CN115521383A - Preparation method of polyanion modified cellulose - Google Patents
Preparation method of polyanion modified cellulose Download PDFInfo
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- CN115521383A CN115521383A CN202211342425.1A CN202211342425A CN115521383A CN 115521383 A CN115521383 A CN 115521383A CN 202211342425 A CN202211342425 A CN 202211342425A CN 115521383 A CN115521383 A CN 115521383A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 210
- 239000001913 cellulose Substances 0.000 title claims abstract description 210
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 141
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 60
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 56
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims abstract description 53
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006467 substitution reaction Methods 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 239000002585 base Substances 0.000 claims abstract description 28
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 28
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000742 Cotton Polymers 0.000 claims abstract description 27
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 21
- 230000004048 modification Effects 0.000 claims abstract description 21
- 239000008213 purified water Substances 0.000 claims abstract description 19
- 238000006266 etherification reaction Methods 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical class [H]O* 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 47
- 239000011259 mixed solution Substances 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000007873 sieving Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000002956 ash Substances 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 238000004380 ashing Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 claims description 9
- 238000006011 modification reaction Methods 0.000 claims description 9
- 239000012086 standard solution Substances 0.000 claims description 9
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920001131 Pulp (paper) Polymers 0.000 claims description 7
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 238000011056 performance test Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 244000025254 Cannabis sativa Species 0.000 claims description 5
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 5
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 5
- 235000009120 camo Nutrition 0.000 claims description 5
- 235000005607 chanvre indien Nutrition 0.000 claims description 5
- 239000011487 hemp Substances 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 3
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229920003086 cellulose ether Polymers 0.000 description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 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 2
- 239000000463 material Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
Abstract
The invention discloses a preparation method of polyanion modified cellulose, which relates to the technical field of modification preparation of macromolecular compounds, and comprises the following raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and also comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose and 100-130 parts of cesium hydroxide with the concentration of 48% -52%; according to the polyanion modified cellulose, short fibers of natural cotton are used as raw materials, strong alkali cesium hydroxide solution is added for alkalization reaction, then alcohol mixture and monochloroacetic acid are carried out for etherification reaction, and the polyanion cellulose with high purity is generated after the natural cellulose is subjected to first modification treatment, so that the effects of full alkalization and etherification reaction and full substitution of hydroxyl in the cellulose are achieved.
Description
Technical Field
The invention relates to the technical field of modification preparation of high molecular compounds, in particular to a preparation method of polyanion modified cellulose.
Background
Polyanionic cellulose PAC is a water-soluble cellulose ether derivative prepared by chemically modifying natural cellulose, has excellent heat-resistant stability, salt resistance and antibacterial property, and is suitable for all industrial fields where CMC is applicable, including yarn sizing agents in textile industry, oil-resistant smoothing agents in paper pulp in paper making industry, daily necessities detergents in daily chemical industry, latex stabilizers in rubber industry, tackifiers, water-retaining agents, suspending agents and the like in drilling industry; the PAC prepared by modifying natural cellulose has better reaction uniformity, higher substitution degree, better transparency, better salt resistance and heat resistance than CMC, and has wide application industry field, and the performance is continuously strengthened along with the high quality pursuit of industry application, therefore, the modification process breaks through therewith, and the performance is improved and optimized.
The existing polyanion modified cellulose preparation method is to modify and prepare the polyanion modified cellulose in salt resistance, high temperature resistance, high viscosity and water retention, and is used for treating the falling of clay fine particles on a well wall, the water filtration loss in a well and the stabilization of a soft soil structure in the well drilling industry, PAC is used as an inhibitor and a fluid loss reducer, and the dispersion and the expansion of the clay and the shale are inhibited in a high-salt medium, so that the pollution of the well wall is controlled; the existing preparation process of polyanion modified cellulose has the problems that the proportion of raw materials is unscientific, the ideal PAC performance cannot be achieved, the substitution degree of the prepared polyanion cellulose is in the range of 0.85-1.4, and the substitution degree and the performance cannot be accurately controlled; therefore, the higher the substitution degree of PAC can be, the stronger its properties are, so that in the process of preparing the modified polyanionic cellulose, it is required to further deeply study to stabilize and control the high substitution degree of the polyanionic cellulose.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of polyanion modified cellulose, which solves the problems that the traditional preparation method of polyanion modified cellulose has the defects of unscientific raw material proportioning, insufficient reaction and poor substitution degree improvement effect, and the performance effect of the polyanion modified cellulose is not very ideal.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of polyanion modified cellulose comprises the raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking out 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 6000-10000r/min, sieving the natural cellulose by a 60-80-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong alkali reaction kettle, adding 90-120 parts of cesium hydroxide with the concentration of 48% -52% into the powdery natural cellulose, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ and the reaction time to be 30-40min, and obtaining alkalized cellulose A after the reaction;
s2, carrying out secondary alkalization reaction, taking out a flask, adding 25-30 parts of ethanol, 10-15 parts of isopropanol and 5-10 parts of n-butanol at the temperature of 20 ℃ to prepare a mixed solution P, and dividing the mixed solution P into two P parts of 1 1 And P 2 Using a mixture P 1 And 10 parts of cesium hydroxide with the concentration of 48-52% are sequentially added into the strong alkali reaction kettle, and are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 20-30min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 120-150 parts of monochloroacetic acid and mixed liquid P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 50-70 ℃ and the reaction time to be 40-60min, and after the reaction, removing the mixed solution by adopting a centrifugation method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 250-300 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on the sulfonic group and carboxyl at the reaction temperature of 70-90 ℃ for 30-40min, washing the mixture with purified water after reaction, sieving for 2-3 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and a performance test are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
Preferably, the natural cellulose includes cotton, hemp, silk and animal hair, the cellulose with high content is cotton and hemp, the silk and animal hair with high content is protein, and the polyanionic cellulose is cotton adopting short fiber refined cotton or wood pulp processed by plant fiber, wherein the cotton fiber cellulose content of the cotton is up to 94%, and the hemp fiber cellulose content of the wood pulp is 60-80%, therefore, the refined cotton fiber is adopted in the embodiment.
Preferably, the cesium hydroxide is an inorganic compound of white crystalline powder, has the characteristics of strong basicity, corrosivity, deliquescence and water solubility, has a molecular formula of CsOH, a molecular weight of 149.91 and a density of 3.675g/cm 3 The melting point is 272 ℃, csOH and refined cotton fiber are subjected to alkalization modification reaction, specifically, carboxyl on cellulose is acidic, after cesium hydroxide solution is absorbed, alkali fiber salt and water are generated by modification, and the alkalization equation is [ C ] 6 H 7 O 2 (OH) 3 ] n +nCsOH→[C 6 H 7 O 2 (OH) 2 OCs] n +nH 2 O; in the alkalization reaction, the adsorption capacity and the swelling degree of the natural cellulose to cesium hydroxide are related to the temperature and the concentration, and the dissolving rate of the natural cellulose modified into the alkali cellulose is related to the addition of a mixture of ethanol and isopropanol, wherein in the alkalization process, the polarity of a solution medium is higher, the number M of hydroxyl groups of anhydroglucose units in the generated alkali cellulose, which are reacted with CsOH, is lower, the polarity of an alcohol mixed solution is lower than that of water, the M value of the alkali cellulose can be increased, the morphological structure and the fine structure of the natural cellulose are changed, and the hemicellulose, impurities and cellulose with low degree of polymerization are dissolvedAnd the purity and the performance of the polyanionic cellulose are improved.
Preferably, the monochloroacetic acid is an organic compound of white crystalline powder, exists in three forms of alpha, beta and gamma, and has a molecular formula of ClCH 2 COOH, molecular weight 94.497, density 1.58g/cm 3 The boiling point is 189 deg.C, critical pressure is 5.78MPa, it is soluble in water, alcohol, ether, chloroform and carbon disulfide, and is used as carboxymethylating agent for preparing polyanionic cellulose.
Preferably, the ethanol is a volatile, colorless, transparent liquid organic compound having the formula C 2 H 6 O, molecular weight of 46.07, is saturated monohydric alcohol with hydroxyl group, and the ethanol solution density is 0.7893g/cm at 20 deg.C 3 The preparation method comprises the steps of carrying out addition reaction of ethylene and water vapor by a direct hydration method under the conditions of an organophosphorus catalyst, high temperature and high pressure to obtain the catalyst; the isopropanol is an organic compound of colorless transparent liquid, and the molecular formula of the isopropanol is C 3 H 8 O, molecular weight of 60.095, density of 0.7855g/cm 3 The critical pressure is 4.76MPa, and the catalyst is characterized by being dissolved in water, ethanol, ether, benzene and chloroform organic solvent; the n-butanol is an organic compound of colorless transparent liquid and has a molecular formula of C 4 H 10 O, molecular weight 74.122, density 0.81g/cm 3 The cellulose ether has the characteristics of slightly dissolving in water, ethanol and ether, wherein the melting point is-89 ℃, the critical pressure is 4.414MPa, and the cellulose ether is prepared by preparing a mixed solution of ethanol, isopropanol and n-butanol according to the mass ratio of 3-5 to 1-3.
Preferably, the chlorosulfonic acid is a colorless liquid inorganic compound of the formula ClHSO 3 Molecular weight of 116.524 and density of 1.753g/cm 3 Melting point of-80 deg.C, critical pressure of 8.5MPa, insolubility in carbon disulfide, carbon tetrachloride, chloroform, acetic acid and dichloromethane, and can be used as sulfonating agent for polyanionic celluloseAn intermediate modified by reaction with polyanionic cellulose.
Preferably, the strong base reaction kettle is a reaction vessel for synthesizing chemical substances under certain temperature and pressure conditions, has the characteristics of high temperature resistance, high pressure resistance, corrosion resistance and high purity, and is structurally composed of a reaction kettle body, a kettle cover, a jacket, a stirrer, a rotating shaft and a driving device.
Preferably, the membrane type sulfonator is a process of sulfonating polyanionic cellulose in a multi-tube membrane type reactor to generate sulfonic acid, absorbing tail gas with alkali liquor to generate sulfite, and then introducing air for oxidation to generate sulfate, and the structure of the membrane type sulfonator consists of a cylinder body, an inner cavity and a plurality of branch tube plates.
Preferably, the ashing method is to remove organic matters in the sample by using high temperature, dissolve the residual ash by using acid to be used as a solution to be detected of the sample, specifically take out the prepared polyanion modified cellulose, put the sample in a crucible, gradually raise the temperature to 500-600 ℃, burn for 3h to completely ash the sample, convert the sample into Cs 2 And O, dissolving the ashes in a standard hydrochloric acid solution with the concentration of 0.1mol/L, titrating excessive hydrochloric acid by using a cesium hydroxide standard solution with the concentration of 50%, and detecting by using methyl red as an indicator.
Preferably, the raw materials of the natural cellulose, the cesium hydroxide, the monochloroacetic acid, the ethanol, the isopropanol, the n-butanol and the chlorosulfonic acid are all purchased from Nanjing Taiye chemical new materials Co; the disintegrator, strong base reactor, flask, and membrane sulfonator reaction equipment are all purchased from Shanghai Begal Intelligent science and technology, inc.
(III) advantageous effects
The invention provides a preparation method of polyanion modified cellulose, which has the following beneficial effects:
(1) According to the polyanion modified cellulose, short fibers of natural cotton are used as raw materials, strong alkali cesium hydroxide solution is added for alkalization reaction, then alcohol mixture and monochloroacetic acid are carried out for etherification reaction, and the polyanion cellulose with high purity is generated after the natural cellulose is subjected to first modification treatment, so that the effects of full alkalization and etherification reaction and full substitution of hydroxyl in the cellulose are achieved.
(2) The polyanion modified cellulose is subjected to modification sulfonation reaction through chlorosulfonic acid to generate the polyanion modified cellulose, the property of the substitution degree is enhanced and highlighted, the function of stabilizing and controlling the high substitution degree of the polyanion cellulose is realized, and the effects of improving the viscosity and the using duration of the polyanion modified cellulose are achieved.
Detailed Description
All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The invention provides a technical scheme that: a preparation method of polyanion modified cellulose comprises the raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 10000r/min, sieving the natural cellulose through an 80-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong alkali reaction kettle, adding 90 parts of cesium hydroxide with the concentration of 48% into the strong alkali reaction kettle, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ and the reaction time to be 30min, and obtaining alkalized cellulose A after reaction;
s2, carrying out secondary alkalization reaction, taking out the flask, and adding 25 parts of ethanol, 10 parts of isopropanol and 5 parts of n-butanol at the temperature of 20 ℃ to prepare the productMixing the liquid P, and dividing the mixed liquid P into two parts P of 1 1 And P 2 Using a mixed solution P 1 And 10 parts of cesium hydroxide with the concentration of 48% are sequentially added into a strong alkali reaction kettle, and are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 30min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 120 parts of monochloroacetic acid and the mixed solution P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 50 ℃ and the reaction time to be 40min, and after the reaction, removing the mixed solution by adopting a centrifugal method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 250 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on sulfonic group and carboxyl, wherein the reaction temperature is 70 ℃, the reaction time is 30min, after the reaction, cleaning the mixture with purified water, sieving for 2 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and a performance test are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
The natural cellulose comprises cotton, bast fibers, silk and animal hair, the cellulose with high content is the cotton and the bast fibers, the silk and the animal hair with high content are protein, and the polyanionic cellulose is prepared from cotton which adopts short fiber refined cotton or wood pulp which is processed by plant fibers, wherein the cotton fiber cellulose content of the cotton is up to 94 percent, and the bast fiber cellulose content of the wood pulp accounts for 60 to 80 percent, so the refined cotton fibers are adopted in the embodiment.
Wherein the cesium hydroxide is an inorganic compound of white crystalline powder, has the characteristics of strong basicity, corrosivity, deliquescence and water solubility, has a molecular formula of CsOH, a molecular weight of 149.91 and a density of 3.675g/cm 3 The melting point is 272 ℃, csOH and refined cotton fiber are subjected to alkalization modification reaction, specifically, carboxyl on cellulose is acidic, and after cesium hydroxide solution is absorbed, alkali fiber salt and water are generated by modification, wherein the alkalization equation is [ C ] 6 H 7 O 2 (OH) 3 ] n +nCsOH→[C 6 H 7 O 2 (OH) 2 OCs] n +nH 2 O; in the alkalization reaction, the adsorption capacity and the swelling degree of natural cellulose to cesium hydroxide are related to the temperature and the concentration, and the dissolving rate of the natural cellulose modified into the alkali cellulose is related to the addition of a mixture of ethanol and isopropanol, wherein in the alkalization process, the larger the polarity of a solution medium is, the lower the hydroxyl number value M of a anhydroglucose unit in the generated alkali cellulose in reaction with CsOH is, the polarity of an alcohol mixed solution is smaller than that of water, the M value of the alkali cellulose can be improved, the morphological structure and the fine structure of the natural cellulose are changed, hemicellulose, impurities and cellulose with low polymerization degree are dissolved, and the purity and the performance of polyanionic cellulose are improved.
Wherein the monochloroacetic acid is an organic compound of white crystalline powder, exists in three forms of alpha, beta and gamma, and has a molecular formula of ClCH 2 COOH, molecular weight 94.497, density 1.58g/cm 3 The boiling point is 189 deg.C, critical pressure is 5.78MPa, it is soluble in water, alcohol, ether, chloroform and carbon disulfide, and is used as carboxymethylating agent for preparing polyanionic cellulose.
Wherein the ethanol is a volatile, colorless and transparent liquid organic compound with a molecular formula of C 2 H 6 O, molecular weight of 46.07, is saturated monohydric alcohol with hydroxyl group, and the ethanol solution density is 0.7893g/cm at 20 deg.C 3 The preparation method is to catalyze ethylene and water vapor in organic phosphorusUnder the conditions of high temperature and high pressure, the additive is prepared by the direct hydration method; the isopropanol is an organic compound of colorless transparent liquid, and the molecular formula of the isopropanol is C 3 H 8 O, molecular weight of 60.095, density of 0.7855g/cm 3 The critical pressure is 4.76MPa, and the catalyst is characterized by being dissolved in water, ethanol, ether, benzene and chloroform organic solvent; the n-butanol is an organic compound of colorless transparent liquid and has a molecular formula of C 4 H 10 O, molecular weight 74.122, density 0.81g/cm 3 The cellulose ether has the characteristics of slightly dissolving in water, ethanol and ether, wherein the melting point is-89 ℃, the critical pressure is 4.414MPa, and the cellulose ether is prepared by preparing a mixed solution of ethanol, isopropanol and n-butanol according to the mass ratio of 3-5 to 1-3.
Wherein the chlorosulfonic acid is a colorless liquid inorganic compound with a molecular formula of ClHSO 3 Molecular weight of 116.524 and density of 1.753g/cm 3 The melting point is-80 ℃, the critical pressure is 8.5MPa, the sulfonated polyaniline derivative has the characteristics of insolubility in carbon disulfide, carbon tetrachloride and solubility in chloroform, acetic acid and dichloromethane, and is used as a sulfonating agent of polyanionic cellulose and an intermediate for reaction and modification with the polyanionic cellulose.
The strong base reaction kettle is a reaction vessel for synthesizing chemical substances under certain temperature and pressure conditions, has the characteristics of high temperature resistance, high pressure resistance, corrosion resistance and high purity, is structurally composed of a reaction kettle body, a kettle cover, a jacket, a stirrer, a rotating shaft and a driving device, and is automatically configured by utilizing the existing intelligent technology and carrying out temperature, pressure, speed and time parameters during the chemical reaction of the strong base reaction kettle.
The membrane sulfonator is a process of sulfonating polyanionic cellulose in a multi-tube membrane reactor to generate sulfonic acid, absorbing tail gas by using alkali liquor to generate sulfite, and introducing air to oxidize to generate sulfate, and the membrane sulfonator structurally comprises a cylinder body, an inner cavity and a plurality of branch tube plates.
The ashing method comprises the steps of removing organic matters in a sample by utilizing high temperature, dissolving the residual ash by using acid to serve as a solution to be detected of the sample, taking out the prepared polyanion modified cellulose, putting the sample in a crucible, gradually heating to 500-600 ℃, burning for 3 hours to completely ash the sample, and converting the sample into Cs 2 And O, dissolving the ashes in a standard hydrochloric acid solution with the concentration of 0.1mol/L, titrating excessive hydrochloric acid by using a cesium hydroxide standard solution with the concentration of 50%, and detecting by using methyl red as an indicator.
Wherein the natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol and chlorosulfonic acid are all purchased from Nanjing Taiye New chemical materials Co Ltd; the pulverizer, the strong base reaction kettle, the flask, and the membrane sulfonator reaction equipment are all purchased from Shanghai Bigaer Intelligent science and technology, inc.
Example 2
The invention provides a technical scheme that: a preparation method of polyanion modified cellulose comprises the raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 10000r/min, sieving the natural cellulose with a 60-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong base reaction kettle, adding 110 parts of cesium hydroxide with the concentration of 50% into the natural cellulose, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ during the reaction, and reacting for 40min to obtain alkalized cellulose A after the reaction;
s2, carrying out secondary alkalization reaction, taking out the flask, and adding 25 parts of ethanol and isopropanol at the temperature of 20 DEG C10 parts of n-butanol and 5 parts of n-butanol, and dividing the mixed solution into two parts of P, namely 1 1 And P 2 Using a mixed solution P 1 And 10 parts of cesium hydroxide with the concentration of 50% are sequentially added into a strong alkali reaction kettle, and are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 20min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 120 parts of monochloroacetic acid and the mixed solution P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 70 ℃ and the reaction time to be 60min, and after the reaction, removing the mixed solution by adopting a centrifugal method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 250 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on the sulfonic group and carboxyl at the reaction temperature of 70 ℃ for 30min, washing the mixture with purified water after the reaction, sieving for 2 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and a performance test are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
Example 3
The invention provides a technical scheme that: a preparation method of polyanion modified cellulose comprises the raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 10000r/min, sieving the natural cellulose through an 80-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong alkali reaction kettle, adding 120 parts of cesium hydroxide with the concentration of 52% into the strong alkali reaction kettle, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ and the reaction time to be 40min during reaction, and obtaining alkalized cellulose A after reaction;
s2, carrying out secondary alkalization reaction, taking out a flask, adding 30 parts of ethanol, 15 parts of isopropanol and 5 parts of n-butyl alcohol at the temperature of 20 ℃ to prepare a mixed solution P, and dividing the mixed solution P into two parts P of 1 1 And P 2 Using a mixture P 1 And 10 parts of cesium hydroxide with the concentration of 52% are sequentially added into the strong alkali reaction kettle, and then are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 20min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 150 parts of monochloroacetic acid and the mixed solution P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 70 ℃ and the reaction time to be 60min, and after the reaction, removing the mixed solution by adopting a centrifugal method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 300 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on the sulfonic group and carboxyl, wherein the reaction temperature is 90 ℃, the reaction time is 40min, after the reaction, cleaning the mixture with purified water, sieving for 3 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and a performance test are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
Example 4
The invention provides a technical scheme that: a preparation method of polyanion modified cellulose comprises the raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and comprises a pulverizer, a strong base reaction kettle, a flask and membrane sulfonator reaction equipment, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 10000r/min, sieving the natural cellulose with a 80-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong base reaction kettle, adding 120 parts of cesium hydroxide with the concentration of 52% into the natural cellulose, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ during the reaction, and reacting for 40min to obtain alkalized cellulose A after the reaction;
s2, carrying out secondary alkalization reaction, taking out a flask, adding 30 parts of ethanol, 10 parts of isopropanol and 10 parts of n-butyl alcohol at the temperature of 20 ℃ to prepare a mixed solution P, and dividing the mixed solution P into two parts P of 1 1 And P 2 Using a mixed solution P 1 And 10 parts of cesium hydroxide with the concentration of 52% are sequentially added into a strong alkali reaction kettle, and are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 30min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 150 parts of monochloroacetic acid and the mixed solution P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 70 ℃ and the reaction time to be 60min, and after the reaction, removing the mixed solution by adopting a centrifugal method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 300 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on the sulfonic group and carboxyl, wherein the reaction temperature is 80 ℃, the reaction time is 40min, after the reaction, cleaning the mixture with purified water, sieving for 3 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and a performance test are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
The substitution degree DS, viscosity and PH value of the prepared polyanion modified cellulose are changed by a detection instrument and a calculation method under the condition of 20 ℃ by combining the methods shown in examples 1 to 4 and adopting an ashing method and a water dissolving method. The following table is obtained:
| degree of substitution DS | Viscosity of the oil | pH value of | Duration of time | |
| Example 1 | 1.26 | 59mPa.s | 7.5 | 50h |
| Example 2 | 1.21 | 55mPa.s | 7.1 | 48h |
| Example 3 | 1.33 | 64mPa.s | 8.1 | 53h |
| Example 4 | 1.29 | 62mPa.s | 7.8 | 52h |
The working principle is as follows: the method comprises the steps of adding strong alkali cesium hydroxide solution into short fiber of natural cotton serving as a raw material to carry out an alkalization reaction, carrying out an etherification reaction on an alcohol mixture and monochloroacetic acid, carrying out primary modification treatment on natural cellulose to generate polyanionic cellulose with high purity, carrying out modification sulfonation reaction through chlorosulfonic acid to generate polyanionic modified cellulose, and scientifically proportioning raw material components to control the substitution degree and improve the performance of the polyanionic modified cellulose.
In summary, the polyanion modified cellulose is prepared by using short fibers of natural cotton as a raw material, adding a strong alkali cesium hydroxide solution for an alkalization reaction, then carrying out an etherification reaction on an alcohol mixture and monochloroacetic acid, carrying out a first modification treatment on the natural cellulose to generate the polyanion cellulose with high purity, and then carrying out a modification sulfonation reaction on the natural cellulose by using chlorosulfonic acid to generate the polyanion modified cellulose, so that the problem that the substitution degree and the performance of the polyanion modified cellulose cannot be accurately controlled in the conventional preparation of the polyanion modified cellulose is solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of polyanion modified cellulose is characterized by comprising raw materials of natural cellulose, cesium hydroxide, monochloroacetic acid, ethanol, isopropanol, n-butanol, chlorosulfonic acid and purified water, and reaction equipment of a pulverizer, a strong base reaction kettle, a flask and a membrane sulfonator, wherein the raw materials are counted according to the mass part ratio: 100 parts of natural cellulose, 100-130 parts of cesium hydroxide with the concentration of 48-52%, 120-150 parts of monochloroacetic acid, 25-30 parts of ethanol, 10-15 parts of isopropanol, 5-10 parts of n-butanol and 250-300 parts of chlorosulfonic acid; the preparation method comprises the following steps:
s1, performing primary alkalization reaction, taking out 100 parts of natural cellulose, placing the natural cellulose into a grinder, stirring and smashing at a stirring speed of 6000-10000r/min, sieving the natural cellulose by a 60-80-mesh fine sieve after stirring to obtain powdery natural cellulose, placing the powdery natural cellulose into a strong alkali reaction kettle, adding 90-120 parts of cesium hydroxide with the concentration of 48% -52% into the powdery natural cellulose, performing alkalization reaction, controlling the reaction temperature to be 20 ℃ and the reaction time to be 30-40min, and obtaining alkalized cellulose A after the reaction;
s2, carrying out secondary alkalization reaction, taking out a flask, adding 25-30 parts of ethanol, 10-15 parts of isopropanol and 5-10 parts of n-butanol at the temperature of 20 ℃ to prepare a mixed solution P, and dividing the mixed solution P into two P parts of 1 1 And P 2 Using a mixture P 1 And 10 parts of cesium hydroxide with the concentration of 48-52% are sequentially added into a strong alkali reaction kettle, and are subjected to full alkalization reaction with the alkalized cellulose A again at the reaction temperature of 20 ℃ for 20-30min, so that the alkalized cellulose B is obtained after the reaction;
s3, etherification substitution reaction, taking out the flask, and adding 120-150 parts of monochloroacetic acid and mixed liquid P at the temperature of 20 DEG C 2 Mixing to form a mixed solution R, taking out the strong base reaction kettle, sequentially adding the alkalized cellulose B and the mixed solution R into the strong base reaction kettle, carrying out etherification reaction, controlling the reaction temperature to be 50-70 ℃ and the reaction time to be 40-60min, and after the reaction, removing the mixed solution by adopting a centrifugal method, and drying, grinding and sieving to obtain polyanionic cellulose C;
s4, carrying out sulfonic group modification treatment, taking out the membrane sulfonator, adding 250-300 parts of chlorosulfonic acid and polyanionic cellulose C, mixing, carrying out modification reaction on the sulfonic group and carboxyl at the reaction temperature of 70-90 ℃ for 30-40min, washing the mixture with purified water after the reaction, sieving for 2-3 times, drying, grinding and sieving to obtain polyanionic modified cellulose D;
s5, a substitution degree ashing method and performance tests are carried out, wherein the ashing method is adopted, a part of polyanion modified cellulose D sample is taken out, high-temperature burning is carried out to form ash, a standard solution of hydrochloric acid is added to titrate and dissolve the ash, a methyl red indicator is added, the reaction time is slow, and the substitution degree DS is calculated; and taking out beaker purified water by adopting a water dissolving method, slowly adding a part of polyanion modified cellulose D sample into the beaker, fully dissolving and stirring, and testing the viscosity, the PH value and the duration of the polyanion modified cellulose D.
2. The method for producing a polyanionic-modified cellulose according to claim 1, wherein the method comprises: the natural cellulose includes cotton, hemp, silk and animal hair, and the polyanionic cellulose is prepared from cotton processed by short fiber refined cotton or wood pulp processed by plant fiber, wherein the cotton cellulose content of the cotton is up to 94%, and the hemp cellulose content of the wood pulp is 60-80%, so the refined cotton fiber is adopted in the embodiment.
3. The method for producing a polyanionic-modified cellulose according to claim 1, wherein the method comprises: the cesium hydroxide is an inorganic compound of white crystalline powder, has a molecular formula of CsOH, a molecular weight of 149.91 and a density of 3.675g/cm 3 The melting point is 272 ℃, csOH and refined cotton fiber are subjected to alkalization modification reaction, specifically, carboxyl on cellulose is acidic, and after cesium hydroxide solution is absorbed, alkali fiber salt and water are generated by modification, wherein the alkalization equation is [ C ] 6 H 7 O 2 (OH) 3 ] n +nCsOH→[C 6 H 7 O 2 (OH) 2 OCs] n +nH 2 O。
4. The method for preparing a polyanionic-modified cellulose according to claim 1, wherein: the monochloroacetic acid is an organic compound of white crystalline powder, exists in three forms of alpha, beta and gamma, and has a molecular formula of ClCH 2 COOH, molecular weight 94.497, density 1.58g/cm 3 The boiling point is 189 ℃ and the critical pressure is 5.78MPa, and the carboxymethyl agent is used for preparing polyanionic cellulose.
5. The method for preparing a polyanionic-modified cellulose according to claim 1, wherein: the ethanol is a volatile, colorless and transparent liquid organic compound, and the molecular formula of the ethanol is C 2 H 6 O, molecular weight of 46.07, is saturated monohydric alcohol with hydroxyl group, and the ethanol solution density is 0.7893g/cm at 20 deg.C 3 (ii) a The isopropanol is an organic of colorless transparent liquidA compound of formula C 3 H 8 O, molecular weight of 60.095, density of 0.7855g/cm 3 The critical pressure is 4.76MPa; the n-butanol is an organic compound of colorless transparent liquid and has a molecular formula of C 4 H 10 O, molecular weight 74.122, density 0.81g/cm 3 The melting point is-89 ℃, and the critical pressure is 4.414MPa.
6. The method for preparing a polyanionic-modified cellulose according to claim 1, wherein: the chlorosulfonic acid is a colorless liquid inorganic compound with a molecular formula of ClHSO 3 Molecular weight of 116.524, density of 1.753g/cm 3 The melting point is-80 ℃ and the critical pressure is 8.5MPa.
7. The method for producing a polyanionic-modified cellulose according to claim 1, wherein the method comprises: the strong base reaction kettle is a reaction vessel for synthesizing chemical substances under certain temperature and pressure conditions, and the structure of the strong base reaction kettle consists of a reaction kettle body, a kettle cover, a jacket, a stirrer, a rotating shaft and a driving device.
8. The method for producing a polyanionic-modified cellulose according to claim 1, wherein the method comprises: the membrane type sulfonator is a process that sulfonation reaction is carried out between polyanionic cellulose and multi-tube membrane type reactor to generate sulfonic acid, tail gas is absorbed by alkali liquor to generate sulfite, and then air is introduced for oxidation to generate sulfate, and the structure of the membrane type sulfonator is composed of a cylinder body, an inner cavity and a plurality of branch tube plates.
9. The method for preparing a polyanionic-modified cellulose according to claim 1, wherein: the ashing method is characterized in that organic matters in a sample are removed at high temperature, the residual ash is dissolved by acid and is used as a solution to be detected of the sample, specifically, the prepared polyanion modified cellulose is taken out of the sample, the sample is put in a crucible to be gradually heated to 500-600 ℃, and the sample is burnt for 3h to be completely ashed and converted into Cs 2 O in a concentration of 0.1molThe standard hydrochloric acid solution of/L is used for dissolving ashes, and then the excessive hydrochloric acid is titrated by using a cesium hydroxide standard solution with the concentration of 50%, and methyl red is used as an indicator for detection.
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