CN101735544A - PVA (polyvinyl alcohol) matrix poly-N-isopropyl acrylamide microgel and preparation method thereof - Google Patents
PVA (polyvinyl alcohol) matrix poly-N-isopropyl acrylamide microgel and preparation method thereof Download PDFInfo
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- CN101735544A CN101735544A CN200910117682A CN200910117682A CN101735544A CN 101735544 A CN101735544 A CN 101735544A CN 200910117682 A CN200910117682 A CN 200910117682A CN 200910117682 A CN200910117682 A CN 200910117682A CN 101735544 A CN101735544 A CN 101735544A
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Abstract
The invention discloses PVA (polyvinyl alcohol) matrix poly-N-isopropyl acrylamide microgel, which takes polyvinyl alcohol (PVA) as a matrix material and is prepared by comprising the following steps of: 1, dissolving PVA, adding nano-CaCO3, dispersing by ultrasonic wave to form a thin layer, and cooling for gelatinization; 2, placing the PVA thin layer into a glutaraldehyde solution for soaking to form a highly crosslinked network; and soaking and drying to obtain a porous PVA matrix carrying Na2SO3; 3, soaking the matrix into a monomer NIPAm water solution for polymerization; and 4, washing gel, removing impurities, and drying to obtain the PVA matrix poly-N-isopropyl acrylamide microgel. The microgel material is prepared by taking the PVA which has good biodegradability and biocompatibility as the matrix, can be used as materials, such as drug control release gel, temperature control optical switch in special environment and the like, or devices, and can be used as a reversible temperature control optical switch element in a thin film external form in a moist state.
Description
Technical field
The present invention relates to susceptibility macromolecule hydrogel technical field, particularly a kind of temperature sensitivity polyvinyl alcohol (PVA) matrix poly-N-isopropyl acrylamide microgel material the invention still further relates to this microgel preparation methods.
Background technology
The susceptibility macromolecule hydrogel is applied in many fields as material, for example, discharges separation membrane, light control material, biomaterial, organizational project etc. in controlled delivery of pharmaceutical agents.The biomedical applications of environment sensitive type macromole and hydrogel thereof more is reflected on medicine immobilization and the controllable release.Conventional way is: pharmaceutical pack is embedded in hydrogel or by in its microcapsule of making, the release rate of embedding medicinal can be realized via the regulation and control of gel volume.With matrix poly-N-isopropyl acrylamide (PNIPAm) is example, water soluble drug at room temperature is easy to be absorbed and enters in the swollen PNIPAm gel, after the gel preparation that carries medicine enters human body,, cause gel to shrink and extrude medicine and solvent because human body temperature is higher than its volume phase transition temperature.Dewatering medicament then is absorbed and immobilization when the gel volume transformation temperature is above, and when reducing temperature, the conformation of PNIPAm stretches, and dies down with the association of dewatering medicament, and medicine disengages via diffusion.By adjusting the volume phase transition temperature of carrier macromole or macromolecule hydrogel, can also realize the administration of body interior orientation, promptly local heating undergoes phase transition pharmaceutical carrier around target organ, discharges medicine.
With the carrier of temperature sensitivity macromolecule hydrogel network, become one of the focus in environment sensitive polymer applied research field as the medicine sustained release.Temperature sensitive drug delivery system can be accepted the variation of outside temperature and automatic adjustment release speed makes the concentration of drug molecule remain on proper level, and this point is extremely important, also is that the conventional medicament release vehicle can't be compared.There is lowest critical solution temperature (LCST) in particularly crosslinked poly N-isopropyl acrylamide (PNIPAm) as a kind of typical temperature-sensitive macromolecular hydrogel, when this temperature volume can take place and change mutually, has been widely used as the carrier of medicine sustained release.Yet crosslinked PNIPAm hydrogel can not biological degradation, does not also have biocompatibility, must remove in body with operating method after the use, but because it belongs to soft material, physical strength is very poor, brings very big difficulty to surgical operation; The temperature-responsive of next pure PNIPAm gel, i.e. the swelling of gel/contraction transformation depends on its size, and more little gel can show the fast more response of transformation mutually.Existing for this reason document is reported for work the relevant PNIPAm of raising gel as the performance of drug release carrier, comprises preparation organic/inorganic plural gel, and the synthetic down response fast of special conditions PNIPAm gel is by emulsion polymerization prepared PNIPAm microgel etc.The microgel of prior art for preparing is mainly as coatings additive(s) (Xing Honglong etc., number of patent application 200610118725.6), drug release carrier (Ding Jiandong etc., patent No. 200410017390.X), isolation technique (Li Hong etc., and preparation technology's relative complex number of patent application 200810150474.9) etc..
Summary of the invention
The purpose of this invention is to provide a kind of is matrix with the PVAC polyvinylalcohol biodegradable, that biocompatibility is good, polyvinyl alcohol (PVA) the matrix poly-N-isopropyl acrylamide microgel material of the method preparation by free yl solution polymerization makes it can be as material or device application such as temperature control optical switch in medicine sustained release gel and the particular surroundings.The invention still further relates to this microgel preparation methods.
Purpose of the present invention is achieved through the following technical solutions:
A kind of PVA matrix poly-N-isopropyl acrylamide microgel material is a body material with the PVAC polyvinylalcohol film, and poly-N-isopropyl acrylamide microgel is uniformly distributed on the PVA body material.
Described PVA matrix poly-N-isopropyl acrylamide microgel material is prepared from by following technological process:
A. with PVA 80 ℃ of dissolvings down in deionized water, stir and press nano-CaCO down
3With the PVA mass ratio be that 1: 10～3: 10 ratio adds nano-CaCO in solution
3, disperse in the ultrasonic wave, will contain nano-CaCO
3PVA solution move in the tetrafluoroethylene groove and to form the thick thin layer of 2-3mm, be cooled to 30 ℃ of gelation 24h;
B. the PVA thin layer of gelation places the glutaraldehyde solution of 15-20mL2wt% to soak 24h, makes it form highly cross-linked network; Then this cross-linked network is placed dilute hydrochloric acid to soak 1 all also thorough washing thoroughly to remove nano-CaCO
3With other impurity, then at the Na of 0.15wt%
2SO
3Soak 24h in the solution, vacuum-drying under the room temperature obtains being loaded with Na
2SO
3The porous PVA matrix;
C. this is loaded with Na
2SO
3The porous PVA matrix be dipped in the aqueous solution of monomer NIPAm, at 0.01～0.02g N, N '-methylene-bisacrylamide (MBAm) and 0.003-0.006g ammonium persulphate (APS) exist down, polyreaction 24h is carried out in nitrogen protection;
D. after reaction is finished, take out the gel thorough washing, to remove unreacted monomer and linking agent and other impurity, vacuum-drying at room temperature obtains the PVA matrix poly-N-isopropyl acrylamide microgel.
The size of described poly-N-isopropyl acrylamide microgel is by regulating the size control of micropore in the PVA matrix.
The present invention is a matrix with the PVAC polyvinylalcohol biodegradable, that biocompatibility is good, polyvinyl alcohol (PVA) the matrix poly-N-isopropyl acrylamide microgel material of the method preparation by free yl solution polymerization, can be as material or device application such as temperature control optical switch in medicine sustained release gel and the particular surroundings, under moisture state, with the film like profile as reversible temperature control optical switch element.
Utilize the temperature sensitivity PVA matrix poly-N-isopropyl acrylamide microgel material of prepared of the present invention to test in order to following means:
(temperature sensitivity of sample is represented than ESR by the equilibrium swelling of measuring under the differing temps (20-45 ℃): the xerogel sample that will weigh is dipped in the distilled water of differing temps for Infrared spectroscopy (FT-IR), scanning electron microscope analysis (SEM), thermogravimetic analysis (TGA) (TGA) and temperature sensitive property testing, respectively behind the abundant swelling 24h, take out gel, wipe its surperficial moisture rapidly away with filter paper and weigh, press ESR=(W
e-W
d)/W
dFormula is calculated at each temperature equilibrium swelling than ESR, W in the formula
eBe the quality of gel under this temperature, W
dIt is the quality of xerogel sample.In addition, the temperature sensitivity of sample also can be directly characterizes qualitatively with the method for digital photographing).By the resulting PVA matrix poly-N-isopropyl acrylamide microgel of the present invention, press C=(W
2-W
1)/W
1Calculate the relative content (C) of PNIPAm microgel, the results are shown in the following table.
The content of PNIPAm microgel in the table sample
The present invention has following advantage:
1. the present invention makes the PVA matrix poly-N-isopropyl acrylamide microgel material that makes have more application prospect owing to used Biodegradable material PVA.
2. the prepared micro-gel particles of the present invention does not independently exist, and is processed into cavernous biodegradable PVA sheeting but depend on, and is dispersed in the PVA matrix.
3. in the PVA matrix poly-N-isopropyl acrylamide microgel material of gained of the present invention, the size of poly-N-isopropyl acrylamide microgel and content can be by adjusting nano-CaCO
3Consumption control.
4. the PVA matrix poly-N-isopropyl acrylamide microgel material of gained of the present invention is not yielding under the complete swelling state, because in PVA matrix crosslinked, used excessive glutaraldehyde solution, so that the whole material that obtains has higher physical strength, be convenient to control and the operation.
5. the PVA matrix poly-N-isopropyl acrylamide microgel material of gained of the present invention, has and pure poly N-isopropyl acrylamide temperature sensitivity much at one between 30-33 ℃ from transparent to the transition temperature of opaque state.
6. the PVA matrix poly-N-isopropyl acrylamide microgel material of gained of the present invention can be made arbitrary shape, and its film thickness is easy to control, is particularly suitable for being used as temperature control optical switch in medicine sustained release gel and the particular surroundings.
Description of drawings
Fig. 1 is the infrared spectra synoptic diagram of microgel material of the present invention;
Fig. 2 is the sem photograph of microgel material of the present invention;
Fig. 3 is thermal weight loss data of the present invention, swelling power and temperature sensitivity curve data collection of illustrative plates;
Fig. 4 is the temperature sensitivity graphic representation of gel sample;
The mutually transformation of Fig. 5 PVA matrix poly-N-isopropyl acrylamide microgel (H2) in water is (transparent
Opaque) behavior figure.
Embodiment
Embodiment 1
1, with 2g PVA 80 ℃ of dissolvings down in the 20mL deionized water, stirs the nano-CaCO that in solution, adds 0.2g down
3, disperse 30min in the ultrasonic wave, make nano-CaCO
3Uniform distribution will contain nano-CaCO
3PVA solution move in the tetrafluoroethylene groove and to form the thick thin layer of 2-3mm, be cooled to 30 ℃ of gelation 24h.
2, the PVA thin layer of gelation soaks 24h in the glutaraldehyde solution of 30mL2wt%, makes it form highly cross-linked network.Then this cross-linked network is placed dilute hydrochloric acid to soak 1 week and thorough washing, thoroughly to remove nano-CaCO
3With other impurity.Then at the Na of 0.15wt%
2SO
3Soak 24h in the solution, vacuum-drying under the room temperature obtains being loaded with Na
2SO
3The porous PVA matrix.
3, this matrix is dipped in the aqueous solution of monomer NIPAm (0.500g), in the presence of MBAm (0.01g) and APS (0.003g), polyreaction 24h is carried out in nitrogen protection.
4, after reaction is finished, take out the gel thorough washing, to remove other impurity such as unreacted monomer and linking agent, vacuum-drying at room temperature obtains the PVA matrix poly-N-isopropyl acrylamide microgel.Product can characterize with means such as FT-IR, TEM, TG-DTA and digital photographings.
1, with 2g PVA 80 ℃ of dissolvings down in the 20mL deionized water, stirs the nano-CaCO that in solution, adds 0.6g down
3, disperse 40min in the ultrasonic wave.To contain nano-CaCO
3PVA solution move in the tetrafluoroethylene groove and to form the thick thin layer of 2-3mm, be cooled to 30 ℃ of gelation 24h.
2, the PVA thin layer of gelation soaks 24h in the glutaraldehyde solution of 30mL2wt%, makes it form highly cross-linked network.Then this cross-linked network is placed dilute hydrochloric acid to soak 1 all also thorough washing thoroughly to remove nano-CaCO
3With other impurity.Then at the Na of 0.15wt%
2SO
3Soak 24h in the solution, vacuum-drying under the room temperature obtains being loaded with Na
2SO
3The porous PVA matrix.
3, this matrix is dipped in the aqueous solution of monomer NIPAm (0.800g), in the presence of MBAm (0.02g) and APS (0.006g), polyreaction 24h is carried out in nitrogen protection.
4, after reaction is finished, take out the gel thorough washing, to remove other impurity such as unreacted monomer and linking agent, vacuum-drying at room temperature obtains the PVA matrix poly-N-isopropyl acrylamide microgel.Product can characterize with means such as FT-IR, TEM, TG-DTA and digital photographings.
Claims (3)
1. a PVA matrix poly-N-isopropyl acrylamide microgel material is characterized in that with the PVAC polyvinylalcohol film be body material, and poly-N-isopropyl acrylamide microgel is uniformly distributed on the PVA body material.
2. method for preparing PVA matrix poly-N-isopropyl acrylamide microgel material as claimed in claim 1 is characterized in that being prepared from by following technological process:
A. PVA is dissolved in 10 times of 80 ℃ of dissolvings down in the deionized water of its weight, stirs and press nano-CaCO down
3With the PVA mass ratio be that 1: 10～3: 10 ratio adds nano-CaCO in solution
3, disperse 30min at least in the ultrasonic wave, will contain nano-CaCO
3PVA solution move in the tetrafluoroethylene groove and to form the thick thin layer of 2-3mm, be cooled to 30 ℃ of gelation 24h;
B. the PVA thin layer of gelation places the glutaraldehyde solution of 15-20mL2wt% to soak 24h, makes it form highly cross-linked network; Then this cross-linked network is placed dilute hydrochloric acid to soak 1 all also thorough washing thoroughly to remove nano-CaCO
3With other impurity, then at the Na of 0.15wt%
2SO
3Soak 24h in the solution, vacuum-drying under the room temperature obtains being loaded with Na
2SO
3The porous PVA matrix;
C. this is loaded with Na
2SO
3The porous PVA matrix be dipped in the aqueous solution of monomer NIPAm, at 0.01～0.02g N, N '-methylene-bisacrylamide and 0.003-0.006g ammonium persulphate exist down, polyreaction 24h is carried out in nitrogen protection;
D. after reaction is finished, take out the gel thorough washing, to remove unreacted monomer and linking agent and other impurity, vacuum-drying at room temperature obtains the PVA matrix poly-N-isopropyl acrylamide microgel.
3. PVA matrix poly-N-isopropyl acrylamide microgel preparation methods as claimed in claim 2, the size that it is characterized in that described poly-N-isopropyl acrylamide microgel is by regulating the size control of micropore in the PVA matrix.
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| CN102816340A (en) * | 2012-09-06 | 2012-12-12 | 北京理工大学 | Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film |
| CN103242554A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院化学研究所 | Nanometer plural gel and preparation method thereof |
| CN105017554A (en) * | 2014-04-16 | 2015-11-04 | 中国科学院理化技术研究所 | Method for preparing nano-microporous polymer thin-film material |
| CN105754277A (en) * | 2016-03-16 | 2016-07-13 | 黑龙江省科学院技术物理研究所 | Method for preparing polyvinyl alcohol/poly-N-NIPAM temperature-sensitive core-shell micro-spheres |
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| CN102796267A (en) * | 2012-09-06 | 2012-11-28 | 北京理工大学 | Sodium-alginate-based temperature-sensitive polymer aquagel smart dimming film and preparation method thereof |
| CN102816340A (en) * | 2012-09-06 | 2012-12-12 | 北京理工大学 | Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film |
| CN102816340B (en) * | 2012-09-06 | 2017-05-17 | 北京理工大学 | Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film |
| CN103242554A (en) * | 2013-05-13 | 2013-08-14 | 中国科学院化学研究所 | Nanometer plural gel and preparation method thereof |
| CN105017554A (en) * | 2014-04-16 | 2015-11-04 | 中国科学院理化技术研究所 | Method for preparing nano-microporous polymer thin-film material |
| CN105017554B (en) * | 2014-04-16 | 2018-11-23 | 中国科学院理化技术研究所 | A method of preparing nanoporous polymeric thin-film material |
| CN105754277A (en) * | 2016-03-16 | 2016-07-13 | 黑龙江省科学院技术物理研究所 | Method for preparing polyvinyl alcohol/poly-N-NIPAM temperature-sensitive core-shell micro-spheres |
| CN106423291A (en) * | 2016-09-30 | 2017-02-22 | 天津大学 | Preparation and application of nano-silver-carrying PNIPAM/PVA composite thermosensitive gel |
| CN106423291B (en) * | 2016-09-30 | 2019-09-20 | 天津大学 | A kind of preparation and its application of the PNIPAM/PVA compound temperature-sensitive gel of carrying nano silver |
| CN106577741A (en) * | 2016-12-20 | 2017-04-26 | 广州聚禅现代农业研究院有限公司 | Sustained-release agent of insecticide and preparation method thereof |
| CN109485876A (en) * | 2018-11-12 | 2019-03-19 | 西安交通大学 | A kind of preparation method of base catalysis PVA gel beads |
| CN109851713A (en) * | 2019-03-30 | 2019-06-07 | 华南理工大学 | A kind of controlled architecture water-setting sebific duct of dual enhancing and preparation method thereof |
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Open date: 20100616 |