CN109651623A - Improve the method and gained polyacrylamide hydrogel of polyacrylamide hydrogel adhesion property - Google Patents

Improve the method and gained polyacrylamide hydrogel of polyacrylamide hydrogel adhesion property Download PDF

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CN109651623A
CN109651623A CN201811382958.6A CN201811382958A CN109651623A CN 109651623 A CN109651623 A CN 109651623A CN 201811382958 A CN201811382958 A CN 201811382958A CN 109651623 A CN109651623 A CN 109651623A
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modifier
added
dopamine
polyacrylamide hydrogel
acrylamide
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CN109651623B (en
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曹平
曹一平
贝中武
黄园
尤庆亮
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Jianghan University
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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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0063—Glycosaminoglycans or mucopolysaccharides, e.g. keratan sulfate; Derivatives thereof, e.g. fucoidan
    • C08B37/0072—Hyaluronic acid, i.e. HA or hyaluronan; Derivatives thereof, e.g. crosslinked hyaluronic acid (hylan) or hyaluronates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2433/00—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
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide

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Abstract

The present invention provides a kind of method and gained polyacrylamide hydrogel for improving polyacrylamide hydrogel adhesion property.It the described method comprises the following steps that the modifier and soluble tetraborate of hyaluronic acid or the grafting dopamine of its salt are uniformly mixed by (1) in deionized water, form the first cross-linked network；(2) acrylamide, crosslinking agent is added, then initiator and tetramethylethylenediamine are added under condition of ice bath, it polymerize at 0~4 DEG C after mixing, obtain polyacrylamide hydrogel, wherein, in step (1), the dopamine grafting rate of the modifier is 30%~32%, and the mass ratio of the modifier and tetraborate is 5:(2~1)；The mass ratio of modifier is (18~20) in the acrylamide and step (1) being added in step (2): 1, the hyaluronate is sylvite or sodium salt.The method can greatly improve the adhesion property of polyacrylamide hydrogel obtained.

Description

Improve the method and gained polyacrylamide aqueous amine of polyacrylamide hydrogel adhesion property Gel
Technical field
The present invention relates to bio-medical material, in particular to a kind of method for improving polyacrylamide hydrogel adhesion property And gained polyacrylamide hydrogel.
Background technique
Selfreparing hydrogel is that one kind can quickly self-regeneration fault interface and be restored initial after structure is damaged The hydrogel material of performance.Since it is with good self-healing properties, the service life of material can not only be extended, also can be improved The security performance of material, therefore be widely used in fields such as bio-sensing, bionic skin and wearable electronics.
The most selfreparing hydrogels reported at present, which require certain environmental stimuli, can just complete, but also lack Weary certain adhesion property needs to achieve the effect that adherency by other means.Research shows that the pedal gland cell of marine mussel A kind of byssus with adhesion property can be secreted out of, dihydroxyphenylalanine and lysine are rich in.When attachment proteins and base Body contact when, rise adhesive attraction catechol group and lysine can with matrix occur it is certain react so that mussel mucus can Realize the adherency on the different materials surface such as from metal to organic matter.It is inspired by the unique adhesiveness of mussel, it will by chemical method Dopamine is grafted on some high molecular segments, makes it have the adhesiveness of mussel, to be used to prepare with adhesion characteristics Hydrogel becomes the hot spot of present scholar's research.Chinese patent literature CN108264611A discloses a kind of polyacrylamide aqueous amine Gel forms interpenetrating networks with the Sodium Hyaluronate of dopamine graft modification, improves the adherency of gained polyacrylamide hydrogel Performance.
In the implementation of the present invention, inventor's discovery is in the prior art the prior art has at least the following problems: polyacrylamide The adhesion property of hydrogel needs further to be improved.
Summary of the invention
In consideration of it, the present invention provides a kind of method and gained polyacrylamide for improving polyacrylamide hydrogel adhesion property Aqueous amine gel.
Specifically, according to the first aspect of the invention, the embodiment of the invention provides a kind of raising polyacrylamide aqueous amines The method of gel adhesion property, comprising the following steps:
(1) modifier and soluble tetraborate of hyaluronic acid or the grafting dopamine of its salt are mixed in deionized water It closes uniformly, forms the first cross-linked network；
(2) acrylamide, crosslinking agent is added, initiator and tetramethylethylenediamine are then added under condition of ice bath, mixing is equal It polymerize at 0~4 DEG C after even, obtains polyacrylamide hydrogel,
Wherein,
In step (1), the dopamine grafting rate of the modifier is 30%~32%, the modifier and tetraborate Mass ratio is 5:(2~1)；The mass ratio of modifier is (18~20) in the acrylamide and step (1) being added in step (2): 1, the hyaluronate is sylvite or sodium salt.
Preferably, the modifier is grafted dopamine by amidation process by hyaluronic acid or its salt and obtains.
As the prior art, the hyaluronic acid of low molecular weight or its salt facilitate dopamine and are modified to it, preferably thoroughly The molecular weight ranges of bright matter acid or its salt are 10kDa~1000kDa, more preferably 10kDa~100kDa (such as 20kDa, 40kDa Deng).
Specifically, the modifier is obtained by following methods:
Under room temperature, 1g hyaluronic acid or its salt are weighed, the PBS buffer solution of 100~120mL 1mol/L is added, stirs Mixing and adjusting the pH of solution until completely dissolved is 4~6, sequentially adds 1- (the 3- dimethylamino of 0.47~0.50g of catalyst Propyl) -3- ethyl carbodiimide and 0.28~0.30g n-hydroxysuccinimide, dissolution is sufficiently stirred, is passed through N225~ 30min removes the air in three-necked flask to prevent dopamine to be oxidized, and 0.47~0.56g DOPA amine salt is added under condition of ice bath 10~12h of reaction at 0~4 DEG C of dissolution is sufficiently stirred, wherein dopamine hydrochloride, 1- (3- dimethylaminopropyl) -3- in hydrochlorate Ethyl carbodiimide and the molar ratio of n-hydroxysuccinimide are (1~1.2): 1:1 obtains the modifier after purification.
Further specifically, the purification method particularly includes:
Solution after reaction is placed in bag filter, with the deionized water dialysis that pH is 4~6 remove unreacted raw material and By-product is freeze-dried the solution in bag filter, obtains the modifier.The molecular cut off of bag filter can be by ability Field technique personnel select as the case may be, for example, 14kDa.
Preferably, crosslinking agent described in step (2) is N, and N- methylene-bisacrylamide, the initiator is persulfuric acid Ammonium.
It is furthermore preferred that every 0.5g acrylamide addition 0.6~1mg N in step (2), N- methylene-bisacrylamide, 0.02~0.05g ammonium persulfate and 5~10 μ L tetramethylethylenediamines.
It is furthermore preferred that the concrete operation step of step (2) are as follows:
Acrylamide, N,N methylene bis acrylamide stirring is added；Ammonium persulfate is added under condition of ice bath, it is to be mixed After dissolution, tetramethylethylenediamine ice bath stirring is added to dissolving, mixed liquor is transferred in mold immediately, is subsequently placed in 0~4 DEG C It polymerize in refrigerator, the polyacrylamide hydrogel can be obtained.
According to the second aspect of the invention, the embodiment of the invention provides polyacrylamide hydrogels obtained by the above method Glue.
The beneficial effect of technical solution provided in an embodiment of the present invention includes at least:
The embodiment of the invention provides a kind of polyacrylamide hydrogel and preparation method thereof, polyacrylamide hydrogel is viscous Attached performance is greatly improved.
The polyacrylamide hydrogel is by dopamine (DA) modified linear macromolecule hyaluronic acid or its salt and four boron The first network and the second network polyacrylamide (PAM) composition that hydrochlorate (Borax) crosslinking obtains.This method is dexterously avoided The shortcomings that phenolic hydroxyl group on dopamine molecule is consumed in traditional adherency hydrogel preparation engineering can reach and improve adhesiveness, enhancing The purpose of tensile property.Meanwhile a large amount of boron ester bond is formed between the hydroxyl on tetraborate and Sodium Hyaluronate, it imparts viscous The good self-healing properties of attached water gel.The adhesion property of hydrogel is mentioned substantially importantly, introducing tetraborate It rises.The adherency hydrogel of selfreparing prepared by this method can operate in intelligent wearable device (sensor), direct to adhere to In the skin of human body, can to avoid between strain transducer and skin interface debonding and friction, help to detect bio signal With the accuracy for improving detection.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other Attached drawing.
Fig. 1 is the ultraviolet-visible spectrogram of gained dopamine modified hyaluronic acid sodium in embodiment 1.
Fig. 2 is the nmr spectrum of dopamine modified hyaluronic acid sodium prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 gained polyacrylamide hydrogel of embodiment.
Fig. 4 is embodiment 1, comparative example 1,2 gained hydrogel of comparative example to the adhesion strength histogram of quartz glass.
Fig. 5 be embodiment 1, comparative example 1,2 gained hydrogel of comparative example tensile strength figure.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, below in conjunction with attached drawing to embodiment of the present invention make into One step it is described in detail.
According to the first aspect of the invention, the embodiment of the invention provides a kind of raising polyacrylamide hydrogel adhesivenesses The method of energy, comprising the following steps:
(1) modifier and soluble tetraborate of hyaluronic acid or the grafting dopamine of its salt are mixed in deionized water It closes uniformly, forms the first cross-linked network；
(2) acrylamide, crosslinking agent is added, initiator and tetramethylethylenediamine are then added under condition of ice bath, mixing is equal It polymerize at 0~4 DEG C after even, obtains polyacrylamide hydrogel,
Wherein,
In step (1), the dopamine grafting rate of the modifier is 30%~32%, the modifier and tetraborate Mass ratio is 5:(2~1)；The mass ratio of modifier is (18~20) in the acrylamide and step (1) being added in step (2): 1, the hyaluronate is sylvite or sodium salt.
Preferably, the modifier is grafted dopamine by amidation process by hyaluronic acid or its salt and obtains.
As the prior art, the hyaluronic acid of low molecular weight or its salt facilitate dopamine and are modified to it, preferably thoroughly The molecular weight ranges of bright matter acid or its salt are 10kDa~1000kDa, more preferably 10kDa~100kDa (such as 20kDa, 40kDa Deng).
Specifically, the modifier is obtained by following methods:
Under room temperature, 1g hyaluronic acid or its salt are weighed, the PBS buffer solution of 100~120mL 1mol/L is added, stirs Mixing and adjusting the pH of solution until completely dissolved is 4~6, sequentially adds 1- (the 3- dimethylamino of 0.47~0.50g of catalyst Propyl) -3- ethyl carbodiimide and 0.28~0.30g n-hydroxysuccinimide, dissolution is sufficiently stirred, is passed through N225~ 30min removes the air in three-necked flask to prevent dopamine to be oxidized, and 0.47~0.56g DOPA amine salt is added under condition of ice bath 10~12h of reaction at 0~4 DEG C of dissolution is sufficiently stirred, wherein dopamine hydrochloride, 1- (3- dimethylaminopropyl) -3- in hydrochlorate Ethyl carbodiimide and the molar ratio of n-hydroxysuccinimide are (1~1.2): 1:1 obtains the modifier after purification.
Further specifically, the purification method particularly includes:
Solution after reaction is placed in bag filter, with the deionized water dialysis that pH is 4~6 remove unreacted raw material and By-product is freeze-dried the solution in bag filter, obtains the modifier.The molecular cut off of bag filter can be by ability Field technique personnel select as the case may be, for example, 14kDa.
Preferably, crosslinking agent described in step (2) is N, and N- methylene-bisacrylamide, the initiator is persulfuric acid Ammonium.The intensity etc. that the dosage of crosslinking agent, initiator etc. can be needed to obtain by those skilled in the art according to hydrogel requires It is determined by experiment.
It is furthermore preferred that every 0.5g acrylamide addition 0.6~1mg N in step (2), N- methylene-bisacrylamide, 0.02~0.05g ammonium persulfate and 5~10 μ L tetramethylethylenediamines.
It is furthermore preferred that the concrete operation step of step (2) are as follows:
Acrylamide, N,N methylene bis acrylamide stirring is added；Ammonium persulfate is added under condition of ice bath, it is to be mixed After dissolution, tetramethylethylenediamine ice bath stirring is added to dissolving, mixed liquor is transferred in mold immediately, is subsequently placed in 0~4 DEG C It polymerize (time is determined according to requirements such as the intensity of target polypropylene amide hydrogel, such as 12h) in refrigerator, can be obtained The polyacrylamide hydrogel.
According to the second aspect of the invention, the embodiment of the invention provides polyacrylamide hydrogels obtained by the above method Glue.
The beneficial effect of technical solution provided in an embodiment of the present invention includes at least:
The embodiment of the invention provides a kind of polyacrylamide hydrogel and preparation method thereof, polyacrylamide hydrogel is viscous Attached performance is greatly improved.
In following embodiments, agents useful for same information is as follows.
Experimental drug Specification Manufacturer
Acrylamide ≥98.0 Sinopharm Chemical Reagent Co., Ltd.
1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride 98% Aladdin reagent (Shanghai) Co., Ltd.
N-hydroxysuccinimide 98% Aladdin reagent (Shanghai) Co., Ltd.
Dopamine hydrochloride > 98% Sigma-Aldrich
Low molecular weight sodium hyaluronate 36kDa Bloomage Freda Biopharm Co., Ltd.
N'N- methylene-bisacrylamide 96% Acros Organics
Tetramethylethylenediamine 99% Aladdin reagent (Shanghai) Co., Ltd.
Ammonium persulfate AR Sinopharm Chemical Reagent Co., Ltd.
Dipotassium hydrogen phosphate AR Sinopharm Chemical Reagent Co., Ltd.
Potassium dihydrogen phosphate AR Sinopharm Chemical Reagent Co., Ltd.
Sodium chloride AR Sinopharm Chemical Reagent Co., Ltd.
Potassium chloride AR Sinopharm Chemical Reagent Co., Ltd.
Experimental result test is as follows with characterizing method:
The ultraviolet spectra of 1.HAC characterizes
The UV- of HAC is measured within the scope of 200nm~500nm using Japanese 2550 ultraviolet-uisible spectrophotometer of Shimadzu UV Vis map, test sample are the HAC aqueous solution of 0.5mg/mL,
2.HAC nuclear magnetic resonance spectroscopy (1H-NMR)
It is composed using the hydrogen of 400 nmr determination HAC of AVANCE.HAC is dissolved in neon Dai Shuizhong (D2O), is then shifted It is tested into nuclear magnetic tube, obtains HAC's1H-NMR spectrum.
3. the microscopic appearance of hydrogel characterizes
Using the internal structure of cold field emission scanning electron microscope (SU8010) observation hydrogel.Before test, by water-setting Glue freeze-drying, then it is quenched disconnected, do metal spraying processing in sample section in liquid nitrogen, to observe its internal microcosmic shape Looks.
4. hydrogel stretches and adhesion property test
Newly think carefully that universal tensile machine (CMT6503) stretches hydrogel and adhesion property is tested using Shenzhen, tests It is preceding first to return to zero, loading speed 50mm/min, gauge length 10mm.Hydrogel sample specification for tensile property test is length 3 repeat samples are arranged in 50mm, width 10mm, thickness 5mm, every group of sample.The sample specification of hydrogel for viscosity performance test For long 20mm, width 20mm, thickness 5mm, 3 repeat samples are arranged in every group of sample.
Embodiment 1
Prepare the PBS buffer solution (1L) of 0.01mol/L
800mL deionized water, 7.9g sodium chloride, 0.2g potassium chloride, 0.24g di(2-ethylhexyl)phosphate are sequentially added in the volumetric flask of 1L Hydrogen potassium and 1.8g dipotassium hydrogen phosphate, magnetic agitation dissolves at normal temperature, adjusts pH value of solution 7.2~7.4 with the HCl of 1mol/L, most Afterwards plus distilled water is settled to 1L, and the PBS buffer solution of 0.01mol/L can be obtained, and solution allocation completion is placed in 4 DEG C of refrigerators It saves.
Prepare dopamine modified hyaluronic acid sodium (HAC)
1. under room temperature, weighing 1g Sodium Hyaluronate, it is fitted into three-necked flask, adds the PBS of 100mL 1mol/L Buffer solution and suitable magneton, the pH that stirring adjusts solution until completely dissolved is 5, sequentially adds catalyst 0.476g's The n-hydroxysuccinimide (NHS) of 1- (3- dimethylaminopropyl) -3- ethyl carbodiimide (EDC) and 0.286g, sufficiently Stirring and dissolving is passed through N2 30min and removes the air in three-necked flask to prevent dopamine to be oxidized, is added under condition of ice bath 0.566g dopamine hydrochloride (DA) is sufficiently stirred at 4 DEG C of dissolution and reacts 12h, and wherein molar ratio is n (DA): n (EDC): n (NHS)=1.2:1:1.
2. the solution after reaction is placed in the bag filter that molecular cut off is 14kDa, the deionized water for being 4-6 with pH is saturating Analysis removes unreacted raw material and by-product, is freeze-dried to the solution in bag filter.
Fig. 1 is the ultraviolet-visible spectrogram of gained dopamine modified hyaluronic acid sodium, and 280nm has stronger ultraviolet suction in figure Receiving peak is the benzene ring structure in dopamine, it was demonstrated that it is grafted successfully, in the case where wavelength is more than 300nm, and not additional peak, table The conjugation catechol of bright HAC is not oxidized.
Fig. 2 is the nmr spectrum of gained dopamine modified hyaluronic acid sodium, is calculated by nmr spectrum The grafting rate 32% of dopamine.
The preparation of polyacrylamide hydrogel
(1) 0.01g Borax is taken to be added in the deionized water of 2.0ml first, stirring is added after it is completely dissolved 0.025g HAC continues to stir 30min the first cross-linked network of formation.
(2) 0.5g acrylamide, the stirring of 0.0006g N,N methylene bis acrylamide is then added.In the condition of ice bath After dissolution to be mixed, 10 μ L tetramethylethylenediamine ice bath stirrings are added to dissolving, immediately with one in lower addition 0.03g ammonium persulfate Secondary property dropper is drawn mixed liquor and is transferred in mold, is subsequently placed in 4 DEG C of refrigerators and polymerize 12h, polyacrylamide aqueous amine can be obtained Gel (abbreviation PAM-HAC-Borax hydrogel).Scanning electron microscope (SEM) photograph is as shown in Figure 3.
Comparative example 1
0.025mgHAC, 0.5g acrylamide, 0.0006g N,N methylene bis acrylamide is taken to be added to 2ml deionization Stirring and dissolving in water.0.03g ammonium persulfate is added under condition of ice bath, after dissolution to be mixed, 10 μ L tetramethylethylenediamines are added Ice bath stirring is drawn mixed liquor with disposable dropper immediately and is transferred in mold, be subsequently placed in 4 DEG C of refrigerators and polymerize to dissolving Polyacrylamide hydrogel can be obtained in 12h.
Comparative example 2
Take 0.5g acrylamide, 0.0006g N,N methylene bis acrylamide be added in 2ml deionized water stir it is molten Solution.0.03g ammonium persulfate is added under condition of ice bath, after dissolution to be mixed, 10 μ L tetramethylethylenediamine ice bath stirrings are added extremely Dissolution is drawn mixed liquor with disposable dropper immediately and is transferred in mold, is subsequently placed in 4 DEG C of refrigerators and polymerize 12h, can be obtained Polyacrylamide hydrogel.
As shown in Figure 4, Figure 5, PAM-HAC-Borax hydrogel is 38.07KPa to the adhesion strength of quartz glass, is 2.92 times of HAC-PAM hydrogel adhesion strength, 4.21 times of PAM；The tensile strength of PAM-HAC-Borax hydrogel is about 42KPa, 1.6 times of about pure PAM (26KPa), 2 times of HAC-PAM (20KPa) hydrogel.
PAM-HAC-Borax hydrogel in polyacrylamide network due to, comprising the cross-linked network of HAC and Borax, drawing Hydrogen bond action during stretching between the crosslinking and HAC and PAM of HAC and Borax can effectively carry out dissipation of energy, so that Hydrogel has good ductility, and elongation at break can reach 2600%.
Although the catechol group that dissociates in HAC-PAM hydrogel, which can assign hydrogel, has good draftability, Catechol group can consume a certain amount of initiator, be unfavorable for the polymerization of acrylamide, so that the tensile strength of hydrogel (20KPa) is reduced.And the catechol group being added in the hydrogel of Borax on HAC can form boron ester bond between Borax, It can consumption to avoid initiator to catechol group.Simple poly- propionamide network energy is not easy to dissipate, extension at break Rate is only 1200%.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this Within the protection scope of invention.

Claims (9)

1. a kind of method for improving polyacrylamide hydrogel adhesion property, which comprises the following steps:
(1) modifier of hyaluronic acid or the grafting dopamine of its salt and soluble tetraborate are mixed in deionized water It is even, form the first cross-linked network；
(2) acrylamide, crosslinking agent is added, initiator and tetramethylethylenediamine are then added under condition of ice bath, after mixing It polymerize at 0~4 DEG C, obtains polyacrylamide hydrogel,
Wherein,
In step (1), the dopamine grafting rate of the modifier is 30%~32%, the quality of the modifier and tetraborate Than for 5:(2~1)；The mass ratio of modifier is (18~20) in the acrylamide and step (1) being added in step (2): 1, institute Stating hyaluronate is sylvite or sodium salt.
2. the method as described in claim 1, which is characterized in that the modifier is anti-by amidation by hyaluronic acid or its salt Dopamine should be grafted to obtain.
3. method according to claim 2, which is characterized in that the molecular weight of the hyaluronic acid or its salt be 10kDa~ 1000kDa。
4. method according to claim 2, which is characterized in that the modifier is obtained by following methods:
Under room temperature, weigh 1g hyaluronic acid or its salt, be added the PBS buffer solution of 100~120mL 1mol/L, stirring to The pH that solution is adjusted after being completely dissolved is 4~6, sequentially adds 1- (the 3- dimethylamino third of 0.47~0.50g of catalyst Base) -3- ethyl carbodiimide and 0.28~0.30g n-hydroxysuccinimide, dissolution is sufficiently stirred, is passed through N225~ 30min removes the air in three-necked flask to prevent dopamine to be oxidized, and 0.47~0.56g DOPA amine salt is added under condition of ice bath 10~12h of reaction at 0~4 DEG C of dissolution is sufficiently stirred, wherein dopamine hydrochloride, 1- (3- dimethylaminopropyl) -3- in hydrochlorate Ethyl carbodiimide and the molar ratio of n-hydroxysuccinimide are (1~1.2): 1:1 obtains the modifier after purification.
5. method as claimed in claim 4, which is characterized in that the purification method particularly includes:
Solution after reaction is placed in bag filter, removes unreacted raw material and by-product with the deionized water dialysis that pH is 4~6 Object is freeze-dried the solution in bag filter, obtains the modifier.
6. method according to any one of claims 1 to 5, which is characterized in that crosslinking agent described in step (2) is N, and N- is sub- Bisacrylamide, the initiator are ammonium persulfate.
7. method as claimed in claim 6, which is characterized in that 0.6~1mg N is added in every 0.5g acrylamide in step (2), N- methylene-bisacrylamide, 0.02~0.05g ammonium persulfate and 5~10 μ L tetramethylethylenediamines.
8. method as claimed in claim 6, which is characterized in that the concrete operation step of step (2) are as follows:
Acrylamide, N,N methylene bis acrylamide stirring is added；Ammonium persulfate, dissolution to be mixed are added under condition of ice bath Afterwards, tetramethylethylenediamine ice bath stirring is added to dissolving, mixed liquor is transferred in mold immediately, is subsequently placed in 0~4 DEG C of refrigerator The polyacrylamide hydrogel can be obtained in middle polymerization.
9. the polyacrylamide hydrogel that any one of claim 1-8 the method obtains.
CN201811382958.6A 2018-11-20 2018-11-20 Method for improving adhesion performance of polyacrylamide hydrogel and obtained polyacrylamide hydrogel Active CN109651623B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825793A (en) * 2020-07-14 2020-10-27 陕西科技大学 Double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel and preparation method thereof
CN112023109A (en) * 2020-08-12 2020-12-04 山东百多安医疗器械股份有限公司 Self-repairing hemostatic film capable of being adhered and preparation method thereof
CN112169019A (en) * 2020-09-10 2021-01-05 南方医科大学 Direct-writing forming 3D printing biological ink and preparation method thereof
CN113512133A (en) * 2021-05-26 2021-10-19 江苏诺瓦立医疗用品有限公司 Preparation method of biological tissue adhesive
CN113683787A (en) * 2021-08-04 2021-11-23 华中科技大学同济医学院附属协和医院 Hydrogel material with secondary crosslinking characteristic and preparation method and application thereof
CN114874523A (en) * 2022-04-22 2022-08-09 常州艾龙森汽车饰件有限公司 Antibacterial flame-retardant high-viscosity polyethylene film, and preparation method and application thereof
CN115322514A (en) * 2022-10-13 2022-11-11 南通汇潜新材料科技有限公司 Polyformaldehyde engineering plastic and preparation method thereof
CN115490805A (en) * 2022-09-30 2022-12-20 郑州轻工业大学 Hydrogel based on redox reaction initiation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101921481A (en) * 2010-07-27 2010-12-22 北京化工大学 Gel prepared by in situ crosslinking hyaluronic acid and polyaspartic acid and preparation method thereof
CN105086001A (en) * 2015-09-13 2015-11-25 长春工业大学 Hyaluronic acid-gelatin/acrylamide double-network aquagel and preparation method thereof
CN108264611A (en) * 2018-01-30 2018-07-10 江汉大学 A kind of preparation method from the superpower hydrogel of adherency

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101921481A (en) * 2010-07-27 2010-12-22 北京化工大学 Gel prepared by in situ crosslinking hyaluronic acid and polyaspartic acid and preparation method thereof
CN105086001A (en) * 2015-09-13 2015-11-25 长春工业大学 Hyaluronic acid-gelatin/acrylamide double-network aquagel and preparation method thereof
CN108264611A (en) * 2018-01-30 2018-07-10 江汉大学 A kind of preparation method from the superpower hydrogel of adherency

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R.L.惠斯特勒等: "《淀粉的化学与工艺学》", 31 August 1988, 中国食品出版社出版 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111825793A (en) * 2020-07-14 2020-10-27 陕西科技大学 Double-bonded eugenol crosslinked mussel-like high-adhesion hydrogel and preparation method thereof
CN111825793B (en) * 2020-07-14 2022-07-29 陕西科技大学 Double-bonded eugenol crosslinked mussel-imitated high-adhesion hydrogel and preparation method thereof
CN112023109A (en) * 2020-08-12 2020-12-04 山东百多安医疗器械股份有限公司 Self-repairing hemostatic film capable of being adhered and preparation method thereof
CN112169019A (en) * 2020-09-10 2021-01-05 南方医科大学 Direct-writing forming 3D printing biological ink and preparation method thereof
CN112169019B (en) * 2020-09-10 2021-11-02 南方医科大学 Direct-writing forming 3D printing biological ink and preparation method thereof
CN113512133A (en) * 2021-05-26 2021-10-19 江苏诺瓦立医疗用品有限公司 Preparation method of biological tissue adhesive
CN113683787A (en) * 2021-08-04 2021-11-23 华中科技大学同济医学院附属协和医院 Hydrogel material with secondary crosslinking characteristic and preparation method and application thereof
CN113683787B (en) * 2021-08-04 2023-07-21 华中科技大学同济医学院附属协和医院 Hydrogel material with secondary crosslinking characteristic and preparation method and application thereof
CN114874523A (en) * 2022-04-22 2022-08-09 常州艾龙森汽车饰件有限公司 Antibacterial flame-retardant high-viscosity polyethylene film, and preparation method and application thereof
CN115490805A (en) * 2022-09-30 2022-12-20 郑州轻工业大学 Hydrogel based on redox reaction initiation
CN115490805B (en) * 2022-09-30 2023-08-18 郑州轻工业大学 Hydrogel initiated based on redox reaction
CN115322514A (en) * 2022-10-13 2022-11-11 南通汇潜新材料科技有限公司 Polyformaldehyde engineering plastic and preparation method thereof

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