CN114395938B - Starch-based hydrophobic paper, preparation method and application thereof - Google Patents

Starch-based hydrophobic paper, preparation method and application thereof Download PDF

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CN114395938B
CN114395938B CN202111375742.9A CN202111375742A CN114395938B CN 114395938 B CN114395938 B CN 114395938B CN 202111375742 A CN202111375742 A CN 202111375742A CN 114395938 B CN114395938 B CN 114395938B
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starch
paper
modified starch
based hydrophobic
mixing
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CN114395938A (en
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张帆
王丕新
徐昆
白云刚
王超
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Paper (AREA)

Abstract

The invention relates to the technical field of functional materials, in particular to starch-based hydrophobic paper, a preparation method and application thereof. The preparation method of the starch-based hydrophobic paper comprises the following steps: a) Stirring and mixing paper material and N, N-dimethylacetamide to obtain paper pulp; mixing modified starch, hydrophobic silica particles and N, N-dimethylacetamide to obtain a modified starch solution; b) Stirring and mixing the modified starch solution and the paper pulp to obtain mixed slurry; c) And stirring and mixing the mixed slurry and glutaraldehyde solution, and carrying out suction filtration to obtain the starch-based hydrophobic paper. The starch-based hydrophobic paper is used as an oil-water separation material and is suitable for demulsification and separation of water-in-oil emulsion, and higher oil-water separation efficiency can be obtained. The invention takes the starch and the silicon dioxide as the additives, which not only can reduce the cost of raw materials, but also can ensure that the prepared separation membrane has biodegradability, and the starch is renewable and has wide sources, thereby being convenient for the mass production and the application of the separation membrane.

Description

Starch-based hydrophobic paper, preparation method and application thereof
The present application claims priority from chinese patent application filed at 22, 09, 2021, under the application number 202111108078.1, entitled "a starch-based hydrophobic paper, method for making same, and use thereof", the entire contents of which are incorporated herein by reference.
Technical Field
The invention relates to the technical field of functional materials, in particular to starch-based hydrophobic paper, a preparation method and application thereof.
Background
The paper material is a green material taking plant fiber as a main raw material, has the characteristics of a flexible material and a rigid material, and plays an important role in social and economic construction and daily life of human beings. Paper materials themselves have micron-sized pores formed by interweaving fibers with layers of fibers, and thus are common substrates for many discrete materials. However, cellulose and hemicellulose which are the main components of the paper have a large number of hydrophilic hydroxyl groups, so that the paper has super-strong hydrophilicity and is extremely easy to absorb water, swell and damage, and the application of the paper in the field of oil-water separation is limited. In order to overcome the defect of paper caused by water absorption and expand the application field, the inherent hydrophilicity of the paper is firstly changed, and the paper is endowed with stable hydrophobicity; in addition, a graded micro-nano structure is constructed on the surface of the water-in-oil emulsion to further amplify the wettability of the water-in-oil emulsion, so that the water-in-oil emulsion can obtain stable super-hydrophobicity under oil and is applied to demulsification and separation of the water-in-oil emulsion.
Currently, common methods for making hydrophobic paper are surface sizing paper making and internal sizing paper making. The hydrophobic paper prepared by the surface sizing method has higher requirements on equipment, and uneven distribution of sizing agents is easy to cause uneven surface mechanical properties and hydrophobic distribution. Thus, internal sizing paper making is becoming the primary method of making hydrophobic paper. The internal sizing agent mainly comprises rosin sizing agent, synthetic sizing agent and paraffin sizing agent. These sizing agents are chemically structured with both hydrophilic and hydrophobic groups and adhere well to the surface of the paper fibers, similar to a film that completely encapsulates each individual paper fiber. The paper prepared by the method has greatly improved hydrophobicity and mechanical strength, but the demulsification and separation of the water-in-oil emulsion are difficult to realize due to the lack of assistance of layered micro-nano structures. Therefore, the layered micro-nano structure is constructed on the paper material, the unique wettability is endowed, and the application of the paper material in the field of oil-water separation is expanded to become a current research hot spot.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a starch-based hydrophobic paper, a preparation method and application thereof, which are suitable for demulsification and separation of water-in-oil emulsion.
The invention provides a preparation method of starch-based hydrophobic paper, which comprises the following steps:
a) Stirring and mixing paper material and N, N-dimethylacetamide to obtain paper pulp;
mixing modified starch, hydrophobic silica particles and N, N-dimethylacetamide to obtain a modified starch solution;
b) Mixing the modified starch solution and the paper pulp to obtain mixed slurry;
c) And stirring and mixing the mixed slurry and glutaraldehyde solution, and carrying out suction filtration to obtain the starch-based hydrophobic paper.
Preferably, in step a), the mass ratio of paper material to N, N-dimethylacetamide in the pulp is 1:50 to 100.
Preferably, in the step a), in the modified starch solution, the mass ratio of the modified starch, the hydrophobic silica particles and the N, N-dimethylacetamide is 0.2 to 1:0.2 to 0.75:50.
preferably, in step a), the modified starch is prepared according to the following method:
and (3) carrying out esterification reaction on the starch, palmitoyl chloride and perfluoro-sunflower-base triethoxysilane at the temperature of 75-85 ℃ to obtain the modified starch.
Preferably, the molar ratio of the starch, the palmitoyl chloride and the perfluoro-sunflower-based triethoxysilane is 1:1.5 to 4:0.5 to 1.5;
after the esterification reaction, the method further comprises the following steps:
precipitating with deionized water, vacuum filtering, cleaning, and oven drying.
Preferably, in step B), the stirring and mixing of the modified starch solution and the pulp comprises:
adding the modified starch solution into the stirred pulp, and continuing stirring for a period of time;
the stirring is continued for 12-24 hours.
Preferably, in the step C), the mass concentration of the glutaraldehyde solution is 5% -15%;
the pH value of the glutaraldehyde solution is 1-3.
Preferably, in the step C), the volume ratio of the mixed slurry to glutaraldehyde solution is 1:0.2 to 1.
The invention also provides the starch-based hydrophobic paper prepared by the preparation method.
The invention also provides application of the starch-based hydrophobic paper as an oil-water separation material.
The invention provides a preparation method of starch-based hydrophobic paper, which comprises the following steps: a) Stirring and mixing paper material and N, N-dimethylacetamide to obtain paper pulp; mixing modified starch, hydrophobic silica particles and N, N-dimethylacetamide to obtain a modified starch solution; b) Stirring and mixing the modified starch solution and the paper pulp to obtain mixed slurry; c) And stirring and mixing the mixed slurry and glutaraldehyde solution, and carrying out suction filtration to obtain the starch-based hydrophobic paper. The starch-based hydrophobic paper is used as an oil-water separation material and is suitable for demulsification and separation of water-in-oil emulsion, and higher oil-water separation efficiency can be obtained. In addition, the invention takes the starch and the silicon dioxide as additives, which not only can reduce the cost of raw materials, but also can ensure that the prepared separation membrane has biodegradability, and the starch is renewable and wide in source, thereby being convenient for the mass production and application of the separation membrane.
Drawings
FIG. 1 is an SEM image of a base paper of example 1 of the invention;
FIG. 2 is an SEM image of a starch-based hydrophobic paper of example 1 of the invention;
FIG. 3 is an enlarged view of FIG. 2 in accordance with the present invention;
FIG. 4 is a graph showing the n-hexane contact angle test of the starch-based hydrophobic paper of example 1 of the present invention in air;
FIG. 5 is a graph showing the contact angle of water drops in air for the starch-based hydrophobic paper of example 1 of the present invention;
FIG. 6 is a graph showing the water drop contact angle test of the starch-based hydrophobic paper of example 1 in n-hexane;
FIG. 7 is an SEM image of a starch-based hydrophobic paper of comparative example 1;
FIG. 8 shows an oil-water separator using starch-based hydrophobic paper according to example 8 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of starch-based hydrophobic paper, which comprises the following steps:
a) Stirring and mixing paper material and N, N-dimethylacetamide to obtain paper pulp;
mixing modified starch, hydrophobic silica particles and N, N-dimethylacetamide to obtain a modified starch solution;
b) Stirring and mixing the modified starch solution and the paper pulp to obtain mixed slurry;
c) And stirring and mixing the mixed slurry and glutaraldehyde solution, and carrying out suction filtration to obtain the starch-based hydrophobic paper.
The paper material and N, N-dimethylacetamide are stirred and mixed to obtain paper pulp.
In certain embodiments of the invention, the paper material is base paper.
In certain embodiments of the invention, the mass ratio of paper material to N, N-dimethylacetamide in the pulp is 1:50 to 100. In certain embodiments, the mass ratio of paper material to N, N-dimethylacetamide in the pulp is 1:50.
in certain embodiments of the invention, the paper material is mixed with N, N-dimethylacetamide with stirring at room temperature.
The invention mixes modified starch, hydrophobic silicon dioxide particles and N, N-dimethylacetamide to obtain modified starch solution.
In certain embodiments of the present invention, the modified starch solution has a mass ratio of modified starch, hydrophobic silica particles, and N, N-dimethylacetamide of 0.2 to 1:0.2 to 0.75:50. in certain embodiments, the modified starch solution has a mass ratio of modified starch, hydrophobic silica particles, and N, N-dimethylacetamide of 0.5:0.2 to 0.75:50. in certain embodiments, the modified starch solution has a mass ratio of modified starch, hydrophobic silica particles, and N, N-dimethylacetamide of 0.5:0.3: 50. 0.5:0.2: 50. 0.5:0.5:50 or 0.5:0.75:50.
in certain embodiments of the invention, the modified starch is prepared according to the following method:
and (3) carrying out esterification reaction on the starch, palmitoyl chloride and perfluoro-sunflower-base triethoxysilane at the temperature of 75-85 ℃ to obtain the modified starch.
In certain embodiments of the invention, the molar ratio of starch, palmitoyl chloride, and perfluorosunflower-based triethoxysilane is 1:1.5 to 4:0.5 to 1.5. In certain embodiments, the molar ratio of starch, palmitoyl chloride, and perfluorosunflower-based triethoxysilane is 1:3:0.6.
in certain embodiments of the invention, the temperature of the esterification reaction is 80 ℃. In certain embodiments of the invention, the time of the esterification reaction is 3 to 5 hours. In certain embodiments, the time of the esterification reaction is 5 hours.
In certain embodiments of the present invention, after the esterification reaction, further comprising:
precipitating with deionized water, vacuum filtering, cleaning, and oven drying.
In certain embodiments of the invention, the number of suction washes is 2-3. In certain embodiments, the number of suction washes is 2.
The steps of the suction filtration cleaning and drying are not particularly limited, and the steps of the suction filtration cleaning and drying which are well known to those skilled in the art can be adopted.
And after the modified starch solution is obtained, stirring and mixing the modified starch solution and the paper pulp to obtain mixed slurry.
In certain embodiments of the invention, agitating and mixing the modified starch solution and the pulp comprises: adding the modified starch solution to the stirred pulp and continuing to stir for a period of time.
In certain embodiments of the invention, the stirring is continued for a period of time ranging from 12 to 24 hours. In certain embodiments, stirring is continued for a period of 24 hours.
The method of stirring and mixing is not particularly limited, and stirring and mixing methods well known to those skilled in the art may be employed.
And after the mixed slurry is obtained, stirring and mixing the mixed slurry and glutaraldehyde solution, and carrying out suction filtration to obtain the starch-based hydrophobic paper.
In certain embodiments of the present invention, agitating and mixing the mixed slurry with the glutaraldehyde solution includes: glutaraldehyde solution is added to the stirred mixed slurry and stirring is continued for a period of time.
In certain embodiments of the invention, the stirring is continued for a period of time ranging from 12 to 24 hours. In certain embodiments, stirring is continued for a period of 24 hours.
In the invention, the glutaraldehyde solution is a crosslinking agent. In certain embodiments of the invention, the glutaraldehyde solution has a mass concentration of 5% to 15%. In certain embodiments, the glutaraldehyde solution has a concentration of 10% by mass. In certain embodiments of the invention, the glutaraldehyde solution has a pH of 1 to 3. In certain embodiments, the glutaraldehyde solution has a pH of 1. In certain embodiments of the invention, the volume ratio of the mixed slurry to glutaraldehyde solution is 1:0.2 to 1. In certain embodiments, the volume ratio of the mixed slurry to glutaraldehyde solution is 1:0.2.
the method of the present invention is not particularly limited, and the method of the suction filtration known to those skilled in the art may be used.
In certain embodiments of the invention, drying is also included after the suction filtration.
In some embodiments of the present invention, the drying may be oven drying, drying to constant weight.
The invention also provides the starch-based hydrophobic paper prepared by the preparation method.
The invention also provides application of the starch-based hydrophobic paper as an oil-water separation material. The starch-based hydrophobic paper is used as an oil-water separation material to carry out demulsification and separation of water-in-oil emulsion, so that higher oil-water separation efficiency can be obtained. The applicant thus claims the use of said starch-based hydrophobic paper as an oil-water separation material.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe in detail a starch-based hydrophobic paper, its preparation method and application, but should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are all commercially available.
Example 1
1) 1g of base paper is added into 50g of N, N-dimethylacetamide and stirred at room temperature to obtain uniform paper pulp;
2) Esterifying 1g (0.005 mol) of starch, 4.5g (0.015 mol) of palmitoyl chloride and 2g (0.003 mol) of perfluoro-sunflower-base triethoxysilane at 80 ℃ for 5 hours, precipitating with deionized water, filtering, cleaning for 2 times, and drying to obtain modified starch TOHTES-PC-St;
3) Dispersing 0.5g of modified starch TOHTES-PC-St and 0.3g of hydrophobic silica particles with 50g of N, N-dimethylacetamide to obtain a modified starch solution;
4) Adding the modified starch solution into the stirred paper pulp, and continuously stirring for 24 hours to obtain mixed slurry;
5) Adding glutaraldehyde solution with the mass concentration of 10% and the pH value of 1 into the mixed slurry, wherein the volume ratio of the mixed slurry to the glutaraldehyde solution is 1:0.2, continuing stirring for 24 hours to fully crosslink the additive and the paper fiber;
6) Finally, removing redundant solvent by suction filtration, and drying the obtained paper in an oven to constant weight to obtain the starch-based hydrophobic paper.
In this example, the base paper was subjected to sem analysis, and the result is shown in fig. 1. Fig. 1 is an SEM image of the base paper of example 1 of the present invention.
In this example, the obtained starch-based hydrophobic paper was subjected to scanning electron microscope analysis, and the result is shown in fig. 2. Fig. 2 is an SEM image of the starch-based hydrophobic paper of example 1 of the present invention. Fig. 3 is an enlarged view of fig. 2 in accordance with the present invention. As can be seen from fig. 3, innumerable fibers are interlaced to form micro-scale channels, and the nano-scale hydrophobic silica particles uniformly wrap each fiber, so that a layered micro-nano structure is successfully constructed on the surface of the paper.
The contact angle test of oil drop (n-hexane) in air was also performed on the obtained starch-based hydrophobic paper in this example, the starch-based hydrophobic paper was fixed on a glass slide with a double sided tape, and a drop of 2 μl of n-hexane was dropped on the surface of the paper with a contact angle meter, and the result is shown in fig. 4. Fig. 4 is a graph showing n-hexane contact angle test of the starch-based hydrophobic paper of example 1 of the present invention in air. As can be seen from fig. 4, in air, the n-hexane contact angle of the starch-based hydrophobic paper is 34.3 °, and the starch-based hydrophobic paper has better oleophilic performance.
The contact angle test of water drop in air was also performed on the obtained starch-based hydrophobic paper in this example, the starch-based hydrophobic paper was fixed on a glass slide with double sided tape, and 2 μl of water drop was dropped on the surface of the paper with a contact angle meter, and the result is shown in fig. 5. Fig. 5 is a graph showing a water drop contact angle test of the starch-based hydrophobic paper of example 1 of the present invention in air. As can be seen from fig. 5, in air, the water drop contact angle of the starch-based hydrophobic paper is 136.8 degrees, and the starch-based hydrophobic paper has better hydrophobic performance.
The contact angle test of water drop in n-hexane was also performed on the obtained starch-based hydrophobic paper in this example, the starch-based hydrophobic paper was fixed on a glass slide with double sided tape, and put in a small box containing n-hexane, and a drop of 2 μl of water was dropped on the surface of the paper with a contact angle meter, and the result is shown in fig. 6. Fig. 6 is a graph showing a water drop contact angle test of the starch-based hydrophobic paper of example 1 of the present invention in n-hexane. As can be seen from fig. 6, in n-hexane, the water drop contact angle of the starch-based hydrophobic paper was 165.5 °, and the paper had super-hydrophobicity under oil.
Comparative example 1
1) 1g of base paper is added into 50g of N, N-dimethylacetamide and stirred at room temperature to obtain uniform paper pulp;
2) Esterifying 1g of starch, 4.5g of palmitoyl chloride and 2g of perfluoro-sunflower-base triethoxysilane at 80 ℃ for 5 hours, precipitating with deionized water, filtering, cleaning for 2 times, and drying to obtain modified starch TOHTES-PC-St;
3) Dissolving 0.5g of modified starch TOHTES-PC-St with 50g of N, N-dimethylacetamide to obtain a modified starch solution;
4) Adding the modified starch solution into the paper pulp, and continuously stirring and mixing for 24 hours to obtain mixed slurry;
5) 50mL of glutaraldehyde solution with the mass concentration of 10% and the pH value of 1 is added into the mixed slurry, and stirring is continued for 24 hours, so that the additive and the paper fiber are fully crosslinked;
6) Finally, removing redundant solvent by suction filtration, and drying the obtained paper in an oven to constant weight to obtain the starch-based hydrophobic paper.
The comparative example was subjected to scanning electron microscope analysis of the obtained starch-based hydrophobic paper, and the result is shown in fig. 7. Fig. 7 is an SEM image of the starch-based hydrophobic paper of comparative example 1 of the present invention. As can be seen from fig. 7, the hydrophobically modified starch tightly surrounds each fiber due to its good compatibility with the paper fibers, and the fiber surface becomes smooth and even.
Comparative example 2
The difference from comparative example 1 is that in step 3), the amount of modified starch TOHTES-PC-St used was 0.2g, resulting in a starch-based hydrophobic paper.
Comparative example 3
The difference from comparative example 1 is that in step 3), the amount of modified starch TOHTES-PC-St used was 0.75g, resulting in a starch-based hydrophobic paper.
Comparative example 4
The difference from comparative example 1 is that in step 3), the amount of modified starch TOHTES-PC-St used was 1g, resulting in a starch-based hydrophobic paper.
Example 2
The difference from example 1 is that in step 3) the amount of hydrophobic silica particles is 0.2g, resulting in a starch-based hydrophobic paper.
Example 3
The difference from example 1 is that in step 3) the amount of hydrophobic silica particles is 0.5g, resulting in a starch-based hydrophobic paper.
Example 4
The difference from example 1 is that in step 3) the amount of hydrophobic silica particles is 0.75g, resulting in a starch-based hydrophobic paper.
Water contact angle in air (WCA), water contact angle Under Oil (UOWCA) test for starch-based hydrophobic papers:
according to the contact angle test method of example 1, the present example gives the water drop contact angle test results (WCA) of the starch-based hydrophobic papers of examples 1 to 4 and comparative examples 1 to 4 in air, and the water drop contact angle test results (UOWCA) of the starch-based hydrophobic papers of examples 1 to 4 and comparative examples 1 to 4 in n-hexane, as shown in table 1.
Water-in-oil emulsion separation efficiency (R) and separation flux (F) test:
the starch-based hydrophobic paper was placed between two glass vessels (as shown in fig. 8, fig. 8 shows an oil-water separator using starch-based hydrophobic paper according to example 8 of the present invention, span80, which is 3% of the total weight, was added to water as a surfactant, and emulsified with toluene at a volume ratio of 10:90 to prepare a water-in-oil emulsion, the emulsion was poured into the apparatus shown in fig. 8 to separate, the water content of the filtrate was subjected to shape analysis using a karst moisture meter, the separation efficiency R was calculated according to formula (1), the separation flux F was calculated according to formula (2), and the results are shown in table 1.
Separation efficiency R (%) = (1-C p /C 0 )×100％ (1)；
In the formula (1), C 0 : water content before separation,%; c (C) p : the water content in the filtrate after separation,%.
Separation flux F (L/m) 2 ·h)＝V/(A·T) (2)；
In the formula (2), V: the volume of the separated filtrate, L; a: effective separation area of paper material, m 2 The method comprises the steps of carrying out a first treatment on the surface of the T is separation time, h.
TABLE 1 Water in air contact Angle (WCA), water under oil contact Angle (UOWCA), water-in-oil emulsion separation efficiency (R) and separation flux (F) for starch-based hydrophobic papers of examples 1 to 4
Figure BDA0003363930090000091
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A preparation method of starch-based hydrophobic paper comprises the following steps:
a) Stirring and mixing paper material and N, N-dimethylacetamide to obtain paper pulp;
mixing modified starch, hydrophobic silica particles and N, N-dimethylacetamide to obtain a modified starch solution; in the modified starch solution, the mass ratio of the modified starch to the hydrophobic silica particles to the N, N-dimethylacetamide is 0.2-1: 0.2 to 0.75:50;
the preparation method of the modified starch comprises the following steps:
carrying out esterification reaction on starch, palmitoyl chloride and perfluorodecyl triethoxysilane at 75-85 ℃, precipitating with deionized water, carrying out suction filtration, cleaning and drying to obtain modified starch;
b) Mixing the modified starch solution and the paper pulp to obtain mixed slurry;
c) And stirring and mixing the mixed slurry with glutaraldehyde solution, filtering, and drying to obtain the starch-based hydrophobic paper.
2. The method according to claim 1, wherein in the step a), the mass ratio of the paper material to the N, N-dimethylacetamide in the pulp is 1:50 to 100.
3. The method according to claim 1, wherein the molar ratio of starch, palmitoyl chloride and perfluorodecyl triethoxysilane is 1:1.5 to 4:0.5 to 1.5.
4. The method of preparing according to claim 1, wherein in step B), the stirring and mixing of the modified starch solution and the pulp comprises:
adding the modified starch solution into the stirred pulp, and continuing stirring for a period of time;
the stirring is continued for 12-24 hours.
5. The method according to claim 1, wherein in step C), the glutaraldehyde solution has a mass concentration of 5% to 15%;
the pH value of the glutaraldehyde solution is 1-3.
6. The method according to claim 1, wherein in step C), the volume ratio of the mixed slurry to glutaraldehyde solution is 1:0.2 to 1.
7. A starch-based hydrophobic paper produced by the production method according to any one of claims 1 to 6.
8. The use of the starch-based hydrophobic paper of claim 7 as an oil-water separation material.
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