CN1314727C - Hydrogel capable of degrading and sensing to environment and preparation process and using thereof - Google Patents
Hydrogel capable of degrading and sensing to environment and preparation process and using thereof Download PDFInfo
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- CN1314727C CN1314727C CNB2004100127761A CN200410012776A CN1314727C CN 1314727 C CN1314727 C CN 1314727C CN B2004100127761 A CNB2004100127761 A CN B2004100127761A CN 200410012776 A CN200410012776 A CN 200410012776A CN 1314727 C CN1314727 C CN 1314727C
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Abstract
The present invention relates to degradable environment-sensitive hydrogel whose structural formula is disclosed in the right graph. Polylactic acid and epoxy compounds are mixed, and after 30 wt% to 50 wt% of inorganic hydroxide water solution is added, the obtained solution carried out a copolymerization reaction at 0 DEG C to 120 DEG C for 2 to 20 hours, which obtains the degradable environment-sensitive hydrogel. The degradable environment-sensitive hydrogel can be used as a biodegradable material in the fields of drug controlled release, tissue engineering, soil water storage or the control of desert, etc. The present invention has the advantages of rich raw material source, simpler preparation method and lower cost. The degradable environment-sensitive hydrogel has good water absorption performance, and the swelling behavior of the degradable environment-sensitive hydrogel can be automatically regulated and degraded along with the change of environment pH values and organic solvents. Thus, the degradable environment-sensitive hydrogel has wide application prospect on a plurality of fields of agriculture, environment, biomedicine, etc.
Description
Technical field
The present invention relates to degradable environmental sensitive hydrogels and method for making thereof and purposes, belong to chemical field.
Background technology
Up to the present, the hydrogel by the synthetic method preparation mainly is poly-(N-N-isopropylacrylamide) and polyacrylic acid and derivatives class hydrogel.They all be by vinyl monomer through the hydrogel that polyaddition reaction obtains, all join between the monomer by carbon-carbon bond, chemical stability is strong, is difficult to take place biological degradation and environment degradable, range of application is restricted.
Summary of the invention
The object of the present invention is to provide class degradable environmental sensitive hydrogels and its production and use.
Technical scheme provided by the invention is: the degradable environmental sensitive hydrogels, generate by copolymerization by poly(lactic acid) and epoxy compounds, and contain the substructure unit of poly(lactic acid) and polyepoxide in its chemical structure; Structural formula is:
Wherein, the crosslinked polyepoxide of R=; M=sodium ion or potassium ion.The relative molar fraction of each fragment polymkeric substance in l, m, n, the r=multipolymer, l+m+n+r=1.Wherein, l=0-0.4, m=0-0.4, l+m=0.01-0.4; N+r=0.6-0.99.The relative molar fraction of poly(lactic acid) on p, each side chain of q=multipolymer, p+q=1, p=0-1 wherein, q=0-p.
A kind of in poly-(D, L-lactic acid), poly-(L-lactic acid), poly-(D-lactic acid), poly-(meso-lactic acid) and their multipolymer, blend and the three-dimensional mixture of poly(lactic acid) in the above-mentioned hydrogel; The polymerization degree is 1-10,000.Its chemical structure meets following general formula:
Copolymer of poly lactic acid in the above-mentioned hydrogel, blend are made up of poly-(D, L-lactic acid), poly-(L-lactic acid), poly-(D-lactic acid), poly-(meso-lactic acid) more than 2 kinds or 2 kinds respectively; Three-dimensional mixture is made up of poly-(L-lactic acid) and poly-(D-lactic acid).The molar fraction of each component is from 0.01-0.99.
The crosslinked polyepoxide of R=in the above-mentioned hydrogel, structural formula is:
The relative molar fraction of two repeated structural units in the crosslinked polyepoxide of x, y=, x+y=1, x=0-1 wherein, y=1-x.
The structural formula of the epoxy compounds in the above-mentioned hydrogel is:
All or part of poly(lactic acid) exists in the mode of poly(lactic acid) sodium and poly(lactic acid) potassium in the above-mentioned hydrogel structure; The relative proportion of poly(lactic acid) sodium and poly(lactic acid) potassium was from 100: 0 to 0: 100.
The present invention also provides the preparation method of above-mentioned hydrogel, and poly(lactic acid) is mixed with epoxy compounds, carries out copolymerization 2-20 hour at 0 ℃-120 ℃ behind the adding 30wt%-50wt% inorganic base aqueous solution.Polymerisate is put into apparatus,Soxhlet's, is that solvent is removed unreacted monomer and impurity with 95wt% ethanol, and vacuum-drying promptly gets the degradable environmental sensitive hydrogels.
Above-mentioned mineral alkali is sodium hydroxide, potassium hydroxide and alkaline, inorganic salts yellow soda ash, salt of wormwood, sodium bicarbonate and saleratus.
In the above-mentioned hydrogel structure between poly(lactic acid) and the polyepoxide substructure unit by linking by the ester bond that generates after poly(lactic acid) and the open loop of epoxy compound polymerization and ehter bond, wherein ester bond can be disconnected the degraded that causes hydrogel by series of chemical such as hydrolysis, enzymolysis, and the eventual degradation product is lactic acid and glycol derivative.Therefore hydrogel of the present invention can be used as Biodegradable material and uses in fields such as medicine sustained release, organizational project, soil water storage or desertification control.
The used main raw material poly(lactic acid) of the present invention can be formed by the lactic acid direct condensation.Lactic acid belongs to renewable resources by the preparation of starch biological fermentation.The raw material sources of hydrogel are abundant, the preparation method is fairly simple because the present invention prepares, and need not conditions such as high temperature, high pressure and high vacuum, and therefore the hydrogel preparation cost that the present invention relates to is lower.The degradable environmental sensitive hydrogels that the present invention relates to has good water absorbing properties, its swelling behavior can be regulated and degradable automatically along with the variation of environment potential of hydrogen and organic solvent, will have broad application prospects at numerous areas such as agricultural, environment and biomedicines.
Embodiment
By the following examples the present invention is elaborated.
Embodiment 1: add 50 gram D in churned mechanically round-bottomed flask is housed, L-poly(lactic acid) (n=80-100) and 400 milliliters of epoxy chloropropane are after fully stirring, add 100 gram aqueous sodium hydroxide solutions (50wt%), stirring heating 80 ℃ of reactions 5 hours, obtains white gels.White gels is put into apparatus,Soxhlet's, with 95% ethanol unreacted monomer and impurity in the white gels are removed, vacuum-drying gets the poly(lactic acid) hydrogel, and yield is 95%.Its water-intake rate is 50.
Embodiment 2: add 35 gram D in churned mechanically round-bottomed flask is housed, L-poly(lactic acid) (n=20-30) and 300 milliliters of epoxy chloropropane are after fully stirring, 100 gram potassium hydroxide aqueous solutions (50wt%), stirring heating, control is reflected to be carried out under 100 ℃ 10 hours, obtained white gels.White gels is put into apparatus,Soxhlet's, with 95wt% ethanol unreacted monomer and impurity in the white gels are removed, vacuum-drying gets the poly(lactic acid) hydrogel, and yield is 94%.Its water-intake rate is 200.
Embodiment 3: in churned mechanically round-bottomed flask is housed, add 20 grams poly-(meso-lactic acid) (n=20-30) with 100 milliliters of epoxy chloropropane, after fully stirring, the sodium hydroxide and the 75 gram potassium hydroxide aqueous solutions that add 50 gram 50wt%, stirring heating, control is reflected to be carried out under 80 ℃ 8 hours, obtained white gels.White gels is put into apparatus,Soxhlet's, with 95% ethanol unreacted monomer and impurity in the white gels are removed, vacuum-drying gets the poly(lactic acid) hydrogel, and yield is 94%.Its water-intake rate is 1500.
Embodiment 4: add 50 gram L-poly(lactic acid) (n=10-20) and 400 milliliters of epoxy chloropropane in churned mechanically round-bottomed flask is housed, after fully stirring, add 150 milliliters of aqueous sodium carbonates (30wt%), stirring heating, control is reflected to be carried out under 120 ℃ 8 hours, obtained white gels.White gels is put into apparatus,Soxhlet's, with 95wt% ethanol unreacted monomer and impurity in the white gels are removed, vacuum-drying gets the poly(lactic acid) hydrogel, and yield is 98%.Its water-intake rate is 1000.
Embodiment 5: add 50 gram D-poly(lactic acid) (n=100-120) and 400 milliliters of epoxy chloropropane in churned mechanically round-bottomed flask is housed, after fully stirring, add 150 gram wet chemicals (30wt%), stirring heating, control is reflected to be carried out under 120 ℃ 15 hours, obtained white gels.White gels is put into apparatus,Soxhlet's, with 95wt% ethanol unreacted monomer and impurity in the white gels are removed, vacuum-drying gets the poly(lactic acid) hydrogel, and yield is 95%.Its water-intake rate is 500.Its water-intake rate is 800.
Embodiment 6: the charging capacity of pressing embodiment 1 adds L-poly(lactic acid) (n=10-20) and epoxy chloropropane, after fully stirring, adds 100 gram 50wt% aqueous sodium hydroxide solutions, and control is reflected to be carried out under 120 ℃ 12 hours, obtained white gels.Hydrogel after the purification is abundant swelling under the pH=7 condition.Swelling takes place to go fast in the hydrogel after the swelling under the pH=3 condition.Adjust pH value of aqueous solution, swelling with go swelling process to carry out repeatedly.
Embodiment 8: add 50 gram D in churned mechanically round-bottomed flask is housed, L-poly(lactic acid)/L-copolymer of poly lactic acid (n=1000) and 400 milliliters of epoxy chloropropane after fully stirring, add 100 grams, 50% aqueous sodium hydroxide solution, control is reflected to be carried out under 120 ℃ 20 hours, obtained white gels.Hydrogel after the purification is abundant swelling in water.Swelling takes place to go fast in the hydrogel after the swelling in the 70wt% aqueous ethanolic solution.When water and 70wt% aqueous ethanolic solution are used alternatingly, swelling with go swelling process to carry out repeatedly.
Embodiment 9: prepare poly(lactic acid) by the lactic acid polycondensation, polymerization degree n=10-20.After by the charging capacity of embodiment 1 this poly(lactic acid) and epoxy chloropropane fully being stirred, add 100 gram 50wt% aqueous sodium hydroxide solutions, control is reflected to be carried out under 120 ℃ 12 hours, obtained white gels.Hydrogel after the purification begins degraded after soaking 5 days under the pH=7 condition.Do not observe the existence of hydrogel after 20 days.
Embodiment 10: the charging capacity of pressing embodiment 1 adds L-poly(lactic acid) (n=10-20) and epoxy chloropropane, after fully stirring, adds 100 gram 50wt% aqueous sodium hydroxide solutions, and control is reflected to be carried out under 120 ℃ 12 hours, obtained white gels.Hydrogel after the purification fully goes swelling after freeze-drying and dehydrating under the pH=3 condition.Behind the white solid grind up shape that obtains with the former medicine thorough mixing of Ibuprofen BP/EP.The percentage composition of Ibuprofen BP/EP in mixture is 10%.The tablet that this mixture is pressed into constant release in the phosphoric acid buffer of pH=7 goes out Ibuprofen BP/EP, can keep time of releasing 20 hours.
Claims (6)
1. the degradable environmental sensitive hydrogels is characterized in that: made by laxative remedy, poly(lactic acid) is mixed with epoxy compounds, carried out copolymerization 2-20 hour at 0 ℃-120 ℃ behind the adding 30wt%--50wt% inorganic base aqueous solution; Polymerisate is put into apparatus,Soxhlet's, is that solvent is removed unreacted monomer and impurity with 95wt% ethanol, and vacuum-drying promptly gets the degradable environmental sensitive hydrogels.
2. hydrogel according to claim 1 is characterized in that: poly(lactic acid) is selected from a kind of in poly-(D, L-lactic acid), poly-(L-lactic acid), poly-(D-lactic acid), poly-(meso-lactic acid) and their multipolymer, blend and the three-dimensional mixture; The polymerization degree is 1-10,000; Its chemical structure meets following general formula:
3. hydrogel according to claim 2 is characterized in that: copolymer of poly lactic acid, blend are made up of poly-(D, L-lactic acid), poly-(L-lactic acid), poly-(D-lactic acid), poly-(meso-lactic acid) more than 2 kinds or 2 kinds respectively; Three-dimensional mixture is made up of poly-(L-lactic acid) and poly-(D-lactic acid); The molar fraction of each component is from 0.01-0.99.
4. according to claim 1 or 2 or 3 described hydrogels, it is characterized in that: the crosslinked polyepoxide of R=, structural formula is:
The relative molar fraction of two repeated structural units in the crosslinked polyepoxide of x, y=, x+y=1, x=0-1 wherein, y=1-x.
5. according to claim 1 or 2 or 3 described hydrogels, it is characterized in that: the structural formula of epoxy compounds is:
6. according to claim 1 or 2 or 3 described hydrogels, it is characterized in that: all or part of poly(lactic acid) exists in the mode of poly(lactic acid) sodium and poly(lactic acid) potassium in the copolymer aquagel structure of poly(lactic acid) and polyepoxide; The relative proportion of poly(lactic acid) sodium and poly(lactic acid) potassium was from 100: 0 to 0: 100.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100127761A CN1314727C (en) | 2004-02-26 | 2004-02-26 | Hydrogel capable of degrading and sensing to environment and preparation process and using thereof |
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| CNB2004100127761A CN1314727C (en) | 2004-02-26 | 2004-02-26 | Hydrogel capable of degrading and sensing to environment and preparation process and using thereof |
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| CN1560110A CN1560110A (en) | 2005-01-05 |
| CN1314727C true CN1314727C (en) | 2007-05-09 |
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| CN107474233A (en) * | 2017-08-20 | 2017-12-15 | 芜湖通全科技有限公司 | A kind of preparation method of PLA base epoxy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55135111A (en) * | 1979-04-09 | 1980-10-21 | Showa Denko Kk | Production of highly water-absorbing hydrogel |
| CN1366531A (en) * | 2000-04-25 | 2002-08-28 | 关西涂料株式会社 | Aqueous polyurethane gel, process for producing same, and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55135111A (en) * | 1979-04-09 | 1980-10-21 | Showa Denko Kk | Production of highly water-absorbing hydrogel |
| CN1366531A (en) * | 2000-04-25 | 2002-08-28 | 关西涂料株式会社 | Aqueous polyurethane gel, process for producing same, and use thereof |
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