CN101812157B - Synthesis method of polymeric (N-isopropyl acrylamide)/attapulgite composite hydrogel - Google Patents
Synthesis method of polymeric (N-isopropyl acrylamide)/attapulgite composite hydrogel Download PDFInfo
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- CN101812157B CN101812157B CN201010142502XA CN201010142502A CN101812157B CN 101812157 B CN101812157 B CN 101812157B CN 201010142502X A CN201010142502X A CN 201010142502XA CN 201010142502 A CN201010142502 A CN 201010142502A CN 101812157 B CN101812157 B CN 101812157B
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Abstract
The invention discloses a synthesis method of polymeric (N-isopropyl acrylamide)/attapulgite composite hydrogel, which comprises the following steps of: putting attapulgite, cetyl trimethyl ammonium bromide and distilled water into a reactor to supersonically process for 24h according to the mass ratio of (5-2):1:(100-200); washing upper layer suspension liquid with alcohol and water; drying under the temperature of 70 DEG C to obtain modified attapulgite; dispersing the attapulgite into the distilled water to prepare 0.02-0.03g/mL dispersion liquid; dissolving the 0.1-0.8mL of attapulgite dispersion liquid, 0.5-1.5g of N-isopropyl acrylamide and 10-20mg of N-N'methylene bisacrylamide distilled water; entering nitrogen for 20-50min; adding ammonium persulfate/sodium pyrosulfite, the weight of which is 0.4-0.5% of that of the N-isopropyl acrylamide; polymerizing in thermostatic water bath at 25 DEG C for 24h to obtain gel; and dipping the gel with distilled water under room temperaturefor 3-5d to obtain the composite hydrogel. The composite hydrogel is induced with the attapulgite in PNIPAM, thereby improving the water absorbability and the bore diameter of the PNIPAM, improving the swelling ratio, and being good for embedding and absorbing the medicine.
Description
Technical field
The present invention relates to the synthetic method of chemical field, be specifically related to a kind of synthetic method of poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel.
Background material
In recent years, organic/inorganic composite material becomes the focus of material science research.Attapulgite (Attapulgite as the desirable strongthener of macromolecular material, ATP), it belongs to sepiolite group, be transformed by montmorillonite, it is silicate minerals with moisture magnalium of typical layers chain-like structure, be a kind of natural monodimension nanometer material, have features such as specific surface area is big, chemical stability good, high adsorption capacity.Recent decades, attapulgite clay has had widely at industry fields such as building materials, agricultural chemicals, chemical fertilizer, chemical industry sorbent material, catalyzer, sewage disposal, printing, coating, binding agent, sun power, oil, plastics to be used.Because the good absorption property of attapulgite, greatly developed at pharmaceutical sector, occur in succession with attapulgite and similar mineral product, and carried out deep research at preparation, pharmacology and clinicing aspect as medicinal raw material.
Along with biomedical researchdevelopment, the preparation of functional organic/inorganic composite material more and more is subjected to people's attention.Poly-(N-N-isopropylacrylamide) (PNIPAM) phase transition temperature of gel about 32 ℃, approaching with human body temperature, become the focus of present biomedical sector research.Yet PNIPAM is relatively poor as its water-absorbent of modal temperature-sensitive hydrogel, and not high its Application Areas that makes of equilibrium swelling rate is restricted.Therefore, improve the water-absorbent of PNIPAM gel, improve its swelling ratio and have important practical significance.
Summary of the invention
The objective of the invention is to: the synthetic method that a kind of poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel is provided, the composite aquogel that is obtained by this synthetic method is an attapulgite of introducing high adsorption capacity in PNIPAM, improved the water-absorbent of PNIPAM, and increased the wide aperture, improved the swelling ratio of PNIPAM, help embedding and absorption, thereby widen the range of application of PNIPAM medicine.
Technical solution of the present invention is that the step of this synthetic method is as follows:
1, with exsiccant attapulgite, tensio-active agent cetyl trimethylammonium bromide, distilled water by mass ratio (5-2): 1: (100-200) place reactor, magnetic agitation, ultrasonic 24h, discard the reactor bottom deposited material, the upper strata steady suspension earlier with ethanol again the water centrifuge washing drip to the clear liquid of upper strata till the 0.1mol/L silver nitrate solution do not have a white precipitate, 70 ℃ of oven dry in vacuum drying oven at last, grinding is sieved, and obtains organically-modified attapulgite (org-ATP);
2, with above-mentioned org-ATP ultra-sonic dispersion in distilled water, making concentration is the org-ATP dispersion liquid of 0.02-0.03g/ml, attapulgite dispersion liquid, 0.5-1.5g N-N-isopropylacrylamide (NIPAM) and the 10-20mg N-N ' methylene-bisacrylamide (MBA) of 0.1-0.8ml are made its dissolving with the redistilled water stirring, and logical nitrogen 20-50min removes the oxygen in the system;
3, according to N-N-isopropylacrylamide meter, add ammonium persulphate (SPS)/Sodium Pyrosulfite (APS) of the 0.4%-0.5% of its quality, with reactor sealing, stir, put into temperature and be 25 ℃ constant temperature water bath, initiated polymerization, polymerization time 24h;
4, reaction finishes, and the gained gel is at room temperature used distilled water immersion 3-5d, changes first water every 6-8h,, is gathered (N-N-isopropylacrylamide)/attapulgite composite hydrogel at last to remove unreacted monomer, initiator.
The present invention has the following advantages:
1, solved the shortcoming that conventional P NIPAM temperature-sensitive hydrogel water-absorbent is poor, swelling ratio is low, set about, synthesized the temperature-sensitive macromolecular material that a series of apertures are big, adsorptive capacity is high based on attapulgite from the selection of function monomer.
2, poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel preparation method is safe and reliable, simple to operate, and material is easy to get, the reaction conditions gentleness, and reaction medium is a water, aftertreatment is easy.
Description of drawings
Fig. 1 is the swelling kinetics figure (ATP and NIPAM mass ratio be 0.0084: 1,0.014: 1,0.0196: 1, prepared hydrogel respectively be designated as PA01, PA02, PA03) of hydrogel under 25 ℃.
Fig. 2 for poly-(N-N-isopropylacrylamide) (A) and the sem photograph (SEM) of poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel (B).
Embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is restriction to technical solution.
Embodiment 1: synthesize poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel according to following steps:
1, exsiccant attapulgite, tensio-active agent cetyl trimethylammonium bromide, distilled water are placed reactor by mass ratio at 5: 1: 200, magnetic agitation, ultrasonic 24h, discard the reactor bottom deposited material, the upper strata steady suspension earlier with ethanol again the water centrifuge washing drip to the clear liquid of upper strata till the 0.1mol/L silver nitrate solution do not have a white precipitate, 70 ℃ of oven dry in vacuum drying oven at last, grinding is sieved, and obtains organically-modified attapulgite (org-ATP);
2, with above-mentioned org-ATP ultra-sonic dispersion in distilled water, making concentration is the org-ATP dispersion liquid of 0.02g/ml, attapulgite dispersion liquid, 0.5g N-N-isopropylacrylamide (NIPAM) and the 10mg N-N ' methylene-bisacrylamide (MBA) of 0.8ml are made its dissolving with the redistilled water stirring, and logical nitrogen 20min removes the oxygen in the system;
3, according to N-N-isopropylacrylamide meter, add ammonium persulphate (SPS)/Sodium Pyrosulfite (APS) of 0.4% of its quality, with the reactor sealing, stir, put into temperature and be 25 ℃ constant temperature water bath, initiated polymerization, polymerization time 24h;
4, reaction finishes, and the gained gel is at room temperature used distilled water immersion 3d, changes first water every 6h,, is gathered (N-N-isopropylacrylamide)/attapulgite composite hydrogel at last to remove unreacted monomer, initiator.
Embodiment 2: synthesize poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel according to following steps:
1, exsiccant attapulgite, tensio-active agent cetyl trimethylammonium bromide, distilled water are placed reactor by mass ratio at 3.5: 1: 150, magnetic agitation, ultrasonic 24h, discard the reactor bottom deposited material, the upper strata steady suspension earlier with ethanol again the water centrifuge washing drip to the clear liquid of upper strata till the 0.1mol/L silver nitrate solution do not have a white precipitate, 70 ℃ of oven dry in vacuum drying oven at last, grinding is sieved, and obtains organically-modified attapulgite (org-ATP);
2, with above-mentioned org-ATP ultra-sonic dispersion in distilled water, making concentration is the org-ATP dispersion liquid of 0.025g/ml, attapulgite dispersion liquid, 1.0g N-N-isopropylacrylamide (NIPAM) and the 15mg N-N ' methylene-bisacrylamide (MBA) of 0.5ml are made its dissolving with the redistilled water stirring, and logical nitrogen 35min removes the oxygen in the system;
3, according to N-N-isopropylacrylamide meter, add ammonium persulphate (SPS)/Sodium Pyrosulfite (APS) of 0.45% of its quality, with the reactor sealing, stir, put into temperature and be 25 ℃ constant temperature water bath, initiated polymerization, polymerization time 24h;
4, reaction finishes, and the gained gel is at room temperature used distilled water immersion 4d, changes first water every 7h,, is gathered (N-N-isopropylacrylamide)/attapulgite composite hydrogel at last to remove unreacted monomer, initiator.
Embodiment 3: synthesize poly-(N-N-isopropylacrylamide)/attapulgite composite hydrogel according to following steps:
1, exsiccant attapulgite, tensio-active agent cetyl trimethylammonium bromide, distilled water are placed reactor by mass ratio at 2: 1: 100, magnetic agitation, ultrasonic 24h, discard the reactor bottom deposited material, the upper strata steady suspension earlier with ethanol again the water centrifuge washing drip to the clear liquid of upper strata till the 0.1mol/L silver nitrate solution do not have a white precipitate, 70 ℃ of oven dry in vacuum drying oven at last, grinding is sieved, and obtains organically-modified attapulgite (org-ATP);
2, with above-mentioned org-ATP ultra-sonic dispersion in distilled water, making concentration is the org-ATP dispersion liquid of 0.03g/ml, attapulgite dispersion liquid, 1.5g N-N-isopropylacrylamide (NIPAM) and the 20mg N-N ' methylene-bisacrylamide (MBA) of 0.1ml are made its dissolving with the redistilled water stirring, and logical nitrogen 50min removes the oxygen in the system;
3, according to N-N-isopropylacrylamide meter, add ammonium persulphate (SPS)/Sodium Pyrosulfite (APS) of 0.5% of its quality, with the reactor sealing, stir, put into temperature and be 25 ℃ constant temperature water bath, initiated polymerization, polymerization time 24h;
4, reaction finishes, and the gained gel is at room temperature used distilled water immersion 5d, changes first water every 8h,, is gathered (N-N-isopropylacrylamide)/attapulgite composite hydrogel at last to remove unreacted monomer, initiator.
As can be seen from Figure 1: composite aquogel is compared with homopolymerization PNIPAM hydrogel, and the adding of recessed soil has improved the water absorption and swelling rate (SR) of PNIPAM significantly, and along with the increase of recessed native content, the swelling of composite aquogel takes the lead in increasing remarkable back and changes less; As can be seen from Figure 2: have shallow and the blind hole hole in the PNIPAM hydrogel, but composite aquogel exists tangible channel architecture,, thereby help the diffusion of water molecules like this for the water molecules turnover provides the path.
Claims (1)
1. gather the synthetic method of (N-N-isopropylacrylamide)/attapulgite composite hydrogel, it is characterized in that the step of this synthetic method is as follows:
(1), with exsiccant attapulgite, tensio-active agent cetyl trimethylammonium bromide, distilled water by mass ratio (5-2): 1: (100-200) place reactor, magnetic agitation, ultrasonic 24h, discard the reactor bottom deposited material, the upper strata steady suspension earlier with ethanol again the water centrifuge washing drip to the clear liquid of upper strata till the 0.1mol/L silver nitrate solution do not have a white precipitate, 70 ℃ of oven dry in vacuum drying oven at last, grinding is sieved, and obtains organically-modified attapulgite;
(2), with above-mentioned organically-modified attapulgite ultra-sonic dispersion in distilled water, making concentration is the organically-modified attapulgite dispersion liquid of 0.02-0.03g/ml, attapulgite dispersion liquid, 0.5-1.5g N-N-isopropylacrylamide NIPAM and 10-20mg N-N ' the methylene-bisacrylamide MBA of 0.1-0.8ml are made its dissolving with the redistilled water stirring, and logical nitrogen 20-50min removes the oxygen in the system;
(3), according to N-N-isopropylacrylamide meter, add ammonium persulphate/Sodium Pyrosulfite of the 0.4%-0.5% of its quality, with reactor sealing, stir, put into temperature and be 25 ℃ constant temperature water bath, initiated polymerization, polymerization time 24h;
(4), reaction finishes, and the gained gel is at room temperature used distilled water immersion 3-5d, changes first water every 6-8h,, gathered (N-N-isopropylacrylamide)/attapulgite composite hydrogel at last to remove unreacted monomer, initiator.
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| CN103480347A (en) * | 2013-10-11 | 2014-01-01 | 天津汉晴环保科技有限公司 | Preparation method of composite flat membrane for adsorbing heavy metal ions and product thereof |
| CN103554328A (en) * | 2013-10-17 | 2014-02-05 | 滁州友林科技发展有限公司 | Method for preparing pH sensitive hydrogel for adsorbing heavy metal ions and product thereof |
| CN103524671A (en) * | 2013-10-17 | 2014-01-22 | 滁州友林科技发展有限公司 | Method for preparing thermosensitive hydrogel for adsorbing heavy metal ions and product thereof |
| CN103524674A (en) * | 2013-10-17 | 2014-01-22 | 滁州友林科技发展有限公司 | Method for preparing composite hydrogel for adsorbing heavy metal ions and product thereof |
| CN103724569B (en) * | 2013-12-23 | 2015-10-28 | 杨立新 | A kind of Polymer attapulgite plural gel and preparation method thereof |
| CN104163886A (en) * | 2014-03-14 | 2014-11-26 | 淮阴师范学院 | Synthetic method of attapulgite (ATP)-based magnetic temperature-sensitive composite material |
| CN104971632B (en) * | 2015-07-29 | 2017-04-12 | 淮阴师范学院 | Easy-to-wash PVDF (polyvinylidene fluoride) ultrafiltration membrane and preparation method thereof |
| CN107051341B (en) * | 2017-04-25 | 2020-03-17 | 淮阴师范学院 | Preparation method of composite hydrogel with optical temperature sensitivity |
| CN108948624B (en) * | 2018-07-24 | 2020-05-22 | 四川大学 | SBCs/PNIPAM composite material with interpenetrating polymer network structure and preparation method thereof |
| CN109528767A (en) * | 2018-12-20 | 2019-03-29 | 江苏经贸职业技术学院 | A kind of synthetic method based on PNIPAM Yu silver nanoclusters antibiotic preparation |
| CN109970917A (en) * | 2019-04-04 | 2019-07-05 | 黑龙江大学 | A kind of super absorbent resin and preparation method thereof containing montmorillonite |
| CN112113690B (en) * | 2019-06-21 | 2021-12-10 | 清华大学 | Hydrogel composite and preparation method thereof |
| CN111514095B (en) * | 2020-04-29 | 2023-03-14 | 淮阴师范学院 | Target magnetic temperature-sensitive microgel based on attapulgite, synthetic method and application thereof |
| CN112315976B (en) * | 2020-11-16 | 2022-10-11 | 山西大同大学 | Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof |
| CN112480592B (en) * | 2020-11-20 | 2023-03-21 | 杭州巨星科技股份有限公司 | Wear-resistant knife handle rubber coating material |
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| CN1884117A (en) * | 2006-06-29 | 2006-12-27 | 兰州大学 | Attapulgite/polyacrylamide nano composite flocculant and method for preparing same |
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