CN114716572A - One-step preparation process of multi-functionalized nano-cellulose - Google Patents
One-step preparation process of multi-functionalized nano-cellulose Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 45
- 239000001913 cellulose Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 39
- 238000000605 extraction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 14
- 239000002025 wood fiber Substances 0.000 claims abstract description 14
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229920001046 Nanocellulose Polymers 0.000 claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012024 dehydrating agents Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- FDKXTQMXEQVLRF-ZHACJKMWSA-N (E)-dacarbazine Chemical compound CN(C)\N=N\c1[nH]cnc1C(N)=O FDKXTQMXEQVLRF-ZHACJKMWSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- PWVXXGRKLHYWKM-UHFFFAOYSA-N 5-[2-(benzenesulfonyl)ethyl]-3-[(1-methylpyrrolidin-2-yl)methyl]-1h-indole Chemical compound CN1CCCC1CC(C1=C2)=CNC1=CC=C2CCS(=O)(=O)C1=CC=CC=C1 PWVXXGRKLHYWKM-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 244000166124 Eucalyptus globulus Species 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 2
- 241000018646 Pinus brutia Species 0.000 claims description 2
- 235000011613 Pinus brutia Nutrition 0.000 claims description 2
- 241000219000 Populus Species 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000012374 esterification agent Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005886 esterification reaction Methods 0.000 abstract description 28
- 230000032050 esterification Effects 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 10
- 238000006473 carboxylation reaction Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000007709 nanocrystallization Methods 0.000 abstract description 3
- 230000021523 carboxylation Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000012767 functional filler Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000011174 green composite Substances 0.000 abstract 1
- 238000003541 multi-stage reaction Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 235000010980 cellulose Nutrition 0.000 description 9
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 4
- 239000008108 microcrystalline cellulose Substances 0.000 description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 239000002657 fibrous material Substances 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- KQPMFNHZHBLVRR-UHFFFAOYSA-N oxalic acid;hydrochloride Chemical compound Cl.OC(=O)C(O)=O KQPMFNHZHBLVRR-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 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
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/12—Preparation of cellulose esters of organic acids of polybasic organic acids
-
- 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
-
- 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
- C08B3/02—Catalysts used for the esterification
-
- 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
- C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
- C08B3/10—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate with five or more carbon-atoms, e.g. valerate
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- 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
- C08B3/14—Preparation of cellulose esters of organic acids in which the organic acid residue contains substituents, e.g. NH2, Cl
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a one-step preparation process of multi-functionalized nano-cellulose. The method comprises the steps of taking waste lignocellulose rich in cellulose as a raw material, utilizing a multi-component green composite reaction solvent to effectively promote depolymerization of complex and multi-components of the lignocellulose and hydrolysis of an amorphous region of the cellulose to obtain the nano-cellulose, simultaneously carrying out esterification and carboxylation reactions on the surface of the nano-cellulose so as to prepare the nano-cellulose with high esterification, high carboxylation and high crystallinity, and washing and purifying the nano-cellulose to prepare a dry powder sample. The method prepares the multifunctional nano-cellulose based on the waste wood fiber as the raw material, only completes the process design of synchronous nanocrystallization extraction and functionalization modification of the cellulose by a one-step method, prepares the biomass functional particles with specific functional groups and high surface activity, can endow the functional particles with specific properties without additional modification process, and is expected to be used as a polymer reinforced and toughened functional filler or functional coating material.
Description
Technical Field
The invention relates to a preparation process of multi-functionalized nanocellulose, in particular to a one-step preparation process for directly treating waste wood fiber through a green reaction solvent to carry out nano extraction on cellulose and simultaneously carrying out esterification and carboxylation on nanocellulose to obtain multi-functionalized nanocellulose
Background
The nano-cellulose is widely derived from natural plant fibers, has the characteristics of reproducibility, biodegradability and good biocompatibility, and has the advantages of high mechanical strength, good thermal stability, superfine particle size, high length-to-width ratio, network structure, rich surface active groups and the like. However, most of the methods for preparing nanocellulose are strong mineral acids (such as H)2SO4Etc.) hydrolysis, TEMPO oxidation, etc., which has the characteristics of high cost, high toxicity, poor biological safety, etc., and the extraction of the nanocellulose by using a green reaction solvent based on the biomass raw material is considered to be a safer, mild and rapid acquisition mode.
The nano-cellulose has excellent performance and wide application, and various methods for extracting and esterifying the nano-cellulose are available at present. For example, patent CN201611009390.4 discloses a preparation method of malic acid esterified nanocellulose, which is characterized by adding malic acid into the prepared nanocellulose to perform esterification reaction, so as to obtain malic acid esterified nanocellulose; patent CN202110394751.6 discloses a TEMPO oxidation modified straw fiber material and a preparation method and application thereof, which is characterized in that agricultural waste corn straws are modified by TEMPO oxidation, the specific surface area and pore volume of the material are increased, and functional group carboxyl is introduced; patent CN202110809961.7 discloses a method for preparing nanocellulose by an ionic liquid/sulfuric acid system and regulating and controlling the morphology thereof, which is characterized in that microcrystalline cellulose is dissolved (or swelled) in ionic liquid, and then sulfuric acid solution with a certain concentration is added to regenerate and hydrolyze under the assistance of ultrasound to obtain nanocellulose; patent CN202110583793.4 discloses a method for preparing efficient nanocellulose, which is characterized in that: the nano-cellulose is prepared by taking microcrystalline cellulose as a raw material, and carrying out an oxidation reaction on neutral gel-like microcrystalline cellulose obtained by swelling and dialysis in a solution containing a peroxy oxidant. Although there are a number of methods for preparing nanocellulose, the above patents still have the following problems: (1) the method depends on a two-step process, and the cellulose needs to be subjected to functionalization extraction firstly and then esterification and other functionalization reactions, so that the time consumption is long, and the surface activity of the extracted nanocellulose is low; (2) the preparation process does not conform to the concept of 'green chemistry', and reagents such as ionic liquid, concentrated sulfuric acid and TEMPO are utilized, so that the problems of high cost, consumption of organic solvents, strong corrosivity of the reagents, high toxicity and the like exist, and certain damage can be caused to the structure of the nano-cellulose; (3) the process is complicated, ultrasonic and microwave assistance represented by the patent CN201310537950.3 is adopted, the dissolving mode is complicated, an ultrasonic cell crusher is required for preparing powder, the equipment requirement is high, the energy consumption is high, and the extraction cost is relatively high; (4) the cost of extracting raw materials is high, microcrystalline cellulose is required to be used as the raw material, and the high-value utilization of the waste wood fiber cannot be realized.
Disclosure of Invention
In order to solve the problems of high extraction raw material cost, complex process, solvent pollution, low surface activity and the like of the existing preparation method of the nano-cellulose, the invention provides a one-step preparation method of the multi-functionalization nano-cellulose.
The extraction process provided by the invention takes the waste wood fibers with low added value as raw materials, the nanocrystallization extraction and the functionalization modification of the cellulose are synchronously completed through a one-step process, no organic solvent is added in the preparation process, the recycling of a green reaction solvent can be realized, and the product has the advantages of high esterification degree, high carboxyl content, high crystallinity, excellent hydrophilicity and excellent thermal stability. The invention can effectively broaden the high-valued application of the nano-cellulose material.
The technical scheme adopted by the invention is as follows:
the method specifically comprises the following steps:
1) preparing a green reaction solvent: mixing quaternary ammonium salt, organic carboxylic acid, an esterifying agent, a dehydrating agent and a catalyst, and then placing the mixture in a vacuum oven for dehydrating to form homogeneous transparent liquid serving as a reaction solvent;
2) synchronously extracting and functionalizing cellulose: placing the waste wood fiber raw material and the reaction solvent in the step 1) into a three-neck flask, installing a stirring device and a condensation reflux device for reaction, adding deionized water to terminate the reaction and perform ultrasonic treatment after the reaction is finished, filtering the solution through a Buchner funnel to obtain a precipitated solid, and continuously recycling the filtered solution as the reaction solvent in the step 1);
3) purifying the poly-functionalized nano-cellulose: shaking and washing the solid separated out by filtering in the step 2) by using an ethanol water solution, and then grinding the solid to obtain solid powder after freeze drying, thereby obtaining the multi-functionalized nano-cellulose.
In the step 1): the molar ratio of the quaternary ammonium salt to the organic carboxylic acid in the reaction solvent is 1: 1-20; the esterification agent accounts for 0.1-5 wt% of the mass of the reaction solvent; the dehydrating agent accounts for 0.1-2.0 wt% of the mass of the reaction solvent; the catalyst accounts for 1-5 wt% of the mass of the reaction solvent.
In the step 1):
the quaternary ammonium salt is one of choline chloride, chlormequat chloride and dodecyl trimethyl ammonium chloride, and is preferably choline chloride;
the organic carboxylic acid is at least one of formic acid, oxalic acid, lactic acid, citric acid, malic acid, fatty acid and benzoic acid, and preferably oxalic acid and lactic acid;
the esterifying agent is at least one of dibutyl tin dilaurate, p-methyl benzene sulfonic acid, thionyl chloride, DMAP and dimethyl carbonate;
the dehydrating agent is at least one of concentrated sulfuric acid, molecular sieve, DCC, DIC, EDC, anhydrous calcium chloride and soda lime;
the catalyst is at least one of Lewis acid catalysts such as ferric chloride, ferrous oxide, zinc chloride, copper chloride, aluminum chloride, stannous chloride and the like.
In the step 1), the temperature of the vacuum oven is 60-150 ℃, and the water removing time is 1-5 h.
In the step 2): the bath ratio of the reaction solvent to the raw materials is 1-30:1(w/w), the reaction temperature of the reaction solvent and the raw materials is 50-130 ℃, and the reaction time is 2-10 h; the volume ratio of the deionized water for terminating the reaction to the reaction solvent is 1-10: 1.
The stirring mode is magnetic stirring or mechanical stirring.
In the step 2), the waste wood fiber raw material is waste wood fiber rich in cellulose, specifically at least one of poplar, eucalyptus, fir, pine and bamboo, and the size of the waste wood fiber raw material is 10-200 meshes of particles.
In the step 2), the filtered solution is repeatedly used after water is removed by means of rotary evaporation or heating in a vacuum oven.
In the step 3), the volume ratio of the deionized water to the ethanol in the ethanol aqueous solution is 5-20: 1.
The washing mode in the step 3) is at least one of vacuum filtration and high-speed centrifugation.
The invention has the beneficial effects that:
the method prepares the multifunctional nanocellulose based on the waste wood fiber as the raw material, completes the process design of the synchronization of the nanocrystallization extraction and the functionalization modification of the cellulose by a one-step method, prepares the biomass functional particles with specific functional groups and high surface activity, can endow the functional particles with specific performance without additional modification process, has the outstanding advantages of short process flow, simple process, large interface activity and the like, and is expected to be used as a polymer reinforced and toughened functional filler or a functional coating material. The method has the following specific beneficial effects:
(1) the waste wood fiber is used as the raw material, and the method has the advantages of wide raw material distribution, low cost, easy acquisition and the like;
(2) based on the structural characteristics of cellulose, reaction solvents are reasonably configured, depolymerization of complex multiple components of wood fibers and hydrolysis of amorphous regions of cellulose are realized through a one-step method to obtain nano-cellulose, and meanwhile, esterification and carboxylation reactions are carried out on the surface of the nano-cellulose to obtain multi-functionalized nano-cellulose;
(3) the designed process has no organic solvent, and the reaction solvent can be recycled, so that the green chemical concept is met;
(4) the extracted nano cellulose has high degree of esterification, high carboxyl content, high crystallinity, high mechanical strength, good thermal stability and wide application field.
Drawings
FIG. 1 is an infrared spectrum of a multi-functionalized nanocellulose.
FIG. 2 is a scanning electron microscope image of a multi-functionalized nano-cellulose.
Figure 3 is an X-ray diffraction pattern of a multi-functionalized nanocellulose.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The method is based on a designed one-step preparation system of the multi-functionalized nano-cellulose, takes the extraction rate, the carboxyl content, the esterification degree and the crystallinity of the nano-cellulose as main evaluation indexes, and mainly inspects the comprehensive extraction and esterification efficiency of the nano-cellulose caused by the process factors such as the type and the component proportion of organic carboxylic acid, the type of catalyst, the extraction temperature and the like in the system.
Example 1:
1) preparation of green reaction solvent: preparing choline chloride-oxalic acid solution according to the molar ratio of 1:1, and respectively adding 1 wt% of DMAP esterifying agent, 1 wt% of EDC dehydrating agent and 2 wt% of FeCl3Catalyst, and removing water in a vacuum oven at 105 ℃ for 1h to prepare a reaction solvent;
2) extracting nano-cellulose: the waste wood material is put into the reaction solvent according to the bath ratio of 20:1 (agricultural and forestry sawdust: reaction solvent, w/w), stirred and reacted for 4 hours at the temperature of 110 ℃. Then adding deionized water (reaction solvent: deionized water, w/w) according to the ratio of 1:10 to terminate the reaction and fully vibrate, and filtering by a Buchner funnel to obtain precipitated solid; the solution obtained after filtration can be repeatedly recycled as the reaction solvent in the step 1).
3) The precipitated solid obtained was utilized 1: washing with 10 proportion ethanol water solution (ethanol: water, w/w) in a shaking way, freeze-drying, and grinding to obtain solid powder, namely the poly-functionalized nano-cellulose.
As can be seen from fig. 1: at 1740cm-1The peak at (a) is a peak obtained by superimposing the vibrations of the ester group and the carboxyl group-C ═ O-, and indicates that the hydroxyl group of cellulose and the carboxyl group of oxalic acid have undergone esterification.
As can be seen from fig. 2: it can be shown that the sample is a nanocellulose structure with a classical high aspect ratio
As can be seen from fig. 3: from the formula of crystallinity CrI (%) ═ (I)002-Iam)/I002The obtained nano-cellulose CrI is 82.5%.
Examples 2 to 5:
the oxalic acid in the embodiment 1 is replaced by any one of citric acid, lactic acid, fatty acid and benzoic acid, and the rest conditions are the same as the embodiment 1. The results of the extraction and esterification efficiencies for the functionalized nanocellulose in the process conditions of examples 2-5 are shown in table 1.
Table 1 effect of different organic acid systems on extraction and esterification performance of multi-functionalized nanocellulose
The results in table 1 show that the organic carboxylic acid systems have certain extraction and esterification capabilities for nanocellulose, and the extraction and esterification efficiencies for nanocellulose are different due to the difference of performance indexes such as viscosity, acidity and carboxyl content of reaction solvents compounded by different organic carboxylic acids, wherein the extraction and esterification systems represented by lactic acid and oxalic acid have high comprehensive performance, and the extracted nanocellulose has high extraction rate, carboxyl content, esterification degree and crystallinity.
Examples 6 to 9:
FeCl from example 13The catalyst was changed to stannous chloride, zinc chloride, copper chloride, aluminum chloride, and the rest conditions were the same as in example 1. The results of the catalyst types in examples 6-9 on the extraction and esterification efficiencies of the functionalized nanocellulose are shown in table 2.
Table 2 effect of different catalysts on extraction and esterification performance of multi-functionalized nanocellulose crystals
As can be seen from Table 2, the type of catalyst has a significant effect on the properties of the prepared nanocellulose, particularly in that the carboxyl content of the product is greatly different, with aluminum chloride being the best.
Examples 10 to 12:
the molar ratio of oxalic acid to choline chloride in example 1 was changed to 2:1, 3:1, 4:1 (oxalic acid: choline chloride), and the other conditions were the same as in example 1. The results of different choline chloride to organic carboxylic acid ratios on extraction and esterification efficiencies of the multifunctional nanocellulose in examples 10-12 are shown in table 3.
Table 3 effect of different organic carboxylic acid and choline chloride ratios on extraction and esterification performance of multi-functionalized nanocellulose
As can be seen from table 3, with organic carboxylic acids: the extraction rate of choline chloride is continuously reduced when the proportion of choline chloride is increased, the carboxyl content of the product is continuously increased, and the crystallinity is also increased. This is due to the fact that as the molar ratio of the two components increases, the viscosity of the system increases gradually, resulting in a decrease in dissolution performance. However, more carboxylic acid groups lead to an increased degree of esterification and an increased carboxyl content of the product. And the more acidic, the more hydrolyzed the amorphous region and the greater the crystallinity.
Examples 13 to 17:
the reaction temperature of step 2 in example 1 was changed to 70, 80, 90, 100 and 120 ℃ and the other conditions were the same as in example 1. Examples 13-17 analysis of extraction and esterification performance of the functionalized nanocellulose at different extraction temperatures is shown in table 4.
TABLE 4 Effect of different extraction temperatures on extraction and esterification properties of multi-functionalized nanocellulose
| Temperature/. degree.C | Extraction ratio/% | Carboxyl group content/(mmol/g) | Degree of esterification | Degree of crystallinity (%) |
| 70 | 64.1 | 1.29 | 0.25 | 78.1 |
| 80 | 58.5 | 1.43 | 0.31 | 80.2 |
| 90 | 56.4 | 1.57 | 0.38 | 81.9 |
| 100 | 54.1 | 1.60 | 0.39 | 82.8 |
| 120 | 53.3 | 1.62 | 0.40 | 83.3 |
As can be seen from table 4, with the increase of the extraction temperature, the extraction rate of the nanocellulose is slightly decreased, and the carboxyl content, the esterification degree and the crystallinity of the product tend to be stable after increasing. Overall, 100-.
Examples 18 to 20:
the reaction solvent of step 2 in example 1 was recycled after the 2 nd, 3 rd and 4 th reaction solvents, and the other conditions were the same as in example 1.
TABLE 5 influence of the recovery and utilization times of different reaction solvents on the extraction and esterification performance of multi-functionalized nanocellulose
As can be seen from table 5, as the number of times of recycling increases, the extraction rate of nanocellulose, the carboxyl group content, the degree of esterification, and the degree of crystallinity all decrease. In general, the number of times of recycling the reaction solvent is preferably 3.
Claims (8)
1. A one-step preparation process of multi-functionalized nano-cellulose is characterized by comprising the following steps:
1) preparing a green reaction solvent: mixing quaternary ammonium salt, organic carboxylic acid, an esterifying agent, a dehydrating agent and a catalyst, and then placing the mixture in a vacuum oven for dehydrating, wherein the formed homogeneous transparent liquid is a reaction solvent;
2) synchronously performing nano extraction and functionalization modification on cellulose: placing the waste wood fiber raw material and the reaction solvent in the step 1) into a three-neck flask, installing a stirring device and a condensation reflux device for reaction, adding deionized water to terminate the reaction and perform ultrasonic treatment after the reaction is finished, filtering the solution through a Buchner funnel to obtain a precipitated solid, and continuously recycling the filtered solution as the reaction solvent in the step 1);
3) purifying the poly-functionalized nano-cellulose: and (3) oscillating and washing the solid separated out in the step 2) by using an ethanol water solution, and then grinding the solid after freeze drying to obtain solid powder, thereby obtaining the multifunctional nano-cellulose.
2. The one-step preparation process of the multifunctional nanocellulose according to claim 1, characterized in that: in the step 1): the molar ratio of the quaternary ammonium salt to the organic carboxylic acid in the reaction solvent is 1: 1-20; the esterification agent accounts for 0.1-5 wt% of the mass of the reaction solvent; the dehydrating agent accounts for 0.1-2.0 wt% of the mass of the reaction solvent; the catalyst accounts for 1-5 wt% of the mass of the reaction solvent.
3. The one-step process for preparing the multifunctional nanocellulose according to claim 1, wherein the one-step process comprises the following steps: in the step 1):
the quaternary ammonium salt is one of choline chloride, chlormequat chloride and dodecyl trimethyl ammonium chloride;
the organic carboxylic acid is at least one of formic acid, oxalic acid, lactic acid, citric acid, malic acid, fatty acid and benzoic acid, and preferably oxalic acid and lactic acid;
the esterifying agent is at least one of dibutyl tin dilaurate, p-methyl benzene sulfonic acid, thionyl chloride, DMAP and dimethyl carbonate;
the dehydrating agent is at least one of concentrated sulfuric acid, molecular sieve, DCC, DIC, EDC, anhydrous calcium chloride and soda lime;
the catalyst is at least one of ferric chloride, ferrous oxide, zinc chloride, copper chloride, aluminum chloride and stannous chloride.
4. The one-step preparation process of the multifunctional nanocellulose according to claim 1, characterized in that: in the step 1), the temperature of the vacuum oven is 60-150 ℃, and the water removing time is 1-5 h.
5. The one-step preparation process of the multifunctional nanocellulose according to claim 1, characterized in that: in the step 2):
the bath ratio of the reaction solvent to the raw materials is 1-30:1(w/w), the reaction temperature of the reaction solvent and the raw materials is 50-130 ℃, and the reaction time is 2-10 h;
the volume ratio of the deionized water for terminating the reaction to the reaction solvent is 1-10: 1.
6. The one-step preparation process of the multifunctional nanocellulose according to claim 1, characterized in that: in the step 2), the waste wood fiber raw material is waste wood fiber rich in cellulose, specifically at least one wood or bamboo material selected from poplar, eucalyptus, fir, pine and bamboo is used as the raw material, and the size of the particles is 10-200 meshes.
7. The one-step process for preparing the multifunctional nanocellulose according to claim 1, wherein the one-step process comprises the following steps: in the step 2), the filtered solution is repeatedly used after water is removed by means of rotary evaporation or heating in a vacuum oven.
8. The one-step preparation process of the multifunctional nanocellulose according to claim 1, characterized in that: in the step 3), the volume ratio of the deionized water to the ethanol in the ethanol aqueous solution is 5-20: 1.
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