AU2020102808A4 - Hydrophobic enhanced painting and calligraphy paper and preparation method thereof - Google Patents
Hydrophobic enhanced painting and calligraphy paper and preparation method thereof Download PDFInfo
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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
- D21H21/16—Sizing or water-repelling agents
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Abstract
The invention discloses hydrophobic enhanced painting and calligraphy paper and a
preparation method thereof, and belongs to the technical field of papermaking. The
hydrophobic enhanced painting and calligraphy paper provided by the invention comprises
painting and calligraphy paper and a hydrophobic modified nano cellulose coating formed on
the surface of the painting and calligraphy paper, wherein the hydrophobic modified nano
cellulose is prepared by the following steps of: oxidizing and pretreating cellulose by using 2,
2, 6, 6-tetramethyl piperidine oxide to obtain cellulose with carboxyl, and carrying out high
pressure homogenization to obtain the nano cellulose; carrying out hydrophobic modification
on the nano cellulose by adopting a two-step method, wherein firstly, glutaric anhydride and
propionic anhydride are used as reagents of esterification modified nano cellulose; and
secondly, carrying out reaction on 1-tridecylamine and n-decylamine through electrostatic
adsorption to form a complex compound with the esterification modified nano cellulose. Due
to the small size of the nano cellulose adopted by the invention, the nano cellulose is easier to
get deposited on the surface of paper or permeate pores, the water vapor barrier performance
and the hydrophobicity of the paper can be enhanced, and the strength performance of the
painting and calligraphy paper can be obviously improved.
Figures
Fiber pulp Pulverizing Oxidation and Suction filtration
and stirring pretreatment and washing
Centrifugal Anhydride Rotary High pressure
washing modification evaporation homogenization
Amide Centrifugal Dialysis Preparation of
Modified Nano 1n
modification washing separation Cellulose Sizing
Solution
Sizing by
controlling
emulsions with _
different Preparation of Painting and
concentrations Modified Nano calligraphy paper
Cellulose Sizing Oven drying Surface sizing before sizing of
Solution _+ _ modified nano
cellulose sizing
Figure 1
Description
Figures
Fiber pulp Pulverizing Oxidation and Suction filtration and stirring pretreatment and washing
Centrifugal Anhydride Rotary High pressure washing modification evaporation homogenization
Amide Centrifugal Dialysis Preparation of Modified Nano 1n modification washing separation Cellulose Sizing Solution Sizing by controlling emulsions with _ different Preparation of Painting and concentrations Modified Nano calligraphy paper Cellulose Sizing Oven drying Surface sizing before sizing of Solution _+ _ modified nano cellulose sizing
Figure 1
Hydrophobic enhanced painting and calligraphy paper and preparation method thereof
[0001] The invention belongs to the technical field of papermaking and particularly relates to hydrophobic enhanced painting and calligraphy paper and a preparation method thereof.
[0002] The differentiation in water absorption and ink absorption of painting and calligraphy paper has become one of the key links in the production of art paper. For the existing painting and calligraphy paper, plant fiber is used as a material, and is not treated too much, so that the painting and calligraphy paper is easy to absorb moisture and mildew when the humidity is high. In addition, the painting and calligraphy paper has low strength and is easy to get damaged, which is a problem in need of special attention in the production. Therefore, the painting and calligraphy paper in the prior art mainly has the following technical problems:
[0003] 1. Enhancement of Painting and Calligraphy Paper
[0004] Fiber raw materials used by the painting and calligraphy paper are complex, and generally, the fibers are made of barks, bamboo and grass fibers. The tensile force of the fibers is not strong enough, so the fastness is poor, the strength performance of the painting and calligraphy paper such as tension resistance, folding resistance and the like is poor, and the painting and calligraphy paper is easy to get cracked in the process of painting and calligraphy creation, storage or display, thereby causing serious losses. If other chemical enhancers are used, writing effects of the painting and calligraphy paper can be influenced.
[0005] 2. Water Absorption and Ink Absorption of Painting and Calligraphy Paper
[0006] The existing painting and calligraphy paper is subject to relatively single water absorbency and ink absorbency. Generally, the water absorbency and ink absorbency are controlled by a mode of sizing in pulp. This method is often poor in uniformity and will worsen the expressive force of the painting and calligraphy paper. An artist or an art fan pursues the expressive force in the aspects of individuality and microcosmic, so that different requirements for the water absorbency and the ink absorbency of the domestic art paper are proposed, resulting in quite differential requirements; and accurate differential adjustment is difficult to achieve by the mode of sizing.
[0007] 3. Prevention of Dampness and Mildew of Painting and Calligraphy Paper
[0008] As a type of art paper, painting and calligraphy paper often records valuable art contents, but as a material with plant fiber used as the major raw material, the painting and calligraphy paper has large moisture absorption property and is easy to go moldy, especially in the south regions, which can bring mildew and loss to art works.
[0009] Aiming at the problems or defects existing in the prior art, the invention aims to provide hydrophobic enhanced painting and calligraphy paper and a preparation method thereof. The invention mainly utilizes hydrophobic modified nano cellulose to perform surface sizing on the painting and calligraphy paper, so that the technical problems existing in the prior art are solved.
[0010] In order to achieve the above first objective of the present invention, the present invention provides hydrophobic enhanced painting and calligraphy paper which comprises painting and calligraphy paper and a hydrophobic modified nano cellulose coating formed on the surface of the painting and calligraphy paper.
[0011] Further, according to the above technical scheme, the quota of the hydrophobic enhanced 2 painting and calligraphy paper is 40-60g/m .
[0012] Further, according to the above technical scheme, the hydrophobic modified nano cellulose is prepared by the following method, and the method comprises the following steps:
[0013] (1) crushing and evenly stirring, then oxidizing and pretreating the fiber pulp using a TEMPO (2, 2, 6, 6-tetramethylpiperidine oxide)/NaClO/NaBr system, and carrying out suction filtration and washing to obtain oxidized cellulose;
[0014] (2) preparing the oxidized cellulose obtained in the step (1) into a suspension with the concentration of 1-2%, and then carrying out high-pressure homogenization treatment to obtain a nano cellulose suspension;
[0015] (3) performing rotary evaporation on the nano cellulose suspension obtained in the step (2) to obtain gel-shaped nano cellulose; adding N-N-dimethyl formamide into the gel-shaped nano cellulose according to a proportion, performing ultrasonic dispersion and uniformization, heating the mixture to 80-90 °C and stirring the mixture for 4-6 hours at a constant temperature; keeping adding glutaric anhydride, propionic anhydride and 4-dimethylaminopyridine according to a proportion after the stirring, performing ultrasonic dispersion and uniformization to obtain a reaction solution 1; and heating the reaction solution 1 to 80-120 °C and reacting for 4-8 hours at a constant temperature, cooling the mixture after the reaction, and centrifuging and washing the product to obtain esterification modified nano cellulose;
[0016] (4) respectively adding a 1-tridecylamine solution and an n-decylamine solution into the esterification modified nano cellulose obtained in the step (3) according to a proportion, uniformly mixing the mixture to obtain a reaction solution 2, adjusting the pH value of the reaction solution 2 to be neutral, stirring the mixture at a constant temperature of between 40 and 80 °C for a reaction of 2 to 6 hours; and centrifuging and washing the product after the reaction, and finally carrying out a dialysis separation treatment to obtain the hydrophobic modified nano cellulose.
[0017] Preferably, in the technical scheme, the fiber pulp in step (1) is any one of wood pulp, cotton pulp, hemp pulp, bamboo pulp and reed pulp.
[0018] More preferably, in the above technical scheme, the wood pulp is any one of hardwood pulp, needle wood pulp and the like.
[0019] Preferably, according to the above technical scheme, the mass ratio of dry fiber to 2, 2, 6, 6 tetramethylpiperidine oxide, to sodium bromide and to sodium hypochlorite in the fiber slurry in step (1) is 1:0.01-0.02:0.05-0.2:6-10.
[0020] Preferably, according to the above technical scheme, the high-pressure homogenizing treatment in step (2) uses a pressure of 800-1000 bar.
[0021] Preferably, according to the above technical scheme, the number of times of the high pressure homogenization treatment in step (2) is 10-15, and the time of each treatment is 30-60 s.
[0022] Preferably, according to the above technical scheme, the stirring speed in step (3) is 400-800 rpm, more preferably 500-600 rpm.
[0023] Preferably, according to the above technical scheme, in the aqueous suspension of the nano cellulose in step (3), the dosage ratio of the absolute dry nano cellulose to the N-N dimethylformamide in the nano cellulose aqueous suspension in the step (3) is 1-2 parts by mass:
-100 parts by volume, and g: ml is used as a reference between the parts by mass and the parts by volume
[0024] Preferably, according to the above technical scheme, the mass ratio of the absolute dry nano cellulose to glutaric anhydride, to propionic anhydride and to 4-dimethylaminopyridine in the aqueous suspension of the nano cellulose in step (3) is 1:20:20:0.6.
[0025] Preferably, according to the technical scheme, the concentration of the1-tridecylamine solution in the step (4) is 3-6%, and the specific preparation method of the 1-tridecylamine solution is as follows: 3-6 g of 1-tridecylamine is added into 100 mL of N-N dimethylformamide (DMF), and the mixture is stirred uniformly.
[0026] Preferably, according to the above technical scheme, the concentration of the N-decylamine solution in step (4) is 3-6%, and the specific preparation method of the N-decylamine solution is as follows: 3-6 g of n-decylamine is added into 100 mL of N-N dimethylformamide (DMF), and the mixture is stirred uniformly.
[0027] Preferably, according to the above technical scheme, the mass ratio of the esterification modified nano cellulose to the 1-tridecylamine in the 1-tridecylamine solution, to the n-decylamine in the n-decylamine solution in the step (4) is 1:0.1-0.45:0.1-0.45.
[0028] Preferably, according to the above technical scheme, the stirring speed in step (4) is 400-800 rpm, more preferably 600 rpm.
[0029] The second objective of the present invention is to provide a preparation method of the hydrophobic enhanced painting and calligraphy paper, which comprises: preparing the hydrophobic modified nano cellulose into a sizing solution with the concentration of 2-8%, coating the sizing solution on the surface of the painting and calligraphy paper, and drying the painting and calligraphy paper in an oven.
[0030] Further, according to the above technical scheme, the mass ratio of the absolute dry fiber of the painting and calligraphy paper to the absolute dry hydrophobic modified nano cellulose is 1:0.01-0.03.
[0031] Further, according to the technical scheme, the drying temperature is 80-90 °C, and the drying time is 10-30 min.
[0032] Compared with the prior art, the hydrophobic enhanced painting and calligraphy paper and the preparation method thereof have the following beneficial effects:
[0033] (1) The nano cellulose modified by the two-step method is coated on the painting and calligraphy paper in the form of surface sizing, and because the nano cellulose is small in size, the nano cellulose is easier to get deposited on the surface of the paper or permeate pores, and the water vapor barrier performance and hydrophobicity of the paper can be enhanced, so that the nano cellulose is not easy to absorb moisture and mildew when the environmental humidity is high, and thus the storage time of the nano cellulose is prolonged.
[0034] (2) By controlling the process formula of the modified nano cellulose, such as concentration, dosage, surface sizing speed and the like, sizing of the surface of the painting and calligraphy paper is realized, so that different water absorption and ink absorption properties are controlled, and differential adjustment is realized.
[0035] (3) When the modified nano cellulose adopted by the invention is coated on the surface of the painting and calligraphy paper, the strength performance of the painting and calligraphy paper can be obviously improved; and meanwhile, the chemical composition of the modified nano cellulose is the same as the plant fiber of the painting and calligraphy paper, so that the writing on the painting and calligraphy paper would not be adversely affected.
[0036] (4) The nano cellulose adopted in the invention is derived from plant fiber raw materials, and has the advantages of being environment-friendly and degradable, etc.
[0037] Figure 1 is a process flow diagram showing hydrophobic enhanced painting and calligraphy paper according to the present invention.
[0038] The present invention will be described in further detail with reference to the following embodiments, which are implemented on the premise of the technology of the present invention, and detailed embodiments and specific operation procedures will now be given to illustrate the creativity of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
[0039] From the information contained herein, it will be readily apparent to those skilled in the art that various changes may be made in the precise description of the invention without departing from the spirit and scope of the appended claims. It should be understood that the scope of the invention is not limited to the defined processes, natures or compositions because these embodiments and other descriptions are only used for illustratively explain specific aspects of the invention. In fact, various changes which could be made by those skilled in the art or relevant art obviously aiming at the implementations of the invention should be involved in the claims attached.
[0040] All numbers expressing amounts, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the word "about" in order to provide a better understanding of the invention and not to limit the scope of the invention. Thus, unless specifically stated otherwise, the numerical parameters set forth in the specification and the appended claims are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should be considered at least as being derived from the reported significant digits and by conventional rounding methods.
[0041] The method comprises the following steps of: oxidizing and pretreating cellulose by using 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) to obtain cellulose with carboxyl, and then carrying out high-pressure homogenization to obtain nano cellulose; carrying out hydrophobic modification on the nano cellulose by using a two-step method, wherein glutaric anhydride and propionic anhydride are used as reagents for esterification modification of the nano cellulose; and reacting 1 tridecylamine and n-decylamine with the esterification modified nano cellulose through electrostatic adsorption to form a complex, wherein the hydrophobic modification of the nano cellulose is carried out, and finally the water modified nano cellulose is coated on the surface of drawing base paper, and dried.
[0042] Two key properties of painting and calligraphy paper developed in the present invention are water resistance and physical strength properties (tear index, break length, etc.). when the concentration of the modified nano cellulose is higher, the hydrophobic property of the paper is better and the water absorption is poor, and the addition of the modified nano cellulose also slightly improves the physical strength performance, but the influence of the cost and the physical strength of the paper is also needed be considered, so the proper concentration is needed to be selected for surface sizing. According to the invention, the cellulose is oxidized and pretreated at first with 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO), and then high-pressure homogenization is carried out. The dispersion performance of the prepared nano cellulose in water is greatly improved. Because the generated carboxyl group has a negative charge, and there is a charge repulsion effect, thereby improving the dispersion performance.
[0043] According to the invention, glutaric anhydride and propionic anhydride are adopted as a compound anhydride as a reagent for esterifying and modifying the nano cellulose, and the prepared nano cellulose is subjected to esterification reaction, so that the hydrophobicity is obviously improved.
[0044] The 1-tridecylamine and n-decylamine of the present invention react with the esterification modified nano cellulose by electrostatic adsorption to form a complex, so that the hydrophobicity is further improved.
[0045] The concentration of each reagent of the present invention refers to the mass/volume percent concentration of the dispersion and the dispersion medium measured by g/mL.
0046 Embodiment 1
[0047] The preparation method of the hydrophobic enhanced painting and calligraphy paper according to the embodiment comprises the following steps:
[0048] (1) Preparation of Oxidized Cellulose
[0049] The step comprises: preparing 400 mL of a buffer solution with the pH value of 10 by using 0.1 mol/L of sodium carbonate solution and 0.1 mol/L of sodium bicarbonate solution according to the volume ratio of 3:2, and taking 300 mL of the buffer solution in a three-necked flask of 500 mL; weighing 5 g of absolute dry hardwood pulp, crushing the slurry by using a crusher, adding the slurry into the flask, and fully stirring by using a magnetic stirrer; weighing 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide successively and adding the 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide into the flask, weighing a 30% sodium hypochlorite solution of 35ml and putting the solution into the flask after full dissolution, starting a reaction after mixing at a room temperature, and during the reaction, the pH of the reaction liquid is adjusted by the 0.1 mol/L sodium hydroxide solution to about 10, wherein the total reaction time is 18 h; and carrying out suction filtration and washing of the reaction mixture liquid with ionized water after the reaction, obtaining oxidized cellulose, and finally transferring the oxidized cellulose into a clean flask for storage, wherein the mass ratio of the absolute dry hardwood pulp to the 2, 2, 6, 6-tetramethylpiperidine oxide, to the sodium bromide and to the sodium hypochlorite is 1:0.01:0.05:0.6.[0050] (2) Preparation of Nano Cellulose Suspension
[0051] The oxidized cellulose obtained in the step (1) was prepared into a suspension with the concentration of 1%, and the suspension was circulated 10 times using a high-pressure homogenizer for 60 s each treatment, wherein the pressure was set at 1000 bar, so as to obtain a nano cellulose suspension.
[0052] (3) Preparation of Esterification modified Nano Cellulose
[0053] First, 150 g of the aqueous suspension of nano cellulose with the concentration of 1% obtained in the step (2) was subjected to rotary evaporation, so that the suspension became gel; then, the obtained gel-like nano cellulose was transferred into a beaker, and 80 ml of N-N dimethylformamide was added thereto for ultrasonic treatment for 30 minutes, then transferred into a round bottom flask, continuously stirred for 5 h at a speed of 600 rpm in a water bath of 85 °C, then, the glutaric anhydride and propionic anhydride with the mass ratio of 1:1, and the nano cellulose, glutaric anhydride and propionic anhydride and 4-dimethylaminopyridine with the ratio of 1:40:0.6 were added into a round-bottom flask for ultrasonic dispersion of 10 min, a condenser pipe was connected, and a water bath was heated to 100 °C, and the mixture was put into a cold water tank for 10 min and then treated with a centrifugal treatment after 6 h of reaction. After that, methanol and acetone with the ratio of 2:1 were added for multiple times of centrifugal washing; and after multiple times of washing of ionized water, the esterification modified nano cellulose was obtained.
[0054] (4) Preparation of Hydrophobic Modified Nano Cellulose
[0055] The step comprises: adding 4 g of1-tridecylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 1-tridecylamine solution with the concentration of 4%; adding 4 g of N-decylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 4% n-decylamine solution; adding the 1 tridecylamine solution and the n-decylamine solution into the esterification modified nano cellulose obtained in the step (3) according to the proportion, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at 60 °C, and performing a centrifugal separation reaction on the n-decylamine solution for 4 h at the speed of 600 rpm; carrying out multiple times of centrifugation and washing after the reaction till the modified nano cellulose is separated, carrying out centrifugal washing for three times with ethyl alcohol to remove unreacted amine, and finally carrying out a dialysis membrane treatment to the suspension to obtain the hydrophobic modified nano cellulose which is then saved for later use, wherein the mass ratio of the esterification modified nano cellulose to 1-tridecylamine in the 1-tridecylamine solution and to n-decylamine in the n-decylamine solution is 1:0.1:0.1.
[0056] (5) Preparing the hydrophobic modified nano cellulose obtained in the step (4) into a sizing solution with the concentration of 3%, coating the sizing solution on the surface of the painting and calligraphy paper by using a surface sizing machine, putting the surface sizing solution into an oven at the temperature of 90 °C for drying for 20 minutes to obtain the painting and calligraphy paper coated with the nano cellulose,
The quota is 40g/m 2 , wherein the mass ratio of the absolute dry fiber of the painting and calligraphy paper to the absolute dry hydrophobic modified nano cellulose is 1:0.01.
0057 Embodiment 2
[0058] The preparation method of the hydrophobic enhanced painting and calligraphy paper according to the embodiment comprises the following steps:
[0059] (1) Preparation of Oxidized Cellulose
[0060] The step comprises: preparing 400 mL of a buffer solution with the pH value of 9.5 by using 0.1 mol/L of sodium carbonate solution and 0.1 mol/L of sodium bicarbonate solution according to the volume ratio of 1:0.5, and taking 300 mL of the buffer solution in a three-necked flask of 500 mL; weighing 5 g of absolute dry hardwood pulp, crushing the slurry by using a crusher, adding the slurry into the flask, and fully stirring by using a magnetic stirrer; weighing 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide successively and adding the 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide into the flask, weighing a 30% sodium hypochlorite solution of 50 ml and putting the solution into the flask after full dissolution, starting a reaction after mixing at a room temperature, and during the reaction, the pH of the reaction liquid is adjusted by the 0.1 mol/L sodium hydroxide solution to about 9.5, wherein the total reaction time is h; and carrying out suction filtration and washing of the reaction mixture liquid with ionized water after the reaction, obtaining oxidized cellulose, and finally transferring the oxidized cellulose into a clean flask for storage, wherein the mass ratio of the absolute dry hardwood pulp to the 2, 2, 6, 6-tetramethylpiperidine oxide, to the sodium bromide and to the sodium hypochlorite is 1:0.015:0.1:8.
[0061] (2) Preparation of Nano Cellulose Suspension
[0062] The oxidized cellulose obtained in the step (1) was prepared into a suspension with the concentration of 1.5%, and the suspension was circulated 12 times using a high-pressure homogenizer for 40 s each treatment, wherein the pressure was set at 900 bar, so as to obtain a nano cellulose suspension.
[0063] (3) Preparation of Esterification Modified Nano Cellulose
[0064] First, 100 g of the aqueous suspension of nano cellulose with the concentration of 1.5% obtained in the step (2) was subjected to rotary evaporation, so that the suspension became gel; then, the obtained gel-like nano cellulose was transferred into a beaker, and 60 ml of N-N dimethylformamide was added thereto for ultrasonic treatment for 30 minutes, then transferred into a round bottom flask, continuously stirred for 4 h at a speed of 500 rpm in a water bath of 90 °C, then, the glutaric anhydride and propionic anhydride with the mass ratio of 1:1, and the nano cellulose, glutaric anhydride and propionic anhydride and 4-dimethylaminopyridine with the ratio of 1:40:0.6 were added into a round-bottom flask for ultrasonic dispersion of 15 min, a condenser pipe was connected, and a water bath was heated to 120 °C, and the mixture was put into a cold water tank for 20 min and then treated with a centrifugal treatment after 4 h of reaction. After that, methanol and acetone with the ratio of 2:1 were added for multiple times of centrifugal washing; and after multiple times of washing of ionized water, the esterification modified nano cellulose was obtained.
[0065] (4) Preparation of Hydrophobic Modified Nano Cellulose
[0066] The step comprises: adding 3 g of1-tridecylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 1-tridecylamine solution with the concentration of 3%; adding 3 g of N-decylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 4% n-decylamine solution; adding the 1 tridecylamine solution and the n-decylamine solution into the esterification modified nano cellulose obtained in the step (3) according to the proportion, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at 40 °C, and performing a centrifugal separation reaction on the n-decylamine solution for 6 h at the speed of 400 rpm; carrying out multiple times of centrifugation and washing after the reaction till the modified nano cellulose is separated, carrying out centrifugal washing for three times with ethyl alcohol to remove unreacted amine, and finally carrying out a dialysis membrane treatment to the suspension to obtain the hydrophobic modified nano cellulose which is then saved for later use, wherein the mass ratio of the esterification modified nano cellulose to 1-tridecylamine in the 1-tridecylamine solution and to n-decylamine in the n-decylamine solution is 1:0.2:0.2.
[0067] (5) Preparing the hydrophobic modified nano cellulose obtained in the step (4) into a sizing solution with the concentration of 2%, coating the sizing solution on the surface of the painting and calligraphy paper by using a surface sizing machine, putting the surface sizing solution into an oven at the temperature of 80 °C for drying for 30 minutes to obtain the painting and calligraphy paper coated with the nano cellulose, wherein the quota is 50g/m <2 > and the mass ratio of the absolute dry fiber of the painting and calligraphy paper to the absolute dry hydrophobic modified nano cellulose is 1:0.02.
[0068] Embodiment 3
[0069] The preparation method of the hydrophobic enhanced painting and calligraphy paper according to the embodiment comprises the following steps:
[0070] (1) Preparation of Oxidized Cellulose
The step comprises: preparing 400 mL of a buffer solution with the pH value of 9 by using 0.1 mol/L of sodium carbonate solution and 0.1 mol/L of sodium bicarbonate solution according to the volume ratio of 1:1, and taking 300 mL of the buffer solution in a three-necked flask of 500 mL; weighing 5 g of absolute dry hardwood pulp, crushing the slurry by using a crusher, adding the slurry into the flask, and fully stirring by using a magnetic stirrer; weighing 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide successively and adding the 2, 2, 6, 6 tetramethylpiperidine oxide and sodium bromide into the flask, weighing a 30% sodium hypochlorite solution of 60 ml and putting the solution into the flask after full dissolution, starting a reaction after mixing at a room temperature, and during the reaction, the pH of the reaction liquid is adjusted by the 0.1 mol/L sodium hydroxide solution to about 9, wherein the total reaction time is h; and carrying out suction filtration and washing of the reaction mixture liquid with ionized water after the reaction, obtaining oxidized cellulose, and finally transferring the oxidized cellulose into a clean flask for storage, wherein the mass ratio of the absolute dry hardwood pulp to the 2, 2, 6, 6-tetramethylpiperidine oxide, to the sodium bromide and to the sodium hypochlorite is 1:0.02:0.2:10.[0072] (2) Preparation of Nano Cellulose Suspension
[0073] The oxidized cellulose obtained in the step (1) was prepared into a suspension with the concentration of 1%, and the suspension was circulated 15 times using a high-pressure homogenizer for 30 s each treatment, wherein the pressure was set at 800 bar, so as to obtain a nano cellulose suspension.
[0074] (3) Preparation of Esterification Modified Nano Cellulose
[0075] First, 100 g of the aqueous suspension of nano cellulose with the concentration of 2% obtained in the step (2) was subjected to rotary evaporation, so that the suspension became gel; then, the obtained gel-like nano cellulose was transferred into a beaker, and 100 ml of N-N dimethylformamide was added thereto for ultrasonic treatment for 30 minutes, then transferred into a round bottom flask, continuously stirred for 6 h at a speed of 600 rpm in a water bath of 80 °C, then, the glutaric anhydride and propionic anhydride with the mass ratio of 1:1, and the nano cellulose, glutaric anhydride and propionic anhydride and 4-dimethylaminopyridine with the ratio of 1:40:0.6 were added into a round-bottom flask for ultrasonic dispersion of 10 min, a condenser pipe was connected, and a water bath of 80 °C was continued, and the mixture was put into a cold water tank for 10 min and then treated with a centrifugal treatment after 8 h of reaction. After that, methanol and acetone with the ratio of 2:1 were added for multiple times of centrifugal washing; and after multiple times of washing of ionized water, the esterification modified nano cellulose was obtained.
[0076] (4) Preparation of Hydrophobic Modified Nano Cellulose
[0077] The step comprises: adding 6 g of1-tridecylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 1-tridecylamine solution with the concentration of 6%; adding 6 g of N-decylamine into 100 g of N-N dimethylformamide (DMF), and stirring the mixture uniformly to obtain a 6% n-decylamine solution; adding the 1 tridecylamine solution and the n-decylamine solution into the esterification modified nano cellulose obtained in the step (3) according to the proportion, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at 80 °C, and performing a centrifugal separation reaction on the n-decylamine solution for 2 h at the speed of 800 rpm; carrying out multiple times of centrifugation and washing after the reaction till the modified nano cellulose is separated, carrying out centrifugal washing for three times with ethyl alcohol to remove unreacted amine, and finally carrying out a dialysis membrane treatment to the suspension to obtain the hydrophobic modified nano cellulose which is then saved for later use, wherein the mass ratio of the esterification modified nano cellulose to 1-tridecylamine in the 1-tridecylamine solution and to n-decylamine in the n-decylamine solution is 1:0.45:0.45.
[0078] (5) Preparing the hydrophobic modified nano cellulose obtained in the step (4) into a sizing solution with the concentration of 6%, coating the sizing solution on the surface of the painting and calligraphy paper by using a surface sizing machine, putting the surface sizing solution into an oven at the temperature of 80 °C for drying for 15 minutes to obtain the painting and calligraphy paper coated with the nano cellulose, wherein the quota is 60g/m 2, and the mass ratio of the absolute dry fiber of the painting and calligraphy paper to the absolute dry hydrophobic modified nano cellulose is 1:0.03.
[0079] Comparative Embodiment 1
[0080] The painting and calligraphy paper of this comparative embodiment is basically the same as that of the Embodiment 1, except that the surface of the painting and calligraphy paper of this comparative embodiment is not coated with the sizing liquid.
[0081] Physical properties (including water absorption, tear index and breaking length) of the painting and calligraphy paper obtained in the above Embodiments 1-3 and the painting and calligraphy paper of Comparative Embodiment 1 were tested separately, the water absorption test of the painting and calligraphy paper was carried out according to GB/T461.1, and the water absorption time was 60 min; the tear index test of the painting and calligraphy paper was carried out according to GB/T455.1-1989, the breaking length of the painting and calligraphy paper was carried out according to GB/T12914, and the specific test results are shown in Table 1.
[0082] Table 1 Comparison Table of Physical Property Test Results of Painting and Calligraphy Paper of Embodiments 1-3 and Comparative Embodiment 1
[0083]
Water absorption Tear index Breaking length (longitudinal and (longitudinal and (longitudinal and transverse average) transverse average) transverse average)
Embodiment 1 50mm/60min 7.7mN • m2/g 2.3km
Embodiment 2 52mm/60min 7.8mN • m2 /g 2.6km
Embodiment 3 51mm/60min 8.1mN m2/g 2.7km
Comparative 62mm/60min 6.4mN • m2/g 1.1km Embodiment 1
Claims (10)
1. Hydrophobic enhanced painting and calligraphy paper, wherein the hydrophobic enhanced painting and calligraphy paper comprises painting and calligraphy paper and a hydrophobic modified nano cellulose coating formed on the surface of the painting and calligraphy paper.
2. The hydrophobic enhanced painting and calligraphy paper according to claim 1, wherein the 2 quota of the hydrophobic enhanced painting and calligraphy paper is 40-60g/m
3. The hydrophobic enhanced painting and calligraphy paper according to claim 1, wherein the hydrophobic modified nano cellulose is prepared by the following method, and the method comprises the following steps:
(1) Crushing and evenly stirring, then oxidizing and pretreating the fiber pulp using a TEMPO/NaCO/NaBr system, and carrying out suction filtration and washing to obtain oxidized cellulose;
(2) Preparing the oxidized cellulose obtained in the step (1) into a suspension with the concentration of 1-2%, and then carrying out high-pressure homogenization treatment to obtain a nano cellulose suspension;
(3) Performing rotary evaporation on the nano cellulose suspension obtained in the step (2) to obtain gel-shaped nano cellulose; adding N-N-dimethyl formamide into the gel-shaped nano cellulose according to a proportion, performing ultrasonic dispersion and uniformization, heating the mixture to 80-90 °C and stirring the mixture for 4-6 hours at a constant temperature; keeping adding glutaric anhydride, propionic anhydride and 4-dimethylaminopyridine according to a proportion after the stirring, performing ultrasonic dispersion and uniformization to obtain a reaction solution 1; and heating the reaction solution 1 to 80-120 °C and reacting for 4-8 hours at a constant temperature, cooling the mixture after the reaction, and centrifuging and washing the product to obtain esterification modified nano cellulose; and
(4) respectively adding a 1-tridecylamine solution and an n-decylamine solution into the esterification modified nano cellulose obtained in the step (3) according to a proportion, uniformly mixing the mixture to obtain a reaction solution 2, adjusting the pH value of the reaction solution 2 to be neutral, stirring the mixture at a constant temperature of between 40-80 °C for a reaction of 2 6 hours; and centrifuging and washing the product after the reaction, and finally carrying out a dialysis separation treatment to obtain the hydrophobic modified nano cellulose.
4. The hydrophobic enhanced painting and calligraphy paper according to claim 3, wherein the fiber pulp in step (1) is any one of wood pulp, cotton pulp, hemp pulp, bamboo pulp and reed pulp.
5. The hydrophobic enhanced painting and calligraphy paper according to claim 3, wherein the mass ratio of dry fiber to 2, 2, 6, 6-tetramethylpiperidine oxide, to sodium bromide and to sodium hypochlorite in the fiber slurry in step (1) is 1:0.01-0.02:0.05-0.2:6-10.
6. The hydrophobic enhanced painting and calligraphy paper according to claim 3, wherein the dosage ratio of the absolute dry nano cellulose to the N-N-dimethylformamide in the nano cellulose aqueous suspension in the step (3) is 1-2 parts by mass: 60-100 parts by volume, and g: ml is used as a reference between the parts by mass and the parts by volume.
7. The hydrophobic enhanced painting and calligraphy paper according to claim 3, wherein the mass ratio of the absolute dry nano cellulose to glutaric anhydride, to propionic anhydride and to 4 dimethylaminopyridine in the aqueous suspension of the nano cellulose in step (3) is 1:20:20:0.6.
8. The hydrophobic enhanced painting and calligraphy paper according to claim 3, wherein the mass ratio of the esterification modified nano cellulose to the 1-tridecylamine in the 1-tridecylamine solution, to the n-decylamine in the n-decylamine solution in the step (4) is 1:0.1-0.45:0.1-0.45.
9. A preparation method of the hydrophobic enhanced painting and calligraphy paper according to any one of claims 1-8, wherein the method comprises: preparing the hydrophobic modified nano cellulose into a sizing solution with the concentration of 2-8%, coating the sizing solution on the surface of the painting and calligraphy paper, and drying the painting and calligraphy paper in an oven.
10. The preparation method of the hydrophobic enhanced painting and calligraphy paper according to claim 9, wherein the mass ratio of the absolute dry fiber of the painting and calligraphy paper to the absolute dry hydrophobic modified nano cellulose is 1:0.01-0.03.
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| CN115110340A (en) * | 2022-04-24 | 2022-09-27 | 郑州大学 | Multifunctional protective liquid for paper |
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2020
- 2020-10-16 AU AU2020102808A patent/AU2020102808A4/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114687237A (en) * | 2020-12-28 | 2022-07-01 | 广东三和化工科技有限公司 | Environment-friendly type document file protection aerosol paint and preparation method thereof |
| CN115110340A (en) * | 2022-04-24 | 2022-09-27 | 郑州大学 | Multifunctional protective liquid for paper |
| CN115467156A (en) * | 2022-09-28 | 2022-12-13 | 郑州大学 | Test tube brush-shaped plant fiber and preparation method and application thereof |
| CN116556107A (en) * | 2023-03-29 | 2023-08-08 | 郑州大学 | Protective liquid for protecting paper cultural relics |
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