CN106084116A - Hydrogel and preparation method thereof, the application of hydrogel - Google Patents
Hydrogel and preparation method thereof, the application of hydrogel Download PDFInfo
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- CN106084116A CN106084116A CN201610438250.2A CN201610438250A CN106084116A CN 106084116 A CN106084116 A CN 106084116A CN 201610438250 A CN201610438250 A CN 201610438250A CN 106084116 A CN106084116 A CN 106084116A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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Abstract
The present invention provides a kind of hydrogel and preparation method thereof, the application of hydrogel, and it includes providing the methacrylate containing phenyl group and methacrylic acid；Adjust and contain the methacrylate of phenyl group with the concentration of methacrylic acid than being (0.1～0.7): (1～3), carry out copolyreaction and prepare the hydrogel with required pH response lag.The present invention can be by the adjustment by hydrophobic group and addition thereof, it is achieved adjust the pH response lag of hydrogel, and the pH response lag of the hydrogel of prepared acquisition also can be made to move to alkalescence direction.Hydrogel of the present invention can be widely in the sewage disposal or medicament slow release application of different pH value.
Description
[technical field]
The present invention relates to hydrogel material field, particularly relate to a kind of hydrogel and preparation method thereof, the application of hydrogel.
[background technology]
Gel is seen everywhere in our daily life at ordinary times, such as fruit jelly, agar, toothpaste, contact lens, glue-type steel
Pen, hair jelly and other cosmetics etc..Wherein, hydrogel is most commonly seen, and it is a kind of hydrophilic but water-fast macromolecule
Polymer, its character is soft, can the most swelling remain to keep its shape and three-dimensional space network to an equilibrium volume in water
Structure, is a kind of functional high molecule material quickly grown, and has in fields such as biological medicine, enzymatic activity control, molecule separation
It is widely applied.In numerous hydrogels, the intelligent aqueous gel capable that pH is sensitive, because of it is swelling or go the swelling change with pH value and
Change, thus be considered to have broad application prospects in fields such as sewage disposal, medicine transmission and releases.
As a kind of synthesising property stable, purity high, swelling ratio big pH sensitive aquagel is had been disclosed in the prior art,
But the pH response range of this hydrogel remains fixing, is of limited application.Additionally, prior art also discloses one
Plant the pH sensitive aquagel utilizing template copolymerization method to synthesize semi-intercrossing network, due to counterions matrix polymerization in gel
The existence of thing, can change the response lag of pH by changing the structure of gel.Yet with ionic bonds a large amount of in gel
Existence, the pH response lag of gel can be caused to be affected by the ion concentration in environment so that pH sensitivity decline and cannot
PH response lag is controlled.But in the application of hydrogel sensitive for pH, the regulation and control to pH response lag require more to come
The highest, a kind of pH preparation method of sensitive controlled hydrogel is the most urgently provided.
[summary of the invention]
For overcoming the problem that cannot realize being controlled pH response lag in existing gel, the present invention provides a kind of water-setting
Glue and preparation method thereof, the application of hydrogel.
The present invention solves that a technical scheme of above-mentioned technical problem is to provide the preparation method of a kind of hydrogel, its bag
Include following steps: provide the methacrylate containing phenyl group and methacrylic acid；Adjust the methacrylate containing phenyl group
With the concentration of methacrylic acid than for (0.1～0.7): (1～3), carry out copolyreaction and prepare there is required pH threshold of response
The hydrogel of value.
Preferably, the monomer concentration of the described methacrylate containing phenyl group and described methacrylic acid be 1.0～
4.0mol/L。
Preferably, the described methacrylate containing phenyl group include phenyl methacrylate, benzyl methacrylate,
Methacrylic acid-2-ethyl phenoxy, methacrylic acid 2-(4-benzoyl-3-hydroxyphenoxy) ethyl ester, methacrylic acid-2-
The mixture of one or more in hydroxyl Acetoxon diphenyl phthalate or methacrylic acid dicyclohexyl benzene methyl.
Preferably, the preparation method of described hydrogel includes the described methacrylate containing phenyl group and metering system
Acid is dissolved in N, N '-dimethylformamide, dimethyl sulfoxide or N, mixing of one or more in N '-methylene-bisacrylamide
Compound.
Preferably, the preparation method of described hydrogel includes adding cross-linking agent and initiator, and the consumption of described cross-linking agent is
0.05～3mol%, the concentration of described initiator is 0.001～0.10mol/L.
Preferably, described cross-linking agent includes N, N '-methylene-bisacrylamide, N-hydroxy-succinamide or Isosorbide-5-Nitrae-fourth two
One or both mixture in alcohol ethylene oxidic ester；Described initiator includes that Ammonium persulfate., sodium sulfite or azo two are different
One or both mixture in butyronitrile.
Preferably, in the preparation method of described hydrogel, the temperature of reaction is 50 DEG C-90 DEG C.
The present invention solves that another technical scheme of above-mentioned technical problem is to provide a kind of hydrogel, it is by containing phenyl group
Methacrylate react with methacrylic acid copolymer and prepare；Wherein, the methacrylate containing phenyl group and methyl
Acrylic acid concentration is than being (0.1～0.7): (1～3).
Preferably, the pH response lag of described hydrogel is 6.0～8.0.
The present invention solves that another technical scheme of above-mentioned technical problem is to provide the application of a kind of hydrogel, as above institute
The hydrogel stated is in the sewage disposal or medicament slow release of different pH value.
Relative to prior art, hydrogel provided by the present invention and preparation method thereof, the application of hydrogel, can be by right
Methacrylate containing phenyl group and the adjustment of addition thereof, it is achieved adjust the pH response lag of hydrogel, make prepared
The pH response lag of the hydrogel obtained moves to alkalescence direction, so that described hydrogel can have specific aim and be applied to different pH
In the sewage disposal of value or medicament slow release.
[detailed description of the invention]
In order to make the purpose of the present invention, technical scheme and advantage are clearer, below in conjunction with embodiment, to this
Bright it is further elaborated.Should be appreciated that specific embodiment described herein, and need not only in order to explain the present invention
In limiting the present invention.
The first embodiment of the present invention provides the preparation method of a kind of hydrogel, and it includes the metering system containing phenyl group
Acid esters form a polymerization reaction system after mixing with methacrylic acid and react acquisition needed for hydrogel.Wherein, by adjusting
Methacrylate containing phenyl group and the mixed proportion of methacrylic acid, to prepare the institute with required pH response lag
State hydrogel.
The described methacrylate monomer containing phenyl group added in the present invention and the thing of methacrylic acid monomer
The amount concentration of matter is than for (0.1～0.7): (1～3), and the substance withdrawl syndrome of the two monomer is than for (0.1～0.6): (1～
2.4), between the two monomer substance withdrawl syndrome ratio particularly as follows: 0.125:2.37,0.25:2.25,0.125:2.38,
0.101:1.022、0.64:1.92、0.115:1.09、0.16:1.94、0.125:2.97、0.54:3、0.7:2.1、0.29:1、
0.7:3,0.62:2.65 or 0.48:2.77 etc..
Specifically, at least one methacrylate containing phenyl group is dissolved in a reaction dissolvent with methacrylic acid
After, continue to inject cross-linking agent and initiator, be copolymerized the hydrogel needed for acquisition under a shielding gas.Wherein, described
Methacrylate containing phenyl group is hydrophobic monomer, and described methacrylic acid is hydrophilic monomer.
The present invention some preferably in embodiment, the described methacrylate containing phenyl group can include but unrestricted
In: phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-ethyl phenoxy, methacrylic acid 2-(4-benzene first
Acyl group-3-hydroxyphenoxy) ethyl ester, 2-hydroxyethyl methacry-late diphenyl phosphate or methacrylic acid dicyclohexyl benzene first
The mixture of one or more in ester etc..
In some embodiments of the invention, the described methacrylate containing phenyl group is by phenyl methacrylate and methyl
Benzyl acrylate with mass ratio as 1:2.1,1:3,4:1 and 2.5:1 mix after obtain.
In the present invention, the described methacrylate containing phenyl group is preferably phenyl methacrylate and methacrylic acid
One or both mixture in benzyl ester.The described methacrylate monomer containing phenyl group and methacrylic acid monomer
Concentration is 1.0～4.0mol/L, wherein, and the described methacrylate monomer containing phenyl group and the concentration of methacrylic acid monomer
Also may further be 1.5～3.5mol/L.The present invention some preferably in embodiment, the described methacrylic acid containing phenyl group
The concentration of ester monomer and methacrylic acid monomer can be specially 1.0mol/L, 1.2mol/L, 1.5mol/L, 1.6mol/L,
1.7mol/L、1.9mol/L、2.0mol/L、2.1mol/L、2.56mol/L、.2.78mol/L、2.9mol/L、2.97mol/L、
3.0mol/L、3.12mol/L、3.17mol/L、3.21mol/L、3.46mol/L、3.53mol/L、3.76mol/L、3.89mol/
L or 4.0mol/L.
Described reaction dissolvent includes N, N '-dimethylformamide, dimethyl sulfoxide, N, in N '-methylene-bisacrylamide
The mixture of one or more.
Described initiator is including but not limited to the one in Ammonium persulfate., sodium sulfite or azodiisobutyronitrile or two
The mixture planted.In the present invention, described initiator can be the mixture of Ammonium persulfate. and sodium sulfite, and described initiator is also
It can be azodiisobutyronitrile.In the preparation method of hydrogel provided by the present invention, the consumption standard of described initiator is to make
Its concentration is 0.001～0.10mol/L.In the present invention, the concentration of described initiator can be also 0.002～0.035mol/L,
The concentration of described initiator may further be 0.002～0.015mol/L.In the present invention, the concentration of described initiator can be concrete
For: 0.001mol/L, 0.002mol/L, 0.004mol/L, 0.010mol/L, 0.017mol/L, 0.021mol/L,
0.027mol/L、0.032mol/L、0.035mol/L、0.037mol/L、0.04mol/L、0.043mol/L、0.053mol/L、
0.061mol/L、0.069mol/L、0.071mol/L、0.075mol/L、0.079mol/L、0.083mol/L、0.087mol/L、
0.092mol/L, 0.095mol/L or 0.10mol/L.
Described cross-linking agent includes that N, N '-methylene-bisacrylamide, N-hydroxy-succinamide or 1,4-butanediol shrink
One or both mixture in glyceride.The consumption of described cross-linking agent is 0.05～3mol%, and the consumption of described cross-linking agent enters
One step is 0.05mol%, 0.08mol%, 0.11mol%, 0.15mol%, 0.28mol%, 0.35mol%, 0.47mol%,
0.49mol%, 0.58mol%, 0.67mol%, 0.74mol%, 0.79mol%, 0.82mol%, 0.94mol%,
0.99mol%, 1mol%, 1.55mol%, 1.83mol%, 1.97mol%, 2.0mol%, 2.06mol%, 2.3mol%,
2.5mol%, 2.75mol%, 2.89mol%, 2.97mol% or 3.0mol%.
The described methacrylic acid monomer containing phenyl group is hydrophobic group monomer, and the present invention is by methacrylic acid monomer and institute
Stating the methacrylic acid monomer containing phenyl group and carry out copolyreaction, wherein, the temperature of charge of described copolymerization is 50 DEG C～90 DEG C,
Described copolyreaction temperature can be 60～80 DEG C further, described copolyreaction temperature concretely: 50 DEG C, 56 DEG C, 59 DEG C, 61
℃、63.5℃、67℃、69℃、70℃、71.3℃、72.5℃、73.8℃、75.5℃、76.2℃、77.9℃、78.8℃、
80.1 DEG C, 80.5 DEG C, 81.6 DEG C, 83.7 DEG C, 84.6 DEG C, 85.9 DEG C, 86.3 DEG C, 87.5 DEG C, 88 DEG C, 89 DEG C or 90 DEG C.
Described protective gas can be one or more in nitrogen, argon, helium etc..
In the present invention, by the conjugation of hydrophobic group in gel copolymer (methacrylic acid monomer containing phenyl group), from
And make the pH sensitive range scalable of gained hydrogel.Esters containing phenyl ring relies primarily on the hydrophobic of phenyl ring and conjugation makes
PH sensitive range moves to pH alkalescence, and kind and addition by the regulation methyl methacrylate monomer containing phenyl group are controlled
The pH sensitive range of gel processed.
The second embodiment of the present invention provides a kind of hydrogel, and described hydrogel is carried by first embodiment of the invention
The preparation method of the hydrogel of confession is made, and specifically, described hydrogel is at least by the methacrylate containing phenyl group and methyl
Acrylic acid copolymer reaction prepares；Wherein the concentration containing the methacrylate of phenyl group and methacrylic acid than for (0.1～
0.7): (1～3).By adjusting the mixed proportion of the methacrylate containing phenyl group and methacrylic acid, to adjust described water
The pH response lag of gel, also can be adjusted described hydrogel swelling behavior under this pH value further.
Wherein, the described methacrylate monomer containing phenyl group added in the present embodiment and methacrylic acid list
The substance withdrawl syndrome ratio of body may further be (0.1～0.6): (1～2.4), the substance withdrawl syndrome ratio of the two monomer
Particularly as follows: 0.125:2.37,0.25:2.25,0.125:2.38,0.101:1.022,0.64:1.92,0.115:1.09,0.16:
1.94,0.125:2.97,0.54:3,0.7:2.1,0.29:1,0.7:3,0.62:2.65 or 0.48:2.77 etc..
In the present invention, the pH response lag of described hydrogel is 6.0-8.0, and the pH response lag such as described hydrogel can
It is specially 6.01,6.31,6.41,6.56,6.87,6.98,7.21 or 7.68.
The third embodiment of the present invention provides the application of a kind of hydrogel, and hydrogel as described above is used for sewage disposal
Or in medicament slow release application.As described in sewage disposal, the pH response lag of described hydrogel can be adjusted to sewage
PH value matches, thus obtains preferably imbibition effect, thus can enter the harmful substance (such as heavy metal etc.) in sewage
Row absorption, it is achieved more excellent wastewater treatment efficiency.And for example in medicament slow release, the pH response lag of described hydrogel can be adjusted
To corresponding with the pH value of the intestines of drug administration person (pH scope is about 7.4), thus medicine can enter in specific region
Row slow release.
Below, use first embodiment of the invention to be listed below with the specific experiment group of the second embodiment, need explanation
It is that following experimental group is only example, not as concrete restriction.
Experimental group 1
Weigh 2.37mol/L methacrylic acid and 0.125mol/L phenyl methacrylate is dissolved in the N, N ' of 50mL-diformazan
In base formamide solvent, mix homogeneously.Then in mixed solution add 0.16mol%N, N '-methylene-bisacrylamide and
0.012mol/L azodiisobutyronitrile.After above-mentioned solution mix homogeneously, move to test tube rapidly, be passed through nitrogen and carry out after 10 minutes
Seal, be placed in the baking oven of 80 DEG C and carry out reacting 24h, be copolymerized thus obtain hydrogel sample.
Reaction takes out described hydrogel sample after terminating, and is cut into thickness and is about the thick circle sheet of 2-3mm, inserts dehydrated alcohol
In soak after, place in deionized water soak, to remove impurity, finally carry out lyophilization, obtain methacrylic acid
The gel copolymer that phenyl ester is modified.
Experimental group 2
In this experimental group, weigh 2.25mol/L methacrylic acid and 0.25mol/L phenyl methacrylate is dissolved in 50mL
N, N '-solvent dimethylformamide in, mix homogeneously.Then in mixed solution, add 0.16mol%N, N '-di-2-ethylhexylphosphine oxide
Acrylamide and 0.012mol/L azodiisobutyronitrile.Move to, in test tube, be passed through nitrogen by after above-mentioned solution mix homogeneously rapidly
Seal after 10 minutes, be placed in the baking oven of 80 DEG C and carry out reacting 24h, thus obtain hydrogel sample.
Reaction takes out described hydrogel sample after terminating, and is cut into the thick circle sheet of thickness about 2-3mm, inserts in dehydrated alcohol
After immersion, place in deionized water and soak, to remove impurity, finally carry out lyophilization, obtain phenyl methacrylate and change
The gel copolymer of property.
Experimental group 3
In this experimental group, weigh 2.38mol/L methacrylic acid and 0.125mol/L benzyl methacrylate is dissolved in
In the dimethyl sulfoxide solvent of 50mL, mix homogeneously.Then in mixed solution, add 0.16mol%N, N '-di-2-ethylhexylphosphine oxide third
Acrylamide and 0.012mol/L azodiisobutyronitrile.After above-mentioned solution mix homogeneously, move to test tube rapidly, be passed through nitrogen 10 points
Seal after clock, be placed in the baking oven of 80 DEG C and carry out reacting 24h, it is thus achieved that hydrogel sample.
Reaction takes out hydrogel sample after terminating, and is cut into the thick circle sheet of thickness about 2-3mm, inserts in dehydrated alcohol and soak
After, place in deionized water and soak, to remove the impurity of hydrogel sample, finally carry out lyophilization, obtain methyl
The gel copolymer that benzyl acrylate is modified.
Experimental group 4
In this experimental group, weigh 2.25mol/L methacrylic acid and 0.25mol/L benzyl methacrylate is dissolved in
The dimethyl sulfoxide of 50mL and N, N '-dimethylformamide carries out in the mixed solvent mixed with volume ratio 1:1, by above-mentioned material
Mix homogeneously.Then in mixed solution, add 0.16mol%N, N '-methylene-bisacrylamide and 0.012mol/L azo two
Isopropyl cyanide.After above-mentioned solution mix homogeneously, move to test tube rapidly, be passed through nitrogen and seal after 10 minutes, be placed in the baking oven of 80 DEG C
Reaction 24h, it is thus achieved that hydrogel sample.
Reaction takes out gel sample after terminating, and is cut into the thick circle sheet of thickness about 2-3mm, inserts in dehydrated alcohol and soak
After, place in deionized water and soak, to remove impurity, finally carry out lyophilization, obtain benzyl methacrylate modified
Gel copolymer.
Based on experimental group 1 of the present invention, by changing at least one reaction condition to obtain experimental group 5-experimental group 10,
The concrete reaction condition of described experimental group 5-experimental group 10 is as shown in table 1:
Table 1, the reaction condition list of experimental group 5-10 of the present invention
Wherein, in above-mentioned experimental group 5-9, described hydrophilic monomer is methacrylic acid monomer, and described hydrophobic monomer is methyl
Phenyl acrylate, described cross-linking agent is N, N '-methylene-bisacrylamide, and described initiator is azodiisobutyronitrile, above-mentioned
Reaction dissolvent used in experimental group 5～9 is N, N '-dimethylformamide, and its consumption is 50ml.
Above-mentioned experimental group 10 is with the difference of above-mentioned experimental group 5～9: described hydrophobic monomer be phenyl methacrylate with
Benzyl methacrylate obtains after mixing with mass ratio for 1:2.1.
The contrast groups that with experimental group can be contrasted is set forth below, with preparation method provided herein and made
The standby hydrogel obtained is formed to be distinguished:
Contrast groups 1
First 10.76g methacrylic acid is weighed, 0.04gN, N '-methylene-bisacrylamide, at 40 DEG C, they are molten
In deionized water and stir a period of time, to obtain the solution of the clear homogeneous of 50ml.Then in solution, inject 0.07g mistake
Ammonium sulfate and 0.03g sodium sulfite.Test tube is moved to rapidly after above-mentioned solution mix homogeneously, close after being passed through nitrogen 10 minutes
Envelope, is placed in the baking oven of 60 DEG C reaction 24h, it is thus achieved that hydrogel sample.
Reaction takes out gel sample after terminating, and is cut into the thick circle sheet of thickness about 2-3mm, then inserts in deionized water and soak
Bubble removes impurity, then carries out lyophilization, obtains polymethyl acid gel (PMAA).
Contrast groups 2
This contrast groups is with the difference of experimental group 1: weigh 10g methacrylic acid and 4g 2-Propenoic acid, 2-methyl-, isooctyl ester, will
The mixed liquor of above two monomer adds reaction dissolvent N, N '-dimethylformamide to 20ml, after mix homogeneously, now reacts
The total concentration of monomer is 2.5mol/L, subsequently, adds cross-linking agent N, N '-methylene-bisacrylamide and azo in above-mentioned solution
Bis-isobutyronitrile, wherein, the consumption of described cross-linking agent is the 1.5mol% of total monomer number, and the concentration of described initiator is
0.012mol/L。
Other processing steps are identical with experimental group 1.
Contrast groups 3
This contrast groups is with the difference of experimental group 1: weighing mass ratio is the hydrophobic monomer of 50%:20:%:30%, alkali
Property monomer and hydrophilic monomer, wherein, described hydrophobic monomer is cyclohexyl methacrylate, and described alkaline monomer is alkenyl pyrrole
Pyridine, described hydrophilic monomer are methacrylate.In this contrast groups, the mode of polymerisation in solution is used to react, right at this
It is dimethyl sulfoxide than the polymer solvent employed in group；
Other processing steps are identical with experimental group 1.
Based on experimental group 1 of the present invention, by change at least one reaction condition with obtain following contrast groups 4～
10, the concrete reaction condition of described contrast groups 4～10 is as shown in table 2:
Table 2, the reaction condition list of contrast groups 4～10 of the present invention
Wherein, in above-mentioned contrast groups 4～10, described hydrophilic monomer is methacrylic acid monomer, and described hydrophobic monomer is first
Base phenyl acrylate, described cross-linking agent is N, N '-methylene-bisacrylamide, and described initiator is azodiisobutyronitrile, upper
Stating the reaction dissolvent used in contrast groups 4～10 is N, N '-dimethylformamide, and its consumption is 50ml.
The hydrogel sample that above-mentioned experimental group 1～10 contrast groups 1～10 prepares is carried out following performance test:
Swelling behavior performance test
Experimental technique: by experimental group 1～10 and the prepared hydrogel sample obtained of contrast groups 1～10 be dried at 50 DEG C
Prepare xerogel sample.
Weigh a certain amount of xerogel sample, be dipped in the medium of different pH value carrying out equilibrium swelling experiments.Treat that sample fills
Blot the moisture on surface with filter paper after point swelling and weigh weight in the balance, being repeated several times until the constant mass of hydrogel sample, this
Time it is believed that sample swelling ratio reached balance.Swelling ratio SR can calculate by below equation:
Swelling ratio: SR=(We-Wd)/Wd
Wherein, We: the quality of gel during equilibrium swelling；Wd: the weight of xerogel.
In above-mentioned swelling behavior performance test, described pH buffer solution can be by CH3COOH-H3BO3-H3PO4Solution
Formulated with NaOH solution, or be HCl solution.
Experimental result: above-mentioned experimental group 1～10 and the prepared swelling behavior performance test obtained of contrast groups 1～10 are such as
Shown in table 3:
Table 3: experimental group 1～10 and the prepared swelling behavior performance test obtained of contrast groups 1～10
Interpretation:
From table 3 it is observed that the pH threshold of response of the hydrogel sample obtained prepared by experimental group 1～10 of the present invention
Value is partial to alkalescence, and contrast groups 1～3 is then more biased towards in acidity, wherein, and the prepared hydrogel obtained in contrast groups 4～10
The pH response lag of sample is then partial to alkalescence, but the maximum swelling rate of hydrogel sample that contrast groups 4～10 prepares
It is significantly less than the maximum swelling rate of the hydrogel sample that experimental group 1～10 of the present invention prepares, therefore, uses present invention experiment
The imbibition degree of the hydrogel that group 1～10 prepares is the biggest, and the sewage disposal or the medicine that can be used for different pH value delay
The field such as release.
In the present invention, use the pH response water gel that method provided by the present invention prepares, formed by copolymerization
Molecular network, hydrogel contains multiple group, by regulation and control hydrogel in each group content and by control described hydrophilic
The consumption of monomer and hydrophobic monomer, it is possible to obtain pH response lag to the controlled hydrogel material of meta-alkalescence and pH response lag,
And the maximum swelling rate of described hydrogel material can reach preferably effect.
In the above-mentioned experimental group of the present invention 1～10, use the monomer containing hydrophobic group and the metering system containing hydrophilic group
Acid monomers copolymerization, passes through copolyreaction so that in the gel copolymer obtained, hydrophobic group produces conjugation, so that prepared
The pH sensitive range scalable of the hydrogel obtained, the lipid containing phenyl ring relies primarily on the hydrophobic of phenyl ring and conjugation to make pH
Sensitive range moves to alkalescence, is controlled the pH sensitive range of gel by the kind and addition regulating hydrophobic monomer.
Compared with prior art, the sensitive adjustable preparation method of pH provided by the present invention, there is following useful effect
Really:
(1) preparation method of hydrogel provided by the present invention, can prepare the hydrogel sensitive to pH, described water-setting
The pH response lag of glue moves to alkalescence direction, in above-mentioned preparation method, and can be by controlling kind and the use thereof of hydrophobic monomer
Amount controls the pH sensitive range of gel.In the present invention, using the methacrylate containing phenyl group is the fat containing phenyl ring
Class, relies on the hydrophobic group containing phenyl ring and conjugation, employing can be made to contain methacrylate and the metering system of phenyl group
After acid mixing, the pH sensitive range of the prepared hydrogel obtained of reaction can move to alkalescence.
(2) in preparation method provided by the present invention, further to the methacrylate containing phenyl group and methyl-prop
Melting concn ratio between olefin(e) acid is defined to (0.1～0.7): (1～3), therefore, and can be by by hydrophobic group and addition thereof
Adjustment, thus the pH response lag of hydrogel is adjusted, so that described hydrogel can be widely applied to different pH value
In environment.
(3) in preparation method provided by the present invention, the described methacrylate containing phenyl group of prize and institute further
The monomer concentration stating methacrylic acid is defined to 1.0～4.0mol/L, in the scope of above-mentioned restriction, can further improve preparation
The degree of accuracy of pH response lag in the adjustable hydrogel of pH response lag.
(4) in the present invention, further to the type of the described methacrylate containing phenyl group, dissolve described containing phenyl
The reaction dissolvent of methacrylate and the described methacrylic acid of group is further limited, thus can provide the one can be smart
Standard prepares the preparation method of the sensitive adjustable hydrogel of pH, and uses the pH of hydrogel that said method prepares to ring
Answer threshold value can offset to alkalescence, so that the pH response lag of described hydrogel has more specific aim and accuracy.
(5) in the present invention, also cross-linking agent employed in preparation method to described hydrogel and described initiator
Consumption (concentration) and particular type thereof are defined, thus can be further implemented in and make to prepare the sensitive controlled water-setting of pH
The colleague of glue, also can make the imbibition degree of hydrogel relatively big, thus can make that the scope of application of described hydrogel is wider, hydrogel
Using effect more excellent.
(6) in the present invention, methacrylic acid containing phenyl group described in preparation method to described hydrogel further
The limit temperature that ester and described methacrylic acid react is 50 DEG C～90 DEG C, owing to reaction temperature is to final prepared acquisition
The swelling behavior of hydrogel relevant with reaction temperature, therefore, by the restriction to reaction temperature, can obtain and there is controllability more
Strong pH sensitive aquagel.
(7) present invention provides a kind of hydrogel, and described hydrogel is at least by the methacrylate containing phenyl group and methyl
Acrylic acid copolymer reaction prepares；Wherein, the described methacrylate containing phenyl group with the concentration ratio of methacrylic acid is
(0.1～0.7): (1～3), described in the pH response lag of hydrogel for preparing be 6.0～8.0, the pH of obtained hydrogel
The precision of response lag is higher, controllability is higher.
(8) present invention provides the application of a kind of hydrogel, described hydrogel to can be used for different pH value and obtains sewage disposal or medicine
In thing slow release, in described sewage disposal, the pH response lag of described hydrogel can be adjusted to the pH value with sewage and match,
Thus obtain preferably imbibition effect, thus the harmful substance (such as heavy metal etc.) in sewage can be adsorbed, it is achieved
More excellent wastewater treatment efficiency, the especially effect in meta-alkalescence sewage disposal are more excellent.And in medicament slow release, can be by described
The pH response lag of hydrogel adjusts to corresponding with the pH value of the intestines of drug administration person (pH scope is about 7.4), thus can
It is that medicine can carry out slow release in specific region.Visible, hydrogel provided by the present invention has the wider suitability.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all former in the present invention
Any amendment made within then, within equivalent and improvement etc. all should comprise protection scope of the present invention.
Claims (10)
1. the preparation method of a hydrogel, it is characterised in that comprise the following steps: the methacrylate containing phenyl group is provided
With methacrylic acid；The concentration ratio adjusted between methacrylate and the methacrylic acid containing phenyl group is (0.1～0.7):
(1～3), carry out copolyreaction and prepare the hydrogel with required pH response lag.
The preparation method of hydrogel the most as described in the appended claim 1, it is characterised in that:, the described methacrylic acid containing phenyl group
Ester is 1.0～4.0mol/L with the monomer concentration of described methacrylic acid.
The preparation method of hydrogel the most as stated in claim 2, it is characterised in that: the described methacrylate containing phenyl group
Including phenyl methacrylate, benzyl methacrylate, methacrylic acid-2-ethyl phenoxy, methacrylic acid 2-(4-benzene first
Acyl group-3-hydroxyphenoxy) ethyl ester, 2-hydroxyethyl methacry-late diphenyl phosphate or methacrylic acid dicyclohexyl benzene first
The mixture of one or more in ester.
The preparation method of hydrogel the most as described in the appended claim 1, it is characterised in that: the preparation method of described hydrogel include by
The described methacrylate containing phenyl group and methacrylic acid are dissolved in N, N '-dimethylformamide, dimethyl sulfoxide or N,
The mixture of one or more in N '-methylene-bisacrylamide.
The preparation method of hydrogel the most as described in the appended claim 1, it is characterised in that: the preparation method of described hydrogel includes adding
Entering cross-linking agent and initiator, the consumption of described cross-linking agent is 0.05～3mol%, the concentration of described initiator be 0.001～
0.10mol/L。
The preparation method of hydrogel the most as claimed in claim 5, it is characterised in that: described cross-linking agent includes N, N '-methylene
One or both mixture in bisacrylamide, N-hydroxy-succinamide or 1,4-butanediol ethylene oxidic ester；Described draw
Send out agent and include one or both the mixture in Ammonium persulfate., sodium sulfite or azodiisobutyronitrile.
The preparation method of hydrogel the most as described in the appended claim 1, it is characterised in that: in the preparation method of described hydrogel, instead
The temperature answered is 50 DEG C～90 DEG C.
8. a hydrogel, it is characterised in that: described hydrogel is at least by the methacrylate containing phenyl group and metering system
Acid copolyreaction prepares；Wherein, the concentration of the methacrylate containing phenyl group and methacrylic acid than for (0.1～
0.7): (1～3).
Hydrogel the most as claimed in claim 8., it is characterised in that: the pH response lag of described hydrogel is 6.0～8.0.
10. the application of a hydrogel, it is characterised in that: the hydrogel as described in claim 8 or 9 is for different pH value
In sewage disposal or medicament slow release.
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| CN112941913A (en) * | 2021-03-31 | 2021-06-11 | 温州医科大学 | Hydrogel for treating chronic wound surface difficult to heal and preparation method thereof |
| CN113308226A (en) * | 2021-06-07 | 2021-08-27 | 绍兴徐越环境服务有限公司 | Pavement humectant and preparation method thereof |
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| CN106084116B (en) | 2019-02-05 |
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