CN115584657B - Hydrophobic slurry and preparation method and application thereof - Google Patents
Hydrophobic slurry and preparation method and application thereof Download PDFInfo
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- CN115584657B CN115584657B CN202110763507.2A CN202110763507A CN115584657B CN 115584657 B CN115584657 B CN 115584657B CN 202110763507 A CN202110763507 A CN 202110763507A CN 115584657 B CN115584657 B CN 115584657B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002002 slurry Substances 0.000 title claims abstract description 26
- 238000007613 slurry method Methods 0.000 title description 2
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- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002612 dispersion medium Substances 0.000 claims abstract description 16
- 238000004513 sizing Methods 0.000 claims abstract description 15
- 239000004890 Hydrophobing Agent Substances 0.000 claims abstract description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
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- 239000001993 wax Substances 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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Classifications
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention discloses a hydrophobic sizing agent, which comprises the following components: a dispersing substance selected from hydrophobic sheet cellulose or nanocellulose substrate-like cellulose hydrophobic complex; and a dispersion medium selected from biodegradable substances or aqueous hydrophobing agents having a viscosity of 5 to 500 mPa-s; wherein the dispersion substance is dispersed in the dispersion medium. The hydrophobic paper prepared by the hydrophobic sizing agent can achieve the effect of replacing plastic with paper, the paper is modified paper based on cellulose-based materials, no organic solvent is used in the preparation process, the cost is low, the environment is protected, the performance is excellent, and the prepared paper can meet the use requirement through testing, so that the purpose of replacing plastic with paper can be achieved. The prepared paper has the performance equivalent to or even better than the existing industrialized paper. The invention also discloses a preparation method and application of the hydrophobic slurry.
Description
Technical Field
The invention relates to the technical field of hydrophobic paper. More particularly, to a hydrophobic slurry, a preparation method and application thereof.
Background
The existing disposable plastic packaging bags, plastic boxes and the like are widely applied, are not degradable and renewable, and have severe environmental pollution. The simple paper has the defects of poor hydrophobicity, low mechanical strength and the like in the using process, and cannot completely replace plastic products. Therefore, the improvement of hydrophobicity and strength of paper becomes a key to "replacing plastic with paper".
For many years, industrialization has employed various means to improve the water resistance of paper products, such as paper sizing and laminating techniques. The film coating technology adopts polyethylene, polypropylene and other synthetic polymers to finish waterproof modification on paper, and although the technology is mature and has good waterproof performance, the film coating technology has the problem of difficult stripping in the paper recovery process, is not easy to recover, and the waterproof polymer film is not degradable and cannot be a completely environment-friendly hydrophobic paper. In paper sizing, whether internal or surface sizing, the paper is typically hydrophobically modified by lowering the surface energy, such as AKD, styrene-acrylic emulsions, wax emulsions, and the like. Among them, fruit bag paper has been widely used because of its excellent water resistance and low cost. However, the preparation of fruit bag paper is to improve water resistance by paraffin treatment of the surface, and the paraffin paper is not recyclable and degradable, and the modified paper of styrene-acrylic emulsion also has the problem. The pure AKD modified paper only provides water resistance to the paper rather than hydrophobicity, so that when water contacts the paper, it will leave a watermark and as time increases, the water will gradually penetrate the paper. Therefore, along with the issuance and promotion of plastic limiting and plastic prohibiting orders, the preparation of biomass-based hydrophobic paper capable of replacing plastics with light weight, high strength and full degradation becomes a urgent problem to be solved.
Chinese patent application 201911324729.3 discloses a method for preparing super-hydrophobic paper based on polymer surface modification, which comprises the following steps: weighing polyethylene/polyvinyl chloride/polystyrene particles, pre-dissolving in a solvent containing xylene, adding acetone, mixing uniformly, and preparing impregnating solution to modify paper. Although this method is simple and easy to implement, the synthetic polymer used is not degradable, and thus it is a burden on the environment.
Chinese patent 201910462491.4 discloses a preparation method of tensile type hydrophobic paper, which comprises the following steps: the tensile type hydrophobic paper is obtained by modifying wood pulp by using starch and silicon dioxide and crosslinking by using glutaraldehyde. However, the use of ethanol, polyvinyl alcohol and glutaraldehyde in the preparation of silica increases the production cost and does not allow for the improvement of the lightweight paper.
Chinese patent application 202010402183.5 discloses a preparation method of super-hydrophobic paper, which comprises the following steps: and (3) forming paper fiber slurry modified by tannic acid@octadecylamine microcapsules (TA@ODA) through reaction, centrifuging, flattening and drying the paper fiber slurry to obtain the super-hydrophobic paper. The paper is complex in preparation process, and the paper modified by chemical reaction has certain defects in mass production.
Therefore, it is necessary to provide a new fully degradable hydrophobic paper and a preparation method thereof, so as to solve the problems in the prior art and achieve the purpose of replacing plastics.
Disclosure of Invention
A first object of the present invention is to provide a hydrophobic slurry.
A second object of the present invention is to provide a method for preparing a hydrophobic slurry.
A third object of the present invention is to provide a fully degradable hydrophobic paper.
The fourth object of the invention is to provide a method for preparing the full-degradable hydrophobic paper.
A fifth object of the present invention is to provide the use of a fully degradable hydrophobic paper.
In order to achieve the first object, the present invention provides the following technical solutions:
a hydrophobic slurry comprising:
a dispersing substance selected from hydrophobic sheet cellulose or nanocellulose substrate-like cellulose hydrophobic complex; and
a dispersion medium selected from biodegradable substances or aqueous hydrophobing agents having a viscosity of 5-500 mpa.s;
wherein the dispersion substance is dispersed in the dispersion medium.
Further, the weight ratio of the dispersing substance to the dispersing medium is 1-5:100.
further, the biodegradable substance or the aqueous hydrophobing agent with waterproofness is selected from one or more of chitosan, zein, wheat gliadin, methylcellulose, AKD emulsion and ASA emulsion.
Further, the hydrophobic flaky cellulose is selected from one or more of corncob, paper pulp, wood pulp, bamboo pulp and straw coated by PTFE, the particle transverse and longitudinal size adjustable range of the hydrophobic flaky cellulose is 5-200 mu m, and the thickness adjustable range is 0.4-10 mu m.
Further, the nanocellulose substrate-like cellulose hydrophobic composite is a nanocellulose hydrophobic composite loaded with hydrophobic sheet-like cellulose.
Further, the nanocellulose substrate-like cellulose hydrophobic complex is obtained by loading the hydrophobic sheet-like cellulose on nanocellulose by a shearing force action of 10000rpm-30000 rpm.
In order to achieve the second object, the present invention provides the following technical solutions:
a method of preparing a hydrophobic slurry comprising the steps of:
and uniformly mixing the dispersion substance and a dispersion medium to obtain the hydrophobic slurry.
In order to achieve the third object, the present invention provides the following technical solutions:
a fully degradable hydrophobic paper comprising:
a paper substrate; and
a hydrophobic slurry coating on the surface of the paper substrate;
the hydrophobic slurry coating is prepared from a feedstock comprising the hydrophobic slurry as described in the first object above.
Further, the paper substrate is selected from one of kraft paper, corrugated paper, parchment paper, newsprint paper, white cardboard and printing paper.
In order to achieve the fourth object, the present invention provides the following technical solutions:
a preparation method of full-degradable hydrophobic paper comprises the following steps:
and (3) applying the hydrophobic sizing agent on the surface of the paper base material, and drying to obtain the fully-degradable hydrophobic paper.
To achieve the fifth object, the present invention also protects the use of the fully degradable hydrophobic paper according to the third object in the preparation of hydrophobic paper products.
The beneficial effects of the invention are as follows:
the hydrophobic sizing agent provided by the invention has the advantages of good hydrophobicity, environmental protection, low manufacturing cost and the like. The hydrophobic paper prepared by the hydrophobic slurry can achieve the effect of replacing plastic with paper, the paper is modified paper based on cellulose-based materials, no organic solvent is used in the preparation process, the cost is low, the environment is protected, the performance is excellent, and the prepared paper can meet the use requirement (high strength, good hydrophobicity and good appearance) through testing, so that the purpose of replacing plastic with paper can be achieved. The prepared paper has the performance equivalent to or even better than the existing industrialized paper.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 shows a photograph of a dispersion of sheeted cellulose in different systems of the present invention.
Fig. 2 shows the water contact angle of modified paper in different systems of the invention.
FIG. 3 shows a film formation topography of flaky cellulose according to the present invention (a-1) Zein film; (a-2) 5% zein+2% sheet cellulose film; (b-1) a CS film; (b-2) 2% CS+2% sheet cellulose film.
Fig. 4 shows the topography of the hydrophobic coating of the invention containing platy cellulose (left) and the topography after modification of the paper (right).
Figure 5 shows the macroscopic topography of the paper after modification according to the invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The existing plastic products have the problems of non-degradability, non-regeneration, serious environmental pollution and the like, and some hydrophobic papers are provided for replacing plastic with paper in the prior art, but the hydrophobic papers have the defects of non-degradability, environment friendliness, high cost, light weight, low strength and the like. And the flaky cellulose prepared in the laboratory is difficult to disperse directly in an aqueous solvent due to good hydrophobicity. In order to solve the problems, the invention provides a biomass-based fully-degradable hydrophobic paper which can replace plastics, has light weight, high strength, environmental protection, light weight and easy recycling, and is used in hydrophobic paper products such as packaging paper and the like, thereby realizing paper replacing plastics well.
According to one embodiment of the present invention, there is provided a hydrophobic slurry comprising:
a dispersing substance selected from hydrophobic sheet cellulose or nanocellulose substrate-like cellulose hydrophobic complex; and
a dispersion medium selected from biodegradable substances or aqueous hydrophobing agents having a viscosity of 5-500 mpa.s;
wherein the dispersing substance is dispersed in the dispersing medium, and the weight ratio of the dispersing substance to the dispersing medium is 1-5:100.
The hydrophobic sizing agent can be used as a raw material of a hydrophobic coating of hydrophobic paper, and endows the hydrophobic paper with good hydrophobicity, environmental protection, degradability, improved strength and the like.
It was found that when the viscosity of the biodegradable substance having water repellency is higher than 500mpa·s, the viscosity of the resulting hydrophobic slurry is too high to obtain a uniform coating at the time of coating; when the viscosity is less than 5 mPas, the dispersion medium does not function well to disperse the above-mentioned dispersed substance.
Unless otherwise indicated, the viscosities of the present invention were measured by a viscometer at 25 ℃.
In some examples, the dispersion material is selected from hydrophobic sheet cellulose and the dispersion medium is selected from biodegradable materials having a water repellency of 5-400 mPas, 5-300 mPas, 10-100 mPas, etc.
Illustratively, the hydrophobic platy cellulose has a thickness of 1-100nm; the surface height fluctuation of the hydrophobic flaky cellulose material is within 0.1nm, and the hydrophobic flaky cellulose material has a crystal structure and an orientation structure; more than 80% of the hydrophobic flaky cellulose is a single layer, and the thickness of the hydrophobic flaky cellulose is 4nm plus or minus 1nm; meanwhile, the transverse dimension is 0.1-30 mu m; and the hydrophobic flaky cellulose is of a layered stacked structure, and the basic unit is a nano sheet with the thickness of 4nm plus or minus 1 nm.
Illustratively, the preparation of the hydrophobic sheet cellulose comprises the steps of:
1) Mixing and grinding the cellulose material and PTFE; grinding, and gradually stripping cellulose into a sheet shape;
2) Dispersing the flaky cellulose obtained in the step 1) by ultrasonic, and separating to remove PTFE to obtain a pure cellulose nano-sheet material;
wherein the cellulose material is selected from corncob, paper pulp, wood pulp, bamboo pulp and straw;
further, the grinding in step 1) is performed in a ball mill or a grinding machine; the grinding speed is 200-600 rpm, and the grinding time is 1-48h. After grinding, PTFE is uniformly coated on the surface of the cellulose material, and redundant PTFE is separated and removed to obtain the hydrophobic cellulose.
Since the above-mentioned hydrophobic sheet cellulose has good hydrophobicity and is difficult to disperse in water, it is necessary to select a suitable environment-friendly dispersion medium for dispersing. Illustratively, the biodegradable material or aqueous hydrophobizing agent having a viscosity of 5-500 mPa.s includes, but is not limited to, one or more selected from chitosan, zein, wheat gliadin, methylcellulose, AKD emulsion, ASA emulsion. In the technical scheme, the hydrophobic flaky cellulose can be well dispersed in the dispersion media, and meanwhile, the obtained hydrophobic slurry has good hydrophobicity. It will be appreciated that when the biodegradable material is selected from zein or wheat gliadin, it is desirable to dissolve these proteins in aqueous ethanol prior to use as a dispersion medium; when the biodegradable material is selected from chitosan and methylcellulose, it is required to be dissolved in water to form a liquid state before being used as a dispersion medium.
In addition, the size and the addition amount of the hydrophobic flaky cellulose are controlled, so that the control of the surface roughness of the paper can be better regulated and controlled.
In still other examples, the dispersing substance is selected from nanocellulose-based sheet-like cellulose hydrophobic complexes and the dispersing medium is selected from aqueous hydrophobing agents. The nanocellulose-based sheet-like cellulose hydrophobic complex suitable for use in the present embodiment is preferably a nanocellulose-supported hydrophobic sheet-like cellulose, which is preferably obtainable by supporting the nanocellulose with a shear force of 10000rpm to 30000 rpm. The hydrophobic lamellar cellulose compound in the invention can be well dispersed in the water-based hydrophobizing agent, and the obtained hydrophobic slurry has good hydrophobicity and can be well used in the hydrophobic treatment of hydrophobic paper.
It will be appreciated that when the aqueous hydrophobe is selected from AKD emulsions, ASA emulsions, it is desirable to prepare the nanocellulose substrate-like cellulose hydrophobic complex prior to incorporating it into the aqueous hydrophobe;
yet another embodiment of the present invention provides a method for preparing the hydrophobic slurry as described above, the method comprising the steps of:
and uniformly mixing the dispersion substance and a dispersion medium to obtain the hydrophobic slurry.
Yet another embodiment of the present invention provides a fully degradable hydrophobic paper comprising:
a paper substrate; and
a hydrophobic slurry coating on the surface of the paper substrate;
the hydrophobic slurry coating is prepared from raw materials including the hydrophobic slurry as described above.
In the hydrophobic paper, the hydrophobic slurry can be directly used as a raw material to prepare the hydrophobic slurry coating, or the hydrophobic slurry can be mixed with other components to prepare the hydrophobic slurry coating. The hydrophobic sizing agent coating layer in the embodiment can improve the roughness of the surface of the paper base material to a certain extent, thereby improving the hydrophobicity. In addition, the size and the addition amount of the hydrophobic flaky cellulose are controlled, so that the control of the surface roughness of the paper can be controlled.
The paper substrate suitable for the hydrophobic paper of the present invention may be a sheet material of porous network structure produced from natural plant fibers as a raw material or matrix. Preferably the paper substrate includes, but is not limited to, conventionally used papers selected from kraft paper, corrugated paper, parchment paper, newsprint, white card paper, printing paper and the like.
In this embodiment, the hydrophobic slurry coating may be disposed on one or both surfaces of the paper substrate, and may be specifically selected according to the environment in which the hydrophobic treatment is actually required.
In this embodiment, the application amount of the hydrophobic sizing agent on the paper substrate is 2g/m 2 Above, preferably 3-5g/m 2 。
According to still another embodiment of the present invention, there is provided a method for preparing a full-degradable hydrophobic paper, the method comprising the steps of:
and (3) applying the hydrophobic sizing agent on the surface of the paper base material, and drying to obtain the fully-degradable hydrophobic paper.
Such methods of application include, but are not limited to, coating, knife coating, dip coating, and the like.
In yet another embodiment of the present invention, there is provided the use of a fully degradable hydrophobic paper in the preparation of a hydrophobic paper product.
Among these hydrophobic paper products are, but not limited to, hydrophobic packaging paper, hydrophobic packaging bags, and the like.
The following describes embodiments of the present invention in connection with some specific examples:
example 1
A method of preparing a hydrophobic slurry comprising the steps of:
the preparation method for pure Zein (Zein) comprises the following steps: 5g of Zein was dissolved in 95g of 75% aqueous ethanol. The dispersion is applied to the surface of the paper.
The preparation method for the 5% Zein+2% hydrophobic flaky cellulose comprises the following steps: first, 5g of Zein was dissolved in 95g of a 75% aqueous ethanol solution, and the viscosity was 5.7 mPas. Then, 2g of flaky cellulose (2 g of flaky cellulose with different ball milling time of 4h, 12h, 48h and the like) is added into 100g of 5% Zein, and stirring is carried out at 800-1500rpm, so as to finish the dispersion of the flaky cellulose in the flaky cellulose. The dispersion is coated on the surface of paper, and compared with pure Zein modified paper, the water contact angle is increased from 51.5 degrees to 70.1 degrees.
The preparation method for the 10% Zein+3% flaky cellulose comprises the following steps: first, 10g of Zein was dissolved in 90g of a 75% aqueous ethanol solution, and the viscosity was 8.9 mPas. Then 3g of flaky cellulose (3 g of flaky cellulose with different ball milling time of 4h, 12h, 48h and the like) is added into 100g of 10% Zein, and stirring is carried out at 800-1500rpm, so as to finish the dispersion of the flaky cellulose in the flaky cellulose. The dispersion was applied to the paper surface to increase the water contact angle to 74.6 ° compared to pure Zein modified paper.
The preparation method for 15% Zein+3% flaky cellulose comprises the following steps: 15g of Zein are first dissolved in 85g of a 75% aqueous ethanol solution with a viscosity of 12.5 mPas. Then 5g of flaky cellulose (5 g of flaky cellulose with different ball milling time of 4h, 12h, 48h and the like) is added into 100g of 15% Zein, and stirring is carried out at 800-1500rpm, so as to finish the dispersion of the flaky cellulose in the flaky cellulose. The dispersion was applied to the paper surface to increase the water contact angle to 74.6 ° compared to pure Zein modified paper.
The preparation method for the 1% CS is as follows: 1g of CS was dissolved in 99g of a 2wt% aqueous acetic acid solution. The dispersion is applied to the surface of the paper.
The preparation method for the 1% CS+1% flaky cellulose comprises the following steps: first, 1g of CS was dissolved in 99g of a 2wt% aqueous acetic acid solution, and the viscosity was 158.7 mPas. Then 1g of flaky cellulose (1 g of flaky cellulose with different ball milling time of 4h, 12h, 48h and the like) is added into 100g of CS with 1 percent, and stirring is carried out at 800-1500rpm, so as to finish the dispersion of the flaky cellulose in the flaky cellulose. The dispersion was coated on the surface of paper, and the water contact angle was increased from 109.8 ° to 114.6 ° compared to pure CS modified paper.
The preparation method for the 2% CS+2% flaky cellulose comprises the following steps: first, 2g of CS was dissolved in 98g of a 2wt% aqueous acetic acid solution, and the viscosity was 329.6 mPas. Then, 2g of flaky cellulose (1 g of flaky cellulose with different ball milling time of 4h, 12h, 48h and the like) is added into 100g of 2% CS, and stirring is carried out at 800-1500rpm, so as to finish the dispersion of the flaky cellulose in the flaky cellulose. The dispersion is coated on the surface of paper, and the water contact angle is improved to 120.5 degrees compared with the pure CS modified paper.
Fig. 1 shows a dispersion photograph of sheetlike cellulose in different systems: (a) Pure Zein (Zein), 5% zein+2% platy cellulose, 10% zein+3% platy cellulose, 15% zein+5% platy cellulose in sequence from left to right; (b) Pure Chitosan (CS), 1 percent CS+1 percent platy cellulose and 2 percent CS+2 percent platy cellulose are sequentially arranged from left to right; (c) The 4h hydrophobic flaky cellulose, the pure pulp nano cellulose and the flaky cellulose/nano cellulose premix which are dispersed in water are sequentially arranged from left to right. As can be seen from fig. 1: the sheet cellulose may be dispersed in these degradable substances. FIG. 2 shows that the water contact angle (a) of the modified paper under different systems is pure Zein (Zein), 5% Zein+2% platy cellulose, 10% Zein+3% platy cellulose, 15% Zein+5% platy cellulose, in order from left to right; (b) The hydrophobic paper is composed of pure Chitosan (CS), 1% CS+1% sheet cellulose and 2% CS+2% sheet cellulose in sequence from left to right. As can be seen from fig. 2: as the content of the sheet cellulose increases, the water contact angle increases.
FIG. 3 shows film formation morphology graphs (a-1) Zein films of sheeted cellulose in different systems; (a-2) 5% zein+2% platelet-shaped cellulose film; (b-1) a CS film; (b-2) 2% CS+2% sheet cellulose film. The figures a-1 and b-1 show that the film forming property is good when pure prolamin and chitosan are coated on the surface of paper, and the fiber morphology of the surface of the paper is covered. In the figures, a-2 and b-2 show that after the addition of the hydrophobic flaky cellulose, the flaky cellulose exists on the surface of the paper, so that the roughness is increased and the hydrophobicity is improved.
Comparative example: when the flaky cellulose is directly added into an aqueous solvent, the flaky cellulose cannot enter the system due to high hydrophobicity, so that the flaky cellulose is pre-dispersed by nano cellulose or the flaky cellulose is pre-adhered by a substance with certain viscosity and then added into an aqueous hydrophobizing agent is necessary.
Example 2
And mixing the prepared flaky cellulose/nano-cellulose premix with a hydrophobing agent to prepare a two-dimensional flaky cellulose-based coating, and carrying out hydrophobic modification research on paper. When the premix is doped into the mixture of styrene-acrylic emulsion, AKD emulsion, ASA emulsion, wax emulsion and the like and the flaky cellulose/nano cellulose premix to prepare a coating, and the coating is coated on paper, the roughness of the surface of the paper can be improved to a certain extent, so that the hydrophobicity is improved. The time of selection is that the AKD emulsion or ASA emulsion and other environment-friendly water-based hydrophobing agents are used for preparing degradable hydrophobic paper which can replace plastics. Wherein the regulation of the surface roughness of the paper is regulated by controlling the addition amount of the size of the sheet cellulose.
In some examples, specifically, the method comprises the steps of: firstly, 100g of a 1wt% nano cellulose suspension is selected, mixed into hydrophobic flaky cellulose, the hydrophobic flaky cellulose is loaded on the nano cellulose through the shearing force action of 10000rpm-30000rpm, and then the mixed solution is mixed into an environment-friendly water-based hydrophobic agent. The paper with the best performance is selected for hydrophobic modification, and the printing performance of the modified paper is not affected. In fig. 4, the left side shows the morphology of SEM images in which the hydrophobic coating of the cellulose in tablet form was dropped on the mica sheet mountain and the right side shows the morphology after the hydrophobic coating of the cellulose in tablet form was coated on the paper, and it can be seen from the right image that the cellulose in tablet form was attached to the surface of the fiber of the paper.
Specifically, for loading of the flaky cellulose on the nanocellulose, firstly, 100g of 1wt% nanocellulose water dispersion is taken, then 1g-10g of flaky cellulose is added into nanocellulose aqueous dispersion, and the flaky cellulose is loaded on the nanocellulose through high shearing action (10000 rpm-30000 rpm) for 2-6min, and then added into a hydrophobic system.
For a 1% platy cellulose hydrophobic complex, a cellulose dispersion containing 1g platy cellulose hydrophobic complex is first added to 100g AKD emulsion and then stirred at 800-1500rpm to complete the dispersion of platy cellulose therein. The dispersion was applied to the paper surface and the water contact angle was increased to 126.9 ° compared to pure filter paper (0 °).
For 1.8% of the lamellar cellulose hydrophobic complex, a cellulose dispersion containing 1.8g of lamellar cellulose hydrophobic complex was first added to 100g of AKD emulsion, followed by stirring at 800-1500rpm, to complete the dispersion of lamellar cellulose therein. The dispersion was applied to the paper surface and the water contact angle was increased to 142.1 ° compared to pure filter paper (0 °).
For 2.1% of the lamellar cellulose hydrophobic complex, a cellulose dispersion containing 2.1g of lamellar cellulose hydrophobic complex was first added to 100g of AKD emulsion, followed by stirring at 800-1500rpm, to complete the dispersion of lamellar cellulose therein. The dispersion was applied to the paper surface and the water contact angle was increased to 129.9 ° compared to pure filter paper (0 °).
Selecting hydrophobic sizing agent containing 1.8% of lamellar cellulose hydrophobic compound, coating the hydrophobic sizing agent on the surface of paper, and drying the paper, wherein the coating amount is 3g/m 2 (self-made wrapper in Table 1) and are commercially available in Zara and H&The M packaging paper bags were compared. As shown in table 1, the hydrophobic wrapper was found to have certain advantages.
Table 1 comparison of hydrophobic wrapper with commercially available wrapper
Fig. 5 shows the macroscopic morphology of the packaging paper bag made after modification with a sheetlike cellulose-based hydrophobizing agent. As can be seen from fig. 5, the macroscopic morphology of the paper modified by the hydrophobic slurry containing 1.8% of the lamellar cellulose hydrophobic complex is not changed significantly, which means that the coating does not affect the primary color of the paper. And the printing performance of the modified paper is not affected. Therefore, the two-dimensional cellulose sheet-based hydrophobic coating is an environment-friendly paper waterproof modifier with excellent performance.
In summary, the light paper with high mechanical property provided by the invention is modified by the flaky cellulose-based hydrophobic coating to obtain the packaging paper bag capable of replacing disposable plastic. The fully degradable hydrophobic paper which can replace plastic packaging can play an important role in limiting and prohibiting plastic.
It should be understood that the foregoing examples of the present invention are provided for illustration only and are not intended to limit the embodiments of the present invention, and that various other changes and modifications can be made by those skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all the embodiments, and obvious changes and modifications that come within the scope of the invention are defined by the appended claims.
Claims (6)
1. A fully degradable hydrophobic paper comprising:
a paper substrate; and a hydrophobic slurry coating on the surface of the paper substrate;
the hydrophobic slurry coating is prepared from raw materials comprising hydrophobic slurry;
wherein the hydrophobic sizing agent comprises the following components:
a dispersing substance selected from nanocellulose substrate-like cellulose hydrophobic composites, wherein the nanocellulose substrate-like cellulose hydrophobic composites are nanocellulose hydrophobic composites loaded with hydrophobic sheet-like cellulose; and
a dispersion medium selected from biodegradable substances or aqueous hydrophobing agents having a viscosity of 5-500 mpa.s;
wherein the dispersed substance is dispersed in the dispersion medium;
the biodegradable substance or the water-based hydrophobic agent with waterproofness is selected from one or more of chitosan, zein, wheat gliadin, methylcellulose, AKD emulsion and ASA emulsion;
the hydrophobic flaky cellulose is selected from one or more of corncob, wood pulp, bamboo pulp and straw coated by PTFE, the adjustable range of the particle transverse and longitudinal dimensions of the hydrophobic flaky cellulose is 5-200 mu m, and the adjustable range of the thickness is 0.4-10 mu m; the nanocellulose substrate-like cellulose hydrophobic complex is obtained by loading hydrophobic sheet-like cellulose on nanocellulose through the action of shearing force of 10000rpm-30000 rpm.
2. The fully degradable hydrophobic paper of claim 1, wherein the weight ratio of the dispersing substance to the dispersing medium is 1-5:100.
3. The fully degradable hydrophobic paper of claim 1, wherein the preparation method of the hydrophobic pulp comprises the following steps:
and uniformly mixing the dispersion substance and a dispersion medium to obtain the hydrophobic slurry.
4. The fully degradable hydrophobic paper of claim 1, wherein the paper substrate is selected from one of kraft paper, corrugated paper, parchment paper, newsprint paper, white cardboard.
5. The method for preparing the fully degradable hydrophobic paper according to any one of claims 1 to 4, comprising the following steps:
and (3) applying the hydrophobic sizing agent on the surface of the paper base material, and drying to obtain the fully-degradable hydrophobic paper.
6. Use of a fully degradable hydrophobic paper according to any of claims 1-4 in the preparation of a hydrophobic paper product.
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