CN116411474B - Method for preparing nanocellulose by taking papermaking fine grinding pulp as raw material - Google Patents
Method for preparing nanocellulose by taking papermaking fine grinding pulp as raw material Download PDFInfo
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- CN116411474B CN116411474B CN202310369608.0A CN202310369608A CN116411474B CN 116411474 B CN116411474 B CN 116411474B CN 202310369608 A CN202310369608 A CN 202310369608A CN 116411474 B CN116411474 B CN 116411474B
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- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002994 raw material Substances 0.000 title claims abstract description 10
- 238000000227 grinding Methods 0.000 title claims description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 28
- 239000001913 cellulose Substances 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 11
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000004220 aggregation Methods 0.000 claims abstract 3
- 230000002776 aggregation Effects 0.000 claims abstract 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- FZTPAOAMKBXNSH-UHFFFAOYSA-N 3-trimethoxysilylpropyl acetate Chemical compound CO[Si](OC)(OC)CCCOC(C)=O FZTPAOAMKBXNSH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000002444 silanisation Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000005611 electricity Effects 0.000 abstract 2
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/007—Modification of pulp properties by mechanical or physical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for preparing nanocellulose by taking papermaking fine pulp as a raw material, and relates to the technical field of nanocellulose preparation; the specific method comprises the following steps: firstly, under the high-temperature hydrothermal condition of 120-200 ℃, carrying out hydrolytic polymerization on organosiloxane and refined pulp, and connecting an organosilicon branch on the refined pulp cellulose to facilitate the dispersion of the cellulose; secondly, when the temperature is reduced to 40-80 ℃, adding a certain amount of sodium hypochlorite or persulfate into the dispersion liquid for oxidation reaction to destroy the aggregation structure of cellulose, so that a small amount of hydroxyl groups on cellulose chains are converted into carboxylate with negative electricity, the dispersion of aggregated cellulose is further accelerated due to the negative electricity repulsive interaction, the aggregation of cellulose chains is avoided, and the nano cellulose suspension liquid with good dispersibility and high stability can be obtained; finally, the suspension is filtered and washed to obtain the nanocellulose with the solid content of about 10-20%.
Description
Technical Field
The invention relates to the technical field of preparation of nanocellulose, in particular to a method for preparing nanocellulose by taking papermaking fine grinding pulp as a raw material.
Background
The nano cellulose is a cellulose material with one-dimensional size of 1-100 nm, has the advantages of hydrophilicity, biodegradability, biocompatibility, good mechanical property and the like, and has wide application prospect in degradable composite materials. Nanocellulose is gradually paid attention to by scientific and industrial industries due to the unique advantages of high mechanical strength, high length-diameter ratio, low thermal expansion coefficient, degradability, biocompatibility and the like, and can be applied to the fields of nanocomposite reinforced materials, gel materials, packaging materials, biomedical materials, energy storage materials and the like.
Cellulose is one of the most abundant natural high molecular polymers on earth and is commonly found in plant materials such as wood, bamboo, cotton, hemp and the like. Natural cellulose is a widely-existing renewable resource, and is also the most abundant biopolymer on earth, and is a linear polymer formed by polymerizing cyclic glucose molecules, and has a flat ribbon-shaped conformation. The repeating unit is formed by combining two anhydroglucose units through a beta-1, 4-glycosidic bond. During the formation of cellulose, van der Waals forces and intermolecular hydrogen bonding between hydroxyl groups and oxygen in adjacent molecules promote parallel stacking of multiple cellulose chains to form basic fibrils, which further aggregate into larger size microfibrils. Under the combined action of strong crystallization, polymerization and spinning, microfibril bundles are mutually combined to form a natural fiber structure. It exists in a highly ordered aggregated structure due to hydrogen bonding and van der waals forces. Removing amorphous regions and partial crystalline regions of cellulose to disperse the aggregated cellulose, thereby obtaining the nanocellulose.
The nano cellulose chain contains a large number of hydroxyl groups, the active hydroxyl groups are utilized by a chemical modification method, the active hydroxyl groups are grafted and oxidized as reaction sites, so that intermolecular action is weakened, a grafted cellulose derivative is formed, and the nano cellulose is endowed with more functionality through the introduction of specific functional groups, so that the nano cellulose solution with wide application, good dispersibility and high suspension stability is obtained.
Based on the above, the invention provides a method for preparing nanocellulose by taking papermaking fine pulp as a raw material.
Disclosure of Invention
(one) solving the technical problems
The invention aims to provide a method for preparing a nano cellulose solution with good dispersibility and high suspension stability by taking papermaking fine grinding slurry as a raw material.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing nanocellulose with fine pulp of papermaking as raw materials, will regard fine pulp of papermaking from which lignin and hemicellulose have been removed as raw materials, accelerate the separation of crystalline aggregate cellulose under the high-temperature hydrothermal effect at first, react with organic siloxane, graft the silane group on the cellulose chain; then oxidizing by sodium hypochlorite or persulfate to oxidize part of hydroxyl groups on cellulose chains into carboxyl groups, so that the fiber chains are negatively charged, and a nano cellulose solution with good dispersibility and high suspension stability can be prepared; the method specifically comprises the following steps:
s1, weighing a certain amount of paper-making refined pulp and water, and stirring and dispersing the paper-making refined pulp in the water to prepare a suspension with 2-6% of solid content;
s2, weighing a certain amount of organic siloxane, adding the organic siloxane into the fine pulp suspension for papermaking prepared in the step S1, stirring and dispersing uniformly, then adding the mixture into a hydrothermal autoclave, and sealing the hydrothermal autoclave; wherein the suspension volume is 70% of the autoclave volume;
s3, heating the hydrothermal autoclave to 120-200 ℃ to enable the materials to generate high pressure of 0.2-1.6 MPa, separating papermaking fine pulp cellulose molecules under the high-temperature and high-pressure condition, and carrying out hydrolytic polymerization reaction with organosiloxane for 1-3 h;
s4, after the hydrolysis polymerization reaction is finished, cooling the hydrothermal autoclave to 40-80 ℃, pouring the mixed liquid in the hydrothermal autoclave into a three-mouth reaction flask, adding sodium hypochlorite or persulfate in a certain proportion, and stirring for reaction for 1-3 h;
and S5, after the reaction is finished, carrying out suction filtration and washing on the mixed liquid in the three-mouth reaction flask to obtain a nanocellulose product with the solid content of 10-20%.
Preferably, the papermaking refiner pulp in S1 has a solids content of 10 to 20%.
Preferably, the weight ratio of the organosiloxane to the papermaking refiner pulp in S2 is 1: (10-50).
Preferably, the organosiloxane in S2 is one or more of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, 3-acetoxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, phenyltrimethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyl methyldimethoxysilane.
Preferably, the weight ratio of sodium hypochlorite or persulfate to papermaking refiner pulp in S4 is 1: (10-50).
Preferably, the persulfate in S4 is ammonium persulfate, sodium persulfate, or potassium persulfate.
(III) beneficial effects
The invention is beneficial to the dispersion of the cellulose chains aggregated by fine grinding slurry by utilizing the high activity of water in a high-pressure reaction kettle under high temperature and high pressure, and can directly hydrolyze the organosiloxane without acid catalysis, and silanol generated after hydrolysis can be combined with the hydroxyl groups of the cellulose chains. The method is carried out at high temperature, so that the process is efficient, the reaction time is short, the process is simple, acid or alkali is not needed to be used as a catalyst in the process, the reaction is carried out in a closed system, no volatile matters escape, and the whole method is green and environment-friendly. After the cellulose chain is grafted with silane, part of hydroxyl groups are oxidized into carboxyl groups, so that the chain belt is negatively charged, and the nano cellulose solution with good dispersibility and high suspension stability is obtained.
Drawings
Fig. 1 is a flow chart of a method for preparing nanocellulose by using papermaking fine pulp as a raw material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the method for preparing the nanocellulose by using the papermaking fine pulp comprises the following specific steps:
(1) weighing 20g of papermaking fine grinding slurry with the solid content of 20% and 80g of water, and stirring and dispersing the fine grinding slurry in the water to prepare a suspension with the solid content of 4%;
(2) weighing 1g N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, adding into the fine grinding slurry suspension, stirring and dispersing uniformly, adding into a hydrothermal autoclave, and sealing, wherein the volume of the suspension is about 70% of the volume of the autoclave;
(3) heating the hydrothermal autoclave to 180 ℃ and the pressure is about 1MPa, and under the high-temperature and high-pressure condition, the molecular separation of the fine pulp cellulose is facilitated, and the hydrolysis polymerization reaction is carried out with the organosiloxane, wherein the reaction time is 2 hours;
(4) after the reaction is finished, cooling the hydrothermal autoclave to 70 ℃, pouring the mixed liquid into a three-mouth reaction flask, adding 0.5g of sodium hypochlorite, and stirring for reaction for 1h;
(5) and after the reaction is finished, carrying out suction filtration and washing on the mixed liquid to obtain a nanocellulose product with 17% of solid content.
Example 2:
the method for preparing the nanocellulose by using the papermaking fine pulp comprises the following specific steps:
(1) weighing 20g of papermaking fine grinding slurry with the solid content of 20% and 80g of water, and stirring and dispersing the fine grinding slurry in the water to prepare a suspension with the solid content of 4%;
(2) 1g of gamma-aminopropyl triethoxysilane is weighed, added into the fine grinding slurry suspension, stirred and dispersed uniformly, added into a hydrothermal autoclave, the volume of the suspension is about 70 percent of the volume of the autoclave, and sealed;
(3) heating the hydrothermal autoclave to 150 ℃ and the pressure is about 0.5MPa, and under the high-temperature and high-pressure condition, the separation of fine pulp cellulose molecules is facilitated, and the hydrolysis polymerization reaction is carried out with the organosiloxane for 3 hours;
(4) after the reaction is finished, cooling the hydrothermal autoclave to 60 ℃, pouring the mixed liquid into a three-mouth reaction flask, adding 1g of ammonium peroxodisulfate, and stirring for reaction for 1h;
(5) and after the reaction is finished, carrying out suction filtration and washing on the mixed liquid to obtain a nanocellulose product with the solid content of 14%.
Example 3:
the method for preparing the nanocellulose by using the papermaking fine pulp comprises the following specific steps:
(1) weighing 20g of papermaking fine grinding slurry with the solid content of 20% and 80g of water, and stirring and dispersing the fine grinding slurry in the water to prepare a suspension with the solid content of 4%;
(2) 1g of gamma-glycidol ether oxypropyl trimethoxy silane is weighed, added into the fine grinding slurry suspension, stirred and dispersed uniformly, added into a hydrothermal autoclave, the volume of the suspension is about 70 percent of the volume of the autoclave, and sealed;
(3) heating the hydrothermal autoclave to 180 ℃ and the pressure is about 1MPa, and under the high-temperature and high-pressure condition, the molecular separation of the fine pulp cellulose is facilitated, and the hydrolysis polymerization reaction is carried out with the organosiloxane for 3 hours;
(4) after the reaction is finished, cooling the hydrothermal autoclave to 60 ℃, pouring the mixed liquid into a three-mouth reaction flask, adding 1g of sodium peroxodisulfate, and stirring for reaction for 1h;
(5) and after the reaction is finished, carrying out suction filtration and washing on the mixed liquid to obtain a nanocellulose product with the solid content of 14%.
By combining the descriptions of examples 1-3, it is seen that the present invention facilitates the dispersion of fine pulp agglomerated cellulose chains by exploiting the high activity of water under high temperature hydrothermal conditions and without the need for acid catalyzed bonding with organosiloxanes. After the cellulose chain is grafted with silane, part of hydroxyl groups are oxidized into carboxyl groups, so that the chain belt is negatively charged, and the 10-20% solid content nanocellulose is obtained. The nano cellulose is redispersed in water to obtain nano fiber with solid content of about 3 percent, the dispersing process is rapid, the nano cellulose solution obtained by dispersing is stable, and the nano cellulose solution is not precipitated after standing for more than 1 month.
It should be noted that the term "comprises," "comprising," or any other variation thereof is intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The method for preparing the nano cellulose by taking the fine papermaking pulp as the raw material is characterized in that the fine papermaking pulp is subjected to silanization reaction and oxidation reaction to separate cellulose molecules with highly ordered aggregation structure, so as to prepare the nano cellulose material, and the method specifically comprises the following steps:
s1, weighing a certain amount of paper-making refined pulp and water, and stirring and dispersing the paper-making refined pulp in the water to prepare a suspension with 2-6% of solid content;
s2, weighing a certain amount of organic siloxane, adding the organic siloxane into the fine pulp suspension for papermaking prepared in the step S1, stirring and dispersing uniformly, then adding the mixture into a hydrothermal autoclave, and sealing the hydrothermal autoclave; wherein the suspension volume is 70% of the autoclave volume; wherein, the weight ratio of the organic siloxane to the papermaking fine grinding slurry is 1: (10-50);
s3, heating the hydrothermal autoclave to 120-200 ℃ to enable the materials to generate high pressure of 0.2-1.6 MPa, separating papermaking fine pulp cellulose molecules under the high temperature and high pressure condition, and carrying out hydrolytic polymerization reaction with organosiloxane for 1-3 h;
s4, after the hydrolysis polymerization reaction is finished, cooling the hydrothermal autoclave to 40-80 ℃, pouring the mixed liquid in the hydrothermal autoclave into a three-mouth reaction flask, adding sodium hypochlorite or persulfate in a certain proportion, and stirring for reaction 1-3 h; wherein, the weight ratio of the sodium hypochlorite or persulfate to the papermaking fine grinding slurry is 1: (10-50);
and S5, after the reaction is finished, carrying out suction filtration and washing on the mixed liquid in the three-mouth reaction flask to obtain a nanocellulose product with the solid content of 10-20%.
2. The method for preparing nanocellulose as claimed in claim 1 wherein said papermaking fine pulp in S1 has a solids content of 10-20%.
3. The method for preparing nanocellulose as claimed in claim 1 wherein said organosiloxane in S2 is one or more of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -methacryloxypropyl trimethoxysilane, N- (β -aminoethyl) - γ -aminopropyl triethoxysilane, N- (β -aminoethyl) - γ -aminopropyl trimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, 3-acetoxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, phenyltrimethoxysilane, and N- β - (aminoethyl) - γ -aminopropyl methyldimethoxysilane.
4. The method for preparing nanocellulose as claimed in claim 1 wherein the persulfate in S4 is ammonium persulfate, sodium persulfate or potassium persulfate.
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