CN110835377A - Novel hydrophobically modified nano-cellulose and preparation method and application thereof - Google Patents
Novel hydrophobically modified nano-cellulose and preparation method and application thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 71
- 239000001913 cellulose Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010422 painting Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 29
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims abstract description 28
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims abstract description 13
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000265 homogenisation Methods 0.000 claims abstract description 9
- 229920001046 Nanocellulose Polymers 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 35
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 16
- 229940107304 oxidized cellulose Drugs 0.000 claims description 16
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 16
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007900 aqueous suspension Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 235000014676 Phragmites communis Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 29
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000012466 permeate Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 61
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000004513 sizing Methods 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
- 239000011121 hardwood Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
-
- 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
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses novel hydrophobically modified nano-cellulose and a preparation method and application thereof, belonging to the technical field of functional coatings. Firstly, 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; hydrophobic modification of the nano-cellulose is carried out by adopting a two-step method, and glutaric anhydride and propionic anhydride are used as composite anhydride as reagents for esterifying and modifying the nano-cellulose in the first step; and in the second step, 1-tridecylamine and n-decylamine are reacted with the esterified nano-cellulose through electrostatic adsorption to form a complex, namely the novel hydrophobic modified nano-cellulose. The modified nano-cellulose prepared by the method is coated on the surface of the writing and painting paper, so that the strength performance of the writing and painting paper can be obviously improved, and the nano-cellulose is small in size, so that the nano-cellulose is more easily deposited on the surface of the paper or permeates pores, the water vapor barrier property and the hydrophobicity of the paper can be enhanced, and the storage time can be prolonged.
Description
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to novel hydrophobically modified nano-cellulose and a preparation method and application thereof.
Background
As is well known, in domestic artistic creation, particularly in painting and calligraphy artistic creation, artists or artistic enthusiasts pursue expressive force in individuality and microcosmic aspects, so that the water absorption and color ink reducibility of domestic artistic paper are different, and the difference requirement of products is very large. Therefore, the differential water absorbability and the ink absorbability of the painting and calligraphy paper become one of the key links of the production of the artistic paper. The painting and calligraphy paper has low strength, is easy to damage, has large moisture absorption and is easy to mildew, and the painting and calligraphy paper also has special attention in production.
The painting and calligraphy paper in the prior art mainly has the following technical problems:
1. reinforcing problem of painting and calligraphy paper
The fiber raw materials used by the painting and calligraphy paper are complex, the painting and calligraphy paper is generally made of bark fibers, bamboo fibers and grass fibers, the tension of the fibers is not strong enough, so the fastness is poor, and the painting and calligraphy paper is easy to break in the process of painting and calligraphy, storage or display, and serious loss is caused.
2. Water absorption and ink absorption of painting and calligraphy paper
The existing painting and calligraphy paper has relatively single water absorption and ink absorption. The water absorption and the ink absorption are generally controlled by an internal sizing mode, the method is often poor in uniformity and can cause the expressive force of the writing and painting paper to be poor, artists or artistic enthusiasts pursue the expressive force in individuality and microcosmic aspects, the water absorption and the ink absorption of domestic artistic paper are required to be different, and the difference requirement of products is very large; accurate differentiation adjustment is difficult to achieve through the gluing mode.
3. Moisture-proof and mould-proof problem of painting and calligraphy paper
The writing and drawing paper is used as art paper and often records valuable artistic contents, but as a material mainly made of plant fibers, the writing and drawing paper has high moisture absorption and is easy to mildew, and particularly, the writing and drawing paper is relatively moist in the south, which can cause mildew and loss of art works.
Disclosure of Invention
In view of the problems or defects of the prior art, the present invention aims to provide a novel hydrophobically modified nanocellulose, and a preparation method and applications thereof. The invention mainly utilizes the combination of esterification modification and amide reaction to carry out hydrophobic modification on the nano-cellulose and carry out surface sizing on the writing and painting paper, thereby solving the technical problems of the prior writing and painting paper.
In order to achieve the above objects of the present invention, the present invention designs a novel method for preparing hydrophobically modified nanocellulose: firstly, 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; hydrophobic modification of the nano-cellulose is carried out by adopting a two-step method, and glutaric anhydride and propionic anhydride are used as composite anhydride as reagents for esterifying and modifying the nano-cellulose in the first step; and in the second step, 1-tridecylamine and n-decylamine are reacted with the esterified nano-cellulose through electrostatic adsorption to form a complex, namely the novel hydrophobic modified nano-cellulose.
The technical scheme adopted by the invention is as follows:
a preparation method of novel hydrophobically modified nanocellulose specifically comprises the following steps:
(1) crushing and uniformly stirring fiber slurry, then carrying out oxidation pretreatment on the fiber slurry by adopting a TEMPO (2,2,6, 6-tetramethylpiperidine oxide)/NaClO/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) rotationally evaporating the nano-cellulose suspension obtained in the step (2) to obtain gel-like nano-cellulose; then adding N-N-dimethylformamide into the gel-like nano-cellulose according to the proportion, uniformly dispersing by ultrasonic, heating to 80-90 ℃, and stirring at constant temperature for 4-6 h; after stirring, continuously adding glutaric anhydride, propionic anhydride and 4-dimethylamino pyridine according to the proportion, and obtaining reaction liquid 1 after ultrasonic dispersion is uniform; heating the reaction solution 1 to 80-120 ℃ for constant-temperature reaction for 4-8h, cooling after the reaction is finished, centrifuging and washing a product to obtain esterified modified nano-cellulose;
(4) respectively adding a 1-tridecylamine solution and an n-decylamine solution into the esterified and modified nanocellulose obtained in the step (3) according to the ratio, uniformly mixing to obtain a reaction solution 2, adjusting the pH value of the reaction solution 2 to be neutral, and stirring at constant temperature of 40-80 ℃ for reaction for 2-6 hours; after the reaction is finished, centrifuging and washing the product, and finally carrying out dialysis separation treatment to obtain the novel hydrophobic modified nano-cellulose.
Further, according to the above technical scheme, the fiber pulp in the step (1) may be any one of wood pulp, cotton pulp, hemp pulp, bamboo pulp, reed pulp, and the like.
Preferably, in the above technical solution, the wood pulp is any one of hardwood pulp or softwood pulp.
Further, according to the technical scheme, in the fiber slurry obtained in the step (1), the mass ratio of the oven-dried fiber to the 2,2,6, 6-tetramethylpiperidine oxide to the sodium bromide to the sodium hypochlorite is 1: 0.01-0.02: 0.05-0.2: 6-10.
Further, in the above technical solution, the pressure adopted in the high-pressure homogenization treatment in the step (2) is 800-1000 bar.
Further, in the technical scheme, the high-pressure homogenization treatment in the step (2) is performed for 10-15 times, and the time for each treatment is 30-60 s.
Further, in the above technical solution, the stirring speed in step (3) is 400-800rpm, more preferably 500-600 rpm.
Further, according to the technical scheme, the use amount ratio of the oven-dried nano-cellulose to the N-N-dimethylformamide in the nano-cellulose water suspension in the step (3) is 1-2 parts by mass: 60-100 parts by volume, wherein: the mass portion and the volume portion are as follows: ml is used as a reference.
Further, according to the technical scheme, the mass ratio of the oven-dried nano-cellulose to the glutaric anhydride, the propionic anhydride and the 4-dimethylaminopyridine in the nano-cellulose water suspension in the step (3) is 1: 20: 20: 0.6.
further, in the above technical scheme, the concentration of the 1-tridecylamine solution in the step (4) is 3-6%, and the specific preparation method of the 1-tridecylamine solution is as follows: adding 3-6g of 1-tridecylamine into 100mL of N-N Dimethylformamide (DMF), and uniformly stirring.
Further, in the above technical scheme, the concentration of the n-decylamine solution in the step (4) is 3-6%, and the specific preparation method of the n-decylamine solution is as follows: adding 3-6g of N-decylamine into 100mL of N-N Dimethylformamide (DMF), and uniformly stirring.
Further, in the above technical scheme, the mass ratio of the esterified and modified nanocellulose in the step (4), 1-tridecylamine in the 1-tridecylamine solution, and n-decylamine in the n-decylamine solution is 1: 0.1-0.45: 0.1-0.45.
Further, in the above technical solution, the stirring speed in step (4) is 400-800rpm, and more preferably 600 rpm.
The second purpose of the invention is to provide the novel hydrophobic modified nano-cellulose prepared by the method.
The third purpose of the invention is to provide the application of the novel hydrophobic modified nano-cellulose prepared by the method, which can be used for preparing writing and painting paper.
Compared with the prior art, the novel hydrophobically modified nano-cellulose and the preparation method and the application thereof have the following beneficial effects:
(1) the invention controls the surface sizing of the writing and painting paper by controlling the process formula of the modified nano-cellulose, such as concentration, dosage, surface sizing speed and the like, thereby controlling different water absorbability and ink absorbability and further realizing differential adjustment.
(2) The nanocellulose modified by the two-step method is coated on the writing and painting paper in a surface sizing mode, and the nanocellulose is small in size, so that the nanocellulose is more easily deposited on the surface of the paper or permeates pores, the water vapor barrier property and the hydrophobicity of the paper can be enhanced, and therefore the nanocellulose is less prone to absorb moisture and mildew when the environmental humidity is high, and the storage time of the nanocellulose is prolonged.
(3) The modified nano-cellulose prepared by the method is coated on the surface of the writing and painting paper, so that the strength performance of the writing and painting paper can be obviously improved, and meanwhile, the chemical components of the adopted modified nano-cellulose are the same as those of the plant fibers of the writing and painting paper, so that the writing of the writing and painting paper is not adversely affected.
(4) The nano-cellulose adopted in the invention is derived from plant fiber raw materials, and has the advantages of environmental protection, degradability and the like.
Drawings
Fig. 1 is a flow chart of a preparation process of the novel hydrophobically modified nanocellulose of the present invention.
FIG. 2 is a process flow diagram for preparing writing and painting paper by using the novel hydrophobically modified nanocellulose.
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.
Two key properties of the writing and drawing papers developed in this invention are water resistance and physical strength properties (tear index, length at break, etc.). The higher the concentration of the modified nanocellulose is, the better the hydrophobicity of the paper is, the water absorption is deteriorated, while the addition of the modified nanocellulose slightly improves the physical strength property, but also needs to consider the influence of the cost and the physical strength of the paper, so that it is necessary to select an appropriate concentration for surface sizing. The method firstly uses 2,2,6, 6-tetramethyl piperidine oxide (TEMPO) to oxidize and pretreat the cellulose, and then carries out high-pressure homogenization, the dispersion performance of the prepared nano cellulose in water is greatly improved, and the generated carboxyl has negative charges and has charge repulsion, thereby improving the dispersion performance.
According to the invention, glutaric anhydride and propionic anhydride are used as the composite anhydride as the reagent of the esterification modified nano-cellulose to carry out esterification reaction with the prepared nano-cellulose, so that the hydrophobicity is obviously improved.
The 1-tridecylamine and the n-decylamine of the invention react with the esterified nano-cellulose through electrostatic adsorption to form a complex, so that the hydrophobicity is further improved.
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 novel hydrophobically modified nanocellulose and the preparation method thereof provided by the embodiment of the invention comprise the following specific steps:
(1) preparation of oxidized cellulose
Mixing 0.1mol/L sodium carbonate solution and 0.1mol/L sodium bicarbonate solution according to the volume ratio of 3: 2 preparing 400mL of buffer solution with the pH value of 10, and putting 300mL into a 500mL three-neck flask; weighing 5g of oven-dried hardwood pulp, crushing the pulp by using a crusher, adding the crushed pulp into the flask, and fully stirring by using a magnetic stirrer; weighing 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide in sequence, adding the 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide into the flask, measuring 35ml of 30% sodium hypochlorite solution after the sodium hypochlorite solution is fully dissolved, adding the sodium hypochlorite solution into the flask, uniformly mixing, starting reaction at room temperature, and adjusting the pH of a reaction solution to about 10 by using 0.1mol/L sodium hydroxide solution during the reaction; the total reaction time is 18 hours; after the reaction is finished, carrying out suction filtration and washing on the reaction mixed solution by using deionized water to obtain oxidized cellulose, and finally transferring the oxidized cellulose into a clean beaker for storage; wherein: the mass ratio of the oven-dried hardwood pulp to the 2,2,6, 6-tetramethyl piperidine oxide to the sodium bromide to the sodium hypochlorite is 1: 0.01: 0.05: 6.
(2) preparation of a Nanocellulose suspension
Preparing the oxidized cellulose obtained in the step (1) into a suspension with the concentration of 1%, and circulating for 10 times by using a high-pressure homogenizer, wherein the treatment time is 60s each time, and the pressure is set to be 1000bar, so as to obtain the nano-cellulose suspension.
(3) Preparation of esterification modified nanocellulose
Firstly, 150g of 1% nanocellulose aqueous suspension obtained in step (2) is taken for rotary evaporation, so that the suspension becomes gel-like; the gel-like nanocellulose obtained was then transferred to a beaker and 80ml of N-dimethylformamide was added, sonicated for 30 minutes, then transferred to a round bottom flask, stirred continuously at 600rpm for 5h in a water bath at 85 ℃, then mixed with glutaric anhydride: the mass ratio of the propionic anhydride is 1: 1, nanocellulose: glutaric anhydride, propionic anhydride: the weight ratio of 4-dimethylaminopyridine is 1: 40: 0.6 adding into a round-bottom flask, carrying out ultrasonic dispersion for 10min, connecting a condenser pipe, heating the water bath to 100 ℃, standing in a cold water pool for 10min after 6-hour reaction, and centrifuging. Subsequently, a quantity of methanol was added: acetone ═ 2: and 1, carrying out centrifugal washing for many times, and then washing for many times by using deionized water to obtain the esterified modified nano-cellulose.
(4) Preparation of novel hydrophobically modified nanocellulose
Adding 4g of 1-tridecylamine into 100g N-N Dimethylformamide (DMF), and uniformly stirring to obtain a 4% 1-tridecylamine solution; 4g of N-decylamine was added to 100g N-N Dimethylformamide (DMF), and the mixture was stirred well to obtain a 4% N-decylamine solution. Then adding the 1-tridecylamine solution and the n-decylamine solution into the esterification modified nano-cellulose obtained in the step (3) according to the ratio, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at 60 ℃, and stirring and reacting for 4 hours at the speed of 600 rpm; after the reaction is finished, performing centrifugal washing for many times until the modified nanocellulose is separated, performing centrifugal washing for three times by using ethanol to remove unreacted amine, and finally performing dialysis membrane treatment on the suspension to obtain the novel hydrophobic modified nanocellulose, wherein: the mass ratio of the esterified modified nano-cellulose to the 1-tridecylamine in the 1-tridecylamine solution and the n-decylamine in the n-decylamine solution is 1: 0.1: 0.1.
example 2
The novel hydrophobically modified nanocellulose and the preparation method thereof provided by the embodiment of the invention comprise the following specific steps:
(1) preparation of oxidized cellulose
Mixing 0.1mol/L sodium carbonate solution and 0.1mol/L sodium bicarbonate solution according to the volume ratio of 1: 0.5, preparing 400mL of buffer solution with pH value of 9.5, and putting 300mL into a 500mL three-neck flask; weighing 5g of oven-dried hardwood pulp, crushing the pulp by using a crusher, adding the crushed pulp into the flask, and fully stirring by using a magnetic stirrer; weighing 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide in sequence, adding the 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide into the flask, measuring 50ml of 30% sodium hypochlorite solution after the sodium hypochlorite solution is fully dissolved, adding the sodium hypochlorite solution into the flask, uniformly mixing, starting reaction at room temperature, and adjusting the pH of a reaction solution to about 9.5 by using 0.1mol/L sodium hydroxide solution during the reaction; the total reaction time is 15 hours; after the reaction is finished, carrying out suction filtration and washing on the reaction mixed solution by using deionized water to obtain oxidized cellulose, and finally transferring the oxidized cellulose into a clean beaker for storage; wherein: the mass ratio of the oven-dried hardwood pulp to the 2,2,6, 6-tetramethyl piperidine oxide to the sodium bromide to the sodium hypochlorite is 1: 0.015: 0.1: 8.
(2) preparation of a Nanocellulose suspension
Preparing the oxidized cellulose obtained in the step (1) into a suspension with the concentration of 1.5%, and circulating for 12 times by using a high-pressure homogenizer, wherein the treatment time is 40s each time, and the pressure is set at 900bar to obtain the nano-cellulose suspension.
(3) Preparation of esterification modified nanocellulose
Firstly, taking 100g of nano-cellulose water suspension with the concentration of 1.5 percent obtained in the step (2) for rotary evaporation, so that the suspension becomes gel; the gel-like nanocellulose obtained was then transferred to a beaker and 60ml of N-dimethylformamide was added, sonicated for 30 minutes, then transferred to a round bottom flask, stirred continuously at 500rpm for 4h in a water bath at 90 ℃, then mixed with glutaric anhydride: the mass ratio of the propionic anhydride is 1: 1, nanocellulose: glutaric anhydride, propionic anhydride: the weight ratio of 4-dimethylaminopyridine is 1: 40: 0.6 adding into a round-bottom flask, carrying out ultrasonic dispersion for 15min, connecting a condenser pipe, heating the water bath to 120 ℃, standing in a cold water pool for 20 min after reaction for 4 hours, and then carrying out centrifugal treatment. Subsequently, a quantity of methanol was added: acetone ═ 2: and 1, carrying out centrifugal washing for many times, and then washing for many times by using deionized water to obtain the esterified modified nano-cellulose.
(4) Preparation of novel hydrophobically modified nanocellulose
Adding 3g of 1-tridecylamine into 100g N-N Dimethylformamide (DMF), and uniformly stirring to obtain a 3% 1-tridecylamine solution; 3g of N-decylamine was added to 100g N-N Dimethylformamide (DMF), and the mixture was stirred well to obtain a 3% N-decylamine solution. Then adding the 1-tridecylamine solution and the n-decylamine solution into the esterification modified nano-cellulose obtained in the step (3) according to the ratio, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at 40 ℃, and stirring and reacting for 6 hours at the speed of 400 rpm; after the reaction is finished, performing centrifugal washing for many times until the modified nanocellulose is separated, performing centrifugal washing for three times by using ethanol to remove unreacted amine, and finally performing dialysis membrane treatment on the suspension to obtain the novel hydrophobic modified nanocellulose, wherein: the mass ratio of the esterified modified nano-cellulose to the 1-tridecylamine in the 1-tridecylamine solution and the n-decylamine in the n-decylamine solution is 1: 0.2: 0.2.
example 3
The novel hydrophobically modified nanocellulose and the preparation method thereof provided by the embodiment of the invention comprise the following specific steps:
(1) preparation of oxidized cellulose
Mixing 0.1mol/L sodium carbonate solution and 0.1mol/L sodium bicarbonate solution according to the volume ratio of 1: 1, preparing 400mL of buffer solution with pH being 9, and putting 300mL into a 500mL three-neck flask; weighing 5g of oven-dried hardwood pulp, crushing the pulp by using a crusher, adding the crushed pulp into the flask, and fully stirring by using a magnetic stirrer; weighing 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide in sequence, adding the 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide into the flask, measuring 60ml of 30% sodium hypochlorite solution after the sodium hypochlorite solution is fully dissolved, adding the sodium hypochlorite solution into the flask, uniformly mixing, starting reaction at room temperature, and adjusting the pH of a reaction solution to about 9 by using 0.1mol/L sodium hydroxide solution during the reaction; the total reaction time is 20 hours; after the reaction is finished, carrying out suction filtration and washing on the reaction mixed solution by using deionized water to obtain oxidized cellulose, and finally transferring the oxidized cellulose into a clean beaker for storage; wherein: the mass ratio of the oven-dried hardwood pulp to the 2,2,6, 6-tetramethyl piperidine oxide to the sodium bromide to the sodium hypochlorite is 1: 0.02: 0.2: 10.
(2) preparation of a Nanocellulose suspension
Preparing the oxidized cellulose obtained in the step (1) into a suspension with the concentration of 1%, circulating for 15 times by using a high-pressure homogenizer, wherein the treatment time is 30s each time, and the pressure is set to be 800bar to obtain the nano-cellulose suspension.
(3) Preparation of esterification modified nanocellulose
Firstly, taking 100g of the 2% concentration nanocellulose water suspension obtained in the step (2), and carrying out rotary evaporation to enable the suspension to become gel; the gel-like nanocellulose obtained was then transferred to a beaker and 100ml of N-dimethylformamide was added, sonicated for 30 minutes, then transferred to a round bottom flask, stirred continuously at 600rpm for 6h in a water bath at 80 ℃, then mixed with glutaric anhydride: the mass ratio of the propionic anhydride is 1: 1, nanocellulose: glutaric anhydride, propionic anhydride: the weight ratio of 4-dimethylaminopyridine is 1: 40: 0.6 adding into a round-bottom flask, carrying out ultrasonic dispersion for 10min, switching on a condenser pipe, continuing to react at 80 ℃ in a water bath for 8 hours, standing in a cold water pool for 10 minutes, and then carrying out centrifugal treatment. Subsequently, a quantity of methanol was added: acetone ═ 2: and 1, carrying out centrifugal washing for many times, and then washing for many times by using deionized water to obtain the esterified modified nano-cellulose.
(4) Preparation of novel hydrophobically modified nanocellulose
Adding 6g of 1-tridecylamine into 100g N-N Dimethylformamide (DMF), and uniformly stirring to obtain a 6% 1-tridecylamine solution; 6g of N-decylamine was added to 100g N-N Dimethylformamide (DMF), and the mixture was stirred well to obtain a 6% N-decylamine solution. Then adding the 1-tridecylamine solution and the n-decylamine solution into the esterification modified nano-cellulose obtained in the step (3) according to the ratio, adjusting the pH to be neutral by using sodium hydroxide and hydrochloric acid, placing the solution in an oil bath at the temperature of 80 ℃, and stirring and reacting for 2 hours at the speed of 800 rpm; after the reaction is finished, performing centrifugal washing for many times until the modified nanocellulose is separated, performing centrifugal washing for three times by using ethanol to remove unreacted amine, and finally performing dialysis membrane treatment on the suspension to obtain the novel hydrophobic modified nanocellulose, wherein: the mass ratio of the esterified modified nano-cellulose to the 1-tridecylamine in the 1-tridecylamine solution and the n-decylamine in the n-decylamine solution is 1: 0.45: 0.45.
the novel hydrophobic modified nanocellulose prepared by the embodiments of the invention can be used for preparing writing and painting paper, and specifically, the hydrophobic modified nanocellulose is prepared into a sizing agent with the concentration of 2-8%, the sizing agent is used for coating the sizing agent on the surface of the writing and painting paper, then the writing and painting paper coated with the nanocellulose is obtained by drying the surface sizing agent in an oven, and the obtained writing and painting paper has the ration of 40-60g/m2Wherein: the mass ratio of the absolutely dry fibers of the painting and calligraphy paper to the absolutely dry hydrophobically modified nanocellulose is 1: 0.01-0.03.
The application of the novel hydrophobically modified nanocellulose of the present invention is described in detail by the following specific examples.
Application example 1
The novel hydrophobically modified nanocellulose prepared in example 1 is used for preparing writing and painting paper, and the specific method is as follows:
the novel hydrophobically modified nano-cellulose obtained in example 1 is prepared into a sizing agent with the concentration of 3%, coated on the surface of the writing and painting paper by a surface sizing machine, and then dried in an oven with the temperature of 90 ℃ for 20 minutes to obtain the nano-cellulose coated writing and painting paper with the quantitative of 40g/m2Wherein: the mass ratio of the absolutely dry fibers of the painting and calligraphy paper to the absolutely dry novel hydrophobic modified nanocellulose is 1: 0.01.
application example 2
The novel hydrophobically modified nanocellulose prepared in example 2 is used for preparing writing and painting paper, and the specific method is as follows:
preparing the novel hydrophobic modified nano-cellulose obtained in the example 2 into a sizing solution with the concentration of 2%, coating the sizing solution on the surface of the writing and painting paper by using a surface sizing machine, and then drying the writing and painting paper in an oven at 80 ℃ for 30 minutes to obtain the nano-cellulose coated writing and painting paper, wherein the quantitative amount of the nano-cellulose coated writing and painting paper is 50g/m2Wherein: the mass ratio of the absolutely dry fibers of the painting and calligraphy paper to the absolutely dry novel hydrophobic modified nanocellulose is 1: 0.02.
application example 3
The novel hydrophobically modified nanocellulose prepared in example 3 is used for preparing writing and painting paper, and the specific method is as follows:
the novel hydrophobically modified nanocellulose obtained in example 3 was formulated into a sizing solution with a concentration of 6%, coated on the surface of the writing and painting paper with a surface size press, and then dried in an oven at 80 ℃ for 15 minutes to obtain nanocellulose coated writing and painting paper with a basis weight of 60g/m2Wherein: the mass ratio of the absolutely dry fibers of the painting and calligraphy paper to the absolutely dry novel hydrophobic modified nanocellulose is 1: 0.03.
comparative example 1
The writing and drawing paper of this comparative example is substantially the same as that of application example 1 except that: the present comparative example did not apply the sizing solution to the surface of the writing and drawing paper.
The physical properties (including water absorption, tear index and fracture length) of the writing and drawing papers obtained in the application examples 1 to 3 and the writing and drawing paper of the comparative example 1 were respectively tested, the water absorption of the writing and drawing papers was tested according to GB/T461.1, and the liquid absorption time was 60 min; the tearing index test of the writing paper is tested according to GB/T455.1-1989, the breaking length of the writing paper is tested according to GB/T12914, and the specific test results are shown in Table 1.
TABLE 1 comparison of the results of the physical Properties test of the writing and drawing papers of application examples 1 to 3 and comparative example 1
Claims (10)
1. A preparation method of novel hydrophobic modified nano-cellulose is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) crushing and uniformly stirring fiber slurry, then carrying out oxidation pretreatment on the fiber slurry by adopting a TEMPO/NaClO/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) rotationally evaporating the nano-cellulose suspension obtained in the step (2) to obtain gel-like nano-cellulose; then adding N-N-dimethylformamide into the gel-like nano-cellulose according to the proportion, uniformly dispersing by ultrasonic, heating to 80-90 ℃, and stirring at constant temperature for 4-6 h; after stirring, continuously adding glutaric anhydride, propionic anhydride and 4-dimethylamino pyridine according to the proportion, and obtaining reaction liquid 1 after ultrasonic dispersion is uniform; heating the reaction solution 1 to 80-120 ℃ for constant-temperature reaction for 4-8h, cooling after the reaction is finished, centrifuging and washing a product to obtain esterified modified nano-cellulose;
(4) respectively adding a 1-tridecylamine solution and an n-decylamine solution into the esterified and modified nanocellulose obtained in the step (3) according to the ratio, uniformly mixing to obtain a reaction solution 2, adjusting the pH value of the reaction solution 2 to be neutral, and stirring at constant temperature of 40-80 ℃ for reaction for 2-6 hours; and after the reaction is finished, centrifuging and washing the product, and finally carrying out dialysis separation treatment to obtain the novel hydrophobic modified nano-cellulose.
2. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the fiber pulp in the step (1) is any one of wood pulp, cotton pulp, hemp pulp, bamboo pulp and reed pulp.
3. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: in the fiber slurry obtained in the step (1), the mass ratio of oven-dried fibers, 2,6, 6-tetramethylpiperidine oxide, sodium bromide and sodium hypochlorite is 1: 0.01-0.02: 0.05-0.2: 6-10.
4. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the number of times of the high-pressure homogenization treatment in the step (2) is 10-15, and the pressure adopted by the high-pressure homogenization treatment is 800-1000 bar.
5. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the dosage ratio of the oven-dried nano-cellulose to the N-N-dimethylformamide in the nano-cellulose water suspension in the step (3) is 1-2 parts by mass: 60-100 parts by volume, wherein: the mass portion and the volume portion are as follows: ml is used as a reference.
6. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the mass ratio of the oven-dried nano-cellulose to the glutaric anhydride, the propionic anhydride and the 4-dimethylamino pyridine in the nano-cellulose water suspension in the step (3) is 1: 20: 20: 0.6.
7. the method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the concentration of the 1-tridecylamine solution and the concentration of the n-decylamine solution in the step (4) are both 3-6%.
8. The method for preparing the novel hydrophobically modified nanocellulose according to claim 1, characterized in that: the mass ratio of the esterified and modified nano-cellulose to the 1-tridecylamine in the 1-tridecylamine solution to the n-decylamine in the n-decylamine solution is 1: 0.1-0.45: 0.1-0.45.
9. The novel hydrophobically modified nanocellulose prepared by the method of preparing the novel hydrophobically modified nanocellulose as claimed in any one of claims 1 to 8.
10. Use of the novel hydrophobically modified nanocellulose prepared by the process of any of claims 1 to 8, wherein: can be used for preparing writing and painting paper.
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