylic acid-beta-hydroxy ethyl ester (HEMA), Diisopropyl azodicarboxylate (AIBN) and N, add Virahol wiring solution-forming D in N '-dimethylene bisacrylamide (MBAA) mixed solution; The dried PDMS first network film of step (3) is dipped in the solution D, treat that swelling reaches balance after, in the following reaction 2-5h of 60-90 ℃ of vacuum condition, be warming up to 90-100 ℃ again and keep 1-3h to make reacting completely, obtain PDMS/PHEMA IPN;
(5) eccysis of template
Above-mentioned PDMS/PHEMA IPN is dipped in the Hydrogen chloride, and sonic oscillation is also used deionized water wash under the room temperature condition, to remove the CaCO in the IPN film 3The microparticle template obtains porous IPN.
The molecular weight of polyoxyethylene glycol is 6000 in the said step (1).
CaCl in the said step (1) 2And Na 2CO 3Strength of solution is respectively 0.05-0.3M.
The mass ratio of PEG and SDS is 0.1-0.4 in the said step (1).
The concentration that the middle aluminum-zirconium coupling agent of said step (2) is mixed with the aqueous solution is 1%-4%.
The TEOS in the said step (3) and the mass ratio of PDMS prepolymer are 0.05-0.2; The mass ratio of stannous octoate and PDMS prepolymer is 0.01-0.05; The mass ratio of Virahol and PDMS is 0.4-0.8; CaCO 3The mass ratio of particle and PDMS is 0.05-0.2.
The concentration of AIBN and MBAA is respectively monomeric 0.1-0.3mol% of HEMA and 0.2-0.5mol% in the said step (4).
The mass ratio of HEMA and Virahol is 0.2-0.6 in the said step (4).
The concentration of Hydrogen chloride is 0.5-2wt% in the said step (5).
The present invention is with the CaCO after surface-treated 3Particle is a template, and it is joined in the mixed solution of PDMS prepolymer, TEOS, stannous octoate and Virahol, solidifies to obtain the PDMS first network film; Through the method for order IPN, the above-mentioned PDMS first network film is dipped in the mixed solution of HEMA monomer, linking agent, initiator, Virahol; After treating it swelling reaching balance in this second network monomer solution, heat up and accomplish the polymerization of second network; Gained IPN film is removed CaCO through overpickling 3Little template particles obtains corresponding porous PDMS/PHEMA IPN.
Beneficial effect
(1) preparing method's repeatability of the present invention is strong, and required production unit is simple, is suitable for scale operation;
(2) gained PDMS/PHEMAIPN film has the vesicular structure of mutual perforation, well water-retentivity and stronger medicine carrying ability;
(3) gained porous PDMS/PHEMAIPN proves to have better biocompatibility through the cytotoxicity test, has the potential using value as bio-medical material.
Description of drawings
Fig. 1 (a) CaCO 3Template reaches (b) porous IPN preparation principle;
Fig. 2 CaCO 3IPN product contrast before and after the granular formwork eccysis;
The SEM image of Fig. 3 PDMS/PHEMA IPN vesicular structure;
The infrared spectrogram of Fig. 4 PDMS and corresponding IPN product;
The process that Fig. 5 theophylline discharges from PDMS/PHEMA IPN sample;
The cell survival rate of Fig. 6 PDMS, atresia and porous PDMS/PHEMA-PDMAA IPN;
The situation of the porous PDMS/PHEMA IPN superficial cell growth that each time period microscopic examination of Fig. 7 is arrived.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing 0.3g PEG and be dissolved in 300ml 0.1M CaCl respectively 2With 0.1M Na 2CO 3In the solution, be designated as solution A and solution B respectively; In solution B, add 1.2g SDS thorough mixing; The solution A for preparing is joined in the solution B fast, stir 1min and still aging under 25 ℃ of conditions; Gained CaCO 3Microballoon deposition repeated water washing 5 times, drying for standby;
With the aluminum-zirconium coupling agent compound concentration is 2% aqueous solution, gets the first step gained CaCO 3The microballoon powder joins in this solution; After sonic oscillation is handled, gained suspension-s is poured in the there-necked flask, be warming up to 40 ℃ and continue constant temperature and stir 1h; Filtration, drying, grinding promptly obtain the CaCO through surface-treated 3Template particles;
4g PDMS, 0.4g TEOS, 0.12g stannous octoate are mixed, be dissolved in the 2.67g Virahol, add 0.4g CaCO 3Particle and abundant the stirring are designated as mixture C; Petridish is adorned water to 2/3 place, and mixture C slowly is poured on the water surface and with the petridish sealing, room temperature condition reaction down obtained the PDMS first network film in 3 days; Adopt the Suo Shi extraction process to remove unreacted PDMS prepolymer monomer with normal hexane; Place 60 ℃ of vacuum oven subsequent use the gained PDMS first network film;
Get 4g HEMA monomer, add AIBN, MBAA by the 0.2mol% of monomer ratio and 0.4mol% respectively, in this monomer mixed solution, add 9g Virahol wiring solution-forming D again; The 3rd step gained PDMS first network film is dipped in the solution D, treat that swelling reaches balance after, in 80 ℃ of vacuum conditions reaction 3h down, be warming up to 90 ℃ again and keep 2h to make reacting completely, obtain corresponding PDMS/PHEMA IPN;
Gained IPN is dipped in the Hydrogen chloride of 1wt%, under the room temperature condition sonic oscillation and with deionized water wash for several times to remove the CaCO in the IPN film 3Particle obtains corresponding porous IPN.Fig. 1 is the CaCO of present embodiment preparation 3Template particles and template prepare the schematic diagram of porous silicon hydrogel IPN.Fig. 2 is the contrast photo of PDMS/PHEMAIPN before and after the template eccysis of present embodiment preparation.Fig. 3 is the vesicular structure of the IPN of present embodiment preparation.
Embodiment 2
Take by weighing 0.2g PEG and be dissolved in 100ml 0.05M CaCl respectively 2With 0.05M Na 2CO 3In the solution, be designated as solution A and solution B respectively; In solution B, add 2g SDS thorough mixing; The solution A for preparing is joined in the solution B fast, stir 1min and still aging under 20 ℃ of conditions; Gained CaCO 3Microballoon deposition repeated water washing 4 times, drying for standby;
With the aluminum-zirconium coupling agent compound concentration is 1% aqueous solution, gets the first step gained CaCO 3The microballoon powder joins in this solution; After sonic oscillation is handled, gained suspension-s is poured in the there-necked flask, be warming up to 50 ℃ and continue constant temperature and stir 1.5h; Filtration, drying, grinding promptly obtain the CaCO through surface-treated 3Template particles;
4g PDMS, 0.2g TEOS, 0.04g stannous octoate are mixed, be dissolved in the 1.6g Virahol, add 0.2g CaCO 3Particle and abundant the stirring are designated as mixture C; Petridish is adorned water to 1/2 place, and mixture C slowly is poured on the water surface and with the petridish sealing, room temperature condition reaction down obtained the PDMS first network film in 2 days; Adopt the Suo Shi extraction process to remove unreacted PDMS prepolymer monomer with normal hexane.Place 40 ℃ of vacuum oven subsequent use the gained PDMS first network film;
Get 5g HEMA monomer, add AIBN, MBAA by the 0.1mol% of monomer ratio and 0.5mol% respectively, in this monomer mixed solution, add 12g Virahol wiring solution-forming D again; The 3rd step gained PDMS first network film is dipped in the solution D, treat that swelling reaches balance after, in 60 ℃ of vacuum conditions reaction 5h down, be warming up to 90 ℃ again and keep 3h to make reacting completely, obtain corresponding PDMS/PHEMA IPN;
Gained IPN is dipped in the Hydrogen chloride of 0.5wt%, under the room temperature condition sonic oscillation and with deionized water wash for several times to remove the CaCO in the IPN film 3The microparticle template obtains corresponding porous IPN.Fig. 4 is the infrared spectrogram of the PDMS/PHEMA IPN of pure component PDMS and present embodiment preparation.Fig. 5 is the porous PDMS/PHEMA IPN of the present embodiment preparation dispose procedure to theophylline.
Embodiment 3
Take by weighing 0.4g PEG and be dissolved in 400ml 0.3M CaCl respectively 2With 0.3M Na 2CO 3In the solution, be designated as solution A and solution B respectively; In solution B, add 1g SDS thorough mixing; The solution A for preparing is joined in the solution B fast, stir under 2min and the 30 ℃ of conditions still aging; Gained CaCO 3Microballoon deposition repeated water washing 6 times, drying for standby;
With the aluminum-zirconium coupling agent compound concentration is 4% aqueous solution, gets the first step gained CaCO 3The microballoon powder joins in this solution; After sonic oscillation is handled, gained suspension-s is poured in the there-necked flask, be warming up to 60 ℃ and continue constant temperature and stir 2h; Filtration, drying, grinding promptly obtain the CaCO through surface-treated 3Template particles;
4g PDMS, 0.8g TEOS, 0.2g stannous octoate are mixed, be dissolved in the 3.2g Virahol, add 0.8g CaCO 3Particle and abundant the stirring are designated as mixture C; Petridish is adorned water to 2/3 place, and mixture C slowly is poured on the water surface and with the petridish sealing, room temperature condition reaction down obtained the PDMS first network film in 3 days; Adopt the Suo Shi extraction process to remove unreacted PDMS prepolymer monomer with normal hexane.Place 50 ℃ of vacuum oven subsequent use the gained PDMS first network film;
Get 6g HEMA monomer, add AIBN, MBAA by the 0.3mol% of monomer ratio and 0.2mol% respectively, in this monomer mixed solution, add 10g Virahol wiring solution-forming D again; The 3rd step gained PDMS first network film is dipped in the solution D; After treating that swelling reaches balance,, be warming up to 100 ℃ again and keep 1h to make reacting completely, obtain corresponding PDMS/PHEMA IPN in the following reaction 2h of 90 ℃ of vacuum conditions;
Gained IPN is dipped in the Hydrogen chloride of 2wt%, under the room temperature condition sonic oscillation and with deionized water wash for several times to remove the CaCO in the IPN film 3Particle obtains corresponding porous IPN.Fig. 6 is the PDMS/PHEMA IPN of the PDMS first network film, atresia, and the test result of the porous IPN superficial cell surviving rate of present embodiment preparation.The situation that Fig. 7 grows for porous PDMS/PHEMA-PDMAAIPN Surface L 929 cells that the present embodiment that arrives through microscopic examination prepares.

Claims (5)

1. the preparation method of a porous silicon hydrogel interpenetrating network IPN film comprises:
(1) polyoxyethylene glycol PEG is dissolved in CaCl 2In the solution, be designated as solution A; Polyoxyethylene glycol PEG is dissolved in Na 2CO 3In the solution, be designated as solution B; In said solution B, add sodium lauryl sulphate SDS and mix, add said solution A afterwards, stir 1-2min and 20-30 ℃ still aging, promptly get CaCO 3The microballoon deposition, water washing and precipitating 4-6 time, drying; The mass ratio of said PEG and SDS is 0.1-0.4;
(2) the preparation aluminum-zirconium coupling agent aqueous solution adds above-mentioned dried CaCO then 3The microballoon powder; Behind sonic oscillation, be warming up to 40-60 ℃ and continue constant temperature and stir 1-2h; Filtration, drying, grinding promptly obtain the CaCO through surface-treated 3Template particles;
(3) YSR 3286 PDMS, positive tetraethyl orthosilicate TEOS and stannous octoate are dissolved in Virahol, add the CaCO of step (2) gained 3Particle, and stirring is designated as mixture C; Petridish is adorned water to the 1/2-2/3 place; Mixture C slowly is poured on the water surface and with petridish seals; Room temperature condition reaction down obtained the PDMS first network film in 2-3 days; Adopt the Suo Shi extraction process to remove unreacted PDMS prepolymer monomer, then 40-60 ℃ of vacuum oven with normal hexane; The mass ratio of said TEOS and PDMS prepolymer is 0.05-0.2; The mass ratio of said stannous octoate and PDMS prepolymer is 0.01-0.05; The mass ratio of said Virahol and PDMS is 0.4-0.8; Said CaCO 3The mass ratio of particle and PDMS is 0.05-0.2;
(4), add Virahol wiring solution-forming D in N '-dimethylene bisacrylamide MBAA mixed solution at methylacrylic acid-beta-hydroxy ethyl ester HEMA, Diisopropyl azodicarboxylate AIBN and N; The dried PDMS first network film of step (3) is dipped in the solution D, treat that swelling reaches balance after, in the following reaction 2-5h of 60-90 ℃ of vacuum condition, be warming up to 90-100 ℃ again and keep 1-3h, obtain PDMS/PHEMA IPN; The mass ratio of said HEMA and Virahol is 0.2-0.6; The concentration of said AIBN and MBAA is respectively monomeric 0.1-0.3mol% of HEMA and 0.2-0.5mol%;
(5) above-mentioned PDMS/PHEMA IPN is dipped in the Hydrogen chloride, sonic oscillation also with washing, obtains porous IPN under the room temperature condition.
2. the preparation method of a kind of porous silicon hydrogel interpenetrating network IPN film according to claim 1 is characterized in that: the molecular weight of polyoxyethylene glycol is 6000 in the said step (1).
3. the preparation method of a kind of porous silicon hydrogel interpenetrating network IPN film according to claim 1 is characterized in that: CaCl in the said step (1) 2And Na 2CO 3Strength of solution is respectively 0.05-0.3M.
4. the preparation method of a kind of porous silicon hydrogel interpenetrating network IPN film according to claim 1 is characterized in that: the concentration that the middle aluminum-zirconium coupling agent of said step (2) is mixed with the aqueous solution is 1%-4%.
5. the preparation method of a kind of porous silicon hydrogel interpenetrating network IPN film according to claim 1 is characterized in that: the concentration of Hydrogen chloride is 0.5-2wt% in the said step (5).
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