CN106349465B - Light and temperature dual response copolymer and its synthetic method and aquogel system - Google Patents
Light and temperature dual response copolymer and its synthetic method and aquogel system Download PDFInfo
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Abstract
The invention discloses a kind of light and temperature dual response copolymer and its synthetic method and aquogel system, the polycaprolactone polyethylene glycol polycaprolactone triblock copolymer formed with adjacent nitro benzyl connection hydrophobic segment polycaprolactone and hydrophilic segment polyethylene glycol, wherein, polycaprolactone/polyethyleneglycol chain length ratio is 0.8~1.0.Synthetic method be the double adjacent nitro benzyl polyethylene glycol for containing photosensitive group using both ends as macromole evocating agent, trigger caprolactone monomer that ring-opening polymerisation occurs, polycaprolactone polyethylene glycol polycaprolactone triblock copolymer be made.Hydrogel in the present invention has good light and temperature response characteristics, while also has good biocompatibility and biological degradability, is that a kind of can be used for internal implantation material.
Description
Technical field
The invention belongs to stimuli responsive field of material technology, and in particular to a kind of light and temperature dual response copolymer and its
Synthetic method and aquogel system.
Background technology
For response type polymer as a kind of important intellectual material, its structure and performance can be because of diversified inside or outer
Portion stimulates such as enzyme, sugar, PH, redox, ultrasonic wave, temperature and light change and undergone mutation.In these stimulus, light
It is that one kind is clean, efficiently stimulates means, it can regulates and controls from its exterior to the structure and performance of material.Photoswitch can be controlled
The progress and stopping of light reaction processed, without any additional agents.During the course of the reaction, controlled by adjusting wavelength and the intensity of light
Make the performance of the selectivity reacted, speed and polymer.Many polymer application systems are related to light reaction, including light power
Learn therapy, FRET system, photoinduction polymerization etc..According to the difference of photochemical reaction type, photosensitive group can
It is divided into light heterogeneous group (such as spiro-pyrans, azobenzene), optical cleavage type group (such as adjacent nitro benzyl) and photodimerization type group (such as
Cumarin, cinnamic acid).Adjacent nitro benzyl is a kind of optical cleavage type group, after the ultraviolet light of 365nm wavelength, the group
Phenyl ring can be dissociated with neighbouring oxygen atom or nitrogen-atoms, and the reaction is irreversible.The group is before and after photodestruciton
The change of gel rubber system crosslink density can be caused, so as to change the swelling property of gel, mechanical property etc., or even occurred solidifying
Glue-colloidal sol transformation, therefore with great researching value and it is widely applied prospect.
Photosensitive polyalcohol hydrogel refers to that under the radiation of certain wavelength light volume can occur for polymer gel
Change or a kind of Photosensitive biomaterial of Morphological Transitions.The function of such material is realized and controlled completely by illumination, it is not necessary to is appointed
The effect in what electricity, temperature, magnetic field etc., have the advantages that material it is easy it is controllable, clean, available for biologic medical, cell culture with
And in photoelectric device.In addition to converting light energy into chemical energy and mechanical energy, the wavelength of specific light can also be absorbed effectively transformation
Golden nanometer particle is added into heat energy, such as system, the thermotherapy that local heating is used for cancer is can induce under near-infrared irradiation.
Temperature-sensitive hydrogel is a kind of hydrophilic polymer network, is not related to chemical reaction during gel-forming, point
Physical crosslinking between subchain can be interacted by weak bond (Van der Waals force, hydrophobic interaction and hydrogen bond) etc. formation.By changing
Temperature can regulate and control these hydrophobic interactions or hydrogen bond action, and system can shape by simple sol-gel phase in version
Into hydrogel.Therefore, temperature-sensitive hydrogel preparation process is simple, is not required to organic solvent, is very beneficial for protide isoreactivity medicine
The transmission of thing.
It is nonbiodegradable polymeric material to single light or the response of thermostimulation factor to study at present more, relevant
Light is less in the report of biodegradable polymers hydrogel with thermostimulation factor Application of composite, and in bio-medical field
Application study is also limited.Therefore, the present invention intends introducing adjacent nitro benzyl photoresponse base in Thermo-sensitive biodegradable hydrogel
Group, structure are expected in cell culture, drug controlled release, group with light, the biodegradable hydrogel material of hot double-response
The fields such as weaver's engineering support have significant application value.
The content of the invention
Present invention aim to address above mentioned problem, there is provided a kind of light and temperature dual response copolymer and its synthetic method
And aquogel system.
In order to solve the above technical problems, the technical scheme is that：A kind of light and temperature dual respond copolymer, and this is common
Polymers is formed poly- with adjacent nitro benzyl (ONB) connection hydrophobic segment polycaprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG)
Caprolactone-PEG-PCL triblock copolymer (PCL-ONB-PEG-ONB-PCL), wherein, polycaprolactone/poly- second
Glycol (PCL/PEG) segment number-average molecular weight ratio is 0.8~1.0.
In above-mentioned technical proposal, polyethylene glycol number-average molecular weight is 1000~1500.
In above-mentioned technical proposal, the chemical structural formula of the PCL-PEG-PCL triblock copolymer
Represent as follows：
Wherein, n=10~13.
In structure above, polycaprolactone is a kind of polymer with good biodegradability properties and biocompatibility,
It is widely used in biomedical every field, U.S. FDA ratifies the material and can be used for human body.Polyethylene glycol is a kind of nothing
The good material of poison, biocompatibility, low molecule amount (being less than 40,000) polymer can be excluded external by kidney.Adjacent nitro benzyl
After the ultraviolet light of 365nm wavelength, it may occur that scission of link reacts.The purpose of the present invention is that structure rings with light and temperature dual
The hydrophobic microcell that the hydrogel answered, wherein polycaprolactone are formed in hydrogel, medicine or other guest molecules can be loaded；It is poly-
Ethylene glycol assigns hydrogel temperature response characteristics, i.e., system is sol solution at low temperature, and is then changed into gel in high temperature；
Adjacent nitro benzyl assigns hydrogel response characteristics to light, i.e., under illumination effect, occurs between polycaprolactone and polyethylene glycol segment
Scission of link reacts, and causes caving in or destroying for gel.
A kind of synthetic method of foregoing light and temperature dual response copolymer, in the presence of catalyst, is contained with both ends
The double adjacent nitro benzyl polyethylene glycol (ONB-PEG-ONB) for having photosensitive group are macromole evocating agent, are triggered in a solvent in oneself
Ring-opening polymerisation occurs for ester monomer, and PCL-PEG-PCL triblock copolymer is made：
Said process can be expressed as with reaction equation：
In above-mentioned technical proposal, including step in detail below：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols (ONB), sodium hydride (NaH), anhydrous tetrahydro furan
(THF), tolysulfonyl polyethylene glycol (TsO-PEG-OTs), mole of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride
Than for 1：1.3~1.8,5- hydroxyls -2- nitrobenzyl alcohols and tolysulfonyl the polyethylene glycol mol ratio is 5~10：1,
Anhydrous tetrahydro furan 15-30mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, 1~4h of stirring reaction；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 36-60h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：1.6
~2.0g, catalyst：The one thousandth of caprolactone monomer amount is to a ten thousandth, solvent：20-50mL；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, ring-opening polymerization is carried out under 110 DEG C of counterflow conditions of temperature, the reaction time is 12~36h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
In above-mentioned technical proposal, the purpose of catalyst is easier to make for for reaction, and conventional lactone or lactide open loop gather
Close catalyst all to can be selected, be preferably approved by the FDA in the United States that to can be used for the catalyst of human body be stannous octoate (Sn (Oct)2)。
Reaction dissolvent is the medium as ring-opening polymerization, and it needs satisfaction to draw double adjacent nitro benzyl polyethylene glycol macromoleculars
Send out agent and caprolactone monomer dissolving wherein.In the present invention, it is more preferable control copolymer structure, avoids occurring to solvent
Chain transfer reaction, preferably nonpolar atent solvent, such as toluene.
In above-mentioned technical proposal, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5~1.6, institute
It is 6~8 to state 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol mol ratio：1.
In above-mentioned technical proposal, in step S22, reaction time 24h.
In above-mentioned technical proposal, it is prepared by foregoing light and temperature dual response copolymer, the light and temperature dual
Light and temperature dual response copolymer concentration are 10~30wt% in response water gel system.
The beneficial effects of the invention are as follows：
1st, the hydrogel in the present invention has good temperature response characteristics, i.e., when aqueous copolymers solution concentration is equal to or greatly
In the case of critical gel strength, sol-gel transition occurs near human body temperature for system, and phase transition temperature 25~
Between 37 DEG C, hydrogel that injectable uses is suitable as to use.
2nd, the hydrogel in the present invention has response characteristics to light, due to passing through in copolymer molecule structure between close and distant segment
Adjacent nitro benzyl is connected, and under the irradiation of ultraviolet light, strand can be broken, and cause the avalanche of gel.
3rd, gel component of the invention has good biocompatibility and biological degradability, is a kind of can be used in vivo
It is implanted into material.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to specific embodiment to this
Invention is described further：
Embodiment 1：
A kind of light and temperature dual respond copolymer, are gathered with light sensitivity adjacent nitro benzyl group (ONB) connection hydrophobic segment
The PCL-PEG-PCL triblock copolymer that caprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG) are formed
Thing (PCL-ONB-PEG-ONB-PCL), PCL/PEG segments number-average molecular weight ratio is 0.9 wherein in copolymer.
Hydrophilic segment PEG number-average molecular weight is 1000 in the present embodiment copolymer.
The specific synthesis step of PCL-ONB-PEG-ONB-PCL triblock copolymers is as follows in the present embodiment：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, tosylation
Polyethylene glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5, the 5- hydroxyls -2- nitrobenzoyls
Alcohol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 20mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, stir 1h；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 48h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：
1.8g, catalyst Sn (Oct)2:5/10000ths of amount of monomer, reaction dissolvent toluene：30ml；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, reaction time 24h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
Further, when macromole evocating agent synthesizes in above-mentioned S1, mole of 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride
Than that can also be 1：1.3、1：1.8；The mol ratio of 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol can be with
It is for 5：1、10：1.
Further, mixing time can also be 2h, 3h, 4h in above-mentioned S12.
Further, 12h, 36h are carried out when triblock copolymer synthesizes in above-mentioned S22 under counterflow condition.
The light and temperature dual response water gel system of the present embodiment, are made up of, copolymer exists above-mentioned triblock copolymer
Concentration in the aqueous solution is 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.
Embodiment 2
A kind of light and temperature dual respond copolymer, are gathered with light sensitivity adjacent nitro benzyl group (ONB) connection hydrophobic segment
The PCL-PEG-PCL triblock copolymer that caprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG) are formed
Thing (PCL-ONB-PEG-ONB-PCL), PCL/PEG segments number-average molecular weight ratio is 0.8 wherein in copolymer.
Hydrophilic segment PEG number-average molecular weight is 1000 in the present embodiment copolymer.
The specific synthesis step of PCL-ONB-PEG-ONB-PCL triblock copolymers is as follows in the present embodiment：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, tosylation
Polyethylene glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5, the 5- hydroxyls -2- nitrobenzoyls
Alcohol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 20mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, stir 1h；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 48h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：
1.6g, catalyst Sn (Oct)2：5/10000ths of amount of monomer, reaction dissolvent toluene：30ml；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, reaction time 24h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
Further, when macromole evocating agent synthesizes in above-mentioned S1, mole of 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride
Than that can also be 1：1.3、1：1.8；The mol ratio of 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol can be with
Specifically it is 5：1、10：1.
Further, mixing time can also be 2h, 3h, 4h in above-mentioned S12.
Further, 12h, 36h are carried out when triblock copolymer synthesizes in above-mentioned S22 under counterflow condition.
The light and temperature dual response water gel system of the present embodiment, are made up of, copolymer exists above-mentioned triblock copolymer
Concentration in the aqueous solution is 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.
Embodiment 3
A kind of light and temperature dual respond copolymer, are gathered with light sensitivity adjacent nitro benzyl group (ONB) connection hydrophobic segment
The PCL-PEG-PCL triblock copolymer that caprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG) are formed
Thing (PCL-ONB-PEG-ONB-PCL), PCL/PEG segments number-average molecular weight ratio is 1.0 wherein in copolymer.
Hydrophilic segment PEG number-average molecular weight is 1000 in the present embodiment copolymer.
The specific synthesis step of PCL-ONB-PEG-ONB-PCL triblock copolymers is as follows in the present embodiment：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, tosylation
Polyethylene glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5, the 5- hydroxyls -2- nitrobenzoyls
Alcohol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 20mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, stir 1h；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 48h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：
2.0g, catalyst Sn (Oct)2：5/10000ths of amount of monomer, reaction dissolvent toluene：30ml；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, reaction time 24h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
Further, when macromole evocating agent synthesizes in above-mentioned S1, mole of 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride
Than that can also be 1：1.3、1：1.8；The mol ratio of 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol can be with
It is for 5：1、10：1.
Further, mixing time can also be 2h, 3h, 4h in above-mentioned S12.
Further, 12h, 36h are carried out when triblock copolymer synthesizes in above-mentioned S22 under counterflow condition.
The light and temperature dual response water gel system of the present embodiment, are made up of, copolymer exists above-mentioned triblock copolymer
Concentration in the aqueous solution is 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.
Embodiment 4
A kind of light and temperature dual respond copolymer, are gathered with light sensitivity adjacent nitro benzyl group (ONB) connection hydrophobic segment
The PCL-PEG-PCL triblock copolymer that caprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG) are formed
Thing (PCL-ONB-PEG-ONB-PCL), PCL/PEG segments number-average molecular weight ratio is 0.8 wherein in copolymer.
Hydrophilic segment PEG number-average molecular weight is 1500 in the present embodiment copolymer.
The specific synthesis step of PCL-ONB-PEG-ONB-PCL triblock copolymers is as follows in the present embodiment：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, tosylation
Polyethylene glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5, the 5- hydroxyls -2- nitrobenzoyls
Alcohol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 20mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, stir 1h；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 48h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：
1.6g, catalyst Sn (Oct)2：5/10000ths of amount of monomer, reaction dissolvent toluene：30ml；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, reaction time 24h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
Further, when macromole evocating agent synthesizes in above-mentioned S1, mole of 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride
Than that can also be 1：1.3、1：1.8；The mol ratio of 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol can be with
It is for 5：1、10：1.
Further, mixing time can also be 2h, 3h, 4h in above-mentioned S12.
Further, 12h, 36h are carried out when triblock copolymer synthesizes in above-mentioned S22 under counterflow condition.
The light and temperature dual response water gel system of the present embodiment, are made up of, copolymer exists above-mentioned triblock copolymer
Concentration in the aqueous solution is 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.
Embodiment 5
A kind of light and temperature dual respond copolymer, are gathered with light sensitivity adjacent nitro benzyl group (ONB) connection hydrophobic segment
The PCL-PEG-PCL triblock copolymer that caprolactone (PCL) and hydrophilic segment polyethylene glycol (PEG) are formed
Thing (PCL-ONB-PEG-ONB-PCL), PCL/PEG segments number-average molecular weight ratio is 1.0 wherein in copolymer.
Hydrophilic segment PEG number-average molecular weight is 1500 in the present embodiment copolymer.
The specific synthesis step of PCL-ONB-PEG-ONB-PCL triblock copolymers is as follows in the present embodiment：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, tosylation
Polyethylene glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.5, the 5- hydroxyls -2- nitrobenzoyls
Alcohol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 20mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, added anhydrous
Tetrahydrofuran solution, stir 1h；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, in temperature 70 C reflux condition
Reacted under part, reaction time 48h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：
2.0g, catalyst Sn (Oct)2：5/10000ths of amount of monomer, reaction dissolvent toluene：30ml；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added into reaction vessel
In, catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, reaction time 24h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, system
Obtain PCL-PEG-PCL triblock copolymer.
Further, when macromole evocating agent synthesizes in above-mentioned S1, mole of 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride
Than that can also be 1：1.3、1：1.8；The mol ratio of 5- hydroxyl -2- nitrobenzyl alcohols and tolysulfonyl polyethylene glycol can be with
It is for 5：1、10：1.
Further, mixing time can also be 2h, 3h, 4h in above-mentioned S12.
Further, 12h, 36h are carried out when triblock copolymer synthesizes in above-mentioned S22 under counterflow condition.
The light and temperature dual response water gel system of the present embodiment, are made up of, copolymer exists above-mentioned triblock copolymer
Concentration in the aqueous solution is 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.
One of ordinary skill in the art will be appreciated that embodiment described here is to aid in reader and understands this hair
Bright principle, it should be understood that protection scope of the present invention is not limited to such especially statement and embodiment.This area
Those of ordinary skill can make according to these technical inspirations disclosed by the invention various does not depart from the other each of essence of the invention
The specific deformation of kind and combination, these deform and combined still within the scope of the present invention.
Claims (10)
1. a kind of light and temperature dual response copolymer, it is characterised in that：The copolymer connects hydrophobic segment with adjacent nitro benzyl
The PCL-PEG-PCL triblock copolymer that polycaprolactone and hydrophilic segment polyethylene glycol are formed, wherein,
Polycaprolactone/polyethyleneglycol segment number-average molecular weight ratio is 0.8~1.0.
2. light according to claim 1 and temperature dual response copolymer, it is characterised in that：The number of the polyethylene glycol is equal
Molecular weight is 1000~1500.
3. light according to claim 1 and temperature dual response copolymer, it is characterised in that：The polycaprolactone-poly- second
The chemical structural formula of glycol-polycaprolactone triblock copolymer is as follows：
Wherein, n=10~13.
4. a kind of synthetic method that copolymer is responded according to any described light of claim 1-3 and temperature dual, its feature exist
In：In the presence of catalyst, contain double adjacent nitro benzyl polyethylene glycol of photosensitive group as macromole evocating agent using both ends,
Trigger caprolactone monomer that ring-opening polymerization occurs in solvent, PCL-PEG-PCL triblock copolymer is made
Thing：
Said process can be expressed as with reaction equation：
5. the synthetic method of light according to claim 4 and temperature dual response copolymer, it is characterised in that：Including following
Specific steps：
S1：Prepare double adjacent nitro benzyl polyethylene glycol macromole evocating agents
S11：Weigh following material：5- hydroxyl -2- nitrobenzyl alcohols, sodium hydride, anhydrous tetrahydro furan, the poly- second of tosylation
Glycol, the mol ratio of the 5- hydroxyls -2- nitrobenzyl alcohols and sodium hydride is 1：1.3~1.8, the 5- hydroxyls -2- nitrobenzene
Methanol and tolysulfonyl polyethylene glycol mol ratio are 5~10：1, anhydrous tetrahydro furan 15-30mL：
S12：Under condition of ice bath, 5- hydroxyl -2- nitrobenzyl alcohols and sodium hydride are added in reaction vessel, add anhydrous tetrahydrochysene
Tetrahydrofuran solution, 1~4h of stirring reaction；
S13：After stirring, tolysulfonyl polyethylene glycol is added into reaction vessel, under temperature 70 C counterflow condition
Reacted, reaction time 36-60h, double adjacent nitro benzyl polyethylene glycol macromole evocating agents are made；
S2：Prepare PCL-PEG-PCL triblock copolymer
S21：Weigh following material：Double adjacent nitro benzyl polyethylene glycol macromole evocating agents：1.0g, caprolactone monomer：1.6~
2.0g, catalyst：The one thousandth of caprolactone monomer amount is to a ten thousandth, solvent：20-50mL；
S22：The double adjacent nitro benzyl polyethylene glycol macromole evocating agents weighed, caprolactone monomer are added in reaction vessel, then
Catalyst, solvent are added, is reacted under 110 DEG C of counterflow conditions of temperature, the reaction time is 12~36h；
S23：Reaction product is subjected to precipitation process with frost ether, filtered, and is dried in vacuum drying oven to constant weight, is made poly-
Caprolactone-PEG-PCL triblock copolymer.
6. the synthetic method of the light and temperature dual response copolymer according to claim 4 or 5, it is characterised in that：It is described
Catalyst is stannous octoate.
7. the synthetic method of the light and temperature dual response copolymer according to claim 4 or 5, it is characterised in that：It is described
Solvent is toluene.
8. the synthetic method of light according to claim 5 and temperature dual response copolymer, it is characterised in that：The 5- hydroxyls
The mol ratio of base -2- nitrobenzyl alcohols and sodium hydride is 1：1.5~1.6,5- hydroxyls -2- nitrobenzyl alcohols and to toluene sulphur
Acylated polyethylene glycol mol ratio is 6~8：1.
9. the synthetic method of light according to claim 5 and temperature dual response copolymer, it is characterised in that：Step S22
Middle reflux time is 24h.
10. a kind of light and temperature dual response water gel system, it is characterised in that：By any described light of claim 1-3 and
Temperature dual response copolymer is prepared, light and temperature dual response copolymerization in the light and temperature dual response water gel system
Thing concentration is 10~30wt%.
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