CN110305267A - A kind of high-intensitive response type hydrogel and preparation method thereof based on block copolymer - Google Patents
A kind of high-intensitive response type hydrogel and preparation method thereof based on block copolymer Download PDFInfo
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Abstract
The invention discloses a kind of high-intensitive response type hydrogel and preparation method thereof based on block copolymer, belongs to technical field of material.Utilize the behavior for being self-assembled into micella of response type amphipathic three block copolymer in water, it is set to replace traditional chemical crosslinking agent N, N- methylene diacrylamine carries out free radical polymerization as macromolecules cross-linking point inside system, with monomer, obtains the uniform high tough hydrogel of crosslink density.Response type amphipathic three block copolymer itself used is not charged, and size and stability are hardly influenced by effects of ion intensity or charge, therefore is suitable for most of free yl polymerizating monomers, is conducive to synthesis intelligence and functional form hydrogel.Preparation method of the invention is easy to operate, easily prepared, and raw material safety and stability is easy to store, and preparation process is green safe, and time-consuming short, by-product is few, provides approach for preparation multifunction high intensity hydrogel.The gel prepared has excellent pH response performance and excellent mechanical performance.
Description
Technical field
The invention belongs to material preparation and technical field of environmental management, and in particular to a kind of based on the high-strength of block copolymer
Spend response type hydrogel and preparation method thereof.
Background technique
Response type hydrogel can be widely applied to drug and release because it can carry out perception and response to extraneous stimulation
It puts, organizational project, the fields such as biosensor and underwater robot.But traditional response type hydrogel water content is high, with
And generally will lead to the inhomogeneity of gel network using chemical cross-linking agent, so that stress concentration is easy to when gel stress, because
All relatively low (the < 10Jm of the toughness of this conventional hydrogels-2).The angle how to be designed from molecule and network structure, by high property
The activeness and quietness mechanism of energy hydrogel is combined with response mechanism, prepares the high-intensitive water-setting that can be responded to environmental stimuli
Glue is the problem in science that this field is paid special attention to.
Currently, high-intensitive hydrogel is representational mainly to be had: double-network hydrogel, nano-composite gel, macromolecular
Microsphere hydrogel etc..Combined by the mechanism for enhancing these with ionic group, people are prepared for a series of with high-strength
The response type hydrogel of degree and toughness.However there is also its shortcomings for these hydrogels.For double-network hydrogel, coagulate
The high intensity of glue realizes by sacrificing first network, and the destruction of first network is irreversible, therefore double nets of response type
The reusable performance of network gel is poor.Nano-composite gel, although having good energy dissipation mechanism, repeat performance
It is good, but clay itself is electrically charged, the content of system ionic monomer must control to a very small extent, otherwise be easy to make
At the reunion of clay.These problems limit the progress of high-intensitive response type hydrogel to a certain extent.Therefore it needs to find
It is a kind of mild, and ionic monomeric content is not limited strictly, the method with universality carrys out synthesizing high-strength response
Type gel.
Non-ionic amphipathic three block copolymer can be self-assembled into micella in water, and micella is evenly dispersed in water,
And the distance between micella is certain, so compared to traditional chemical crosslinking gel, the point using micella as macromolecules cross-linking
The crosslink density of gel be uniform.Since the distance between micella is larger, the polymer chain connected between micella is long,
When the length of strand reaches the half of micella distance, physical entanglement can occur for strand, therefore gel has well
Tensile property.When by external force, polymer chain interconnected can be mutually coordinated, and the power that shared is subject to avoids
Stress is concentrated.In addition to this, the micella crosslinking points being assembled into based on non-ionic amphipathic three block copolymer, ionic list
The presence of body will not influence the stability of micella, and micella crosslinking points have universality for functional monomer.Therefore development is based on
The hydrogel of amphipathic three block copolymer is specifically ground for realizing that it is of great significance in the application of multiple fields
Study carefully and yet there are no open report.
Summary of the invention
To solve the above-mentioned problems, the high-intensitive response type hydrogel that the invention discloses a kind of based on block copolymer and
Preparation method, easy to operate, easily prepared, preparation process is green safe, time-consuming short, to prepare multifunction high intensity water-setting
Glue provides approach.
The present invention is to be achieved through the following technical solutions:
A kind of preparation method of high-intensitive response type hydrogel based on block copolymer disclosed by the invention, including it is following
Step:
Step 1: under a nitrogen atmosphere, triethylamine is added into the dichloromethane solution of amphipathic three block copolymer, stirs
It mixes uniformly, instills acryloyl chloride dropwise, 10~48h is stirred at room temperature after finishing in drop, filters；Filtrate is poured into petroleum ether, mistake
The solid being obtained by filtration is dried in vacuo, obtains the acrylated amphipathic three block copolymer of both-end base by filter；
Step 2: it is 5.0 that the acrylated amphipathic three block copolymer of both-end base that step 1 obtains, which is configured to concentration,
×10-4~1.8 × 10-1The aqueous solution of mol/L is added initiator, functional monomer, comonomer acrylamide, is passed through nitrogen
Afterwards, the high-intensitive response type hydrogel based on block copolymer is made in heated at constant temperature.
Preferably, amphipathic three block copolymer and methylene chloride in the dichloromethane solution of amphipathic three block copolymer
Solid-liquid ratio be 10g:(50~500) ml.
Preferably, amphipathic three block copolymer is Pluronic F127, Pluronic P123, Pluronic F68 and general
One of Lan Nike F108 or a variety of.
It is further preferred that the amount of the substance of triethylamine and acryloyl chloride is hydroxylated material in amphipathic three block copolymer
1~20 times of amount.
Preferably, the time for adding of acryloyl chloride is 5~60min.
Preferably, vacuum drying is 2~48h of progress at 20~30 DEG C.
Preferably, initiator is ammonium persulfate or potassium peroxydisulfate；Functional monomer is sodium acrylate, acrylic acid, methyl-prop
Olefin(e) acid dimethylaminoethyl or vinyl imidazole.
Preferably, functional monomer and comonomer acrylamide total concentration are 1~6mol/L, wherein functional monomer and
The ratio of comonomer acrylamide is 1:(0.05~5)；The concentration of initiator is functional monomer and comonomer acryloyl
The 0.05%~0.5% of amine total concentration.
Preferably, the temperature of heated at constant temperature is 45~70 DEG C, and the time is 3~24 hours.
The invention discloses using the high-intensitive response type hydrogel based on block copolymer made from above-mentioned preparation method.
Compared with prior art, the invention has the following beneficial technical effects:
The preparation method of high-intensitive response type hydrogel disclosed by the invention based on block copolymer, firstly, using anti-
The behavior for being self-assembled into micella of the type amphipathic three block copolymer of answering in water makes it replace traditional chemical crosslinking agent N, N- sub-
Methyl diacrylamine carries out free radical polymerization as macromolecules cross-linking point inside system, with monomer, and it is uniform to obtain crosslink density
The tough hydrogel of height.When by external force, polymer chain interconnected can be mutually coordinated, the power that shared is subject to,
Avoid stress concentration.Secondly, response type amphipathic three block copolymer itself is not charged, size and stability are hardly by molten
The influence of liquid ionic strength or charge, therefore it is suitable for most of free yl polymerizating monomers, it is rung convenient for being introduced in hydrogel
Type and functional groups are answered, synthesis intelligence and functional form hydrogel are conducive to.Preparation method of the invention is easy to operate, is easy to make
Standby, raw material safety and stability is easy to store, and preparation process is green safe, and time-consuming short, by-product is few, high for preparation multifunction
Intensity hydrogel provides approach.
Further, amphipathic three block copolymer and dichloromethane in the dichloromethane solution of amphipathic three block copolymer
The solid-liquid ratio of alkane be 10g:(50~500) ml, solid-liquid ratio be lower than this numerical value, reaction speed can be reduced, be unfavorable for reaction progress,
Higher than this numerical value, it is unfavorable for the dissolution of triblock copolymer.
Further, amphipathic three block copolymer using Pluronic F127, Pluronic P123, Pluronic F68,
One of Pluronic F108 or a variety of, different types of amphipathic three block copolymer is because of contained hydrophobe chain segment length
Degree is different, can be self-assembled into various sizes of micella in water, micella plays the role of crosslinking points, therefore energy in gel rubber system
Enough prepare the adjustable gel of network structure, performance.
Further, the amount of the substance of triethylamine and acryloyl chloride is the amount of hydroxylated material in amphipathic three block copolymer
1~20 times, be lower than this ratio, the product graft rate of synthesis is lower, is higher than this ratio, by-product is too many.
Further, the time for adding of acryloyl chloride is 5~60min, and time for adding is too long, and acryloyl chloride is volatile, leads
Reaction raw materials waste is caused, time for adding is too short, reacts insufficient, Product yields are lower.
Further, vacuum drying is 2~48h of progress at 20~30 DEG C, to completely remove the petroleum ether in filter residue.
Further, it is easy to store as initiator using ammonium persulfate or potassium peroxydisulfate, safety, functional monomer is adopted
With sodium acrylate, acrylic acid, dimethylaminoethyl methacrylate or vinyl imidazole, the presence of functional monomer, in difference
Under pH and ionic strength, gel response performance is assigned.
Further, the temperature of heated at constant temperature is 45~70 DEG C, and the time is 3~24 hours, most sharp in this temperature range
In decomposition of initiator, and energy consumption is lower.
High-intensitive response type hydrogel disclosed by the invention using made from the above method based on block copolymer, has
Excellent pH response performance, with the increase of pH, the swelling ratio of gel is gradually increased；With excellent mechanical performance, intensity is high,
It has broad application prospects in fields such as chemical driver, underwater robot, organizational projects
Detailed description of the invention
Fig. 1 is the high-intensitive response type hydrogel based on block copolymer made from the embodiment of the present invention 2 at different pH
Swelling behavior datagram；
Fig. 2 is the compression stress-of the high-intensitive response type hydrogel based on block copolymer made from the embodiment of the present invention 2
Strain figure.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
Step 1: the F108 that 10g is completely dried is dissolved in the there-necked flask for filling 200mL methylene chloride. while stirring
Logical nitrogen after being completely dissolved to F108, is added 1.4g triethylamine, acryloyl chloride (this of 1.2g is slowly added dropwise with dropping funel
When, the amount of the substance of triethylamine and acryloyl chloride used is 10 times of the amount of the substance of hydroxyl in F108 used), control total drop
It is 30min between added-time.After being added dropwise, reaction solution is stirred at room temperature 10h, control entire reaction in anhydrous conditions into
Row.After completion of the reaction, reaction solution is filtered for multiple times, except the triethylamine hydrochloride generated in dereaction.Remaining liq is poured into stone
It is filtered for multiple times in oily ether, it is acrylated that 2h dry at obtained solid in a vacuum drying oven 30 DEG C is obtained both-end base
F108(F108DA)。
Step 2: F108DA being dissolved in deionized water, 0.5h is stirred to dissolution and forms micella, be separately added into persulfuric acid
Potassium, acrylamide, dimethylaminoethyl methacrylate, wherein F108DA concentration is 3.4 × 10-2Mol/L, potassium peroxydisulfate are dense
Degree is 3 × 10-3Mol/L, dimethylaminoethyl methacrylate concentration are 1mol/L, acrylamide concentration 2mol/L, lead to nitrogen
Gas removes the oxygen in solution, obtains after free radical polymerization 10h based on the high-strength of block copolymer in 60 DEG C of thermostat water baths
Spend response type hydrogel.
Embodiment 2
Step 1: the P123 that 10g is completely dried is dissolved in the there-necked flask for filling 200mL methylene chloride. while stirring
Logical nitrogen after being completely dissolved to P123, is added 3.5g triethylamine, acryloyl chloride (this of 3.1g is slowly added dropwise with dropping funel
When, the amount of the substance of triethylamine and acryloyl chloride used is 10 times of the amount of the substance of hydroxyl in P123 used), control total drop
It is 30min between added-time.After being added dropwise, reaction solution is stirred at room temperature 48h, control entire reaction in anhydrous conditions into
Row.After completion of the reaction, reaction solution is filtered for multiple times, except the triethylamine hydrochloride generated in dereaction.Remaining liq is poured into stone
It is filtered for multiple times in oily ether, 20h dry at obtained solid in a vacuum drying oven 25 DEG C is then obtained into both-end base acryloyl
The P123 (P123DA) of change.
Step 2: P123DA being dissolved in deionized water, 0.5h is stirred to dissolution and forms micella, be separately added into persulfuric acid
Ammonium, acrylamide, sodium acrylate, wherein P123DA concentration is 5.0 × 10-4Mol/L, ammonium persulfate concentrations are 3 × 10-3mol/
L, sodium acrylate concentration are 1mol/L, acrylamide concentration 5mol/L, lead to the oxygen in nitrogen removing solution, in 55 DEG C of constant temperature
The high-intensitive response type hydrogel based on block copolymer is obtained in water-bath after free radical polymerization 18h.
Embodiment 3
Step 1: the F68 that 10g is completely dried is dissolved in the there-necked flask for filling 100mL methylene chloride. while stirring
Logical nitrogen after being completely dissolved to F68, is added 1.2g triethylamine, acryloyl chloride (this of 1.1g is slowly added dropwise with dropping funel
When, the amount of the substance of triethylamine and acryloyl chloride used is 5 times of the amount of the substance of hydroxyl in F68 used), control total be added dropwise
Time is 15min.After being added dropwise, reaction solution is stirred at room temperature for 24 hours, entire reaction is controlled and carries out in anhydrous conditions.
After completion of the reaction, reaction solution is filtered for multiple times, except the triethylamine hydrochloride generated in dereaction.Remaining liq is poured into petroleum ether
In be filtered for multiple times, 48h dry at obtained solid in a vacuum drying oven 20 DEG C is obtained into the acrylated F68 of both-end base
(F68DA)。
Step 2: F68DA being dissolved in deionized water, 0.5h is stirred to dissolution and forms micella, be separately added into persulfuric acid
Potassium, acrylamide, sodium acrylate, wherein F68DA concentration is 1.8 × 10-1Mol/L, potassium peroxydisulfate concentration are 5 × 10-3mol/
L, acrylic acid concentration 0.05mol/L, acrylamide concentration 0.95mol/L lead to the oxygen in nitrogen removing solution, at 70 DEG C
Free radical polymerization obtains the high-intensitive response type hydrogel based on block copolymer afterwards for 24 hours in thermostat water bath.
Embodiment 4
Step 1: the F127 that 10g is completely dried is dissolved in the there-necked flask for filling 500mL methylene chloride. while stirring
Logical nitrogen after being completely dissolved to F127, is added 3.2g triethylamine, acryloyl chloride (this of 2.8g is slowly added dropwise with dropping funel
When, the amount of the substance of triethylamine and acryloyl chloride used is 20 times of the amount of the substance of hydroxyl in F127 used), control total drop
It is 60min between added-time.After being added dropwise, reaction solution is stirred at room temperature for 24 hours, control entire reaction in anhydrous conditions into
Row.After completion of the reaction, reaction solution is filtered for multiple times, except the triethylamine hydrochloride generated in dereaction.Remaining liq is poured into stone
It is filtered for multiple times in oily ether, it is acrylated that 36h dry at obtained solid in a vacuum drying oven 25 DEG C is obtained both-end base
F127(F127DA)。
Step 2: F127DA being dissolved in deionized water, 0.5h is stirred to dissolution and forms micella, be separately added into persulfuric acid
Potassium, acrylamide, vinyl imidazole, wherein F127DA concentration is 5.6 × 10-3Mol/L, potassium peroxydisulfate concentration are 8 × 10- 3Mol/L, vinyl imidazole concentration are 3.6mol/L, acrylamide concentration 0.4mol/L, lead to the oxygen in nitrogen removing solution
Gas obtains the high-intensitive response type hydrogel based on block copolymer in 60 DEG C of thermostat water baths after free radical polymerization 16h.
Embodiment 5
Step 1: the F108 that 10g is completely dried is dissolved in the there-necked flask for filling 50mL methylene chloride. while stirring
Logical nitrogen after being completely dissolved to F108, is added 0.14g triethylamine, the acryloyl chloride of 0.12g is slowly added dropwise with dropping funel
(at this point, the amount of the substance of triethylamine used and acryloyl chloride be the amount of the substance of hydroxyl in F108 used 1 times), control are total
Time for adding is 5min.After being added dropwise, reaction solution is stirred at room temperature for 24 hours, control entire reaction in anhydrous conditions into
Row.After completion of the reaction, reaction solution is filtered for multiple times, except the triethylamine hydrochloride generated in dereaction.Remaining liq is poured into stone
It is filtered for multiple times in oily ether, it is acrylated that drying at obtained solid in a vacuum drying oven 25 DEG C is obtained both-end base for 24 hours
F108(F108DA)。
Step 2: F108DA being dissolved in deionized water, 0.5h is stirred to dissolution and forms micella, be separately added into persulfuric acid
Potassium, acrylamide, sodium acrylate, wherein F108DA concentration is 1.7 × 10-3Mol/L, potassium peroxydisulfate concentration are 5 × 10-3mol/
L, dimethylaminoethyl methacrylate concentration are 4mol/L, acrylamide concentration 1mol/L, lead to nitrogen and remove in solution
Oxygen obtains the high-intensitive response type hydrogel based on block copolymer in 60 DEG C of thermostat water baths after free radical polymerization 10h.
In above-described embodiment, the aqueous solution of the acrylated amphipathic three block copolymer of both-end base is using deionized water
Configuration, be that will affect the preparation of subsequent gel because ordinary tap water contains part ion and organic matter.
Step 1 controls entire reaction and carries out in anhydrous conditions, is the hydroxyl because of acryloyl chloride and triblock copolymer
Reaction, if being mixed into moisture content in reaction, acryloyl chloride can preferentially be reacted with water, rather than the hydroxyl with triblock copolymer both ends
Base reaction, to reduce the grafting rate of reaction.
It is the high-intensitive response type hydrogel based on block copolymer made from the embodiment of the present invention 2 in different pH such as Fig. 1
Under swelling behavior, as seen from the figure, gel have excellent pH response performance, with the increase of pH, the swelling ratio of gel
It is gradually increased.
Such as Fig. 2, compression performance test is carried out to gel made from embodiment 2, compresses batten size are as follows: diameter 9mm, height
4mm, 98% compression strain that gel can be born is without destroying, greatest compressive strength 53MPa, and it is excellent to illustrate that gel has
Mechanical performance, this method is easy to operate, gel obtained the fields such as chemical driver, underwater robot, organizational project have
Have broad application prospects.
Claims (10)
1. a kind of preparation method of the high-intensitive response type hydrogel based on block copolymer, which is characterized in that including following step
It is rapid:
Step 1: under a nitrogen atmosphere, triethylamine being added into the dichloromethane solution of amphipathic three block copolymer, stirring is equal
It is even, acryloyl chloride is instilled dropwise, and 10~48h is stirred at room temperature after finishing in drop, filters；Filtrate is poured into petroleum ether, is filtered, it will
The solid vacuum drying being obtained by filtration, obtains the acrylated amphipathic three block copolymer of both-end base；
Step 2: it is 5.0 × 10 that the acrylated amphipathic three block copolymer of both-end base that step 1 obtains, which is configured to concentration,-4
~1.8 × 10-1Initiator, functional monomer, comonomer acrylamide is added in the aqueous solution of mol/L, permanent after being passed through nitrogen
Temperature heating, is made the high-intensitive response type hydrogel based on block copolymer.
2. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In the solid-liquid ratio of amphipathic three block copolymer and methylene chloride is in the dichloromethane solution of amphipathic three block copolymer
10g:(50~500) ml.
3. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In amphipathic three block copolymer is in Pluronic F127, Pluronic P123, Pluronic F68 and Pluronic F108
It is one or more.
4. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as claimed in claim 3
In the amount of the substance of triethylamine and acryloyl chloride is 1~20 times of the amount of hydroxylated material in amphipathic three block copolymer.
5. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In the time for adding of acryloyl chloride is 5~60min.
6. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In vacuum drying is 2~48h of progress at 20~30 DEG C.
7. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In initiator is ammonium persulfate or potassium peroxydisulfate；Functional monomer is sodium acrylate, acrylic acid, dimethylaminoethyl
Ethyl ester or vinyl imidazole.
8. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In functional monomer and comonomer acrylamide total concentration are 1~6mol/L, wherein functional monomer and comonomer propylene
The ratio of amide is 1:(0.05~5)；The concentration of initiator is functional monomer and comonomer acrylamide total concentration
0.05%~0.5%.
9. the preparation method of the high-intensitive response type hydrogel based on block copolymer, feature exist as described in claim 1
In the temperature of heated at constant temperature is 45~70 DEG C, and the time is 3~24 hours.
10. using the high-intensitive response type water based on block copolymer made from any one of claim 1~9 preparation method
Gel.
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| CN111533853A (en) * | 2020-05-22 | 2020-08-14 | 武汉工程大学 | Ionic hydrogel and preparation method thereof |
| CN113943429A (en) * | 2021-10-23 | 2022-01-18 | 西北工业大学 | High-strength anti-fatigue hydrogel and preparation method thereof |
| CN114853529A (en) * | 2022-04-20 | 2022-08-05 | 深圳市芭田生态工程股份有限公司 | Soil loosening water-saving liquid fertilizer and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111154120A (en) * | 2020-01-15 | 2020-05-15 | 西安工程大学 | Conductive hydrogel based on reactive micelle and preparation method and application thereof |
| CN111533853A (en) * | 2020-05-22 | 2020-08-14 | 武汉工程大学 | Ionic hydrogel and preparation method thereof |
| CN113943429A (en) * | 2021-10-23 | 2022-01-18 | 西北工业大学 | High-strength anti-fatigue hydrogel and preparation method thereof |
| CN114853529A (en) * | 2022-04-20 | 2022-08-05 | 深圳市芭田生态工程股份有限公司 | Soil loosening water-saving liquid fertilizer and preparation method and application thereof |
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Application publication date: 20191008 |