CN102492078A - Acrylic acid and polyhedral silsesquioxane copolymerized hydrogel, its preparation method and its purpose - Google Patents
Acrylic acid and polyhedral silsesquioxane copolymerized hydrogel, its preparation method and its purpose Download PDFInfo
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- CN102492078A CN102492078A CN2011103818992A CN201110381899A CN102492078A CN 102492078 A CN102492078 A CN 102492078A CN 2011103818992 A CN2011103818992 A CN 2011103818992A CN 201110381899 A CN201110381899 A CN 201110381899A CN 102492078 A CN102492078 A CN 102492078A
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Abstract
The invention relates to a acrylic acid and polyhedral silsesquioxane copolymerized hydrogel, its preparation method and its purpose, which belongs to the intelligent high-molecular material technical field. According to the invention, a free radical solution polymerization method is used, and a polymer network structure is formed through the chemical crosslinking effect. The polymer possesses pH sensitivity group, and is capable of generating volumetric expansion or shrinkage by changing the environment pH value of environment. The hydrogel of the present invention is taken as a carrier of medicament slow release, the added POSS with minute quantity is capable of obviously reducing the release rate of the medicament coated in the hydrogel, medicament release time can be prolonged simultaneously, the PAA hydrogel possesses good biological compatibility, so that the prepared copolymerized hydrogel possesses potential value on being as the carrier aspect of the slow release medicaments.
Description
Technical field
The invention belongs to the technical field of intelligent macromolecule material, relate to a kind of polyhedron cage-type silsesquioxane and acrylic acid copolymer hydrogel, preparation method and the application on the medicament slow release performance of the pH of having susceptibility.
Background technology
Hydrogel be a kind of can be in water swelling and keep large quantity of moisture and don't dissolved polymers, can form the three-dimensional net structure of hydrogel through polymkeric substance interchain physics or chemically crosslinked effect.Hydrogel has excellent biological compatibility, water permeate, mechanical property, surface property etc.And intelligent aqueous gel capable to be a kind of environmental stimulus to external world such as temperature, pH value, magnetic field, electric field, solvent, light, chemical substance etc. respond, and produce the gel of volume change.Because the responsiveness of this uniqueness of intelligent aqueous gel capable, make aspects such as its fixing, organizational project, transmitter, chemical transformation device, artificial muscle, molsep system have good application prospects at pharmaceutical carrier, organized enzyme.According to the response condition that stimulates to external world, intelligent aqueous gel capable can be divided into temperature-responsive hydrogel, pH responsiveness aquagel, optical Response hydrogel, electric field response hydrogel and magnetic field responsiveness hydrogel etc.At present, maximum to research in the intelligent aqueous gel capable is temperature-sensitive hydrogel and pH sensitive aquagel.
ROHM (PAA) is the pH sensitive polymer, and this hydrogel has ionizable group-COOH.In acidic medium, carboxyl and polymer segment form hydrogen bond, and the gel segmental stretches and motion thereby limited, and polymer molecular chain is twined each other be contraction schedule; And under weak basic condition, nearly all-COOH is ionized into-COO-, and molecule interchain hydrogen bond action weakens; Between gel network, produce simultaneously Coulomb repulsion; This repulsive interaction is outwards expanded gel network, and the wetting ability of polymkeric substance strengthens, and swelling capacity increases.Thereby this specific character of polyacrylic acid hydrogel capable of using, with its carrier as slow releasing pharmaceutical.This hydrogel is contraction schedule in gastric juice, swelling capacity is little, and medicine discharges hardly; And in enteron aisle, along with the rising of environment pH value, ionization can take place in-COOH gradually, and swelling capacity increases, thereby the drug release that is embedded in is wherein come out, and realizes that the fixed point of medicine discharges.
Summary of the invention
One of the object of the invention has been to provide a kind of vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel with pH susceptibility of medicament slow release performance.
Two of the object of the invention has been to provide the preparation method of this copolymer hydrogel, and wherein the structure of simple function group polyhedron cage-type silsesquioxane (POSS) is following:
Three of the object of the invention has been to provide the application of swelling behavior aspect medicament slow release of this copolymer hydrogel.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel; Be made up of vinylformic acid (AA), simple function group polyhedron cage-type silsesquioxane (POSS) and linking agent, vinylformic acid and polyhedron cage-type silsesquioxane form cross-linked network under the linking agent effect; Wherein vinylformic acid and simple function group polyhedron cage-type silsesquioxane are 1: 0.02～0.12 by mass ratio, and the massage of vinylformic acid and linking agent is than being 1: 0.01～0.06.
Described simple function group polyhedron cage-type silsesquioxane (POSS), preferred seven phenyl methyl acryloyl-oxy propyl group polyhedron cage-type silsesquioxanes.Described linking agent, preferred N,N methylene bis acrylamide (MBA).
Vinylformic acid of the present invention and polyhedron cage-type silsesquioxane copolymer hydrogel are the hydrogels with pH susceptibility.
The present invention also provides the preparation method of vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel, and concrete technical scheme is following.
The preparation method of a kind of vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel; With vinylformic acid and polyhedron cage-type silsesquioxane is reaction monomers; With the N,N methylene bis acrylamide is linking agent, selects the radical type initiator for use; With 1: 2 THF of volume ratio (THF) and N (DMF) is mixed solvent; Vinylformic acid and simple function group polyhedron cage-type silsesquioxane are 1: 0.02～0.12 by mass ratio, and vinylformic acid is massaged than being 1: 0.01～0.06 with linking agent, and vinylformic acid and initiator are 1: 0.001～0.005 in molar ratio; Concrete steps are: in mixed solvent, add reaction monomers, add linking agent then, and ultrasonic to dissolving fully; Logical nitrogen, sealing, the initiator that reinjects, 50～70 ℃ of waters bath with thermostatic control are to gel formation; At last the hydrogel that makes is respectively soaked 20～30h with THF, zero(ppm) water respectively, place vacuum drying oven to be dried to constant weight again, can obtain having the pH sensitive aqueous gel of cross-linked network structure.
Described initiator, preferred Diisopropyl azodicarboxylate (AIBN), BPO (BPO) or Potassium Persulphate (K
2S
2O
8).
Logical nitrogen in reaction, sealing, the initiator that reinjects is because air has inhibition to this polyreaction, therefore in reaction mixture, leads to nitrogen, to drain the air in the reaction system.The hydrogel that makes soaks with THF and zero(ppm) water respectively repeatedly, being in order to remove unreacted reaction monomers; After the immersion, can cut into slices places vacuum drying oven to be dried to constant weight again.
The purposes of vinylformic acid of the present invention and polyhedron cage-type silsesquioxane copolymer hydrogel is as the carrier of medicament slow release.
Described carrier as medicament slow release, concrete method can be placed on exsiccant vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel to be dipped in the aqueous solution of medicine and reaches balance, is placed on and is dried to constant weight in the vacuum drying oven.
Described medicine can be a theophylline, and the concentration of aqueous solution of medicine can be 1～10mg/mL; Exsiccant vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel consumption can be that the aqueous solution of every 20mL medicine is placed the 1g copolymer hydrogel.
Described being dipped to reaches balance, can soak 16～36h and realize, the concrete time looks condition such as the concentration of aqueous solution of medicine and decides; Dry in the described vacuum drying oven, can under 35～45 ℃, carry out drying.
The present invention adopts theophylline as slow releasing pharmaceutical; Have relaxing smooth muscle, excited heart flesh and diuretic actions in the theophylline; Its main absorption site is stomach and intestines; But theophylline has hormesis to gastric mucosa, thereby the present invention utilizes the pH susceptibility of polyacrylic acid hydrogel, with its carrier as slow releasing pharmaceutical.Because the blood concentration of effective treatment of theophylline is 10～20 μ g/ml; And polyacrylic acid hydrogel swelling capacity in weakly alkaline environment is too big; The release rate of drugs that is embedded in wherein is too fast, makes the medicine moment in the solution reach very high, does not reach the purpose that drug slow discharges.For improving this performance of polyacrylic acid hydrogel; This experiment is through adding cage-type silsesquioxane (POSS); Come the motion of limiting polymer molecule segment; And increase the cross-linking density of polymkeric substance through the content of linking agent in the controlling polymers, thus reduce the swelling rate of hydrogel, realize the purpose of the slow release of medicine.
The present invention adopts the method for free radical solution polymerization, forms polymer network structure through the chemically crosslinked effect.This polymkeric substance has the pH sensitive groups, thereby the expansion or the contraction of volume can take place with the variation of environment pH value.The present invention comes the motion and the cross-linking density of the molecular chain of controlling polymers network through the consumption that adds simple function group polyhedron cage-type silsesquioxane (POSS) and control linking agent, thereby has improved the swelling behavior of hydrogel.With hydrogel of the present invention is the carrier of medicament slow release, and the adding of minute quantity POSS obviously reduces the release rate of drugs that is coated in the hydrogel, has prolonged pharmaceutical release time simultaneously.Because PAA class hydrogel has excellent biological compatibility, thereby the copolymer hydrogel of the present invention's preparation has the potential using value aspect the carrier of slow releasing pharmaceutical.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of POSS monomer and POSS/AA multipolymer, and as can be seen from the figure POSS is dispersed in the polymeric system uniformly.
Fig. 2 is the stereoscan photograph when hydrogel reached the swelling swelling equilibrium in SGF in 0% o'clock for POSS content.
Fig. 3 is the stereoscan photograph when hydrogel reached the swelling swelling equilibrium in SGF in 8% o'clock for POSS content; The adding that from Fig. 2, Fig. 3, can find out POSS has significantly reduced hydrogel pore size after the swelling in SGF, has promptly reduced the swelling behavior of hydrogel.
Fig. 4 is the stereoscan photograph when hydrogel reached the swelling swelling equilibrium in simulated intestinal fluid in 0% o'clock for POSS content.
Fig. 5 is the stereoscan photograph when hydrogel reached the swelling swelling equilibrium in simulated intestinal fluid in 8% o'clock for POSS content; Can find out that from Fig. 4, Fig. 5 the adding of POSS decreases the aperture that reach swelling equilibrium after of hydrogel simulated intestinal fluid, but varying aperture there be not so obvious in the SGF.
The swelling behavior of hydrogel in simulated intestinal fluid is apparently higher than SGF, and the adding of POSS has significantly reduced the swelling behavior of hydrogel.
Medicine (theophylline) release concentration and the time relation curve of POSS/AA copolymer hydrogel in SGF when Fig. 6 is vinylformic acid 2wt% for dosage of crosslinking agent; In the test dried medicine carrying copolymer hydrogel is joined in the SGF; Survey once its drug release concentration at set intervals, wherein test temperature is 37 ℃.
Medicine (theophylline) release concentration and the time relation curve of POSS/AA copolymer hydrogel in simulated intestinal fluid when Fig. 7 is vinylformic acid 2wt% for dosage of crosslinking agent; In the test dried medicine carrying copolymer hydrogel is joined in the simulated intestinal fluid; Survey once its drug release concentration at set intervals, wherein test temperature is 37 ℃.
Embodiment
Embodiment 1:
6.86ml the mixing solutions of vinylformic acid and the 0.1441g POSS THF (THF) that is dissolved in 20ml and N (DMF) in; Add 0.3083g N,N methylene bis acrylamide (MBA), ultrasonic; It is dissolved fully; Seal behind the logical nitrogen 5min, inject Diisopropyl azodicarboxylate (AIBN)/DMF solution of 0.022g/2ml, place 60 ℃ of water-bath constant temperature 2h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be placed on after the section and be dried to constant weight in the vacuum drying oven.
Embodiment 2:
6.86ml vinylformic acid and 0.8647g POSS are dissolved in the mixing solutions of THF (THF) and N (DMF) of 20ml; Add 0.3083g N,N methylene bis acrylamide (MBA), ultrasonic; It is dissolved fully; Seal behind the logical nitrogen 5min, inject Diisopropyl azodicarboxylate (AIBN)/DMF solution of 0.022g/2ml, place 60 ℃ of water-bath constant temperature 2h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be placed on after the section and be dried to constant weight in the vacuum drying oven.
Embodiment 3:
6.86ml vinylformic acid and 0.5765g POSS are dissolved in the mixing solutions of THF (THF) and N (DMF) of 20ml; Add 0.3083g N,N methylene bis acrylamide (MBA), ultrasonic; It is dissolved fully; Seal behind the logical nitrogen 5min, inject Diisopropyl azodicarboxylate (AIBN)/DMF solution of 0.022g/2ml, place 60 ℃ of water-bath constant temperature 2h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be placed on after the section and be dried to constant weight in the vacuum drying oven.
Embodiment 4:
6.86ml vinylformic acid and 0.2882g POSS are dissolved in the mixing solutions of THF (THF) and N (DMF) of 20ml; Add 0.1542g N,N methylene bis acrylamide (MBA), ultrasonic; It is dissolved fully; Seal behind the logical nitrogen 5min, inject the AIBN/DMF solution of 0.022g/2ml, place 60 ℃ of water-bath constant temperature 2h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be placed on after the section and be dried to constant weight in the vacuum drying oven.
Embodiment 5:
6.86ml vinylformic acid and 0.2882g POSS are dissolved in the mixing solutions of THF (THF) and N (DMF) of 20ml; Add 0.3083g N,N methylene bis acrylamide (MBA), ultrasonic; It is dissolved fully; Seal behind the logical nitrogen 5min, inject BPO (BPO)/DMF solution of 0.0242g/2ml, place 50 ℃ of water-bath constant temperature 1h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be placed on after the section and be dried to constant weight in the vacuum drying oven.
Embodiment 6:
It is that the theophylline aqueous solution of 5mg/mL soaks 24h and reaches balance to it that the dried POSS/AA copolymer hydrogel of 1g that embodiment 1～5 is made places 20mL, concentration; Place 40 ℃ vacuum drying oven to be dried to constant weight this medicine carrying hydrogel then, obtaining with vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel is medicine (theophylline) slow release formulation of carrier.
Comparative example 1:
6.86ml vinylformic acid is dissolved in the zero(ppm) water of 20ml, adds 0.3083g N,N methylene bis acrylamide (MBA), and is ultrasonic, and it is dissolved fully, seals behind the logical nitrogen 5min, injects the Potassium Persulphate (K of 0.1352g/2ml
2S
2O
8)/distilled water solution places 70 ℃ of water-bath constant temperature 1h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be dried to constant weight in the section person of the being placed on vacuum drying oven.
Comparative example 2:
6.86ml vinylformic acid is dissolved in the zero(ppm) water of 20ml, adds 0.9251g N,N methylene bis acrylamide (MBA), and is ultrasonic, and it is dissolved fully, seals behind the logical nitrogen 5min, injects the Potassium Persulphate (K of 0.027g/2ml
2S
2O
8)/distilled water solution places 63 ℃ of water-bath constant temperature 1h.Product is respectively soaked 12h with THF and zero(ppm) water respectively, remove unreacted monomer, be dried to constant weight in the section person of the being placed on vacuum drying oven.
Drug release rate by Fig. 6 and Fig. 7 provide can be found out; The POSS content that comparative example 1,2 makes is the drug release rate of 0% o'clock hydrogel, the vinylformic acid that obviously makes faster than the present invention and the drug release rate of polyhedron cage-type silsesquioxane copolymer hydrogel.
Claims (7)
1. vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel are made up of vinylformic acid, simple function group polyhedron cage-type silsesquioxane and linking agent, and vinylformic acid and polyhedron cage-type silsesquioxane form cross-linked network under the linking agent effect; Wherein vinylformic acid and simple function group polyhedron cage-type silsesquioxane are 1: 0.02～0.12 by mass ratio, and the massage of vinylformic acid and linking agent is than being 1: 0.01～0.06.
2. vinylformic acid according to claim 1 and polyhedron cage-type silsesquioxane copolymer hydrogel is characterized in that, described simple function group polyhedron cage-type silsesquioxane is seven phenyl methyl acryloyl-oxy propyl group polyhedron cage-type silsesquioxanes; Described linking agent is a N,N methylene bis acrylamide.
3. the preparation method of the vinylformic acid of a claim 1 and polyhedron cage-type silsesquioxane copolymer hydrogel; With vinylformic acid and polyhedron cage-type silsesquioxane is reaction monomers; With the N,N methylene bis acrylamide is linking agent, selects the radical type initiator for use; With 1: 2 THF of volume ratio and N is mixed solvent; Vinylformic acid and simple function group polyhedron cage-type silsesquioxane are 1: 0.02～0.12 by mass ratio, and vinylformic acid is massaged than being 1: 0.01～0.06 with linking agent, and vinylformic acid and initiator are 1: 0.001～0.005 in molar ratio; Concrete steps are: in mixed solvent, add reaction monomers, add linking agent then, and ultrasonic to dissolving fully; Logical nitrogen, sealing, the initiator that reinjects, 50～70 ℃ of waters bath with thermostatic control are to gel formation; At last the hydrogel that makes is respectively soaked 20～30h with THF, zero(ppm) water respectively, place vacuum drying oven to be dried to constant weight again.
4. the preparation method of vinylformic acid according to claim 3 and polyhedron cage-type silsesquioxane copolymer hydrogel is characterized in that, described initiator is Diisopropyl azodicarboxylate, BPO or Potassium Persulphate.
5. the purposes of the vinylformic acid of a claim 1 and polyhedron cage-type silsesquioxane copolymer hydrogel is as the carrier of medicament slow release.
6. the purposes of vinylformic acid according to claim 5 and polyhedron cage-type silsesquioxane copolymer hydrogel; It is characterized in that; Described carrier as medicament slow release; Concrete grammar is exsiccant vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel to be placed on to be dipped in the aqueous solution of medicine reach balance, places vacuum drying oven to be dried to constant weight again.
7. according to the purposes of claim 5 or 6 described vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel, it is characterized in that described medicine is a theophylline, the concentration of aqueous solution of medicine is 1～10mg/mL; Exsiccant vinylformic acid and polyhedron cage-type silsesquioxane copolymer hydrogel consumption are that the aqueous solution of every 20mL medicine is placed the 1g copolymer hydrogel.
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Cited By (3)
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| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN106832387A (en) * | 2017-01-09 | 2017-06-13 | 淮阴工学院 | A kind of obdurability polymer/caged silsesquioxane hybrid aerogel and its preparation method and application |
| CN112726210A (en) * | 2021-01-11 | 2021-04-30 | 武汉纺织大学 | Flame-retardant polyamide fabric and preparation method thereof |
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| CN101024751A (en) * | 2007-03-09 | 2007-08-29 | 厦门大学 | Coating material containing POSS acrylate copolymer and preparing method |
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| CN101875708A (en) * | 2009-04-30 | 2010-11-03 | 南京理工大学 | Preparation method of cagelike silsesquioxane-contained polymethyl methacrylate hybrid material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007022367A2 (en) * | 2005-08-16 | 2007-02-22 | Hybrid Plastics, Inc. | Preparation of polyhedral oligomeric silsesquioxane silanols and siloxides functionalized with olefinic groups |
| CN101024751A (en) * | 2007-03-09 | 2007-08-29 | 厦门大学 | Coating material containing POSS acrylate copolymer and preparing method |
| CN101503497A (en) * | 2009-03-02 | 2009-08-12 | 江南大学 | Preparation of star type block acid sensitive nano micelle |
| CN101875708A (en) * | 2009-04-30 | 2010-11-03 | 南京理工大学 | Preparation method of cagelike silsesquioxane-contained polymethyl methacrylate hybrid material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104861098A (en) * | 2015-04-28 | 2015-08-26 | 中科院广州化学有限公司 | Star polymer with pH stimulating responsiveness, preparation method thereof and application |
| CN106832387A (en) * | 2017-01-09 | 2017-06-13 | 淮阴工学院 | A kind of obdurability polymer/caged silsesquioxane hybrid aerogel and its preparation method and application |
| CN106832387B (en) * | 2017-01-09 | 2019-11-26 | 淮阴工学院 | A kind of obdurability polymer/caged silsesquioxane hybrid aerogel and its preparation method and application |
| CN112726210A (en) * | 2021-01-11 | 2021-04-30 | 武汉纺织大学 | Flame-retardant polyamide fabric and preparation method thereof |
| CN112726210B (en) * | 2021-01-11 | 2023-06-30 | 广东柏奴斯股份有限公司 | Flame-retardant nylon fabric and preparation method thereof |
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