CN116515149A - Preparation method of novel cellulose-based hydrophobic film - Google Patents
Preparation method of novel cellulose-based hydrophobic film Download PDFInfo
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- CN116515149A CN116515149A CN202310619503.6A CN202310619503A CN116515149A CN 116515149 A CN116515149 A CN 116515149A CN 202310619503 A CN202310619503 A CN 202310619503A CN 116515149 A CN116515149 A CN 116515149A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 85
- 239000001913 cellulose Substances 0.000 title claims abstract description 80
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 50
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000005016 bacterial cellulose Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 229920001046 Nanocellulose Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 18
- 229920001800 Shellac Polymers 0.000 claims description 14
- 239000004208 shellac Substances 0.000 claims description 14
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims description 14
- 229940113147 shellac Drugs 0.000 claims description 14
- 235000013874 shellac Nutrition 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 244000060011 Cocos nucifera Species 0.000 claims description 7
- 238000004537 pulping Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002522 Wood fibre Polymers 0.000 claims description 5
- 235000013379 molasses Nutrition 0.000 claims description 5
- 239000002025 wood fiber Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000002121 nanofiber Substances 0.000 claims description 4
- 102000008186 Collagen Human genes 0.000 claims description 3
- 108010035532 Collagen Proteins 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229920001436 collagen Polymers 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims 1
- 239000010902 straw Substances 0.000 abstract description 20
- 238000007731 hot pressing Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 235000010980 cellulose Nutrition 0.000 abstract 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 16
- 239000012528 membrane Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 238000010009 beating Methods 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 241001397809 Hakea leucoptera Species 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
- C08J2493/02—Shellac
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a novel cellulose-based hydrophobic film, which comprises the steps of uniformly mixing more than two cellulose dispersion solutions in any proportion, carrying out suction filtration on the mixture to obtain a filter cake, and carrying out hot pressing on the filter cake at 100-110 ℃ for 1-3 hours to obtain the hydrophobic film; the invention prepares the cellulose straw with high mechanical strength, excellent wet stability and economy by coiling the novel cellulose-based hydrophobic film based on the nano-scale entanglement, hydrogen bond connection and generated interfacial adhesion between more than two celluloses with different scales and the space in the interconnected cellulose 3D network filled by lac.
Description
Technical Field
The invention belongs to the field of biomass-based functional materials, relates to the technical field of food materials, and particularly relates to a preparation method of a novel cellulose-based hydrophobic film.
Background
Most petrochemical plastics are not easy to degrade, a large amount of plastics are accumulated to cause environmental pollution, green development is a necessary choice of human progress, and the use of paper instead of plastic is an important strategy for solving the current white pollution and reducing carbon emission. Among them, paper straw is widely popularized because of its good degradability, but the weak mechanical properties of paper straw in water environment have been described by people. In view of this, there is a need for further improvements in the art. From the aspects of sustainable development and durability, the hydrophobic composite film with better mechanical properties and environmental protection is an attractive material in the fields of catering industry, packaging industry and the like.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of a novel cellulose-based hydrophobic film, which takes cellulose with different dimensions and degradable nontoxic shellac resin as raw materials and prepares a hydrophobic film through a paper making process method.
The technical scheme of the invention is as follows:
a process for preparing the novel cellulose-base hydrophobic film includes such steps as proportionally mixing more than two kinds of cellulose dispersions, suction filtering to obtain filter cake, hot pressing at 100-110 deg.C for 1-3 hr, and hot pressing to obtain hydrophobic film.
The cellulose dispersion liquid comprises: nanocellulose dispersions, long cellulose dispersions, bacterial cellulose microgels, and the like.
The above two or more cellulose dispersion solutions are also mixed with degradable nontoxic lac resin dispersion solution, and the mass ratio of cellulose to lac resin is 0.2:0.8-0.8:0.2.
The preparation method of the long fiber dispersion liquid comprises the following steps: soaking a long fiber pulp board in deionized water for 30-40 minutes, crushing the soaked pulp board by a hydraulic pulper, starting a pulper motor to ensure that the pulp is strongly disintegrated and separated into fibers in a wet state, pulping the crushed pulp by a PFI pulping machine to ensure that the pulp concentration is 10%, beating 30g of absolute dry pulp to finally obtain pulp with the beating degree of 45 DEG SR, adding water into the long fiber pulp with the beating degree of 45 DEG SR to prepare long fiber dispersion liquid with the required concentration (such as 1-10% by mass fraction), measuring the pulp concentration by an oven drying method, and refrigerating for standby.
The preparation method of the bacterial cellulose microgel comprises the following steps: the bacterial cellulose is commercially purchased molasses coconuts, deionized water is adopted to clean the molasses coconuts until the conductivity of the washing liquid is consistent with that of the deionized water and TDS=0, 1kg of cleaned coconuts (if the capacity is less than 1L, the deionized water is added to 1L) are taken, and the bacterial cellulose microgel is obtained after 4800r/min for 20min of dispersion, and can be dried to determine the solid content and refrigerated for standby.
The preparation method of the nanocellulose dispersion liquid comprises the following steps: based on needle leaf wood fiber, preparing nano cellulose dispersion liquid by a TEMPO mediated oxidation method, wherein the preparation method comprises the following specific steps of: 35g of needle wood fiber is suspended in 3500mL of deionized water containing 0.84g of TEMPO, 5.25g of sodium bromide and 328.05g of sodium hypochlorite, the pH value is adjusted to 10 by adding 0.1mol/L of HCl and 0.1mol/L of NaOH, TEMPO-mediated oxidation is started, stirring is carried out at 500rpm at room temperature, a sodium hydroxide solution is continuously added during stirring to adjust the pH value until the pH value is 10 and constant, then the mixed solution is poured into a Buchner funnel, the mixed solution is filtered and washed by using deionized water until the washing solution is neutral, the washed nano cellulose is placed in a beaker, sealed by using a preservative film and placed in a refrigerator, and stored at 4 ℃, and water is added according to requirements to prepare nano fiber dispersion liquid with required concentration (such as mass fraction of 1-10%).
The lac resin is bleached lac resin, and the preparation method of the bleached lac resin dispersion liquid comprises the following steps: dissolving bleached lac in ethanol (95 wt.%) to obtain bleached lac ethanol solution with concentration of 6.5wt.%, stirring, dripping the bleached lac ethanol solution into deionized water with temperature of 40 deg.C, preparing bleached lac water-soluble collagen solution under the action of strong electric stirrer at set rotation speed, evaporating ethanol by rotary evaporator, analyzing particle size of the dispersion by particle size analyzer, measuring solid content of the bleached lac resin dispersion, refrigerating, and adding water to obtain bleached lac resin dispersion with required concentration (such as 1-10% by mass).
The novel cellulose-based hydrophobic film prepared by the method is curled, and is bonded by using a lac ethanol solution at a joint to obtain a green pollution-free cellulose straw.
The invention has the beneficial effects that:
the invention uses cellulose and shellac as raw materials, the cellulose is the natural polymer with the most abundant reserves on the earth, the cellulose is the polysaccharide with the most wide distribution and content in the nature, the cellulose with different sizes has strong interaction, can form an interface adhesion effect to form a firmer three-dimensional network structure, and the shellac with small molecular weight can fill the gaps of the three-dimensional network structure among the cellulose, so that the composite film has better mechanical property.
Drawings
FIG. 1 is a laboratory prepared composite membrane and composite pipette diagram;
FIG. 2 is a graph showing the mechanical properties of cellulose straws in comparison ((a) dry strength of cellulose straws in comparison and (b) (c) wet strength of cellulose straws in comparison);
FIG. 3 is a graph of the water absorption of a cellulose straw;
FIG. 4 is a graph showing the water absorption of a pairwise composite cellulose pipette;
FIG. 5 is a wet strength of a straw made by compounding bacterial cellulose with long fibers;
FIG. 6 is a graph showing the mechanical properties of a shellac-cellulose straw versus (a) dry strength versus (b) wet strength;
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but it should be noted that the scope of the present invention is not limited by these examples. Abbreviated herein as BDDE: TEMPO:2, 6-tetramethylpiperidine-nitrogen-oxide; TDS: total amount of dissolved solids; SR, freeness. The long fiber pulp board, the molasses coconut, the needle wood fiber and the bleached lac are all purchased in the market.
The paper sheet forming dryer used in the invention is purchased from Integrifleson precision instruments, inc. of Dongguan, and has the model of IMT-GZ01, and the required voltage is 220V.
Example 1
The preparation of the long cellulose dispersion liquid comprises the following specific steps:
soaking a long fiber pulp board in deionized water for 30-40 minutes, crushing the soaked pulp board by a hydraulic pulper, starting a pulper motor to enable the pulp to be strongly disintegrated in a wet state and separate fibers, pulping the crushed pulp by a PFI pulping machine to determine the pulp concentration to be 10%, beating 30g of absolute dry pulp to finally obtain pulp with the pulp degree of 45 DEG SR, preparing dispersion liquid with different concentrations from the long fiber pulp with the pulp degree of 45 DEG SR, refrigerating for later use, and measuring the solid content by an oven drying method.
Example 2
The preparation method of the bacterial cellulose microgel comprises the following specific steps:
the bacterial cellulose used was a commercially available molasses coco and was rinsed with deionized water until the conductivity of the rinse was consistent with deionized water and tds=0, and then a bacterial cellulose dispersion was prepared by mechanical means: taking 1kg of cleaned coconut (the volume is less than 1L, deionized water is added to 1L), dispersing for 20min by high-speed mechanical shearing (4800 r/min) of a wall breaking machine to obtain bacterial cellulose microgel, refrigerating for later use, and drying to determine the solid content.
Example 3
The preparation method of the nanocellulose dispersion liquid comprises the following specific steps:
based on needle leaf wood fiber, preparing nano cellulose dispersion liquid by a TEMPO mediated oxidation method, wherein the preparation method comprises the following specific steps of: 35g of conifer fiber is suspended in 3500mL of deionized water containing 0.84g of TEMPO, 5.25g of sodium bromide and 328.05g of sodium hypochlorite, the pH value is adjusted to 10 by adding hydrochloric acid with the concentration of 0.1mol/L and NaOH solution with the concentration of 0.1mol/L, TEMPO-mediated oxidation is started, stirring is carried out at 500rpm at room temperature, the pH value is continuously adjusted by adding sodium hydroxide solution with the concentration of 0.1mol/L until the pH value is 10 and constant in the stirring process, then the mixed solution is poured into a Buchner funnel, the washing solution is filtered by deionized water until the washing solution is neutral, the washed cellulose nanofiber is placed in a beaker, water is added or evaporated to remove water to prepare a dispersion with the required concentration, the dispersion is sealed by a preservative film and is placed in a refrigerator and stored at 4 ℃.
Example 4
The preparation method of the lac resin dispersion liquid comprises the following specific steps:
dissolving bleached lac resin in ethanol (95 wt.%) to obtain bleached lac ethanol solution with concentration of 6.5wt.%, stirring uniformly, dripping the bleached lac ethanol solution into deionized water with temperature of 40 deg.C, preparing bleached lac water-soluble collagen solution under the action of strong electric stirrer at set rotation speed, evaporating ethanol by rotary evaporator, analyzing particle size of the dispersion by particle size analyzer, measuring solid content of the bleached lac resin dispersion, refrigerating, and preparing bleached lac resin dispersion with required concentration according to requirement.
Example 5
The preparation method of the novel cellulose-based hydrophobic film comprises the following specific steps:
(1) Taking a long cellulose dispersion liquid with the concentration of 1wt% prepared in example 1, preparing bacterial cellulose microgel in example 2, and preparing a nano cellulose dispersion liquid with the concentration of 1wt% prepared in example 3, mixing according to the mass ratio of nano cellulose to bacterial cellulose to long cellulose of 1:1:1, and stirring for 30 minutes by a mechanical stirrer to obtain uniform slurry with the concentration of 0.16 wt%;
(2) Filtering the slurry obtained in the step (1) through a sand core filter, wherein the filtering membrane is purchased from Shanghai Xingjia sub-purification material factory, and the specification of a mixed cellulose ester microporous filtering membrane (water system) is 110mm 0.22 mu m;
(3) And (3) hot-pressing the filter cake obtained in the step (2) for 1 hour at 100 ℃ by using a paper sheet forming dryer to obtain the cellulose film.
The mass ratio of nanocellulose to bacterial cellulose to long cellulose is changed to be 1:1:2, 2:1:1 and 1:2:1, and other steps and process parameters are the same as those of the embodiment 5, so that cellulose films are respectively prepared.
Comparative example 1
In comparison with example 5, the three cellulose dispersions were not mixed, and the other steps and process parameters were the same as in example 5, to prepare pure long fiber, bacterial cellulose and nanocellulose films, respectively.
Example 6
The preparation method of the novel cellulose-based hydrophobic film comprises the following specific steps:
(1) Taking a long cellulose dispersion liquid with the concentration of 1wt.% prepared in example 1, and a nano cellulose dispersion liquid with the concentration of 2wt.% prepared in example 3, mixing the long cellulose dispersion liquid and the nano cellulose dispersion liquid according to the mass ratio of 0.75:0.25, and obtaining uniform slurry by a mechanical stirrer for 35 minutes;
(2) Filtering the slurry obtained in the step (1) through a sand core filter, wherein the filtering membrane is purchased from Shanghai Xingjia sub-purification material factory, and the specification of a mixed cellulose ester microporous filtering membrane (water system) is 110mm 0.22 mu m;
(3) And (3) hot-pressing the filter cake obtained in the step (2) for 2 hours at 105 ℃ by using a paper sheet forming dryer to obtain the cellulose film.
In comparison with example 6, the cellulose thin film was prepared by changing the mass ratio of long cellulose to nanocellulose to (0.5:0.5) and (0.25:0.75), and other steps and process parameters to be the same as in example 6.
Example 7
The preparation method of the novel cellulose-based hydrophobic film comprises the following specific steps:
(1) Taking the bacterial cellulose microgel prepared in the example 2, and the nano cellulose dispersion liquid with the concentration of 1wt.% prepared in the example 3, mixing according to the mass ratio of the bacterial cellulose to the nano cellulose of 0.75:0.25, and passing through a mechanical stirrer for 35 minutes to obtain uniform slurry with the concentration of 0.16 wt.%;
(2) Filtering the slurry obtained in the step (1) through a sand core filter, wherein the filtering membrane is purchased from Shanghai Xingjia sub-purification material factory, and the specification of a mixed cellulose ester microporous filtering membrane (water system) is 110mm 0.22 mu m;
(3) And (3) hot-pressing the filter cake obtained in the step (2) for 3 hours at 110 ℃ by using a paper sheet forming dryer to obtain the cellulose film.
As compared with example 7, other steps and process parameters of changing the mass ratio of bacterial cellulose to nanocellulose to (0.5:0.5) and (0.25:0.75) are the same as those of example 7, and a cellulose film is prepared.
Example 8
The preparation method of the novel cellulose-based hydrophobic film comprises the following specific steps:
(1) Taking a long cellulose dispersion liquid with the concentration of 1wt.% prepared in example 1, preparing bacterial cellulose microgel in example 2, mixing according to the mass ratio of long cellulose to bacterial cellulose of 0.75:0.25, and passing through a mechanical stirrer for 40 minutes to obtain a uniform slurry with the concentration of 0.16 wt.%;
(2) Adding a shellac resin dispersion liquid into the uniform slurry in the step (1) and uniformly mixing to obtain slurry with the concentration of 0.16wt.%, wherein the mass ratio of cellulose to shellac resin is 0.2:0.8;
(3) Filtering the slurry obtained in the step (2) through a sand core filter, wherein the filtering membrane is purchased from Shanghai Xingjia sub-purification material factory, and the specification of a mixed cellulose ester microporous filtering membrane (water system) is 110mm 0.22 mu m;
(4) And (3) hot-pressing the filter cake obtained in the step (3) for 3 hours at 110 ℃ by using a paper sheet forming dryer to obtain the cellulose film.
Compared with the embodiment 8, the adding amount of the lac resin in the step (2) is adjusted to ensure that the mass ratio of the cellulose to the lac resin is 0.6:0.4, 0.4:0.6 and 0.8:0.2; other steps and process parameters were the same as in example 8 to prepare a cellulose film.
Example 9
As shown in fig. 1, which is a photograph of a laboratory-prepared fibrous membrane and a straw, the fibrous membrane obtained above was wound up, and the bleached lac ethanol solution prepared in example 4 was bonded at a joint to obtain a green pollution-free cellulose straw (the concentration of the slurry may be adjusted as needed, and then the thickness of the membrane and the thickness of the straw may be adjusted), the thickness of each fibrous membrane was measured using a paper thickness gauge manufactured by beijing instrumentation, the thickness at 5 different points was measured, and the average value thereof was determined as the thickness of the membrane, accurate to 0.001mm, and the film thickness was obtained as shown in table 1 below;
TABLE 1 thickness of composite film
Example 10
The mechanical properties and wet stability of the straws prepared in example 9 were tested:
(1) The mechanical properties of the pipettes obtained in example 5 and comparative example 1 were tested, the pure long cellulose pipettes, the pure bacterial cellulose pipettes and the pure nanocellulose pipettes were used as blank control, all the pipettes were cut uniformly to 10mm×50mm size, the thickness was measured with a caliper, the original gauge length between the two clamps was measured with a vernier caliper, the samples were tensile tested using a UTM2502 type electronic universal tester, the dry strength was measured, three parallel samples were prepared, the surface moisture was wiped after 24h of water immersion, and the wet strength was measured with the above method, the pure nanocellulose pipettes were severely deformed after 5 h of immersion in water, without tensile conditions, and a mechanical property comparison graph was obtained, fig. 2, (a) the dry strength of the cellulose pipettes was compared, and (b) (c) the wet strength of the cellulose pipettes was compared, from which bacterial cellulose exhibited excellent mechanical properties, whereas the wet strength of nanocellulose was poor.
(2) The pipettes obtained in example 5 and comparative example 1 were subjected to a test for water absorption performance, the pipettes were uniformly cut into a size of 10mm×50mm, three parallel samples were each cut, the mass was measured with an analytical balance, the surface moisture was erased after being immersed in water for 24 hours, the mass was measured, and the water absorption was calculated according to the following formula:
water absorption = ((B-G)/G) ×100%
Wherein G is the weight of the sample after drying, and B is the weight of the sample after saturation with water; taking the average value of three parallel samples as the water absorption value of the film, wherein the water absorption of a pure long fiber film, a pure bacterial cellulose film and a pure nano cellulose film is measured firstly and used as a blank control value reference; the water absorption of the cellulose pipette is shown in FIG. 3, and it was found by analysis that bacterial cellulose was still less water absorbent and could be used as the cellulose portion of the cellulose-based pipette.
(3) In order to further study the composite effect among cellulose with different scales, the water absorption rate test is carried out on the cellulose straws which are compounded in pairs, the test method is the same as the step (2), the water absorption rate chart 4 is obtained, the mechanical property is the chart 5, and the mechanical property is optimal when the bacterial cellulose of the cellulose-based straw is long fiber=1:3 through analysis and comparison of the mechanical property and the water absorption rate of the composite cellulose straw.
(4) The shellac resin and cellulose composite with the hydrophobic chain segments can endow the material with better hydrophobicity, so that the material has stronger wet stability, stronger interaction exists between the shellac resin and cellulose molecules, the composite film has better strength, so that the mechanical property test is carried out on the shellac-fiber straw prepared in the embodiment 8, as shown in fig. 6, the mass ratio of the immobilized long cellulose to the bacterial cellulose is 0.75:0.25, the shellac resin with different proportions is added, the wet strength of the straw can be improved indeed, the dry strength is best when the shellac addition is 0.6, the wet strength is best when the shellac addition is 0.2, and the wet strength is more important because the straw is used in a wet environment, and the finally determined optimal composition of the novel cellulose base is the shellac long cellulose to the bacterial cellulose mass ratio of 0.2 (0.75 x 0.8): (0.25 x 0.8) =0.2:0.2.
Claims (7)
1. A preparation method of a novel cellulose-based hydrophobic film is characterized in that more than two cellulose dispersion solutions with any proportion are uniformly mixed, the mixture is filtered to obtain a filter cake, and the filter cake is hot-pressed for 1-3 hours at 100-110 ℃ to obtain the hydrophobic film.
2. The method for preparing a novel cellulose-based hydrophobic film according to claim 1, wherein the cellulose dispersion is a nanocellulose dispersion, a long cellulose dispersion, a bacterial cellulose microgel.
3. The method for preparing a novel cellulose-based hydrophobic film according to claim 1, wherein a shellac resin dispersion is further added to the mixture, and the mass ratio of cellulose to shellac resin is 0.2:0.8-0.8:0.2.
4. The method of preparing a novel cellulose-based hydrophobic film according to claim 2, wherein the long fiber dispersion is prepared as follows: soaking a long fiber pulp board in deionized water for 30-40 minutes, crushing the soaked pulp board, pulping after the crushing is completed, finally obtaining pulp with the pulping degree of 45 DEG SR, and adding water into the pulp with the pulping degree of 45 DEG SR to prepare a long fiber dispersion liquid.
5. The method for preparing a novel cellulose-based hydrophobic film according to claim 2, wherein the bacterial cellulose microgel is prepared as follows: and (3) washing the molasses coconuts purchased in the market by adopting deionized water until the conductivity of the washing liquid is consistent with that of the deionized water and TDS=0, taking 1kg of washed coconuts, adding deionized water to 1L, dispersing for 20min through 4800r/min, and obtaining bacterial cellulose microgel, and refrigerating for later use.
6. The method for preparing a novel cellulose-based hydrophobic film according to claim 2, wherein the method for preparing the nanocellulose dispersion liquid comprises the following steps: 35g of needle leaf wood fibers are suspended in 3500mL of deionized water containing 0.84g of TEMPO, 5.25g of sodium bromide and 328.05g of sodium hypochlorite, the pH value is adjusted to 10, the mixture is stirred at 500rpm at room temperature, the pH value is continuously adjusted in the stirring process until the pH value is 10 and constant, the mixture is filtered by deionized water and washed until a washing solution is neutral, the washed nanocellulose is added with water to prepare nanofiber dispersion liquid, and the nanofiber dispersion liquid is stored in a sealing way at 4 ℃.
7. The method for preparing a novel cellulose-based hydrophobic film according to claim 3, wherein the shellac resin dispersion is prepared by: dissolving bleached lac in 95% ethanol solution by mass fraction to prepare 6.5% bleached lac ethanol solution by mass fraction, uniformly stirring, dripping the bleached lac ethanol solution into deionized water at 40 ℃ and preparing bleached lac water-soluble collagen solution under strong stirring, evaporating ethanol by a rotary evaporator, adding water or evaporating to remove water to prepare lac resin dispersion liquid, and refrigerating for later use.
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| CN117050359B (en) * | 2023-10-10 | 2024-01-26 | 天津永续新材料有限公司 | High-definition nano cellulose/resin composite film and preparation method thereof |
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