CN111349251B - Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof - Google Patents
Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof Download PDFInfo
- Publication number
- CN111349251B CN111349251B CN202010228724.7A CN202010228724A CN111349251B CN 111349251 B CN111349251 B CN 111349251B CN 202010228724 A CN202010228724 A CN 202010228724A CN 111349251 B CN111349251 B CN 111349251B
- Authority
- CN
- China
- Prior art keywords
- hydrogel
- acrylic acid
- bentonite
- cellulose
- cucurbituril
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 69
- 239000000440 bentonite Substances 0.000 title claims abstract description 40
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 40
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920002678 cellulose Polymers 0.000 title claims abstract description 32
- 239000001913 cellulose Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 41
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 claims abstract description 23
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 238000010008 shearing Methods 0.000 claims abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 27
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 27
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 21
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920005615 natural polymer Polymers 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 235000008113 selfheal Nutrition 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/02—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
Abstract
The invention discloses a cellulose acrylic acid bentonite hydrogel with controllable mechanical properties and a preparation method thereof, wherein the composite hydrogel is prepared from the following raw materials in parts by weight: 1.0 to 4.0 portions of natural polymer cellulose, 2.0 to 6.0 portions of acrylic acid, 0.2 to 2.0 portions of bentonite, 0.05 to 1.0 portion of eight-membered cucurbituril and 0.1 to 0.2 portion of potassium persulfate. The method comprises the following steps: dissolving to obtain natural polymer cellulose solution; adding acrylic acid into a natural polymer cellulose solution, stirring uniformly, adding an initiator potassium persulfate, introducing nitrogen at room temperature for 10-30 min, adding an eight-membered cucurbituril serving as a cross-linking agent and bentonite, stirring uniformly, and placing in a water bath kettle at 70 ℃ for reacting for 2-8 h; cooling to room temperature, putting the hydrogel into an oven for about 5-12 h, taking out, shearing, putting the hydrogel into the oven, gradually heating, baking and taking out to obtain the composite hydrogel. The invention has controllable mechanical property and can quickly self-heal, and the mechanical property can be regulated and controlled by changing the structure and the acidity of the environment.
Description
Technical Field
The invention belongs to the technical field of natural polymer gel, relates to composite hydrogel and a preparation method thereof, and particularly relates to cellulose acrylic acid bentonite hydrogel with controllable mechanical property and a preparation method thereof.
Background
The traditional cellulose hydrogel has the advantages of no toxicity, biodegradability, biocompatibility and the like, but the application of the traditional cellulose hydrogel is greatly limited due to the defects of weak mechanical property, poor formability and the like caused by the easily damaged internal network structure. In order to solve the problems, researches mainly focus on two aspects, namely, modifying natural cellulose to obtain derivative cellulose hydrogel; on the other hand, cellulose composite hydrogels are obtained by compounding or doping inorganic materials, and these methods all improve mechanical properties. Concentrated H for Chenweike2SO4Preparing nano cellulose Crystals (CNs) by acidolysis of eucalyptus pulp, then simply modifying the CNs under the action of APS, and preparing the high-strength super-tensile CNs/PAM hydrogel material by thermal initiation by taking Acrylamide (AM) as a monomer. Renping Guang and the like successfully prepare the graphene oxide-cellulose-polyvinyl alcohol composite hydrogel by adopting a multiple freezing and thawing method, and the tensile strength and the elongation at break of the graphene oxide-cellulose-polyvinyl alcohol composite hydrogel are improved. Jeanhua Rong et al add acrylamide monomer into bacterial cellulose suspension, and prepare polyacrylamide/bacterial cellulose composite hydrogel with good mechanical properties by adopting an in-situ polymerization method. The Yang Sheng Chun is expressed by N, N，The bentonite/acrylic acid/carboxymethyl cellulose composite gel is prepared by taking methylene bisacrylamide as a cross-linking agent and polyvinyl alcohol (PEG) as a pore-forming agent, and is a porous material with poor mechanical property.
In these methods, either expensive dopants such as graphene or a strong carcinogenic monomer acrylamide are used, the process is complicated, and the biocompatibility of cellulose hydrogel materials is reduced, thereby causing troubles to the further application of the materials. The preparation and application of the cellulose composite hydrogel which is nontoxic, simple in process and excellent in mechanical property are key problems of cellulose hydrogel.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the cellulose acrylic acid bentonite hydrogel with controllable mechanical property and the preparation method thereof, and overcomes the defects of complex preparation process and poor biocompatibility of the existing cellulose hydrogel.
In order to solve the technical problems, the invention adopts the following technical scheme:
the raw materials of the composite hydrogel comprise carboxymethyl cellulose as a base material, acrylic acid, bentonite, an octatomic cucurbituril as a cross-linking agent and potassium persulfate as an initiator.
The invention also comprises the following technical characteristics:
specifically, the feed additive is prepared from the following raw materials in parts by weight: 1.0 to 4.0 parts of carboxymethyl cellulose, 2.0 to 6.0 parts of acrylic acid, 0.2 to 2.0 parts of bentonite, 0.05 to 1.0 part of cucurbituril and 0.1 to 0.2 part of potassium persulfate.
Specifically, the feed is prepared from the following raw materials in parts by weight: 1.5 parts of carboxymethyl cellulose, 4.0 parts of acrylic acid, 0.5 part of bentonite, 0.2 part of cucurbituril and 0.15 part of potassium persulfate.
Specifically, the eight-membered cucurbituril is C48H48 N32 O16。
A preparation method of cellulose acrylic acid bentonite hydrogel with controllable mechanical properties comprises the following steps:
step one, weighing carboxymethyl cellulose, adding deionized water, and performing ultrasonic oscillation to completely dissolve the carboxymethyl cellulose to obtain a carboxymethyl cellulose solution;
step two, adding acrylic acid into the carboxymethyl cellulose solution obtained in the step one, uniformly stirring, adding an initiator potassium persulfate, introducing nitrogen at room temperature for protection for 10-30 min, adding an eight-membered cucurbituril serving as a cross-linking agent and bentonite, uniformly stirring, and placing in a water bath kettle at 70 ℃ for reaction for 2-8 h;
and step three, after the product in the step two is cooled to room temperature, putting the product into an oven for about 5-12 hours, taking out the product, shearing the product into pieces, then putting the pieces into the oven, gradually heating and baking the pieces, and taking out the pieces to obtain the composite hydrogel.
Compared with the prior art, the invention has the following technical effects:
the invention designs a composite network hydrogel based on multiple secondary bonds, which uses natural polymer cellulose (CMC) as base material, non-toxic Acrylic Acid (AA) as monomer, eight-membered cucurbituril (CB 8) as cross linker, and low-cost bentonite to form interlamination staggered. The invention regulates and controls the mechanical property by changing the structure and the environmental acidity, wherein a double-network structure is formed by a cellulose chain and a polyacrylic acid chain, a layered bentonite is doped between networks to form a composite network structure, and the internal physical crosslinking point of the gel can be changed by changing the content of the components to change the mechanical property. And secondly, the cross-linking density of the gel is controlled by adjusting the external acidity after the gel is formed, so that the mechanical property of the gel is regulated and controlled.
The cellulose acrylic acid bentonite hydrogel with controllable mechanical property has the elongation at break of 1647.24 percent, the elastic modulus of 0.0102MPa and the tensile strength of 0.336 MPa. By regulating and controlling the acidity of the environment, the mechanical property of the CMC/AA/bentonite composite hydrogel can be effectively controlled. The elastic modulus is increased by 15 times under the acidic condition and reaches 0.1521MPa; the elongation at break is 0.55 times of the original elongation at break and is 900.35 percent; the tensile strength is 8.1 times of the original tensile strength and reaches 2.73MPa.
The cellulose acrylic acid bentonite hydrogel with controllable mechanical properties has quick self-healing property, and the self-healing time is about 10s.
(IV) the cellulose acrylic acid bentonite hydrogel with controllable mechanical property has the removal rate of organic pollutant methylene blue as high as 97.3%.
The present invention will be explained in further detail with reference to examples.
Drawings
FIG. 1 is an SEM photograph of a composite hydrogel prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the composite hydrogel prepared in example 1 of the present invention after acid soaking.
FIG. 3 is a stress-strain curve of the composite hydrogel prepared in example 1 of the present invention before and after acid soaking.
FIG. 4 is a graph showing the tensile strain of the composite hydrogel prepared in Experimental example 1 of the present invention.
FIG. 5 is a diagram showing the self-healing behavior of the composite hydrogel prepared in example 1 of the present invention.
Fig. 6 is a graph showing the adsorption amount and removal rate of methylene blue adsorbed by the composite hydrogel prepared in example 1 of the present invention at different dosages (T =35 ℃, C0=20 mg/L).
FIG. 7 is a graph showing a sample of the composite hydrogel prepared in comparative example 1.
FIG. 8 is a graph showing a sample of the composite hydrogel prepared in comparative example 2.
FIG. 9 is a stress-strain curve of a composite hydrogel prepared by three examples.
The present invention will be described in further detail with reference to examples.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a cellulose acrylic acid bentonite hydrogel with controllable mechanical properties, which is prepared from the following raw materials in parts by weight: 1.5 parts of carboxymethyl cellulose, 4.0 parts of acrylic acid, 0.5 part of bentonite, 0.2 part of cucurbituril and 0.15 part of potassium persulfate; the eight-membered cucurbituril is C48H48 N32 O16. The method for preparing the eight-element cucurbituril comprises the following steps:
putting 7.0 parts of powdered glycoluril and 3.0 parts of paraformaldehyde into a 100mL three-neck flask, mechanically stirring to uniformly mix the materials, and dropwise adding 4mL of ice concentrated HCl while stirring until reactants are in a gel state; heating until the reactant is dissolved, cooling for 6h, pouring into 80mL of methanol under stirring, fully stirring until white or light yellow solid is separated out, performing suction filtration, and performing vacuum drying to obtain a cucurbituril mixture; fully mixing and dissolving the mixture twice by using 1L of water, stirring for 2h, filtering, washing a filter cake by using 200mL of methanol, and drying and collecting filter cakes (six-membered cucurbituril and eight-membered cucurbituril); the solid obtained in the previous step is recrystallized twice with 6M hydrochloric acid to obtain pure white crystal product, namely the eight-membered cucurbituril (the total yield is 7%).
The preparation method of the cellulose acrylic acid bentonite hydrogel with controllable mechanical properties comprises the following steps:
step one, weighing carboxymethyl cellulose, adding deionized water, and carrying out ultrasonic oscillation to completely dissolve the carboxymethyl cellulose to obtain a carboxymethyl cellulose solution;
step two, adding acrylic acid into the carboxymethyl cellulose solution obtained in the step one, uniformly stirring, adding an initiator potassium persulfate, introducing nitrogen at room temperature for protection for 10-30 min, adding an eight-membered cucurbituril serving as a cross-linking agent and bentonite, uniformly stirring, and placing in a water bath kettle at 70 ℃ for reaction for 2-8 h;
and step three, after the product in the step two is cooled to room temperature, putting the product into an oven for about 5-12 hours, taking out the product, shearing the product into pieces, then putting the pieces into the oven, gradually heating and baking the pieces, and taking out the pieces to obtain the composite hydrogel.
Example 2:
the present embodiment provides a cellulose acrylic bentonite hydrogel with controllable mechanical properties and a preparation method thereof, and the difference between the present embodiment and embodiment 1 is in the raw material ratio, specifically, the raw materials in the present embodiment include, by weight, 1.0 part of carboxymethyl cellulose, 2.0 parts of acrylic acid, 0.2 part of bentonite, 0.05 part of cucurbituril, and 0.1 part of potassium persulfate. This example was carried out in the same manner as example 1 to obtain a composite hydrogel.
Example 3:
the present embodiment provides a cellulose acrylic bentonite hydrogel with controllable mechanical properties and a preparation method thereof, and the difference between the present embodiment and embodiment 1 is in the raw material ratio, specifically, the raw materials in the present embodiment include, by weight, 4.0 parts of carboxymethyl cellulose, 6.0 parts of acrylic acid, 2.0 parts of bentonite, 1.0 part of cucurbituril, and 0.2 part of potassium persulfate. This example was prepared in the same manner as example 1, and a composite hydrogel was prepared in the same manner.
Comparative example 1:
this comparative example is the same as example 1, with the following differences: the experiment of example 1 was repeated by replacing the crosslinker octa-melon ring with N, -methylenebisacrylamide. FIG. 7 shows that the mechanical properties of the composite hydrogel sample prepared in comparative example 1 are very poor, and the mechanical properties of the sample cannot be detected by using a WDW-BO5 type universal testing machine.
Comparative example 2:
this comparative example is the same as example 1, with the following differences: the experiment of example 1 was repeated by changing the crosslinker octa-melon ring to glutaraldehyde. FIG. 8 shows that the mechanical properties of the composite hydrogel sample prepared in comparative example 2 are very poor, and the mechanical properties of the sample cannot be detected by using a WDW-BO5 type universal tester.
And (3) performance testing:
the results of the performance tests of example 1 are shown in FIGS. 1 to 6:
FIG. 1 is an SEM image of a composite hydrogel prepared in example 1, and FIG. 2 is an SEM image of a composite hydrogel prepared in example 1 after acid soaking; as shown in FIG. 1, SEM of CMC/AA/bentonite composite hydrogel shows that the hydrogel is a lamellar structure, the cross-linking density after acid soaking in FIG. 2 is rapidly increased to cause the structure to be more compact, and the same effect is produced after acid soaking in Experimental example 2 and Experimental example 3.
FIG. 3 is a stress-strain curve of CMC/AA/bentonite composite hydrogel prepared in example 1 under neutral and strong acid conditions, wherein the ordinate is tensile force and the abscissa is the ratio of the length change after force application to the original length. As can be seen from the graph, the tensile strength and elastic modulus of the gel significantly increased in the presence of a strong acid, the stress of the composite hydrogel after acid soaking was greatly increased by about six times, and the strain was reduced by about half of the original stress.
The composite hydrogel prepared in experimental example 1 of fig. 4 is subjected to a tensile force deformation graph, and the hydrogel can be rapidly restored to the state of the upper graph of fig. 4 after the lower graph of fig. 4 is pulled, which shows that the hydrogel can be rapidly self-healed, and the self-healing efficiency is high, because the gel has a large number of secondary bond interactions at the fracture surface.
Fig. 5 is a diagram illustrating the composite hydrogel prepared in example 1 after self-healing, and it can be seen from fig. 5 that the composite hydrogel has good mechanical properties after self-healing.
FIG. 6 is a graph showing the variation of the adsorption amount of methylene blue to the composite hydrogel prepared in example 1 according to the addition amount and the removal rate of the gel, wherein curve 1 is a removal rate curve, and curve 2 is the mass of dye adsorbed by the adsorbent per unit mass; it can be seen that the CMC/AA/bentonite composite hydrogel prepared in the example has a good removal effect on the dye methylene blue, because-COO-on the side chain of the gel enables the gel to be charged with negative electricity integrally and the exchange of Na + in the bentonite layer-shaped structure acts together, so that the CMC/AA/bentonite composite hydrogel has a good adsorption effect on the cationic dye. Specifically, in fig. 6, the removal rate profile and the adsorption amount profile per unit mass were substantially the same except that its removal rate was increased from 86.4% to 97.2%. The increase of the removal rate is mainly because when the volume of the solution is fixed with the initial concentration, the active sites combined with the methylene blue are increased along with the increase of the concentration of the adsorbent, so that the concentration of the methylene blue in the solution is reduced, and the removal rate tends to increase; when the amount of the adsorbent is increased, the concentration of the dye in the aqueous solution is unchanged, and the mass of the adsorbent per unit mass for adsorbing the dye is reduced.
(II) the results of the mechanical property tests of examples 1 to 3 are shown in Table 1, from which the elongation at break and the tensile strength value of each example can be seen, wherein the elongation at break and the tensile strength of example 1 are the best.
| Examples | Elongation at break/(%) | Tensile strength/MPa |
| Example 1 | 1647.244 | 0.336 |
| Example 2 | 1532.359 | 0.196 |
| Example 3 | 1094.282 | 0.087 |
(III) the results of the crosslink density performance test of examples 1-3 are shown in Table 2, from which the crosslink density of each example is known, wherein the highest crosslink density of example 1 is seen, and the best mechanical properties are seen.
| Examples | Crosslinking density/10-4 mol cm-3 |
| Example 1 | 22.87 |
| Example 2 | 13.60 |
| Example 3 | 16.15 |
FIG. 9 is a stress-strain curve of a composite hydrogel according to three embodiments of the present invention, in which the ordinate represents tensile force and the abscissa represents elongation at break. From E = PL/a Δ L (where E is the elastic modulus, P is the maximum load, L is the original length of the sample, a is the cross-sectional area of the sample, and Δ L is the elongation at break), the elastic modulus of example 1 was 0.0102MPa, the elastic modulus of example 2 was 0.0064MPa, and the elastic modulus of example 3 was 0.0040MPa. The mechanical properties of example 1 are optimal.
Claims (5)
1. The cellulose acrylic acid bentonite hydrogel with controllable mechanical properties is characterized by being prepared from the following raw materials in parts by weight: 1.5 parts of carboxymethyl cellulose, 4.0 parts of acrylic acid, 0.5 part of bentonite, 0.2 part of cucurbituril and 0.15 part of potassium persulfate.
2. The mechanical property-controllable cellulose acrylic bentonite hydrogel according to claim 1, wherein the eight-membered cucurbituril is C48H48 N32 O16。
3. The cellulose acrylic acid bentonite hydrogel with controllable mechanical properties is characterized by being prepared from the following raw materials in parts by weight: 1.0 part of carboxymethyl cellulose, 2.0 parts of acrylic acid, 0.2 part of bentonite, 0.05 part of cucurbituril and 0.1 part of potassium persulfate.
4. The mechanical property-controlled cellulose acrylic acid bentonite hydrogel according to claim 3, wherein the eight-membered cucurbituril is C48H48 N32 O16。
5. The method for preparing the hydrogel of cellulose acrylic acid bentonite with controllable mechanical properties as claimed in any one of claims 1 to 4, which comprises the following steps:
step one, weighing carboxymethyl cellulose, adding deionized water, and performing ultrasonic oscillation to completely dissolve the carboxymethyl cellulose to obtain a carboxymethyl cellulose solution;
step two, adding acrylic acid into the carboxymethyl cellulose solution obtained in the step one, uniformly stirring, adding an initiator potassium persulfate, introducing nitrogen at room temperature for protection for 10-30 min, adding an octatomic cucurbituril serving as a cross-linking agent and bentonite, uniformly stirring, and placing in a water bath kettle at 70 ℃ for reaction for 2-8 h;
and step three, after the product in the step two is cooled to room temperature, putting the product into an oven for 5-12 h, taking out the product, shearing the product into pieces, then putting the pieces into the oven, gradually heating and baking the pieces, and taking out the pieces to obtain the composite hydrogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228724.7A CN111349251B (en) | 2020-03-27 | 2020-03-27 | Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010228724.7A CN111349251B (en) | 2020-03-27 | 2020-03-27 | Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111349251A CN111349251A (en) | 2020-06-30 |
| CN111349251B true CN111349251B (en) | 2022-11-01 |
Family
ID=71191000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010228724.7A Expired - Fee Related CN111349251B (en) | 2020-03-27 | 2020-03-27 | Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111349251B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112891608B (en) * | 2021-01-29 | 2022-05-24 | 西安建筑科技大学 | Wound dressing of bacterial cellulose-based sericin peppermint oil nanoparticles and preparation method thereof |
| CN113896908B (en) * | 2021-10-11 | 2023-06-23 | 上海大学 | Composite hydrogel, preparation method thereof, thermoelectric dual-drive composite hydrogel intelligent window and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942167B (en) * | 2010-09-10 | 2012-05-23 | 天津工业大学 | Nanometer clay-containing high absorptive hydrogel as well as preparation method and application thereof |
| WO2013124654A1 (en) * | 2012-02-20 | 2013-08-29 | Cambridge Enterprise Limited | Cucurbituril-based hydrogels |
| CN104151459B (en) * | 2014-08-12 | 2016-08-31 | 贵州大学 | Five yuan, hexa-atomic or eight yuan of melon ring bridging acrylate copolymers and preparation method |
| KR102437671B1 (en) * | 2016-10-14 | 2022-08-29 | 오렌 에이. 셔먼 | Cucurbituril-based hydrogels |
-
2020
- 2020-03-27 CN CN202010228724.7A patent/CN111349251B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN111349251A (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111349251B (en) | Cellulose acrylic acid bentonite hydrogel with controllable mechanical property and preparation method thereof | |
| CN112979883B (en) | High-temperature-resistant salt-resistant polymer, and preparation method and application thereof | |
| CN104388063B (en) | Micro-crosslinked polymer fluid loss additive for drilling fluid and preparation method thereof | |
| CN107408699A (en) | Electrode assembly and its manufacture method | |
| CN108395658B (en) | PVDF (polyvinylidene fluoride) -based composite dielectric with self-crosslinking characteristic and preparation method thereof | |
| CN104292524A (en) | Modified natural rubber cable sheath material | |
| CN111871385A (en) | Preparation method and application of coconut shell biomass charcoal composite carboxymethyl cellulose adsorbent | |
| CN112979869A (en) | Hexagonal boron nitride nanosheet hydrogel composite material, and preparation method and application thereof | |
| JPS59120608A (en) | Rubber composition of improved vulcanizability | |
| CN103360536A (en) | Polyvinyl chloride production method adding chain extender to match with later-stage heating process | |
| CN108946722B (en) | Preparation method of spherical active carbon with controllable pore diameter, product and application thereof | |
| CN113279143B (en) | Degradable flame-retardant plant fiber non-woven fabric | |
| CN111826222B (en) | Nitrogen-containing terpolymer biodiesel pour point depressant and preparation method and application thereof | |
| CN110591189B (en) | Hydrothermal double-stimulation-response shape memory polymer material and preparation method thereof | |
| CN111004353B (en) | Preparation method and application of high-strength double-network hydrogel | |
| CN109438760B (en) | Polyacrylate modified expanded graphite and preparation method and application thereof | |
| CN115947921A (en) | Polyurethane and preparation method thereof | |
| KR101922638B1 (en) | Quad-polymer precursors for preparing carbon fibers and methods for making and using same | |
| CN116288776A (en) | Anti-aging ultra-high molecular weight polyethylene fiber material and preparation method thereof | |
| CN114349888B (en) | Ethylene-chlorotrifluoroethylene copolymer for melt blowing and preparation method thereof | |
| EP3546623B1 (en) | Method for producing polyacrylonitrile-based fiber, and polyacrylonitrile-based copolymer used therein | |
| CN112760735A (en) | Flame-retardant polyamide fiber | |
| CN112175128A (en) | Preparation method of acrylamide crosslinked acrylic acid and montmorillonite hydrogel | |
| CN114426675B (en) | Hyperbranched cationic polymer emulsion and application thereof in sludge dewatering | |
| CN111952591B (en) | Aerogel doped polythiophene battery additive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20221101 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |