CN105062019A - Transparent, temperature-sensitive, reversible and biodegradable polyester hydrogel with fast gelling capability, and preparation method thereof - Google Patents
Transparent, temperature-sensitive, reversible and biodegradable polyester hydrogel with fast gelling capability, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to transparent, temperature-sensitive, reversible and biodegradable polyester hydrogel with fast gelling capability and a preparation method thereof. The polyester hydrogel is composed of biodegradable polyester and a medium, wherein the biodegradable polyester adopts multi-element triblock copolymer with special structure characteristics; the hydrogel is obtained through a polymerization process. Compared with similar temperature-sensitive hydrogel, the hydrogel provided by the invention is high in gelling speed and acute in temperature sensitivity, and can form gel in 1.5-15 minutes, which reduces the loss of the polyester hydrogel before and after applying the hydrogel, and facilitates uniform package of water insoluble functional substances. The hydrogel provided by the invention changes little in transparency before and after gelling, unlike common hydrogel which turns to a white turbid system after gelling; the absorbancy to light at 600 nm wavelength is 0.02-0.5 under the condition of 5 mm optical path length; the transparency is high; therefore, the polyester hydrogel is suitable for observing the packaging conditions of functional substances and observing and monitoring the releasing process of the functional substances.
Description
Technical field
The present invention relates to a kind of hydrogel and preparation method thereof, belong to functional high molecule material manufacture and Application Areas, be specifically related to a kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability and preparation method thereof.
Background technology
Hydrogel is hydrophilic polymer network, and it can absorb a large amount of moisture, but can not be dissolved in the water due to the physical crosslinking between polymer chain and chemically crosslinked effect, can only be swelling and keep certain shape.Hydrogel has good biocompatibility, water permeate, and can obtain the hydrogel material of diverse microcosmic stuctures and properties by synthetic.Because hydrogel material water content is high, soft, there is the visco-elasticity as rubber, good biocompatibility and other physics-chem characteristic numerous, obtain research and apply widely in fields such as medicine, physiological hygiene, agricultural gardening, food, makeup, petrochemical complex, environmentfriendly products.Intelligent aqueous gel capable is a kind of comparatively novel type in hydrogel, and it can the change that occurs of sensing external environment or internal state, and environmental change can make response to external world, has feedback function, response function, self-diagnostic function etc.Hydrogel combines with intelligent response to the high containment of functional mass, plasticity-, elasticity, distinctive volume phase transition behavior by intelligent aqueous gel capable, has widened type and the application of hydrogel.Intelligent aqueous gel capable obtains extensive research in the application of a lot of high-end field, as artificial muscle, drug controlled release carrier, chemical converter, memory cell switch, light control material, chemical machinery device etc.Temperature-sensitive hydrogel is a type of intelligent aqueous gel capable, is the type that in hydrogel, Application and Development is more simultaneously.Application number is the Chinese patent application of 201410018764.3, disclose a kind of collagenase temperature-sensitive hydrogel, collagenase temperature-sensitive hydrogel is after being expelled to lesions position, slowly be warming up to body temperature, form in-situ hydrogel, collagenase can discharge by this hydrogel lentamente, makes collagenase concentrate on diseased region and plays drug effect, collagenase temperature-sensitive hydrogel topical can reduce to healthy tissues diffusion, and diffusion decreases 30-80% compared with powder injection Collagenase Type.
The gel matrix of polyalcohol hydrogel comprises natural polymer, modified natural polymer, synthesis polymer.The characteristic of natural polymer hydrogel and modified natural polymer hydrogel affects comparatively large by macromolecular structure, can not regulate structure and the performance of gel, thus can not meet the diversified application demand in each field in very significantly.Synthesis macromolecule hydrogel because the handiness of structure design, raw material sources are convenient, be easy to scale operation because of but main Types in hydrogel.But the type of current synthetic water gel is mainly nondegradable polymer type; the high molecular Environmental compatibility of non-degradable is lower; excessive use easily causes white pollution, and derives from the Nonrenewable resources such as oil, Sweet natural gas, and large-scale application will aggravate energy and resources crisis.Therefore the developing direction that degradable and raw material sources are macromolecule hydrogel in the novel hydrogels of renewable resources is developed.
Degradable polyester is the synthesis type degradable macromolecule that a kind of bio-medical is worth and potentiality are very huge, can manufacture biological tissue and organ, can be used as subsidiary material of performing the operation, also can be used for the manufacture of daily environment protection health product.But the related development work based on the hydrogel of degradable polyester is not but a lot, development about degradable polyester intelligent aqueous gel capable is then relatively less, but degradable polyester is introduced hydrogel field, for the type and Application Areas widening degradable polyester hydrogel, there is important science and practice significance.Degradable polyester is introduced hydrogel preparation, be conducive to the Co ntrolled release characteristic increasing the activeconstituents loaded, increase the type being applicable to the activeconstituents loaded, optimize structure and the Wuli-Shili-Renli system approach of hydrogel.The temperature sensitive intelligent aqueous gel capable of degradable polyester is an emerging technology areas, has vast potential for future development, but current research exploitation is relatively less.The temperature sensitive intelligent aqueous gel capable of the degradable polyester occurred is gel in longer and slower temperature-rise period generally, after gel, system becomes white opacity, reduce temperature gel and cannot revert to colloidal sol, belong to typical irreversible opaque gel, be not suitable for the application scenario repeatedly changed, be not suitable for coagulating application scenario soon, easily cause being separated of hydrophobic function material, be unfavorable for the loading of hydrophobic function material, be not suitable for the release of observation and Study of functional material, gelling temp has more the low temperature situation under present body temperature, be not suitable for the application under high temperature gel condition, be not suitable for being extended to other fields such as functional materials manufacture.
Summary of the invention
The object of the invention is to, provide a kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability and preparation method thereof, this hydrogel can effectively solve the problem.Meet the diversified Co ntrolled release demand of medicine, bioactive ingredients and other functional substance simultaneously, widen type and the application of degradable polyester intelligent aqueous gel capable, promote that degradable polyester intelligent aqueous gel capable manufactures field to composite functional material and expands, discharging relatively fast of practical function composition, the release of coloured functional composition is realized visual, meet the demand of spectrography monitoring release dynamics.
The present invention is achieved through the following technical solutions:
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability, it is characterized in that: described hydrogel is formed primarily of degradable polyester and medium, described medium is deionized water, any one in phosphate buffer solution, the quality of described medium is 3-9 times of described degradable polymer quality, described degradable polyester is polynary triblock copolymer and is made up of following structural unit: oxygen ethylidene, oxygen-1, 3-propylidene, oxygen caproyl, oxygen-2-methyl acetyl, described oxygen-1, 3-propylidene is 0:1-0.4:1 with the ratio of the amount of substance of oxygen ethylidene, the mass ratio of described oxygen-2-methyl acetyl and oxygen caproyl is 0:1-0.4:1, described oxygen ethylidene and oxygen-1, the equal formula weight of number of the block that 3-propylidene is formed is 1500-2500, the equal formula weight of number of the block that described oxygen caproyl and oxygen-2-methyl acetyl are formed and oxygen ethylidene and oxygen-1, the ratio of the equal formula weight of number of the block that 3-propylidene is formed is 1:1.8-1:2.8.
The invention also discloses a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability, comprise the following steps:
(1), weighing number-average molecular weight is that the hydroxyl carbowax of 1500-2500 or both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) join in reactor, weighing ester monomer, catalyzer join in reactor, the mass values of the quality of catalyzer and hydroxyl carbowax or both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) is 1:100-1:2000, measures the aromatic solvent of anhydrous and oxygen-free and joins in reactor;
(2), with the air in high pure nitrogen or high-purity argon gas metathesis reactor, then reaction system is warming up to 140 DEG C-150 DEG C, reaction 20h-30h;
(3), after reaction system is cooled to 40 DEG C-60 DEG C, add sherwood oil wherein, the volume of sherwood oil be the 1-6 of the described aromatic solvent volume of step (1) doubly, remove supernatant liquid after vibration;
(4), in the product of step (3) add sherwood oil, the volume (mL) of sherwood oil is 0.5:1-1.5:1 with the ratio of the quality (g) of the product of step (2), removes supernatant liquid after vibration;
(5), by the product of step (4) dry 20h-30h under 2Pa-100Pa, the condition of 80 DEG C-100 DEG C;
(6) any one medium in deionized water or phosphate buffer solution, is added to the product of step (5), the quality of medium is 3-9 times of described step (5) product quality, the water-sol is obtained by methods such as heating, vibration, coolings, this water-sol can form transparent aquagel under the condition of temperature 35 DEG C-52 DEG C, gel time is 1.5min-15min, when temperature is less than 35 DEG C, revert to again the water-sol of flowing, the gel formed has the higher transparency, under 5mm light path condition to the absorbancy of the light of 600nm wavelength between 0.02-0.5.
Further, in step (1), in described both-end hydroxyl poly-(ethylene oxide-co-propylene oxide), propylene oxide is 0:1-0.4:1 with the ratio of the amount of substance of ethylene oxide, described ester monomer is caprolactone, rac-Lactide, the mass ratio of rac-Lactide and caprolactone is 0:1-0.4:1, described catalyzer is isocaprylic acid zinc, 1-2 kind in stannous octoate, described aromatic solvent is toluene, dimethylbenzene, ethylbenzene, any one in trimethylbenzene, volume (mL) and hydroxyl carbowax or the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of aromatic solvent, the quality of ester monomer and the ratio of (g) are 0.6:1-1.2:1.
Novel hydrogels of the present invention breaches the multinomial characteristic limitation of existing temperature sensitive degradable polyester hydrogel, improve gelation rate and gelling temp, make gelatinous transparent, give gel with good reversibility, thus also widened the Application Areas of degradable polyester temperature-sensitive hydrogel, the fields such as biomedicine, functional materials preparation, oil production and temperature instruction can be widely used in.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is the hydrogel based on degradable polyester, Biodegradable polyester itself can be degraded, the Co ntrolled release of one side practical function composition in the process of degraded, makes hydrogel have high environment and biocompatibility on the other hand.Biodegradable polyester is introduced hydrogel preparation, add the Co ntrolled release characteristic of loaded activeconstituents, add the type being applicable to the activeconstituents loaded, optimize structure and the Wuli-Shili-Renli system approach of hydrogel.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is a kind of temperature sensitive type intelligent aqueous gel capable, but compared with similar temperature-sensitive hydrogel, there is significant performance difference, breach numerous functional limitations of similar temperature-sensitive hydrogel, there is excellent temperature keen, it is genuine temperature-sensitive hydrogel, gelling temp has determinacy accurately, has nothing to do with intensification history, only relevant with the structure of polyester, synthetic method and concentration.The water-sol of specific composition and concentration forms gel at specified temp instead of forms gel in a temperature range or interval, and the temperature-responsive feature of gel is fairly obvious, has nothing to do with the speed in temperature-rise period.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is a kind of temperature sensitive type intelligent aqueous gel capable, but there is very fast gelation rate compared with similar temperature-sensitive hydrogel, gel can be formed in 1.5-15min, extremely be suitable for coagulating applications soon, before being conducive to reducing gel, the loss of polymer sol after using, reduce the economy consumption in application process, reduce the negative impact to adjacent domain, be conducive to improving the production efficiency based on the functional materials manufacturing processed of hydrogel simultaneously, be conducive to the even parcel realizing water-insoluble sexual function material, reduce the separation of the front functional substance of gel parcel from gelling system.This feature, for biomedical applications, is conducive to the utilization ratio improving medicine, reduces toxicity and the pungency of medicine, improves the controlling of dispose procedure.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is a kind of temperature sensitive type intelligent aqueous gel capable, but compared with similar temperature-sensitive hydrogel, before and after inventive gel, transparency change is very little, unlike this type of hydrogel common, white opacity system is become after gel, under 5mm light path condition to the absorbancy of the light of 600nm wavelength between 0.02-0.5, transparency is high, be suitable for the parcel situation of overview function material, be suitable for the dispose procedure of observation and monitoring function material simultaneously.Novel hydrogels of the present invention has high transparency, showing that polymkeric substance realizes gelationization is not form the tight micella that associates but form loose net structure, this gel feature also make gel of the present invention present to be different from existing gel with the interaction of functional component and release characteristics.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is a kind of temperature sensitive type intelligent aqueous gel capable, but compared with similar temperature-sensitive hydrogel, hydrogel of the present invention has the reversibility of gel and colloidal sol phase co-conversion, namely not only thermo-sensitive gel can be realized, temperature sensitive solation can also be realized, this characteristic is conducive to realizing the another kind of Co ntrolled release approach outside Co ntrolled release that single degradation factors causes, strengthens the purpose of Co ntrolled release.Hydrogel of the present invention has gel and the reversibility of colloidal sol phase co-conversion, is also conducive to being applied in the pure field of functional materials of manufacture, also the application of degradable polyester hydrogel can be incorporated into temperature instruction field and alternation control field.
A kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention is a kind of temperature sensitive type intelligent aqueous gel capable, but compared with similar temperature-sensitive hydrogel, hydrogel of the present invention has higher gelling temp, can meet the needs of high temperature application scenario.The gelling temp of hydrogel of the present invention can reach 52 DEG C, improves 15 DEG C than 37 DEG C of existing same gellike.
Why a kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of the present invention has unique excellent specific property as above, has unique diversification composition, block structure and have employed unique synthetic method relevant with the degradable polymer of hydrogel of the present invention.Hydrogel of the present invention is a kind of physical gel, the realization of gel and the interaction between each block in the interaction between degradable polymer, degradable polymer, effect between degradable polymer and medium balance relevant, the present invention by innovation degradable polymer molecular structure and in conjunction with suitable synthesis and preparation method, thus optimize above-mentioned interaction, obtain a kind of novel hydrogels presenting numerous special performance.
Embodiment
Embodiment 1
Weighing 100g number-average molecular weight is 1500, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.4:1, 150g caprolactone, 60g rac-Lactide, 0.8g isocaprylic acid zinc, 0.2g stannous octoate joins in reactor, the 250mL toluene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 20h is reacted under this temperature condition, after reaction system is cooled to 60 DEG C, add 500mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 2Pa, dry 30h under the condition of 80 DEG C, add 2.5L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 8min under 45 DEG C of conditions, gel is 0.2 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 2
Weighing 100g number-average molecular weight is 2500, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.2:1, 240g caprolactone, 40g rac-Lactide, 0.8g isocaprylic acid zinc, 0.2g stannous octoate joins in reactor, the 320mL dimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 150 DEG C, and 30h is reacted under this temperature condition, after reaction system is cooled to 50 DEG C, add 700mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 2Pa, dry 20h under the condition of 100 DEG C, add the phosphate buffer solution that 1.2LpH is 7.4, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 4min under 35 DEG C of conditions, gel is 0.42 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 3
Weighing 100g number-average molecular weight is 1800, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.1:1, 180g caprolactone, 10g rac-Lactide, 0.7g isocaprylic acid zinc joins in reactor, the 240mL ethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 140 DEG C, and 30h is reacted under this temperature condition, after reaction system is cooled to 50 DEG C, add 300mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 100Pa, dry 30h under the condition of 80 DEG C, add 0.9L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 3min under 40 DEG C of conditions, gel is 0.15 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 4
Weighing 100g number-average molecular weight is 1500, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.1:1, 200g caprolactone, 10g rac-Lactide, 1g stannous octoate joins in reactor, the 350mL trimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 60 DEG C, add 400mL sherwood oil wherein, supernatant liquid is removed after vibration, add 250mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add 1.0L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 1.5min under 36 DEG C of conditions, gel is 0.05 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 5
Weighing 100g number-average molecular weight is 2100, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.05:1, 180g caprolactone, 30g rac-Lactide, 0.7g isocaprylic acid zinc joins in reactor, the 350mL trimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 40 DEG C, add 450mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add the phosphate buffer solution that 2.1LpH is 7.4, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 5min under 43 DEG C of conditions, gel is 0.18 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 6
Weighing 100g number-average molecular weight is 2100, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.05:1, 180g caprolactone, 0.7g stannous octoate joins in reactor, the 280mL dimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 140 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 40 DEG C, add 350mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add the phosphate buffer solution that 2.2LpH is 7.4, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 15min under 51 DEG C of conditions, gel is 0.09 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 7
Weighing 100g number-average molecular weight is 1500, propylene oxide and the ratio of the amount of substance of ethylene oxide are the both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) of 0.2:1, 180g caprolactone, 0.9g isocaprylic acid zinc joins in reactor, the 280mL toluene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 140 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 40 DEG C, add 350mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 10Pa, dry 20h under the condition of 90 DEG C, add 1.4L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 7min under 45 DEG C of conditions, gel is 0.12 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 8
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 1500, 150g caprolactone, 60g rac-Lactide, 0.8g isocaprylic acid zinc, 0.2g stannous octoate joins in reactor, the 250mL toluene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 20h is reacted under this temperature condition, after reaction system is cooled to 60 DEG C, add 400mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 2Pa, dry 30h under the condition of 80 DEG C, add 1.8L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 6min under 47 DEG C of conditions, gel is 0.15 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 9
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 2500, 240g caprolactone, 40g rac-Lactide, 0.8g isocaprylic acid zinc, 0.2g stannous octoate joins in reactor, the 320mL dimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 150 DEG C, and 20h is reacted under this temperature condition, after reaction system is cooled to 50 DEG C, add 450mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 2Pa, dry 24h under the condition of 100 DEG C, add the phosphate buffer solution that 1.2LpH is 7.4, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 4min under 37 DEG C of conditions, gel is 0.37 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 10
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 1800, 180g caprolactone, 10g rac-Lactide, 0.7g isocaprylic acid zinc joins in reactor, the 240mL ethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 140 DEG C, and 30h is reacted under this temperature condition, after reaction system is cooled to 50 DEG C, add 300mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 100Pa, dry 30h under the condition of 80 DEG C, add 0.9L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 3min under 40 DEG C of conditions, gel is 0.15 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 11
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 1500, 200g caprolactone, 10g rac-Lactide, 1g stannous octoate joins in reactor, the 350mL trimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 60 DEG C, add 500mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add 1.0L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 1.5min under 35 DEG C of conditions, gel is 0.04 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 12
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 2100, 180g caprolactone, 30g rac-Lactide, 0.7g isocaprylic acid zinc joins in reactor, the 350mL trimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high pure nitrogen metathesis reactor, reaction system is warming up to 150 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 40 DEG C, add 450mL sherwood oil wherein, supernatant liquid is removed after vibration, add 300mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add the phosphate buffer solution that 1.7LpH is 7.4, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 5min under 45 DEG C of conditions, gel is 0.18 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 13
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 2100, 180g caprolactone, 0.5g stannous octoate joins in reactor, the 260mL dimethylbenzene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 140 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 50 DEG C, add 350mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 50Pa, dry 30h under the condition of 80 DEG C, add 1.4L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 11min under 48 DEG C of conditions, gel is 0.11 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Embodiment 14
Weighing 100g number-average molecular weight is the hydroxyl carbowax of 1500, 180g caprolactone, 0.5g isocaprylic acid zinc joins in reactor, the 280mL toluene measuring anhydrous and oxygen-free joins in reactor, with the air in high-purity argon gas metathesis reactor, reaction system is warming up to 140 DEG C, and 25h is reacted under this temperature condition, after reaction system is cooled to 40 DEG C, add 350mL sherwood oil wherein, supernatant liquid is removed after vibration, add 200mL sherwood oil wherein again, supernatant liquid is removed after vibration, product is at 10Pa, dry 20h under the condition of 90 DEG C, add 1.1L deionized water, by heating, vibration, the methods such as cooling obtain the water-sol, this water-sol can form gel through 5min under 43 DEG C of conditions, gel is 0.1 to the absorbancy of the light of 600nm wavelength under 5mm light path condition, the colloidal sol of flowing can be reverted to below gelling temp.
Claims (7)
1. one kind has the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability, it is characterized in that: described hydrogel is formed primarily of degradable polyester and medium, described medium is deionized water, any one in phosphate buffer solution, the quality of described medium is 3-9 times of described degradable polymer quality, described degradable polyester is polynary triblock copolymer and is made up of following structural unit: oxygen ethylidene, oxygen-1, 3-propylidene, oxygen caproyl, oxygen-2-methyl acetyl, described oxygen-1, 3-propylidene is 0:1-0.4:1 with the ratio of the amount of substance of oxygen ethylidene, the mass ratio of described oxygen-2-methyl acetyl and oxygen caproyl is 0:1-0.4:1, described oxygen ethylidene and oxygen-1, the equal formula weight of number of the block that 3-propylidene is formed is 1500-2500, the equal formula weight of number of the block that described oxygen caproyl and oxygen-2-methyl acetyl are formed and oxygen ethylidene and oxygen-1, the ratio of the equal formula weight of number of the block that 3-propylidene is formed is 1:1.8-1:2.8.
2. a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability according to claim 1, is characterized in that comprising the following steps:
(1), weighing number-average molecular weight is that the hydroxyl carbowax of 1500-2500 or both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) join in reactor, weighing ester monomer, catalyzer join in reactor, the mass values of the quality of catalyzer and hydroxyl carbowax or both-end hydroxyl poly-(ethylene oxide-co-propylene oxide) is 1:100-1:2000, measures the aromatic solvent of anhydrous and oxygen-free and joins in reactor;
(2), with the air in high pure nitrogen or high-purity argon gas metathesis reactor, then reaction system is warming up to 140 DEG C-150 DEG C, reaction 20h-30h;
(3), after reaction system is cooled to 40 DEG C-60 DEG C, add sherwood oil wherein, the volume of sherwood oil be the 1-6 of the described aromatic solvent volume of step (1) doubly, remove supernatant liquid after vibration;
(4), in the product of step (3) add sherwood oil, the volume (mL) of sherwood oil is 0.5:1-1.5:1 with the ratio of the quality (g) of the product of step (2), removes supernatant liquid after vibration;
(5), by the product of step (4) dry 20h-30h under 2Pa-100Pa, the condition of 80 DEG C-100 DEG C;
(6) any one medium in deionized water or phosphate buffer solution, is added to the product of step (5), the quality of medium is 3-9 times of described step (5) product quality, the water-sol is obtained by methods such as heating, vibration, coolings, this water-sol can form transparent aquagel under the condition of temperature 35 DEG C-52 DEG C, gel time is 1.5min-15min, when temperature is less than 35 DEG C, revert to again the water-sol of flowing, the gel formed has the higher transparency, under 5mm light path condition to the absorbancy of the light of 600nm wavelength between 0.02-0.5.
3. a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability according to claim 2, it is characterized in that: in step (1), in described both-end hydroxyl poly-(ethylene oxide-co-propylene oxide), propylene oxide is 0:1-0.4:1 with the ratio of the amount of substance of ethylene oxide.
4. a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability according to claim 2, it is characterized in that: in step (1), described ester monomer is caprolactone, rac-Lactide, and the mass ratio of rac-Lactide and caprolactone is 0:1-0.4:1.
5. a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability according to claim 2, it is characterized in that: in step (1), described catalyzer is the 1-2 kind in isocaprylic acid zinc, stannous octoate.
6. a kind of preparation method with the temperature sensitive reversible degradable polyester hydrogel of transparent type of PhastGel ability according to claim 2, it is characterized in that: in step (1), described aromatic solvent is any one in toluene, dimethylbenzene, ethylbenzene, trimethylbenzene, and the volume (mL) of aromatic solvent is 0.6:1-1.2:1 with hydroxyl carbowax or both-end hydroxyl poly-(ethylene oxide-co-propylene oxide), the quality of ester monomer and the ratio of (g).
7. a kind of temperature sensitive reversible degradable polyester hydrogel of transparent type with PhastGel ability of preparing of method according to claim 2, in the application in the fields such as biomedical, functional materials preparation, oil production and temperature instruction.
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| CN1332189A (en) * | 2001-08-14 | 2002-01-23 | 复旦大学 | Degradable chemically crosslinked aquagel and its prepn |
| US20020173586A1 (en) * | 2000-09-28 | 2002-11-21 | Jeong Byeong Moon | Thermogelling biodegradable aqueous polymer solution |
| CN102639593A (en) * | 2009-09-18 | 2012-08-15 | 普罗赛瑞克斯医药发展公司 | Reconstitutable reverse thermal gelling polymers |
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| US20020173586A1 (en) * | 2000-09-28 | 2002-11-21 | Jeong Byeong Moon | Thermogelling biodegradable aqueous polymer solution |
| CN1332189A (en) * | 2001-08-14 | 2002-01-23 | 复旦大学 | Degradable chemically crosslinked aquagel and its prepn |
| CN102639593A (en) * | 2009-09-18 | 2012-08-15 | 普罗赛瑞克斯医药发展公司 | Reconstitutable reverse thermal gelling polymers |
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