CN118406278A - Preparation method of high-toughness carboxymethyl cellulose-based composite film - Google Patents
Preparation method of high-toughness carboxymethyl cellulose-based composite film Download PDFInfo
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- CN118406278A CN118406278A CN202410459132.4A CN202410459132A CN118406278A CN 118406278 A CN118406278 A CN 118406278A CN 202410459132 A CN202410459132 A CN 202410459132A CN 118406278 A CN118406278 A CN 118406278A
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 62
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 61
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 61
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 255
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 49
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 229920002907 Guar gum Polymers 0.000 claims abstract description 20
- 239000000665 guar gum Substances 0.000 claims abstract description 20
- 229960002154 guar gum Drugs 0.000 claims abstract description 20
- 235000010417 guar gum Nutrition 0.000 claims abstract description 20
- 230000005496 eutectics Effects 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims description 187
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 81
- 239000008367 deionised water Substances 0.000 claims description 77
- 229910021641 deionized water Inorganic materials 0.000 claims description 77
- 238000002156 mixing Methods 0.000 claims description 64
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 17
- 229960003237 betaine Drugs 0.000 claims description 17
- 229910052791 calcium Inorganic materials 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 16
- 235000014655 lactic acid Nutrition 0.000 claims description 16
- 239000004310 lactic acid Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract description 3
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 abstract description 2
- 239000012744 reinforcing agent Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010816 packaging waste Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/26—Cellulose ethers
- C08J2301/28—Alkyl ethers
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
-
- 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
- C08J2429/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- 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
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- 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
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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Abstract
The invention discloses a preparation method of a high-toughness carboxymethyl cellulose-based composite film, which uses carboxymethyl cellulose, guar gum and polyvinyl alcohol as a base material of the film, caCl 2 as a film cross-linking agent, and montmorillonite and deep eutectic solvent which are homogenized and respectively used as a reinforcing agent and a plasticizer to finally prepare the high-toughness carboxymethyl cellulose-based composite film. The high-toughness carboxymethyl cellulose-based composite film prepared by the invention has high tensile strength and keeps good elongation at break, the tensile strength can reach 155 MPa at the highest, and the elongation can reach 101 at the highest.
Description
Technical Field
The invention belongs to the technical field of preparation of novel high-toughness carboxymethyl cellulose-based food packaging film materials, and particularly relates to a preparation method of a high-toughness carboxymethyl cellulose-based composite film.
Background
With the rapid development of social economy, a large amount of petroleum-based plastics are applied to daily life, and a large amount of white pollution is generated, so that the development of environment-friendly, pollution-free and sustainable biodegradable plastics is of great importance. Among biodegradable environment-friendly materials, carboxymethyl cellulose (CMC) composite films have great application potential due to the advantages of low cost, reproducibility, wide availability, biodegradability and the like.
The research proves that the mechanical strength of the CMC-based film can be greatly improved by adding nano-filler or metal crosslinking and the like, but the corresponding elongation at break is very low and often not more than 10%, thus limiting the practical application of the high-strength CMC-based film. Polyvinyl alcohol (PVA) has good mechanical properties, a planar zigzag structure and semi-crystalline properties, and the production process does not depend on petroleum, is often used for being blended with other materials with poor mechanical properties, and greatly improves the mechanical properties of the film. In addition, the lamellar structure of montmorillonite (MMT) imparts a large specific surface area and excellent ion exchange capacity, and is therefore commonly used to enhance the tensile strength of CMC-based films. However, the original MMT particles often have agglomeration phenomenon, which limits the exertion of the nano effect.
Guar Gum (GG) and CMC are structurally similar and are often used as blending materials for CMC. Montmorillonite (MMT) is the most commonly used layered silicate, and can increase the density of CMC-based films by forming intercalation in the CMC matrix, thereby increasing the tensile strength of the CMC-based films.
In order to balance the high tensile strength and low elongation at break of the CMC-based film, the particle size of the MMT of the reinforcing material is regulated and the elongation at break of the CMC-based film is enhanced by introducing the flexible high polymer PVA, and meanwhile, the tensile strength is ensured not to be greatly lost, so that the overall toughness of the CMC composite film is improved. Wherein, the homogenization treatment can reduce the grain size range of MMT, enhance the dispersity of MMT in the film matrix, and improve the density of the composite film, thereby improving the tensile strength and the elongation at break of the film. The flexible high polymer PVA can generate hydrogen bond crosslinking with various matrixes of the film, so that the stress of the film is effectively transferred, crack deflection is caused, the purpose of energy consumption is achieved, and the breaking elongation and toughness of the CMC-based film are improved. Therefore, the high-toughness carboxymethyl cellulose-based composite film material has potential application prospect in the field of degradable food packaging, can effectively reduce the pressure of packaging waste on the environment, replaces the traditional petroleum-based food packaging film, and further promotes the realization of environmental protection and sustainable development targets. There is currently no report on this aspect.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a high-toughness carboxymethyl cellulose-based composite film with simple process and low cost, which uses carboxymethyl cellulose, guar gum and polyvinyl alcohol as base materials of the film, caCl 2 as a film cross-linking agent, and montmorillonite and deep eutectic solvent which are homogenized and respectively used as a reinforcing agent and a plasticizer to finally prepare the high-toughness carboxymethyl cellulose-based composite film. The high-toughness carboxymethyl cellulose-based composite film prepared by the invention has high tensile strength and keeps good elongation at break.
The invention adopts the following technical proposal to solve the technical problems, and the preparation method of the high-toughness carboxymethyl cellulose-based composite film is characterized by comprising the following specific processes:
Step S1: dispersing carboxymethyl cellulose in deionized water, and uniformly stirring and mixing to obtain a material A;
Step S2: dispersing guar gum in deionized water, and uniformly stirring and mixing to obtain a material B;
step S3: dispersing montmorillonite in deionized water, stirring for 2h-14d at a stirring rate of 600-1000r/min, centrifuging and ultrasonically treating montmorillonite suspension, and vacuum freeze-drying to obtain a material C;
Step S4: dispersing the material C obtained in the step S3 in the material B obtained in the step S2, and uniformly stirring and mixing to obtain a material D;
step S5: dispersing polyvinyl alcohol in deionized water at 100 ℃ and stirring and mixing uniformly to obtain a material E;
step S6: stirring and mixing betaine, lactic acid and urea at 100 ℃ uniformly to obtain a deep eutectic solvent, namely a material F;
Step S7: stirring and mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 uniformly to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
Step S9: dissolving CaCl 2 in deionized water, and uniformly stirring and mixing to obtain a CaCl 2 solution, namely a material I;
Step S10: and (3) soaking the material H obtained in the step (S8) by using the material I obtained in the step (S9), washing by using deionized water, and drying at room temperature to obtain the target product, namely the high-toughness carboxymethyl cellulose-based composite film.
Further preferably, the concentration of carboxymethyl cellulose in the material A in step S1 is 0.025g/mL.
It is further preferred that the concentration of guar gum in the material B in step S2 is 2.5mg/mL.
Further preferably, the montmorillonite in the step S3 is calcium-based montmorillonite and sodium-based montmorillonite, and the stirring time is 14d.
Further preferably, the montmorillonite concentration in the material D in the step S4 is 2.5mg/mL.
It is further preferred that the concentration of polyvinyl alcohol in the material E in step S5 is from 0.0375 to 0.0875g/mL.
Further preferably, the molar ratio of betaine, lactic acid and urea in the deep eutectic solvent in step S6 is 1:2:1.
Further preferably, the CaCl 2 concentration in the feed I in step S9 is 0.15g/mL.
The preparation method of the high-strength carboxymethyl cellulose-based film material is characterized by comprising the following specific steps of:
step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite or sodium-based montmorillonite in deionized water, stirring for 7d at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
Step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
step S5: dispersing 1.5-3.5g of polyvinyl alcohol in 40mL of deionized water at 100 ℃ and stirring for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
Step S9: dissolving CaCl 2 in deionized water, and stirring at a stirring rate of 600r/min for 10min to prepare 0.15g/mL CaCl 2 solution, namely a material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the target product, namely the high-toughness carboxymethyl cellulose-based composite film, which has high tensile strength and keeps good elongation at break.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention selects the degradable raw materials which are green, nontoxic and harmless and have wide sources, and can reduce the preparation cost of the biodegradable materials;
2. According to the invention, carboxymethyl cellulose, guar gum and polyvinyl alcohol are used as substrates, homogenized montmorillonite is used as an enhancer, a betaine deep eutectic solvent is used as a plasticizer, caCl 2 is used as a cross-linking agent, the toughness of a sample can be obviously improved, the tensile strength can reach 155MPa, and the elongation at break can reach 101%;
3. The carboxymethyl cellulose film prepared by the invention has excellent mechanical property, and the tensile strength and the elongation at break performance are superior to those of the same type of carboxymethyl cellulose film and the traditional petroleum-based film.
Drawings
FIG. 1 is a graph showing the tensile strength of the products H1 to H10 prepared in examples 1 to 6 and comparative examples 1 to 4;
FIG. 2 is a scatter plot of mechanical properties of CMC-based composite films in recent years;
FIG. 3 is an infrared spectrum of products H1-H10 prepared in examples 1-6 and comparative examples 1-4;
FIG. 4 is an XRD diffraction pattern of the products H1-H10 prepared in examples 1-6 and comparative examples 1-4;
FIG. 5 is a graph of UV spectrum vs. transmittance for the products H4, H5, H6, H9 and H10 prepared in examples 4, 5, 6 and comparative examples 1, 4;
FIG. 6 is a schematic representation of the change in water contact angle for the preparation of products H1-H10 of examples 1-6 and comparative examples 1-4.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
step S3: dispersing the calcium-based montmorillonite in deionized water at normal temperature, stirring for 7 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating the calcium-based montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material E;
step S6: mixing the material D obtained in the step S4, the material E obtained in the step S5 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material F;
step S7: coating the material F obtained in the step S6 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material G;
Step S8: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material H;
step S9: and (3) soaking the material G obtained in the step S7 by using the material H obtained in the step S8, washing by using deionized water after 5min, and drying at room temperature to obtain the product H1.
Example 2
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing the calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating the calcium-based montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material E;
step S6: mixing the material D obtained in the step S4, the material E obtained in the step S5 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material F;
step S7: coating the material F obtained in the step S6 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material G;
Step S8: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material H;
Step S9: and (3) soaking the material G obtained in the step (S7) in the material H obtained in the step (S8), washing with deionized water after 5min, and drying at room temperature to obtain the product H2.
Example 3
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing sodium montmorillonite in deionized water at normal temperature, stirring for 7 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating the sodium montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material E;
step S6: mixing the material D obtained in the step S4, the material E obtained in the step S5 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material F;
step S7: coating the material F obtained in the step S6 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material G;
Step S8: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material H;
step S9: and (3) soaking the material G obtained in the step (S7) in the material H obtained in the step (S8), washing with deionized water after 5min, and drying at room temperature to obtain the product H3.
The target products H1-H3 were obtained by examples 1-3 and subjected to tensile testing, and found that the target product H2 had the highest tensile strength after 14 days of treatment with the calcium-based montmorillonite, and then the optimum concentration of PVA was continuously investigated with the 14-day-pretreated calcium-based montmorillonite as a reinforcing filler.
Example 4
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: dispersing 1.5g PVA in 40mL deionized water at 100 ℃ and stirring for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the product H4.
Example 5
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: dispersing 2.5g PVA in 40mL deionized water at 100 ℃ and stirring for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the product H5.
Example 6
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: 3.5g PVA is dispersed in 40mL deionized water at 100 ℃ and stirred for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the product H6.
Comparative example 1
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
step S3: dispersing 0.12g of calcium montmorillonite in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material C;
step S4: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material D;
Step S5: mixing the material C obtained in the step S3, the material D obtained in the step S4 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material E;
step S6: coating the material E obtained in the step S5 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material F;
step S7: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15G/mL CaCl 2 solution, namely material G;
Step S8: soaking the material F obtained in the step S6 in the material G obtained in the step S7, washing with deionized water after 5min, and drying at room temperature to obtain the product H7.
Comparative example 2
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing 0.12g of sodium montmorillonite in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material C;
step S4: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material D;
Step S5: mixing the material C obtained in the step S3, the material D obtained in the step S4 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material E;
step S6: coating the material E obtained in the step S5 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material F;
step S7: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15G/mL CaCl 2 solution, namely material G;
Step S8: soaking the material F obtained in the step S6 in the material G obtained in the step S7, washing with deionized water after 5min, and drying at room temperature to obtain the product H8.
Comparative example 3
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
Step S5: dispersing 0.5g PVA in 40mL deionized water at 100 ℃ and stirring for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the product H9.
Comparative example 4
Step S1: dispersing 2g of carboxymethyl cellulose in 80mL of deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
step S2: dispersing 0.2g guar gum in 20mL deionized water at normal temperature, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite in deionized water at normal temperature, stirring for 14 days at a stirring rate of 800r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
step S4: dispersing 0.12g of the material C obtained in the step S3 in the material B obtained in the step S2 at normal temperature, and stirring for 2 hours at a stirring rate of 600r/min to obtain a material D;
step S5: dispersing 4g of PVA in 40mL of deionized water at 100 ℃ and stirring for 2 hours at a stirring rate of 600r/min to obtain a material E;
Step S6: mixing 0.43g of betaine, 0.36g of lactic acid and 0.21g of urea at 100 ℃ and stirring at a stirring rate of 600r/min for 2 hours to obtain a deep eutectic solvent, namely a material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 at room temperature, and stirring for 4 hours at a stirring rate of 600r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: under the normal temperature condition, caCl 2 is dissolved in deionized water, and the mixture is mixed for 10min at the stirring rate of 600r/min to prepare 0.15g/mL CaCl 2 solution, namely material I;
step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5min, and drying at room temperature to obtain the product H10.
Product H1 was cut to 8mm by 30mm size. And a universal material testing machine is used for carrying out tensile test on the product H1, the effective length of a sample on a clamp is 10mm, and the clamping part of the clamp protects the sample and prevents inaccurate data caused by damage of the sample. The tensile properties of the products H2-H10 were tested in the same way. Product H1 was cut to 10mm x 10mm shape and size, the sample was guaranteed to be dry, and product H1 was subjected to water contact angle testing. The products H2-H10 were tested for water contact angle in the same manner. Product H1 was cut to 10mm by 50mm shape and size and product H4 was subjected to visible light transmittance analysis using an ultraviolet-visible spectrophotometer. The products H5, H6, H8 and H9 were tested for transmittance and UV resistance by the same method.
The properties of the samples in all examples are as follows: as shown in FIG. 1, which shows the tensile curves of the products H1-H10 obtained in examples 1-6 and comparative examples 1-4, the tensile strengths of the products H1-H6 obtained in examples 1-6 were 195.1MPa, 233.6MPa, 148.3MPa, 94.8MPa, 155.1MPa and 58.9MPa, respectively, and the corresponding elongations were 49.6%, 33.8%, 24.7%, 60.8%, 105.7% and 275.4%, respectively; the tensile strengths of the products H7-H10 obtained in comparative examples 1-4 were 186.3MPa, 132.9MPa, 79.4MPa and 47.5MPa, respectively, and the corresponding elongations were 44.2%, 39.9%, 38.2% and 303.7%, respectively. Comparing H1 and H2, it is found that the longer the montmorillonite stirring time is, the stronger the tensile strength of the film is, and the smaller the breaking elongation is. By comparing H1 and H3, the mechanical properties of the calcium-based montmorillonite enhanced film are superior to those of sodium-based montmorillonite. It is found by observation that after PVA is added, the breaking elongation performance of the carboxymethyl cellulose-based composite film is far higher than that before PVA is added, and after proper proportion is controlled, the composite film still has better toughness and tensile strength. In combination with the complex environment of practical application, the tensile strength and the elongation at break are comprehensively considered, and the product H5 has better tensile strength of 155.1MPa and elongation at break of 105.7 percent. As shown in FIG. 5, the ultraviolet blocking rate of the product H5 to below 280nm reaches 100%, and the ultraviolet blocking rate of 280-320nm also reaches 65.5%, which shows that the product H5 has good ultraviolet blocking effect in practical application. As shown in FIG. 6, the water contact angle of the product H5 reaches 90.39 degrees, and the surface product H5 has good hydrophobic property, so that the product H5 is promoted to be applied to the fields of food packaging and the like.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The preparation method of the high-toughness carboxymethyl cellulose-based composite film is characterized by comprising the following specific processes:
Step S1: dispersing carboxymethyl cellulose in deionized water, and uniformly stirring and mixing to obtain a material A;
Step S2: dispersing guar gum in deionized water, and uniformly stirring and mixing to obtain a material B;
Step S3: dispersing montmorillonite in deionized water, stirring at a stirring rate of 600-1000 r/min for 2-h-14 and d, centrifuging and ultrasonically treating montmorillonite suspension, and vacuum freeze-drying to obtain material C;
Step S4: dispersing the material C obtained in the step S3 in the material B obtained in the step S2, and uniformly stirring and mixing to obtain a material D;
step S5: dispersing polyvinyl alcohol in deionized water at 100 ℃ and stirring and mixing uniformly to obtain a material E;
step S6: stirring and mixing betaine, lactic acid and urea at 100 ℃ uniformly to obtain a deep eutectic solvent, namely a material F;
Step S7: stirring and mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1 uniformly to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
Step S9: dissolving CaCl 2 in deionized water, and uniformly stirring and mixing to obtain a CaCl 2 solution, namely a material I;
Step S10: and (3) soaking the material H obtained in the step (S8) by using the material I obtained in the step (S9), washing by using deionized water, and drying at room temperature to obtain the target product, namely the high-toughness carboxymethyl cellulose-based composite film.
2. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the concentration of carboxymethyl cellulose in the material A in the step S1 is 0.025 g/mL.
3. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the concentration of guar gum in the material B in the step S2 is 2.5 mg/mL.
4. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the montmorillonite in the step S3 is calcium-based montmorillonite and sodium-based montmorillonite, and the stirring time is 14 d.
5. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the concentration of montmorillonite in the material D in the step S4 is 2.5 mg/mL.
6. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the concentration of the polyvinyl alcohol in the material E in the step S5 is 0.0375-0.0875 g/mL.
7. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the molar ratio of betaine, lactic acid and urea in the deep eutectic solvent in the step S6 is 1:2:1.
8. The method for producing a high-toughness carboxymethyl cellulose-based composite film according to claim 1, characterized in that: the concentration of CaCl 2 in the feed I in step S9 was 0.15 g/mL.
9. The method for preparing the high-toughness carboxymethyl cellulose-based composite film according to claim 1, which is characterized by comprising the following specific steps:
step S1: dispersing 2 g carboxymethyl cellulose in 80 mL deionized water, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material A;
Step S2: dispersing 0.2 g guar gum in 20 mL deionized water, and uniformly stirring and mixing at a stirring rate of 600r/min to obtain a material B;
Step S3: dispersing calcium-based montmorillonite or sodium-based montmorillonite in deionized water, stirring for 7d at a stirring rate of 800 r/min, centrifuging and ultrasonically treating montmorillonite suspension for 3 times, and vacuum freeze-drying to obtain a material C;
Step S4: dispersing the material C obtained in the step S3 of 0.12-g in the material B obtained in the step S2, and stirring 2-h at a stirring rate of 600r/min to obtain a material D;
Step S5: dispersing 1.5-3.5 g polyvinyl alcohol in 40 mL deionized water at 100 ℃, and stirring at a stirring rate of 600 r/min for 2h to obtain a material E;
Step S6: mixing 0.43g betaine, 0.36g lactic acid and 0.21g urea at 100deg.C, and mixing at stirring rate of 600 r/min for 2h to obtain deep eutectic solvent as material F;
Step S7: mixing the material D obtained in the step S4, the material E obtained in the step S5, the material F obtained in the step S6 and the material A obtained in the step S1, and stirring 4 to h at a stirring rate of 600 r/min to obtain a material G;
Step S8: coating the material G obtained in the step S7 on a polytetrafluoroethylene plate and drying at room temperature to obtain a material H;
step S9: dissolving CaCl 2 in deionized water, and stirring at a stirring rate of 600 r/min for 10min to prepare 0.15 g/mL CaCl 2 solution, namely material I;
Step S10: and (3) soaking the material H obtained in the step (S8) in the material I obtained in the step (S9), washing with deionized water after 5 min, and drying at room temperature to obtain the target product, namely the high-toughness carboxymethyl cellulose-based composite film which has high tensile strength and keeps good elongation at break.
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