CN110804105A - Fluorine-containing hydrophobic oil-resistant modified nano-cellulose for food packaging paper and preparation method thereof - Google Patents
Fluorine-containing hydrophobic oil-resistant modified nano-cellulose for food packaging paper and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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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
- 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
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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
- 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
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/28—Polyesters
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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
- 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
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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
- 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
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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
- 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
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
Abstract
The invention discloses fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper and a preparation method thereof, and belongs to the technical field of functional materials. The method comprises the steps of diluting oxidized nano-cellulose into nano-cellulose water suspension with the concentration of 1-1.5%, evaporating to obtain gel-like nano-cellulose, and modifying the nano-cellulose by trifluoroacetic anhydride and 2, 2-difluoroethylamine in sequence to obtain the fluorine-containing hydrophobic oil-resistant modified nano-cellulose. The nano-cellulose modified by fluorine-containing hydrophobic oil-resistant has good water resistance and film-forming property, and can form a uniform film layer after being coated on the surface of food packaging paper, so that the permeation of water vapor and oxygen can be effectively prevented, and the shelf life of food is prolonged; in addition, because the nano-cellulose has large specific surface area and abundant hydroxyl groups, the nano-cellulose can be tightly combined with fibers, so that the binding force among the fibers and the strength of paper are improved, and the use reliability of food packaging paper is improved.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper and a preparation method thereof.
Background
With the improvement of environmental protection consciousness and the promulgation of national plastic banning orders, plastic is no longer used as a packaging material in many areas, but recyclable, degradable and white pollution-free paper is used instead. However, the food wrapping paper has the disadvantages of poor oxygen resistance and water vapor resistance under the condition of high environmental humidity, so that the using effect and the safety of the packaged food are affected, and the adoption of waxing or film coating also has safety risks. Therefore, the invention aims at the problem and develops a novel hydrophobic modified nano cellulose composite emulsion as a surface sizing agent to improve the environmental adaptability of food packaging paper and simultaneously improve the oil resistance of the food packaging paper.
The technical problems to be solved by the invention are as follows:
1. safety problem of food packaging paper
The general food wrapping paper is usually coated with wax or sprayed on the surface of paper to improve the water and oil resistance of the paper. However, whether the surface of the food packaging paper is waxed or coated with the film is safe is also a concern of government, public and technical personnel in related fields, and certain potential safety hazards exist for the surface of the food packaging paper to be waxed or coated with the film; for example, wax coated paper is used for containing hot water, which can melt paraffin on the inner wall of the paper cup and possibly harm the health. In addition, the wax and the polymer film bring troubles in the process of recycling waste paper, and the waste paper pulp is difficult to be processed cleanly, thereby affecting the environmental sanitation and the environmental safety.
2. The strength and the obstruction of food packaging paper
Under the condition of high environmental humidity, water vapor of common food packaging paper can easily permeate into paper pores, and the water absorption of the paper is high, so that the physical strength of the paper is obviously reduced, the paper is easy to break, and the food packaged by the paper can be damaged; in addition, the oxygen and water vapor blocking capability of the food packaging paper is weakened, so that the packaged food is easy to deteriorate and difficult to meet the high requirements of food packaging.
For the above reasons, the present application has been made.
Disclosure of Invention
In view of the problems or defects of the prior art, the invention aims to provide fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper and a preparation method thereof. The invention adopts fluorine-containing modified nano-cellulose to replace paraffin or laminating film to carry out surface sizing on the food packaging base paper. The nano-cellulose has the advantages of biodegradability, wide source, safety, environmental protection and the like, and the modified nano-cellulose is safe, reliable, waterproof and oilproof; therefore, the method has great development prospect when being applied to food packaging paper.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper specifically comprises the following steps:
(1) diluting oxidized nano-cellulose into nano-cellulose water suspension with the concentration of 1-1.5%, and evaporating to obtain gel-like nano-cellulose; then uniformly mixing the gel-like nano cellulose with a dispersing agent N-N-dimethylformamide, and continuously stirring for 3-6h at a constant temperature of 85-90 ℃; adding trifluoroacetic anhydride and 4-dimethylaminopyridine into the reaction system, stirring and dispersing uniformly, heating to 100 ℃, continuing to react for 3-6h, cooling, and washing the product to obtain esterified modified nanocellulose;
(2) adding a 2, 2-difluoroethylamine solution into the esterified modified nanocellulose obtained in the step (1) according to a ratio, uniformly mixing to obtain a mixed reaction solution, adjusting the pH value of the reaction solution to be neutral, and stirring and reacting at a constant temperature of 60-70 ℃ for 4-6 hours; and after the reaction is finished, centrifuging and washing the product, and finally performing dialysis treatment to obtain the fluorine-containing hydrophobic oil-resistant modified nano-cellulose.
Further, in the above technical solution, the oxidized nanocellulose (ToCN) in step (1) is prepared by processing a fiber slurry by a TEMPO oxidation-mechanical method.
Further, according to the technical scheme, the mass ratio of the nano-cellulose to trifluoroacetic anhydride to 4-dimethylaminopyridine in the step (1) is 1: 30-50: 0.5-2.0.
Further, in the above technical scheme, the concentration of the 2, 2-difluoroethylamine solution in the step (2) is 2-5%, and the specific preparation method of the 2, 2-difluoroethylamine solution is as follows: adding 2-5g of 2, 2-difluoroethylamine into 100mL of N-N Dimethylformamide (DMF), and uniformly stirring.
Further, in the technical scheme, the mass ratio of the esterified modified nanocellulose in the step (2) to 2, 2-difluoroethylamine is 1: 0.3-0.6.
Further, in the above technical scheme, the constant temperature stirring reaction in the step (2) is specifically a constant temperature reaction under the stirring speed condition of 500-600 rpm.
The second purpose of the invention is to provide the fluorine-containing hydrophobic oil-resistant modified nano-cellulose for food packaging paper prepared by the method.
The third purpose of the invention is to provide the application of the fluorine-containing hydrophobic oil-resistant modified nano-cellulose prepared by the method in food packaging paper.
Compared with the prior art, the fluorine-containing hydrophobic oil-resistant modified nano-cellulose for the food packaging paper and the preparation method thereof have the following beneficial effects:
(1) for the problems of strength and barrier property of food packaging, the invention adopts fluorine-containing hydrophobic modified nano-cellulose and compounds chitosan and polylactic acid (PLA) to be applied to food packaging paper. The fluorine-containing hydrophobically modified nano-cellulose has good water resistance and film forming property, and can form a uniform film layer after being coated on the surface of food packaging paper, thereby effectively blocking the permeation of water vapor and oxygen and further prolonging the shelf life of food; in addition, because the nano-cellulose has large specific surface area and rich hydroxyl groups, the nano-cellulose can be tightly combined with fibers, so that the binding force among the fibers and the strength of paper are improved, and the use reliability of food packaging paper is improved; in addition, the added chitosan and polylactic acid (PLA) can also improve the physical property and antibacterial property of paper, and the chitosan and the PLA are compounded to apply glue on the surface of the paper, so that the oxygen and water vapor barrier property and the physical strength property of the food packaging paper under the condition of high environmental humidity can be improved.
(2) For the safety problem of food packaging paper, the invention adopts fluorine-containing modified nano-cellulose to replace paraffin or a drench film to carry out surface sizing on the food packaging paper. The nano-cellulose has the advantages of biodegradability, wide source, safety, environmental protection and the like, and the modified nano-cellulose is safe, reliable, waterproof and oilproof; therefore, the method has great development prospect when being applied to food packaging paper.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing fluorine-containing hydrophobic oil-resistant modified nanocellulose;
FIG. 2 is a process flow chart of preparing food wrapping paper by using the fluorine-containing hydrophobic oil-resistant modified nano-cellulose of the invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The three key properties of the food wrapping paper developed in the present invention are oxygen barrier, water vapor barrier and physical strength properties. The invention designs a novel method, trifluoroacetic anhydride is used as a reagent for esterifying and modifying the nano-cellulose, and the reagent and hydroxyl groups on the nano-cellulose are subjected to esterification reaction, so that the hydrophobicity is obviously improved; 2, 2-difluoroethylamine reacts with the esterification modified nanocellulose through electrostatic adsorption to form a complex, so that the hydrophobicity is further improved. Because the adopted fluorine-containing modifier is adopted, the oil resistance of the product is improved. The food packaging paper with the surface glued by the nano-cellulose can be used in a humid environment. The effect of the invention is mainly influenced by the concentration of the modified nano-cellulose; the higher the concentration is, the better the oxygen and water vapor resistance is, and the better the strength performance is; but the influence of cost is also considered, so that proper concentration needs to be selected to be compounded with chitosan and PLA for surface sizing, and the oil-proof performance and the antibacterial performance of the food packaging paper can be improved by adopting the chitosan.
The nano-cellulose adopted in the invention is derived from plant fiber raw materials, and has the advantages of safety, environmental protection, degradability and the like.
The concentration of each reagent of the present invention refers to the mass/volume percent concentration of the dispersoid and the dispersion medium in g/mL.
Example 1
The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper specifically comprises the following steps:
(1) first, an aqueous 1.5% nanocellulose suspension was prepared by adding water to commercially available nanocellulose (prepared by TEMPO oxidation-mechanical treatment of softwood pulp fibers), and the aqueous 1.5% nanocellulose suspension was evaporated in a reactor to make the suspension gel-like. Adding a dispersing agent N-N-dimethylformamide and gelatinous nano-cellulose into another reactor according to the proportion, uniformly mixing, continuously stirring for 6h at the constant temperature in the reactor at 85 ℃, then adding trifluoroacetic anhydride and 4-dimethylaminopyridine (wherein the mass ratio of the nano-cellulose to the trifluoroacetic anhydride to the 4-dimethylaminopyridine is 1: 50: 2.0), dispersing for 20min, heating to 100 ℃, reacting for 6h, cooling for 30min, and washing with ethanol, acetone and deionized water to obtain the esterified modified nano-cellulose.
(2) Adding 5g of 2, 2-difluoroethylamine into 100mL of N-N Dimethylformamide (DMF) to prepare a 5% 2, 2-difluoroethylamine solution; and (2) adding a 2, 2-difluoroethylamine solution into the reaction vessel according to the proportion, and mixing with the esterified modified nano-cellulose aqueous solution prepared in the step (1). Then sodium hydroxide and hydrochloric acid are used for adjusting the pH value to be neutral, the mixture is placed in an oil bath at the temperature of 70 ℃, and the reaction is stirred for 6 hours at the speed of 600 rpm. Wherein: the mass ratio of the esterified modified nano-cellulose to the 2, 2-difluoroethylamine is 1: 0.6. after the reaction is finished, centrifugal washing is carried out for multiple times until the modified nano-cellulose is separated out, and then centrifugal washing is carried out for three times by using ethanol to remove unreacted amine. And (4) carrying out dialysis membrane treatment on the suspension to obtain the fluorine-containing hydrophobic oil-resistant modified nanocellulose, and storing for later use.
Example 2
The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper specifically comprises the following steps:
(1) first, a 1% nanocellulose aqueous suspension was prepared by adding water to commercially available nanocellulose (prepared by TEMPO oxidation-mechanical treatment of softwood pulp fibers), and the 1% nanocellulose aqueous suspension was evaporated in a reactor to make the suspension gel-like. Adding a dispersing agent N-N-dimethylformamide and gelatinous nano-cellulose into another reactor according to the proportion, uniformly mixing, continuously stirring for 3h at the constant temperature of 90 ℃ in the reactor, adding trifluoroacetic anhydride and 4-dimethylaminopyridine (wherein the mass ratio of the nano-cellulose to the trifluoroacetic anhydride to the 4-dimethylaminopyridine is 1: 50: 1.0), dispersing for 15min, heating to 100 ℃, reacting for 5h, cooling for 30min, and washing with ethanol, acetone and deionized water to obtain the esterified modified nano-cellulose.
(2) Adding 2g of 2, 2-difluoroethylamine into 100mL of N-N Dimethylformamide (DMF) to prepare a 2% 2, 2-difluoroethylamine solution; then adding a 2, 2-difluoroethylamine solution into the reaction vessel according to the proportion, and mixing the solution with the esterified nano-cellulose aqueous solution. Then sodium hydroxide and hydrochloric acid are used for adjusting the pH value to be neutral, the mixture is placed in an oil bath at the temperature of 65 ℃, and the reaction is stirred for 4 hours at the speed of 600 rpm. Wherein: the mass ratio of the esterified modified nano-cellulose to the 2, 2-difluoroethylamine is 1: 0.3. after the reaction is finished, centrifugal washing is carried out for multiple times until the modified nano-cellulose is separated out, and then centrifugal washing is carried out for three times by using ethanol to remove unreacted amine. And (4) carrying out dialysis membrane treatment on the suspension to obtain the fluorine-containing hydrophobic oil-resistant modified nanocellulose, and storing for later use.
Example 3
The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper specifically comprises the following steps:
(1) first, an aqueous 1.2% nanocellulose suspension was prepared by adding water to commercially available nanocellulose (prepared by TEMPO oxidation-mechanical treatment of softwood pulp fibers), and the aqueous 1.2% nanocellulose suspension was evaporated in a reactor to make the suspension gel-like. Adding a dispersing agent N-N-dimethylformamide and gelatinous nano-cellulose into another reactor according to the proportion, uniformly mixing, continuously stirring for 4h at the constant temperature of 90 ℃ in the reactor, adding trifluoroacetic anhydride and 4-dimethylaminopyridine (wherein the mass ratio of the nano-cellulose to the trifluoroacetic anhydride to the 4-dimethylaminopyridine is 1: 50: 0.5), dispersing for 10min, heating to 100 ℃, reacting for 3h, cooling for 30min, and washing with ethanol, acetone and deionized water to obtain the esterified modified nano-cellulose.
(2) Adding 3g of 2, 2-difluoroethylamine into 100mL of N-N Dimethylformamide (DMF) to prepare a 3% 2, 2-difluoroethylamine solution; then adding a 2, 2-difluoroethylamine solution into the reaction vessel according to the proportion, and mixing the solution with the esterified nano-cellulose aqueous solution. Then sodium hydroxide and hydrochloric acid are used for adjusting the pH value to be neutral, the mixture is placed in an oil bath at 60 ℃, and the reaction is stirred for 5 hours at the speed of 500 rpm. Wherein: the mass ratio of the esterified modified nano-cellulose to the 2, 2-difluoroethylamine is 1: 0.5. after the reaction is finished, centrifugal washing is carried out for multiple times until the modified nano-cellulose is separated out, and then centrifugal washing is carried out for three times by using ethanol to remove unreacted amine. And (4) carrying out dialysis membrane treatment on the suspension to obtain the fluorine-containing hydrophobic oil-resistant modified nanocellulose, and storing for later use.
The fluorine-containing hydrophobic oil-resistant modified nanocellulose prepared by the above embodiments of the invention can be used for preparing hydrophobic oil-resistant food packaging paper.
The food packaging paper disclosed by the invention consists of food packaging base paper and a hydrophobic oil-resistant coating formed on the surface of the food packaging base paper; the hydrophobic oil-repellent coating is formed of a surface sizing agent comprising chitosan, polylactic acid (PLA) and modified nanocellulose, wherein: the modified nano-cellulose is the fluorine-containing hydrophobic oil-resistant modified nano-cellulose.
Further, according to the technical scheme, the mass ratio of the food packaging base paper to the surface sizing agent is 1: 0.08-0.15.
Further, according to the technical scheme, the quantitative amount of the food packaging paper is 36-38g/m2Water absorptionThe surface roughness is 18-20g/m2The transverse tearing index is 8.2-8.7 mN.m2The water-based paint has the advantages of specific weight percent, specific surface area, cross-sectional average tensile index of 44-48 N.m/g, oil resistance grade of not less than 7, oxygen permeability of 8.5-11cm 3/(. square meter.24 h), and water vapor permeability of 137-142 g/(. square meter.24 h).
The preparation method of the food packaging paper comprises the following steps:
(a) preparing fiber slurry: 2-6 parts by mass of a mixed pulp board and 994-998 parts by volume of water are pulped in a hydrapulper for 20min to obtain mixed pulp with the concentration of 0.2-0.6%, then the mixed pulp is sequentially subjected to primary secondary purification by a conical slag remover, primary secondary screening by a pressure screen and 3 series pulp refining by a conical refiner to obtain fiber pulp with the beating degree of 40-55 DEG SR, and the fiber pulp is pumped into a pulping tank for later use;
(b) preparing a surface sizing agent: preparing 2-6% of hydrophobic oil-resistant modified nano-cellulose into suspension, compounding the suspension with chitosan and polylactic acid (PLA), and preparing a surface sizing solution with the concentration of 5-8% for later use after uniformly stirring; wherein: the mass ratio of the hydrophobic oil-resistant modified nano-cellulose to the chitosan to the PLA is 1: 5-10: 10-20 parts of;
(c) making of food packaging paper: adding auxiliary agents of cationic starch and cationic polyacrylamide into a pulp preparation box, uniformly mixing with the fiber pulp obtained in the step (a) from a pulp forming pool, diluting to an online concentration of 0.1-0.6%, making wet paper sheets by using a fourdrinier machine, squeezing, primarily drying, coating modified nano cellulose by using a surface sizing machine, and drying to obtain the food packaging paper.
Further, in the above technical solution, the mass part and volume part of step (a) are g: mL was used as a reference.
Further, according to the technical scheme, the mixed pulp plate in the step (a) is prepared by mixing the components in a mass ratio of 1: 1 hardwood pulp and softwood pulp.
Further, in the above technical scheme, the mass ratio of the fiber slurry in the step (c) to the cationic starch and the cationic polyacrylamide is 100: 0.5-1: 0.5-1.
The preparation of food wrapping paper using the fluorine-containing hydrophobic oil-resistant modified nanocellulose obtained in examples 1 to 3 of the present invention is further illustrated by specific application examples.
Application example 1
A method for preparing food packaging paper by using the fluorine-containing hydrophobic oil-resistant modified nano-cellulose obtained in example 1, wherein the method comprises the following steps:
(a) preparing slurry: pulping 6g of mixed pulp board and 994mL of water in a hydrapulper for 20min to obtain mixed pulp with the concentration of 0.6%, then sequentially carrying out primary and secondary purification by a conical slag remover, primary and secondary screening by a pressure screen and 3 series pulp grinding by conical refiners to obtain fiber pulp with the beating degree of 55 DEG SR, and pumping the fiber pulp into a pulping tank for later use;
wherein: the mixed pulp plate is prepared from the following components in percentage by mass of 1: 1 hardwood pulp and softwood pulp.
(b) Preparing a nano-cellulose surface sizing agent: preparing 6% suspension of the fluorine-containing hydrophobic oil-resistant modified nanocellulose obtained in the example 1, compounding the suspension with chitosan and polylactic acid (PLA), and preparing a surface sizing solution with the concentration of 8% for later use after uniformly stirring;
wherein: the mass ratio of the fluorine-containing hydrophobic oil-resistant modified nano-cellulose to the chitosan to the PLA is 1: 10: 20;
(c) making of food packaging paper: sequentially adding auxiliary agents cationic starch and cationic polyacrylamide into a pulp preparation box, uniformly mixing with the fiber pulp obtained in the step (a) from a pulp forming pool, diluting to an online concentration of 0.6%, papermaking with a 300mm test fourdrinier papermaking machine, squeezing, primarily drying to obtain food packaging base paper, coating the surface sizing solution obtained in the step (b) on the surface of the food packaging base paper by using a surface sizing machine, and drying to obtain the food packaging paper;
wherein: the mass ratio of the fiber slurry to the cationic starch and the cationic polyacrylamide is 100: 1: 1;
the mass ratio of the food packaging base paper to the nano-cellulose surface sizing agent is 1: 0.08.
application example 2
A method for preparing food packaging paper by using the fluorine-containing hydrophobic oil-resistant modified nano-cellulose obtained in example 2, wherein the method comprises the following steps:
(a) preparing slurry: pulping 2g of mixed pulp board and 998mL of water in a hydrapulper for 20min to obtain mixed pulp with the concentration of 0.2%, then sequentially carrying out primary and secondary purification by a conical slag remover, primary and secondary screening by a pressure screen and 3 series pulp grinding by conical refiners to obtain fiber pulp with the beating degree of 50 DEG SR, and pumping the fiber pulp into a pulping tank for later use;
wherein: the mixed pulp plate is prepared from the following components in percentage by mass of 1: 1 hardwood pulp and softwood pulp.
(b) Preparing a nano-cellulose surface sizing agent: preparing the fluorine-containing hydrophobic oil-resistant modified nanocellulose obtained in the example 2 into 4% suspension, compounding the suspension with chitosan and polylactic acid (PLA), and preparing a surface sizing solution with the concentration of 6% for later use after uniformly stirring;
wherein: the mass ratio of the fluorine-containing hydrophobic oil-resistant modified nano-cellulose to the chitosan to the PLA is 1: 5: 10;
(c) making of food packaging paper: sequentially adding auxiliary agents cationic starch and cationic polyacrylamide into a pulp preparation box, uniformly mixing with the fiber pulp obtained in the step (a) from a pulp forming pool, diluting to an online concentration of 0.1%, papermaking with a 300mm test fourdrinier papermaking machine, squeezing, primarily drying to obtain food packaging base paper, coating the surface sizing solution obtained in the step (b) on the surface of the food packaging base paper by using a surface sizing machine, and drying to obtain the food packaging paper;
wherein: the mass ratio of the fiber slurry to the cationic starch and the cationic polyacrylamide is 100: 0.8: 0.8;
the mass ratio of the food packaging base paper to the nano-cellulose surface sizing agent is 1: 0.1.
application example 3
A method for preparing food packaging paper by using the fluorine-containing hydrophobic oil-resistant modified nano-cellulose obtained in example 3, wherein the method comprises the following steps:
(a) preparing slurry: pulping 4g of mixed pulp board and 996mL of water in a hydrapulper for 20min to obtain mixed pulp with the concentration of 0.4%, then sequentially carrying out primary and secondary purification by a conical slag remover, primary and secondary screening by a pressure screen and 3 series pulp grinding by conical refiners to obtain fiber pulp with the beating degree of 40 DEG SR, and pumping the fiber pulp into a pulping tank for later use;
wherein: the mixed pulp plate is prepared from the following components in percentage by mass of 1: 1 hardwood pulp and softwood pulp.
(b) Preparing a nano-cellulose surface sizing agent: preparing 2% suspension of the fluorine-containing hydrophobic oil-resistant modified nanocellulose obtained in the example 3, compounding the suspension with chitosan and polylactic acid (PLA), and preparing a surface sizing solution with the concentration of 5% for later use after uniformly stirring;
wherein: the mass ratio of the fluorine-containing hydrophobic oil-resistant modified nano-cellulose to the chitosan to the PLA is 1: 8: 15;
(c) making of food packaging paper: sequentially adding auxiliary agents cationic starch and cationic polyacrylamide into a pulp preparation box, uniformly mixing with the fiber pulp obtained in the step (a) from a pulp forming pool, diluting to an online concentration of 0.3%, papermaking with a 300mm test fourdrinier papermaking machine, squeezing, primarily drying to obtain food packaging base paper, coating the surface sizing solution obtained in the step (b) on the surface of the food packaging base paper by using a surface sizing machine, and drying to obtain the food packaging paper;
wherein: the mass ratio of the fiber slurry to the cationic starch and the cationic polyacrylamide is 100: 0.5: 0.5;
the mass ratio of the food packaging base paper to the nano-cellulose surface sizing agent is 1: 0.15.
comparative example 1
A method of making a wrapping paper for food of the present comparative example, the method comprising the steps of:
(a) preparing slurry: pulping 6g of mixed pulp board and 994mL of water in a hydrapulper for 20min to obtain mixed pulp with the concentration of 0.6%, then sequentially carrying out primary and secondary purification by a conical slag remover, primary and secondary screening by a pressure screen and 3 series pulp grinding by conical refiners to obtain fiber pulp with the beating degree of 55 DEG SR, and pumping the fiber pulp into a pulping tank for later use;
wherein: the mixed pulp plate is prepared from the following components in percentage by mass of 1: 1 hardwood pulp and softwood pulp.
(c) Making of food packaging paper: adding auxiliary agent cationic starch and cationic polyacrylamide into a pulp preparation box in sequence, uniformly mixing with the fiber pulp obtained in the step (a) from a pulp forming pool, diluting to have an online concentration of 0.6%, papermaking with a 300mm test fourdrinier papermaking machine, squeezing, and drying to obtain food packaging base paper, wherein: the mass ratio of the fiber slurry to the cationic starch and the cationic polyacrylamide is 100: 1: 1.
the physical properties (including water absorption, tear index, tensile index, oxygen permeability, water vapor permeability, and the like) of the food wrappers obtained in the above application examples 1 to 3 and the food wrapper of comparative example 1 were respectively tested. The above physical performance indexes of the food packaging paper are tested by adopting a general method of paper standardized detection. For example, the water absorption test is as described in GB/T1540-2002, the tear index test is as described in GB/T455.1-1989, the tensile index is as described in GB/T12914-2008, the oil repellency rating is as described in TAPPI T559, and the oxygen permeability is as described in Standard GB/T19789-2005; the detection standard GB/T1037-1988 for the water vapor permeability is tested, and the specific test results are shown in Table 1.
Table 1 comparative table of results of physical property test of food wrap paper prepared by using examples 1 to 3 and comparative example 1
As can be seen from the data of example 1 and comparative example 1 in Table 1, the food wrapping paper before and after the surface sizing of the fluorine-containing hydrophobic oil-resistant modified nanocellulose of the invention has the advantages of obviously reduced water absorption, obviously improved physical strength, improved oil resistance, reduced oxygen permeability of 87.7 percent and reduced water vapor permeability of 83.9 percent.
Claims (7)
1. A preparation method of fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) diluting oxidized nano-cellulose into nano-cellulose water suspension with the concentration of 1-1.5%, and evaporating to obtain gel-like nano-cellulose; then uniformly mixing the gel-like nano cellulose with a dispersing agent N-N-dimethylformamide, and continuously stirring for 3-6h at a constant temperature of 85-90 ℃; adding trifluoroacetic anhydride and 4-dimethylaminopyridine into the reaction system, stirring and dispersing uniformly, heating to 100 ℃, continuing to react for 3-6h, cooling, and washing the product to obtain esterified modified nanocellulose;
(2) adding a 2, 2-difluoroethylamine solution into the esterified modified nanocellulose obtained in the step (1) according to a ratio, uniformly mixing to obtain a mixed reaction solution, adjusting the pH value of the reaction solution to be neutral, and stirring and reacting at a constant temperature of 60-70 ℃ for 4-6 hours; and after the reaction is finished, centrifuging and washing the product, and finally performing dialysis treatment to obtain the fluorine-containing hydrophobic oil-resistant modified nano-cellulose.
2. The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper according to claim 1, characterized in that: the oxidized nano-cellulose in the step (1) is prepared by processing fiber slurry by a TEMPO oxidation-mechanical method.
3. The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper according to claim 1, characterized in that: the mass ratio of the nano-cellulose to trifluoroacetic anhydride to 4-dimethylaminopyridine in the step (1) is 1: 30-50: 0.5-2.0.
4. The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper according to claim 1, characterized in that: the concentration of the 2, 2-difluoroethylamine solution in the step (2) is 2-5%.
5. The preparation method of the fluorine-containing hydrophobic oil-resistant modified nanocellulose for food packaging paper according to claim 1, characterized in that: the mass ratio of the esterified modified nano-cellulose to 2, 2-difluoroethylamine in the step (2) is 1: 0.3-0.6.
6. The fluorine-containing hydrophobic oil-resistant modified nanocellulose prepared by the method for preparing fluorine-containing hydrophobic oil-resistant modified nanocellulose according to any one of claims 1 to 5.
7. Use of the fluorine-containing hydrophobic oil-resistant modified nanocellulose prepared by the method of any one of claims 1 to 5 in food packaging paper.
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