CN103497279B - Preparation method of amphoteric cellulose material - Google Patents
Preparation method of amphoteric cellulose material Download PDFInfo
- Publication number
- CN103497279B CN103497279B CN201310483448.9A CN201310483448A CN103497279B CN 103497279 B CN103497279 B CN 103497279B CN 201310483448 A CN201310483448 A CN 201310483448A CN 103497279 B CN103497279 B CN 103497279B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- mentioned
- preparation
- quaternized
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 56
- 239000001913 cellulose Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims abstract description 16
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 235000010980 cellulose Nutrition 0.000 claims description 47
- 229920000742 Cotton Polymers 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 11
- 229920000297 Rayon Polymers 0.000 claims description 11
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 11
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 11
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 4
- 239000004627 regenerated cellulose Substances 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000020 Nitrocellulose Substances 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 18
- 150000002500 ions Chemical class 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000005956 quaternization reaction Methods 0.000 abstract 1
- 238000006277 sulfonation reaction Methods 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 125000000129 anionic group Chemical group 0.000 description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002594 sorbent Substances 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 150000001449 anionic compounds Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- -1 cation compound Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of an amphoteric cellulose material, which comprises the steps of firstly carrying out alkali pretreatment on cellulose to obtain alkaline cellulose to realize hydroxyl activation, then carrying out quaternization modification on the alkaline cellulose by using 3-chloro-2-hydroxypropyl trimethyl ammonium chloride as an etherifying agent to obtain quaternized cellulose, then using ceric ammonium nitrate as an initiator, and carrying out sulfonation treatment on the quaternized cellulose by using a monomer 2-acrylamide-2-methylpropanesulfonic acid, thereby realizing the amphoteric cellulose. The preparation condition is relatively mild, the process is simple, the operation is convenient, the scale is easy, the industrial popularization prospect is good, the product adsorption capacity is strong, the method can be used in the fields of heavy metal ion wastewater, organic wastewater treatment and the like, and the method can also be used as a functional carrier of other materials.
Description
Technical field
The present invention relates to a kind of preparation method of amphoteric fibers material, be specifically related to the preparation method of quaternary ammonium-sulfonated cellulose, belong to material modification manufacture field.
Background technology
Mierocrystalline cellulose is natural organic renewable resources the abundantest on the earth, whole world annual production is more than 1,000 hundred million tons, and with Mierocrystalline cellulose state be utilized less than 1/10 of total amount, very most Mierocrystalline cellulose is not utilized or is not used appropriately, as being dissipated with the burning of stalk, timber etc. or the discharge of relevant waste, not only serious environment pollution, more causes the great wasting of resources.Along with day by day deeply concerned to environmental requirement of the rapid decline of the reserves such as Nonrenewable resources oil, coal and various countries, Mierocrystalline cellulose as renewable green resource, its widely application potential be subject to the attention of vast researcher already.Therefore, to research, the exploitation of cellulose resource and derivative thereof, significant.
Namely amphoteric cellulose carries out modification by one or more reactions in oxidation, esterification, etherificate, crosslinked and graft copolymerization to Mierocrystalline cellulose, and possesses the modified-cellulose of cation group and anionic group while obtaining.Amphoteric cellulose has its unique advantage when using as sorbing material; because all kinds of sewage composition is often all extremely complicated; usually can containing different electrical pollutent; when containing cation group and anionic group in sorbent material simultaneously; can realize the active adsorption to electronegative in sewage and positively charged pollutent, its range of application is expanded greatly simultaneously.This be other single electrical ionic sorbent material far can not and effect.Cui Zhimin etc. take bagasse as raw material, react with methacrylic acid and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, obtain the amphoteric cellulose simultaneously containing carboxyl and quaternary ammonium group, the adsorptive power specific activity charcoal of modified sorbent material to the emerald green blue dyestuff of positively charged ion and acid yellow dye improves 19.7% and 33.2%, to Pb
2+, Zn
2+, Cu
2+, Cr
2o
7 2-exchange adsorption attached ability average specific activity charcoal improve 7.4 times.
Cation group in amphoteric cellulose sorbent material generally includes amino, quaternary ammonium group or pyridyl etc., can the negatively charged ion of adsorption zone negative charge or compound; The anionic group be often introduced into then is generally the one in carboxyl, sulfonic group, phosphate, can the positively charged ion of adsorption zone positive charge or compound.Because the reason that modification is relatively easy, wherein more common positively charged ion, anionic group are respectively amino and carboxyl, in fact its adsorptive power is all not as good as corresponding quaternary ammonium group and sulfonic group, but quaternary ammonium group and sulfonic group are incorporated in Mierocrystalline cellulose and are not easy to realize, so at present also not about the report of this method of modifying simultaneously.CAT (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride) is a kind of liquid active cationic etherifying agent, is widely used in the fields such as paper industry, daily chemical industry, petroleum industry and water treatment industry.AMPS (2-acrylamide-2-methyl propane sulfonic) is extremely potential negatively charged ion organic intermediate, has multiple excellent properties, is widely used in the fields such as weaving, water treatment, oil production, plastics, papermaking and coating.The AMPS monomer in the current whole world about 1/3 is used for water treatment industry, and the homopolymer of AMPS or the multipolymer with the monomer such as acrylamide, vinylformic acid, can be used for the field such as sewage disposal, purifying air.External a large amount of use shows, using AMPS as sewage-treating agent, its consumption is few and successful is better than existing polyacrylamide water conditioner.More domestic big and medium-sized cities sewage disposals at present bring into use AMPS, and consumption is in rising tendency year by year.3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and 2-acrylamide-2-methyl propane sulfonic have respective advantage in sewage disposal, if a kind of method can be had the two can be combined, play synergy, be then a kind of sorbing material of performance brilliance, have a extensive future.
Summary of the invention
For solving the deficiencies in the prior art, the object of the invention is to the defect overcoming prior art, a kind of method preparing both sexes quaternary ammonium-sulfonated cellulose is provided, preparation condition is gentle, the quaternary ammonium obtained-sulfonated cellulose macrostructure is fluffy, microtexture porous, to electronegative negatively charged ion, anionic compound and positively charged positively charged ion, cation compound, there is good adsorptive power, effluent containing heavy metal ions, organic wastewater process or the functional vector as other material can be applied to and use.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A preparation method for amphoteric fibers cellulosic material, comprises the steps:
S1, Mierocrystalline cellulose is placed in the sodium hydroxide solution that mass concentration is 0.5% ~ 5%; bath raio 1:20 ~ 1:80; after boiling 30 ~ 120min; filter or extract and be placed in the sodium hydroxide solution that mass concentration is 5% ~ 30%; bath raio 1:20 ~ 1:80; leave standstill at 20 ~ 40 DEG C or vibration 30 ~ 180min, takes out and clean, dry, obtain alkali cellulose;
S2, above-mentioned alkali cellulose is joined in reaction medium by bath raio 1:10 ~ 1:80, dripping mass concentration under stirring is successively 10% ~ 30% sodium hydroxide solution and etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 30 ~ 50 DEG C of reaction 2 ~ 5h, wherein the mass volume ratio of alkali cellulose and sodium hydroxide is 1:0.5 ~ 1:3, the mass ratio of alkali cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1:1 ~ 1:3, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol successively, absolute ethanol washing, dry to constant weight, obtain quaternized cellulose,
S3, above-mentioned quaternized cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, logical shielding gas protection, 30 ± 5 DEG C are stirred 10 ~ 30min, by the mass ratio of quaternized cellulose and ceric ammonium nitrate 1:0.2 ~ 1:3, ceric ammonium nitrate is added in above-mentioned reaction system, after stirring reaction 10 ~ 60min, by the mass ratio of quaternized cellulose and 2-acrylamide-2-methyl propane sulfonic 1:1 ~ 1:5, sulfonated monomers 2-acrylamide-2-methyl propane sulfonic is added in above-mentioned system, after stirring reaction 30 ~ 180min, whole reaction system is transferred in 50 ~ 70 DEG C, continue stirring reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, dry to constant weight, obtain quaternary ammonium-sulfonated cellulose.
Aforementioned fibers element is selected from natural cellulose fibrid and goods, regenerated cellulose fibrid and goods, cellulose family plant or material, Microcrystalline Cellulose.
Aforementioned natural cellulose fibrid and goods are cotton or numb, and regenerated cellulose fibrid and goods are viscose fiber or bamboo pulp fiber, and cellulose family plant or material are stalk or timber.
Shielding gas in abovementioned steps S3 is nitrogen or other rare gas element.
Previous reaction medium is one or more in deionized water, acetone, Virahol, methyl alcohol, ethanol.
Usefulness of the present invention is:
(1) with natural polymer Mierocrystalline cellulose for main raw material, preparation both sexes quaternary ammonium-sulfonated cellulose, cheaper starting materials is easy to get, and material possesses recyclability, degradability, efficient adsorption, and safety and environmental protection, non-secondary pollution;
(2) can realize cellulosic quaternized and sulfonated modification by two-step approach, technique is simple, and easy to operate, easy mass-producing, has good industrialization promotion prospect;
(3) quaternary ammonium prepared-sulfonated cellulose good hydrophilic property, reactive behavior is strong, macrostructure is fluffy, microtexture porous, can the simultaneously negatively charged ion of adsorption zone negative charge, anionic compound and positively charged positively charged ion, cation compound, high adsorption capacity, can be used in the field such as effluent containing heavy metal ions, treatment of Organic Wastewater, and the functional vector that also can be used as other material uses.
Accompanying drawing explanation
Fig. 1 is the quaternized cotton fibre of embodiments of the invention 1 gained, quaternary ammonium-sulfonated cotton fibre contrasts figure with the infrared spectra of raw cotton fiber before modified;
The scanning electron microscope (SEM) photograph of the raw cotton fiber that Fig. 2 adopts for embodiments of the invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the quaternized cotton fibre of embodiments of the invention 1 gained;
Fig. 4 is the scanning electron microscope (SEM) photograph of embodiments of the invention 1 gained quaternary ammonium-sulfonated cotton fibre;
Fig. 5 is that embodiments of the invention 1 gained quaternary ammonium-sulfonated cotton fibre is to Cu
2+, Pb
2+, Congo red and methylene blue Static Adsorption kinetic curve figure.
Embodiment
Do concrete introduction below in conjunction with the drawings and specific embodiments to the present invention, raw material of the present invention and reagent are commercially available.
embodiment 1:
Take cotton fibre 10g, be placed in the sodium hydroxide solution that 400ml mass concentration is 2%, boil 90min, take out after cooling, extract and be placed in the sodium hydroxide solution that 300ml mass concentration is 18%, under normal temperature, leave standstill 120min, taking-up deionized water wash, dries, obtains alkaline cotton fibre.
Get 5.0g alkalescence cotton fibre, be placed in the there-necked flask that 300ml acetone is housed, slowly dripping 5ml mass concentration under electric stirring is 30% sodium hydroxide solution, drip 9g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride again, after 45 DEG C of water-bath 3h, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, dry to constant weight, obtain quaternized cotton fibre.
The quaternized cotton fibre of 5.0g and 400ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 15min in 30 DEG C, adds 10g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 15g is added again after reaction 25min; after reaction 60min, system is transferred in 60 DEG C and continues reaction 3.0h, take out product, naturally cooling; successively through deionized water, acetone, ether filtering and washing; airing 60min under normal temperature, dries to constant weight, obtains quaternary ammonium-sulfonated cotton fibre.
embodiment 2:
Take viscose fiber 10g, be placed in the sodium hydroxide solution that 300ml mass concentration is 1%, boil 60min, take out after cooling, extract and be placed in the sodium hydroxide solution that 280ml mass concentration is 15%, under normal temperature, leave standstill 90min, taking-up deionized water wash, dries, obtains alkaline viscose fiber.
Get 6.0g alkaline viscose fiber, be placed in the there-necked flask that 320ml acetone is housed, slowly dripping 6ml mass concentration under electric stirring is 30% sodium hydroxide solution, drip 15g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride again, after 50 DEG C of water-bath 200min, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, dry to constant weight, obtain quaternized viscose fiber for 40 DEG C.
The quaternized viscose fiber of 5.0g and 350ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 10min under normal temperature, adds 7.5g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 10g is added again after reaction 20min; after reaction 60min, system is transferred in 50 DEG C and continues reaction 150min, take out product, naturally cooling; successively through deionized water, acetone, ether filtering and washing; normal temperature airing 40min, dries to constant weight, obtains quaternary ammonium-sulfonated viscose fiber.
embodiment 3:
Take Microcrystalline Cellulose 10g, be placed in the sodium hydroxide solution that 250ml mass concentration is 0.5%, boil 60min, suction filtration after cooling, be placed in the sodium hydroxide solution that 200ml mass concentration is 10%, under normal temperature, leave standstill 120min, take out and use deionized water filtering and washing, dry, obtain alkaline Microcrystalline Cellulose.
Get 8.0g alkalescence Microcrystalline Cellulose, be placed in the there-necked flask that 200ml acetone is housed, slowly dripping 8ml mass concentration under magnetic agitation is 10% sodium hydroxide solution, drip 16g 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride again, after 45 DEG C of water-bath 3h, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol, absolute ethanol washing successively, dry to constant weight, obtain quaternized Microcrystalline Cellulose for 60 DEG C.
The quaternized Microcrystalline Cellulose of 5.0g and 200ml deionized water is added in there-necked flask; logical nitrogen protection, stirs 10min in 25 DEG C, adds 9g ceric ammonium nitrate; 2-acrylamide-2-methyl propane sulfonic 15g is added again after reaction 20min; after reaction 50min, system is transferred in 50 DEG C and continues reaction 200min, take out product, while hot suction filtration; and successively through deionized water, acetone, washed with diethylether; normal temperature airing 30min, dries to constant weight, obtains quaternary ammonium-sulfonated Microcrystalline Cellulose.
material and Performance Detection:
For embodiment 1, adopt infrared spectrometer to carry out examination of infrared spectrum to raw cotton fiber (curve A), quaternized cotton fibre (curve B), quaternary ammonium-sulfonated cotton fibre (curve C) before modified, spectrogram is see Fig. 1, obviously visible, 1060cm
-1place belongs to the flexural vibration peak of-OH in cellulose macromolecule and the stretching vibration peak of C-O-C, has remarkable enhancing respectively at quaternized cotton fibre, quaternary ammonium-sulfonated cotton fibre; And in quaternary ammonium-sulfonated cotton fibre 1649.9cm
-1and 1552.6cm
-1place has occurred that obvious amide I band (σ C=O) and acid amides II are with (δ N-H) absorption peak; In addition, 1430.4cm
-1(δ C-H) place is the charateristic avsorption band of cotton fibre crystallizing field, and along with quaternized and sulfonated modified, this absorption peak strength obviously reduces and even disappears, and has downtrending as seen through modified cotton fibre degree of crystallinity.
Fig. 2 to Fig. 4 is respectively the scanning electron microscope (SEM) photograph of the raw cotton fiber before modified in embodiment 1, quaternized cotton fibre and quaternary ammonium-sulfonated cotton fibre.Contrast can find, raw cotton fiber smooth surface, has a small amount of fold; Obviously there is tectum on quaternized cotton fibre surface, and dense distribution a large amount of micropore, and aperture is all at nano level; Quaternary ammonium-sulfonated cotton fibre surface then adds some flaps, the vesicular structure before simultaneously remaining on quaternized cotton fibre basis; The change of this form of fiber surface, be the result that quaternized and sulfonated monomer is introduced, fibre crystallinity all can be caused to decline, and this is consistent with infrared test result.Also show that priority is all successful to quaternized, the sulfonated modification of cotton fibre simultaneously.
Fig. 5 is that the obtained quaternary ammonium-sulfonated cotton fibre of embodiment 1 is to Cu
2+, Pb
2+, Congo red and methylene blue Static Adsorption kinetic curve figure.The condition of this adsorption experiment is: metal ion, dye solution are original pH, and starting point concentration is 250mg/L, and adsorption temp is 303K.As seen from the figure, quaternary ammonium-sulfonated cotton fibre is to Pb
2+and Cu
2+absorption in 3h, 4h, reach balance respectively, saturated extent of adsorption is about 61.4mg/g and 74.8mg/g respectively; Absorption that is Congo red to anionic dyestuff and cationic dyestuff methylene blue all reaches balance in 6h, and saturated extent of adsorption is then respectively up to 142mg/g and 87.1mg/g, and adsorption effect is better than prior art widely.This has also proved the conclusion that Fig. 1, Fig. 2-Fig. 4 obtains, show that to quaternized, the sulfonated modification of cotton fibre be all successful, product quaternary ammonium-sulfonated cotton fibre carries a large amount of functional cation groups and anionic group, can be widely used in heavy metal ion and the macromolecular Adsorption of organism, the functional vector that also can be used as other material uses.
Adopt same equipment and condition to the raw material viscose fiber in embodiment 2, quaternized viscose fiber, raw material Microcrystalline Cellulose in quaternary ammonium-sulfonated viscose fiber and embodiment 3, quaternized Microcrystalline Cellulose, quaternary ammonium-sulfonated Microcrystalline Cellulose is tested, result all shows: the macrostructure of obtained quaternary ammonium-sulfonated fiber is fluffy, microtexture porous, there is both sexes characteristic, can the negatively charged ion of simultaneously adsorption zone negative charge, anionic compound and positively charged positively charged ion, cation compound, high adsorption capacity, can be used in effluent containing heavy metal ions, the fields such as treatment of Organic Wastewater, also the functional vector that can be used as other material uses.
To sum up, preparation method of the present invention successfully can carry out modification to Mierocrystalline cellulose, and the obtained both sexes quaternary ammonium-sulfonated cellulose simultaneously containing cationic quaternary ammonium group and anionic sulfonic acid group, technique is simple, easy to operate, easy mass-producing.
More than show and describe ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (5)
1. a preparation method for amphoteric fibers cellulosic material, is characterized in that, comprises the steps:
S1, Mierocrystalline cellulose is placed in the sodium hydroxide solution that mass concentration is 0.5% ~ 5%; bath raio 1:20 ~ 1:80; after boiling 30 ~ 120min; filter or extract and be placed in the sodium hydroxide solution that mass concentration is 5% ~ 30%; bath raio 1:20 ~ 1:80; leave standstill at 20 ~ 40 DEG C or vibration 30 ~ 180min, takes out and clean, dry, obtain alkali cellulose;
S2, above-mentioned alkali cellulose is joined in reaction medium by bath raio 1:10 ~ 1:80, dripping mass concentration under stirring is successively 10% ~ 30% sodium hydroxide solution and etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 30 ~ 50 DEG C of reaction 2 ~ 5h, wherein the mass volume ratio of alkali cellulose and sodium hydroxide is 1:0.5 ~ 1:3, the mass ratio of alkali cellulose and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 1:1 ~ 1:3, after reaction terminates, regulate product pH value to neutral with dilute hydrochloric acid, suction filtration also uses methyl alcohol successively, absolute ethanol washing, dry to constant weight, obtain quaternized cellulose,
S3, above-mentioned quaternized cellulose is joined in deionized water by bath raio 1:30 ~ 1:100, logical shielding gas protection, 30 ± 5 DEG C are stirred 10 ~ 30min, by the mass ratio of quaternized cellulose and ceric ammonium nitrate 1:0.2 ~ 1:3, ceric ammonium nitrate is added in above-mentioned reaction system, after stirring reaction 10 ~ 60min, by the mass ratio of quaternized cellulose and 2-acrylamide-2-methyl propane sulfonic 1:1 ~ 1:5, sulfonated monomers 2-acrylamide-2-methyl propane sulfonic is added in above-mentioned system, after stirring reaction 30 ~ 180min, whole reaction system is transferred in 50 ~ 70 DEG C, continue stirring reaction 2 ~ 5h, take out product, naturally cooling, successively through deionized water, acetone, ether filtering and washing, airing 30 ~ 120min under normal temperature, dry to constant weight, obtain quaternary ammonium-sulfonated cellulose.
2. the preparation method of a kind of amphoteric fibers cellulosic material according to claim 1, is characterized in that, above-mentioned Mierocrystalline cellulose is selected from natural cellulose fibrid and goods, regenerated cellulose fibrid and goods or Microcrystalline Cellulose.
3. the preparation method of a kind of amphoteric fibers cellulosic material according to claim 2, is characterized in that, above-mentioned natural cellulose fibrid and goods are cotton or numb, and above-mentioned regenerated cellulose fibrid and goods are viscose fiber or bamboo pulp fiber.
4. the preparation method of a kind of amphoteric fibers cellulosic material according to claim 1, is characterized in that, above-mentioned shielding gas is nitrogen or other rare gas element.
5. the preparation method of a kind of amphoteric fibers cellulosic material according to any one of claim 1-3, is characterized in that, above-mentioned reaction medium is one or more in deionized water, acetone, Virahol, methyl alcohol, ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310483448.9A CN103497279B (en) | 2013-10-16 | 2013-10-16 | Preparation method of amphoteric cellulose material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310483448.9A CN103497279B (en) | 2013-10-16 | 2013-10-16 | Preparation method of amphoteric cellulose material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103497279A CN103497279A (en) | 2014-01-08 |
| CN103497279B true CN103497279B (en) | 2015-07-29 |
Family
ID=49862550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310483448.9A Expired - Fee Related CN103497279B (en) | 2013-10-16 | 2013-10-16 | Preparation method of amphoteric cellulose material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103497279B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650294B (en) * | 2014-12-14 | 2017-07-07 | 苏州大学 | A kind of diamine oxime modified cellulosic materials, preparation method and applications |
| CN106047331A (en) * | 2016-06-27 | 2016-10-26 | 梅庆波 | Method for preparing clean fracturing fluid by synthesizing ampholytic surfactant through linen fibers |
| CN107243330B (en) * | 2017-08-09 | 2020-04-28 | 陕西科技大学 | Amphoteric adsorbent prepared from vinasse and preparation method and application thereof |
| CN107446166A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of amphoteric cellulose composite of supported nano zinc oxide and preparation method thereof |
| CN107541954A (en) * | 2017-09-17 | 2018-01-05 | 赵兵 | PEDOT:PSS/ chitosans/nano silver wire functionalization cotton fiber |
| CN107558216A (en) * | 2017-09-17 | 2018-01-09 | 赵兵 | Graphene oxide/chitosan/nano silver wire functionalization cotton fiber |
| CN107344094A (en) * | 2017-09-17 | 2017-11-14 | 赵兵 | A kind of amphoteric cellulose sorbing material and preparation method thereof |
| CN107503125A (en) * | 2017-09-17 | 2017-12-22 | 赵兵 | A kind of conductive cotton fiber based on nano silver wire nano-Ag particles |
| CN107602931A (en) * | 2017-09-17 | 2018-01-19 | 赵兵 | A kind of amphoteric cellulose composite of loading nano silvery and preparation method thereof |
| CN107558190A (en) * | 2017-09-17 | 2018-01-09 | 赵兵 | The nano silver wire conduction cotton fiber of conducting polymer parcel |
| CN107558189A (en) * | 2017-09-17 | 2018-01-09 | 赵兵 | A kind of Multifunctional cotton fiber based on nano silver wire network |
| CN107501620A (en) * | 2017-09-17 | 2017-12-22 | 赵兵 | A kind of carbon nano tube compound material and preparation method based on amphoteric cellulose |
| CN107903335A (en) * | 2017-11-21 | 2018-04-13 | 常州可赛成功塑胶材料有限公司 | A kind of preparation method of heat-resistance type clay stabilization agent material |
| CN109133298A (en) * | 2018-08-31 | 2019-01-04 | 合肥绿洁环保科技有限公司 | A kind of preparation method of paint spray booth recirculated water flocculant |
| CN111085172A (en) * | 2019-12-31 | 2020-05-01 | 济南市农业科学研究院 | Modified straw paper fiber, preparation method and application of modified straw paper fiber as nitrate radical adsorbent |
| CN113842895A (en) * | 2021-10-04 | 2021-12-28 | 桂林理工大学 | Preparation method and application of quaternized modified microcrystalline cellulose adsorbent |
| CN116393104A (en) * | 2023-04-17 | 2023-07-07 | 昆明理工大学 | Preparation method and application of modified corn stalk composite filter column |
-
2013
- 2013-10-16 CN CN201310483448.9A patent/CN103497279B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103497279A (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103497279B (en) | Preparation method of amphoteric cellulose material | |
| CN103497278B (en) | Amphoteric cellulose material and application thereof | |
| CN101759808B (en) | Method for preparing modified polyamine porous starch | |
| CN106914225B (en) | A kind of preparation method of cellulose base bifunctional adsorbent | |
| CN102716728B (en) | Preparation method of modified bagasse cellulose based heavy metal adsorbent | |
| CN102489259B (en) | Graphene oxide/cellulose compound material as well as preparation method and application of same | |
| CN105148868A (en) | Preparation method of nano-crystalline cellulose-based composite aerogel type organic dye absorption material | |
| CN107082894B (en) | A kind of double-network hydrogel adsorbent and preparation method thereof and application as heavy metal absorbent | |
| CN109174023B (en) | Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof | |
| CN103159896B (en) | The preparation of cellulose graft acrylic copolymer and the application as adsorbent | |
| CN103212378B (en) | Preparation method and application of citric acid modified palm tree bark adsorbing agent | |
| CN101239303A (en) | Alkalization modifying method of luffa and use thereof | |
| CN105131185A (en) | Pineapple waste hemicellulose based pH sensitive type porous hydrogel as well as preparation method and application thereof | |
| CN103551124A (en) | Preparation method for adsorbent for treating dye wastewater | |
| CN103447013A (en) | Method for preparing graphene/chitosan adsorbent and application method thereof | |
| CN109012638B (en) | Preparation method of carboxylated hierarchical porous cellulose adsorption balls | |
| CN101239306A (en) | Method for preparing etherification luffa and application of it in metallic ion adsorption | |
| CN103406153A (en) | Method for preparing cellulose-based macroporous gel compound Cu2O visible-light-driven photocatalyst | |
| CN104014313B (en) | A kind of modification wheat husk adsorbent | |
| CN104829788A (en) | Preparation method for chitosan/2-acrylamido-2-methyl AMPS hydrogel | |
| CN105061607A (en) | Lithium-ion imprinted polymer and preparation method thereof | |
| Shao et al. | Cellulose based cation-exchange fiber as filtration material for the rapid removal of methylene blue from wastewater | |
| CN107973365B (en) | Adsorbent for treating dye-containing wastewater, preparation method and application thereof | |
| CN103464119A (en) | Preparation method and application of modified cysteine palm bark adsorbent | |
| CN115055170A (en) | Wood-based modified nano-cellulose water purification material with high adsorption performance and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chen Yuyue Inventor after: Xiong Jiaqing Inventor after: Lin Hong Inventor before: Chen Yuyue Inventor before: Xiong Jiaqing Inventor before: Lin Hong Inventor before: Su Gonglei |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHEN YUYUE XIONG JIAQING LIN HONG SU GONGLEI TO: CHEN YUYUE XIONG JIAQING LIN HONG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 Termination date: 20171016 |