CN116731365A - High-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film and preparation method thereof - Google Patents
High-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 50
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 50
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 50
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 45
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 33
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 33
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims description 85
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- 230000005588 protonation Effects 0.000 claims description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 14
- 230000006750 UV protection Effects 0.000 claims description 13
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 11
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 235000002949 phytic acid Nutrition 0.000 claims description 11
- 239000000467 phytic acid Substances 0.000 claims description 11
- 229940068041 phytic acid Drugs 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 abstract description 15
- 230000008961 swelling Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 238000001816 cooling Methods 0.000 description 7
- 238000000502 dialysis Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
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- 239000011734 sodium Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229920006321 anionic cellulose Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
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- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible 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
- 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
- C08J2405/04—Alginic acid; Derivatives thereof
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of a high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film, which belongs to the technical field of preparation of carboxymethyl cellulose-based films. The high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film prepared by the invention has the advantages of higher water resistance (water contact angle, solubility and swelling rate are 105 degrees, 20.3 percent and 93 percent respectively), ultraviolet blocking performance (94.8 percent), excellent tensile strength (60 MPa) and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of carboxymethyl cellulose-based films, and particularly relates to a preparation method of a carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance.
Background
Conventional packaging materials are typically prepared from non-renewable petroleum sources, which pose a significant environmental hazard due to their non-degradability. Therefore, there is a need to develop a biodegradable packaging material that can replace the conventional plastic. Among the numerous renewable biopolymer materials, cellulose has the characteristics of good biocompatibility, reproducibility, non-toxicity, and the like. Among them, sodium carboxymethyl cellulose (CMC-Na) is a water-soluble anionic cellulose ether, has excellent film forming ability and good gas barrier property, can form a transparent, flexible film, and is widely used for manufacturing biodegradable packaging films. Sodium Alginate (SA) is a natural polyanion polysaccharide which is renewable, good in biocompatibility and convenient to process, and is widely applied to the fields of food, medicine, packaging and the like because of good solubility, thickening property, film forming property and the like. The SA and CMC-Na can be blended to prepare a transparent film with good mechanical properties, but the SA and CMC-Na structures have a large number of hydrophilic hydroxyl groups and ionized carboxyl groups, so that the film has the problem of poor water resistance and stability under high humidity conditions. In order to solve the above problems, various strategies for improving water resistance have been proposed by researchers, such as polymer blending, metal ion chelation, ionized carboxyl group protonation, and the like.
In order to enhance the water resistance and further enhance the mechanical property of the carboxymethyl cellulose/sodium alginate composite film, the ionized carboxyl protonation strategy can change the ionized carboxyl groups of CMC-Na and SA into carboxyl (-COOH), so that the electrostatic repulsive interaction between high molecular chains is reduced, stronger intramolecular and intermolecular hydrogen bonds can be formed between the protonated-COOH and the original-OH, the three-dimensional network structure inside the film is enhanced, and the number of exposed hydroxyl groups is reduced, so that the water resistance and the mechanical property of the film are improved. In addition, good ultraviolet blocking property is one of important properties of transparent packaging materials, and ultraviolet radiation can cause problems such as food deterioration, aging of high polymer products such as fibers and the like. In recent years, carbon Quantum Dots (CQDs) have high water solubility, excellent biocompatibility, low cytotoxicity, multi-surface functional groups, photoluminescence, and other characteristics, and have become functional fillers for packaging applications. The CQDs are subjected to surface functional group modification so as to generate interface interaction with the matrix polymer, thereby improving the ultraviolet blocking performance and mechanical performance of the film.
According to the invention, green and nontoxic CQDs are selected as ultraviolet blocking additives, and an ionized carboxyl protonation strategy is further adopted for ion exchange, so that the water resistance and ultraviolet blocking performance of the carboxymethyl cellulose/sodium alginate composite film can be effectively improved, and the obtained film material has a wide application prospect in the field of water-resistant ultraviolet blocking plastic films.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a carboxymethyl cellulose/sodium alginate composite film with simple preparation process, low cost, high strength, water resistance and ultraviolet resistance, which uses CMC-Na and SA as main materials of the composite film, uses CQDs as ultraviolet blocking materials of the film, mechanically stirs the mixed materials at room temperature to promote the materials to be mixed uniformly, coats the mixed materials on a polytetrafluoroethylene plate for drying, and adopts an acetic acid dipping ion exchange mode to carry out ionization carboxyl protonation to prepare the carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance. The carboxymethyl cellulose/sodium alginate composite film prepared by the invention has the advantages of excellent water resistance, ultraviolet blocking performance (94.8%), high tensile strength (60 MPa) and the like.
The invention adopts the following technical proposal to solve the technical problems, and the preparation method of the carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance is characterized by comprising the following specific processes:
step S1, dissolving citric acid, phytic acid and urea in deionized water, transferring to a 100mL high-pressure reaction kettle after ultrasonic treatment, reacting for a certain time at high temperature to obtain a yellowish-brown mixed solution, centrifuging, dialyzing and freeze-drying a cooled product to obtain carbon quantum dot powder serving as a material A;
step S2, at room temperature, dissolving glycerol, sodium carboxymethylcellulose and sodium alginate in deionized water, and mixing at a stirring rate of 400r/min to obtain a material B;
step S3, adding the material A into the material B, and continuously stirring at a stirring rate of 400r/min to obtain a material C;
s4, coating the material C on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D;
and S5, immersing the material D in acetic acid with a certain concentration for protonation treatment for a certain time, and then repeatedly cleaning the film with absolute ethyl alcohol to remove sodium acetate generated in the protonation process of the film surface, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance of the target product.
Further limiting, the feeding ratio of the citric acid to the phytic acid to the urea in the step S1 is 5:5:2, and the reaction condition is 160-200 ℃ for 6 hours.
Further defined, the feeding ratio of glycerol, sodium carboxymethylcellulose and sodium alginate in the step S2 is 4:9:3.
Further defined, the feeding ratio of the material A in the step S3 is 1:100-5:100.
Further defined, in step S5, the substance D is protonated by impregnation with 98% to 100% acetic acid.
The preparation method of the high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film disclosed by the invention is characterized by comprising the following specific steps of:
step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, ultrasonically transferring to a 100mL high-pressure reaction kettle, reacting at 160-200 ℃ for 6 hours to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48 hours, freeze-drying, and grinding to obtain carbon quantum dot powder which is a material A;
step S2: 1g of glycerol, 2.25g of carboxymethyl cellulose and 0.75g of sodium alginate are dissolved in deionized water and then mixed for 1h at a stirring rate of 400r/min at room temperature to obtain a material B;
step S3: adding the material A into the material B at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C;
s4, coating the material C on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D;
and S5, immersing the material D in 98% -100% acetic acid for protonation treatment for 30-150 min, and then repeatedly cleaning the surface of the film by using absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance as a target product. The carboxymethyl cellulose/sodium alginate composite film has excellent water resistance, ultraviolet blocking performance (94.8%) and high tensile strength (60 MPa).
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention selects the biodegradable material which is green, wide in source and biocompatible, and can reduce the preparation cost of the biodegradable film;
2. according to the invention, CMC-Na and SA are used as substrates, CQDs synthesized by a hydrothermal synthesis method are used as ultraviolet blocking materials, and the ultraviolet blocking rate of the film can be obviously improved on the premise of ensuring certain transparency of the carboxymethyl cellulose/sodium alginate composite film, and the blocking rate can reach 94.8%;
3. the prepared high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film has excellent water resistance, tensile strength and toughness, and the ionization carboxyl protonation of CMC-Na and SA by utilizing acetic acid reduces the electrostatic repulsion between high polymer chains, so that stronger intramolecular and intermolecular hydrogen bonds are formed, and the aim of improving the water resistance is fulfilled while the strength and toughness of the film are improved.
Drawings
FIG. 1 is a sample diagram of the target products CS1-CS3 prepared in examples 1-3;
FIG. 2 is an X-ray diffraction pattern of the target products CS1-CS3 prepared in examples 1-3;
FIG. 3 is an infrared spectrum of the target products CS1-CS3 prepared in examples 1-3;
FIG. 4 is a graph of ultraviolet spectrum-transmittance of the target products CS1-CS3 prepared in examples 1-3 and the products CS6-CS7 prepared in comparative examples 1-2;
FIG. 5 is a graph showing tensile strength of the objective products CS1-CS3 prepared in examples 1-3 and the products CS6-CS7 prepared in comparative examples 1-2;
FIG. 6 is a water-soluble chart of the objective products CS1-CS3 prepared in examples 1-3 and the products CS6-CS7 prepared in comparative examples 1-2;
FIG. 7 is a graph (a) showing water contact angle measurements of the objective products CS1-CS3 prepared in examples 1-3 and the objective products CS6-CS7 prepared in comparative examples 1-2, and a graph (b) showing swelling ratios of the objective products CS1-CS3 prepared in examples 1-3.
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: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, ultrasonically transferring to a 100mL high-pressure reaction kettle, reacting at 200 ℃ for 6 hours to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48 hours, freeze-drying, and grinding to obtain a carbon quantum dot material A1;
step S2: at room temperature, 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water and mixed for 1h at a stirring rate of 400r/min to obtain a material B1;
step S3: adding the material A1 into the material B1 at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C1;
step S4: coating the material C1 on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D1;
step S5: immersing the material D1 in 98% -100% acetic acid for protonation treatment for 30min, then repeatedly cleaning the surface of the film by absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film CS1 with high strength, water resistance and ultraviolet resistance of the target product.
Example 2
Step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, ultrasonically transferring to a 100mL high-pressure reaction kettle, reacting at 200 ℃ for 6 hours to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48 hours, freeze-drying, and grinding to obtain a carbon quantum dot material A2;
step S2: 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water at room temperature and mixed for 1h at a stirring rate of 400r/min to obtain a material B2;
step S3: adding the material A2 into the material B2 at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C2;
step S4: coating the material C2 on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D2;
step S5: immersing the material D2 in 98% -100% acetic acid for protonation treatment for 90min, then repeatedly cleaning the surface of the film by absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film CS2 with high strength, water resistance and ultraviolet resistance of the target product.
Example 3
Step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, carrying out ultrasonic treatment for 20min, transferring to a 100mL high-pressure reaction kettle, reacting at 200 ℃ for 6h to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48h, and grinding after freeze drying to obtain a material A3;
step S2: 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water at room temperature and mixed for 1h at a stirring rate of 400r/min to obtain a material B3;
step S3: adding the material A3 into the material B3 at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C3;
step S4: coating the material C3 on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D3;
step S5: immersing the material D3 in 98% -100% acetic acid for protonation treatment for 150min, then repeatedly cleaning the surface of the film by absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film CS3 with high strength, water resistance and ultraviolet resistance of the target product.
Example 4
Step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, carrying out ultrasonic treatment for 20min, transferring to a 100mL high-pressure reaction kettle, reacting at 160 ℃ for 6h to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48h, and grinding after freeze drying to obtain a material A4;
step S2: 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water at room temperature and mixed for 1h at a stirring rate of 400r/min to obtain a material B4;
step S3: adding the material A4 into the material B4 at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C4;
step S4: coating the material C4 on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D4;
step S5: immersing the material D4 in 98% -100% acetic acid for protonation treatment for 150min, then repeatedly cleaning the surface of the film by absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film CS4 with high strength, water resistance and ultraviolet resistance of the target product.
Example 5
Step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, carrying out ultrasonic treatment for 20min, transferring to a 100mL high-pressure reaction kettle, reacting at 180 ℃ for 6h to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48h, and grinding after freeze drying to obtain a material A5;
step S2: 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water at room temperature and mixed for 1h at a stirring rate of 400r/min to obtain a material B5;
step S3: adding the material A5 into the material B5 at a feeding ratio of 2:100, and continuously stirring for 1h at a stirring rate of 400r/min to obtain a material C5;
step S4: coating the material C5 on a polytetrafluoroethylene plate, and drying at 30% RH and 40 ℃ to obtain a material D5;
step S5: immersing the material D5 in 98% -100% acetic acid for protonation treatment for 150min, then repeatedly cleaning the surface of the film by absolute ethyl alcohol to remove sodium acetate generated in the protonation process, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film CS5 with high strength, water resistance and ultraviolet resistance of the target product.
Comparative example 1
Step S1: fully dissolving 2.8g of citric acid, 2.8g of phytic acid and 1.12g of urea in deionized water, ultrasonically transferring to a 100mL high-pressure reaction kettle, reacting at 200 ℃ for 6 hours to obtain a yellowish-brown mixed solution, cooling to room temperature, centrifuging to remove larger particles, dialyzing the supernatant with a dialysis bag for 48 hours, freeze-drying, and grinding to obtain a carbon quantum dot material A6;
step S2: at room temperature, 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water and mixed for 1h at a stirring rate of 400r/min to obtain a material B6;
step S3: adding 0.06g of material A6 into material B6, and continuously stirring for 1h at a stirring rate of 400r/min to obtain material C6;
step S4: material C6 was coated on a polytetrafluoroethylene plate and dried at 30% RH at 40℃to give the product CS6.
Comparative example 2
Step S1: at room temperature, 1g of glycerol, 2.25g of sodium carboxymethylcellulose and 0.75g of sodium alginate are dissolved in deionized water and mixed for 1h at a stirring rate of 400r/min to obtain a material A7;
step S2: material A7 was coated on a polytetrafluoroethylene plate and dried at 30% RH at 40℃to give the product CS7.
Cutting the target product CS1 into a shape and a size of 10mm multiplied by 10mm, guaranteeing the drying of the sample, and respectively testing the water solubility, the swelling rate and the water contact angle of the target product CS1. The target product CS1 was cut into a 10mm×50mm shape and size, and the target product CS1 was subjected to visible light transmittance analysis using an ultraviolet-visible spectrophotometer. Cutting a target product CS1 into a shape of 5mm multiplied by 30mm, using a universal material testing machine to carry out a tensile test on the target product CS1, wherein the effective length of a sample on a clamp is 10mm, and protecting the sample by a clamping part of the clamp to prevent inaccurate data caused by damage of the sample. The tensile properties of the target products CS2, CS3 and the comparative examples CS6, CS7 were measured in the same manner.
The properties of the samples in the examples are as follows: as shown in FIG. 4, for the UV-visible spectra obtained in examples 1-3 and comparative examples 1-2, the average UV-blocking rate of the target product CS3 reached 94.8%, and the average UV-blocking rates of the products CS6, CS7 obtained in comparative examples 1-2 were 87% and 73.9%, respectively, indicating that CQDs can effectively improve the UV-blocking performance of the film. As shown in FIG. 5, the tensile strengths of the target products CS1 to CS3 obtained in examples 1 to 3 and the products CS6 and CS7 obtained in comparative examples 1 to 2 were 50.79MPa, 58.59MPa and 60.24MPa, respectively, and the corresponding elongations were 78.83%, 108.25% and 123.12%, respectively, and the tensile strengths of the target products CS1 to CS3 obtained in examples 1 to 3 and the products CS6 and CS7 obtained in comparative examples 1 to 2 were 41.04MPa and 46.70MPa, respectively, and the corresponding elongations were 102.86% and 85.31%, respectively. As shown in FIG. 6, which shows the water solubility profiles of the target products CS1 to CS3 obtained in examples 1 to 3, the solubilities of the target products CS1 to CS3 obtained in examples 1 to 3 were 53%, 25.2% and 20.3%, respectively. Fig. 7 shows graphs (b) of the water contact angle (a) and the swelling ratio obtained in examples 1 to 3 and comparative examples 1 to 2, in which the contact angle of the target CS3 was 105 ° as seen from the graph (a), and the swelling ratios of the target CS1 to CS3 obtained in examples 1 to 3 were 706.4%, 117.5% and 93%, respectively, indicating a significant improvement in the water resistance of the target CS3. The result shows that the target product CS3 has excellent water resistance, ultraviolet blocking performance and tensile strength, and has potential application prospect in the field of degradable plastics.
The comparative example shows that the carboxymethyl cellulose/sodium alginate composite film without CQDs has poor ultraviolet blocking performance, and the mechanical property and the water resistance of the composite film without ionized carboxyl protonation can not meet the use requirement well. The CQDs of the invention obviously improves the ultraviolet blocking performance of the carboxymethyl cellulose/sodium alginate composite film, and the ionization carboxyl protonation strategy ensures that the composite film has excellent water resistance, higher tensile strength and toughness.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing embodiments, it will be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, 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 principles of the invention.
Within the scope of the present invention. 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 (5)
1. A preparation method of a carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance is characterized by comprising the following specific processes:
step S1: dissolving citric acid, phytic acid and urea in deionized water, ultrasonically transferring to a 100mL high-pressure reaction kettle, reacting for a certain time at high temperature to obtain a yellowish-brown mixed solution, centrifuging, dialyzing and freeze-drying a cooled product to obtain carbon quantum dot powder as a material A;
step S2: at room temperature, dissolving glycerol, sodium carboxymethylcellulose and sodium alginate in deionized water, and mixing at a stirring rate of 400r/min to obtain a material B;
step S3: adding the material A into the material B, and continuously stirring at a stirring rate of 400r/min to obtain a material C;
step S4: coating the material C on a polytetrafluoroethylene plate, and drying at 40 ℃ under the relative humidity of 30% (30% RH) to obtain a material D;
step S5: immersing the material D in acetic acid with a certain concentration for protonation treatment for a certain time, then repeatedly cleaning the film with absolute ethyl alcohol to remove sodium acetate generated in the surface protonation process of the film, and drying at room temperature to obtain the carboxymethyl cellulose/sodium alginate composite film with high strength, water resistance and ultraviolet resistance as a target product.
2. The method for preparing the high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film according to claim 1, wherein the method comprises the following steps: the feeding ratio of the citric acid to the phytic acid to the urea in the step S1 is 5:5:2, and the reaction condition is 160-200 ℃ for 6 hours.
3. The method for preparing the high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film according to claim 1, wherein the method comprises the following steps: the feeding ratio of glycerol, sodium carboxymethylcellulose and sodium alginate in the step S2 is 4:9:3.
4. The method for preparing the high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film according to claim 1, wherein the method comprises the following steps: in the step S3, the feeding ratio of the material A to the material B is 1:100-5:100.
5. The method for preparing the high-strength, water-resistant and ultraviolet-resistant carboxymethyl cellulose/sodium alginate composite film according to claim 1, wherein the method comprises the following steps: in the step S5, the material D is soaked in 98% -100% acetic acid for protonation treatment.
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| CN117065074B (en) * | 2023-10-12 | 2023-12-22 | 太平洋康泰科学仪器（济南）有限公司 | Composite electrostatic spinning nanofiber dressing containing PDRN and preparation method thereof |
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