CN103601852A - Method for modifying cellulose and derivatives thereof - Google Patents
Method for modifying cellulose and derivatives thereof Download PDFInfo
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- CN103601852A CN103601852A CN201310564306.5A CN201310564306A CN103601852A CN 103601852 A CN103601852 A CN 103601852A CN 201310564306 A CN201310564306 A CN 201310564306A CN 103601852 A CN103601852 A CN 103601852A
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Abstract
The invention relates to a graft modification method of cellulose and derivatives thereof. According to the method, other monomers are initiated to perform graft modification in the presence of a catalyst by utilizing hydroxyls on the surfaces of the cellulose and derivatives thereof. The graft modification is performed in a nitrogen atmosphere, the reaction temperature is 30-100 DEG C, the reaction time is 0.5-48 hours, and the modified cellulose-based material is obtained after the reaction is finished. A filter tip rod produced by adding the modified graft polymer into a cigarette filter has an obvious smoke adsorption effect, harmful ingredients in the smoke can be selectively retained, and the comprehensive performance is excellent. The used raw materials are low in cost, the process method is simple, the reaction system can be repeatedly used, the energy consumption is low, the preparation cost is reduced, and the method has good market application prospects and is an important method for industrial conversion and utilization of the cellulose and derivatives thereof.
Description
Technical field
The present invention relates to the preparing technical field of modified-cellulose and derivatived cellulose, is the graft-modification method of a kind of Mierocrystalline cellulose and derivatived cellulose specifically.
Background technology
In recent years, along with the day by day serious and pay attention to day by day of people to environment protection of white pollution problems, exploitation completely biodegradable material becomes the focus trend of scientific development gradually.Mierocrystalline cellulose derives from trees, cotton, fibre of flax for textile material and other agricultural byproducts widely, is the inexhaustible renewable resources of occurring in nature.Meanwhile, can be degradable by microorganism or bacterium in natural environment, be a kind of eco-friendly macromolecular material.But in cellulosic molecule and a large amount of hydrogen bond of intermolecular existence, thereby its indissoluble, difficulty melt, and limited its processing and application, therefore need to carry out derivatize to Mierocrystalline cellulose.
Industrialized derivatived cellulose has cellulose ethanoate (CA) at present, cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) etc., but because the action pane between its melt temperature and degradation temperature is too little, derivatived cellulose is still shaped to master with solution aspect industrial application.At some, need in melt-processed special applications, need to add a large amount of micromolecular softening agent, and these micromolecular softening agent exist and to ooze out and the problem such as pollution in use procedure.
In the chemical modification of numerous Mierocrystalline celluloses and derivative thereof, graft copolymerization is a kind of method of modifying flexibly and effectively, by graft copolymerization, different functional groups can be incorporated into cellulosic backbone, cellulose base graft copolymer that can be different from the angle processability of Molecular Structure Design, when retaining Mierocrystalline cellulose excellent properties, by the specific functional groups of introducing, improve the performance of cellulose-based material.
Summary of the invention
The object of the present invention is to provide a kind of good stability, technique is simple, easy and simple to handle, widely applicable novel grafting modified-cellulose and the preparation method of derivative thereof.
The graft-modification method of Mierocrystalline cellulose of the present invention and derivative thereof is carried out as follows: the polymerization single polymerization monomer reaction soln of Mierocrystalline cellulose or derivatived cellulose, polymerization single polymerization monomer and solvent is added in there-necked flask, add again catalyzer, under nitrogen atmosphere, temperature of reaction is 30-100 ℃, reaction times is 0.5-48h, react the complete modified-cellulose sill that obtains, the mass ratio of Mierocrystalline cellulose or derivatived cellulose and catalyzer is 5-100:1, and polymerization single polymerization monomer reaction soln concentration is 0.1mol/L-10 mol/L; The mass volume ratio of Mierocrystalline cellulose or derivatived cellulose and polymerization single polymerization monomer reaction soln is 1:10-1000g/ml.
Described derivatived cellulose comprises a kind of in rhodia, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, methylcellulose gum, ethyl cellulose, carboxymethyl cellulose etc.
Described polymerization single polymerization monomer comprises methyl methacrylate, vinylbenzene, glycidyl methacrylate, methacrylic acid-2-hydroxy methacrylate, allylamine, 4-vinylpridine, vinyl pyrrolidone, NIPA, acrylamide, vinylformic acid, styracin, toxilic acid, Sodium styrene sulfonate, vinyl sulfonic acid sodium, a kind of in 2-acrylamide-2-methyl propane sulfonic etc.
Described catalyzer comprises a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, hydrogen peroxide, ammonium persulphate, Sodium Persulfate, benzoyl peroxide, the benzoyl peroxide tert-butyl ester, methylethyl ketone peroxide, potassium permanganate, ceric ammonium nitrate, potassium bichromate, iron(ic) chloride etc.
Described solvent comprises water, ethanol, methyl alcohol, benzene,toluene,xylene, methylene dichloride, ethylene dichloride, trichloromethane, normal hexane, hexanaphthene, ether, acetone, acetonitrile, tetrahydrofuran (THF), pyridine, dimethyl sulfoxide (DMSO), N, dinethylformamide, a kind of in N,N-dimethylacetamide etc.
The present invention is mainly the hydroxyl that utilizes Mierocrystalline cellulose and derivatived cellulose surface, under the effect of catalyzer, causes other monomers and carries out graft modification.The applicable most olefin monomer of the present invention, and can, by changing reaction conditions, select different graftomer can obtain the cellulose base graftomer of the modification of difference in functionality.Technological operation is simple, and reaction conditions is gentle, is applicable to large-scale industrialization and produces.The functional modification cellulose base graftomer that the present invention obtains, for cigarette filter tip aspect, prepares filter stick, and it is obvious to flue gas adsorption effect, objectionable constituent in selective retention flue gas preferably, excellent combination property; Raw material that the inventive method is used is inexpensive, processing method simple, reaction system can be reused, energy consumption is low, reduced preparation cost, has good market application foreground, is by one of important method of Mierocrystalline cellulose and derivatives industry trans-utilization thereof.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described reactant all can obtain from open commercial sources if no special instructions.
Embodiment 1
First with polymerization single polymerization monomer vinylformic acid and solvent DMF, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 0.1mol/L vinylformic acid-DMF.
By 0.1mol/L vinylformic acid-N of 10g Mierocrystalline cellulose and 200ml, dinethylformamide polymerization single polymerization monomer reaction soln adds in there-necked flask, add again 0.1g catalyzer azo-bis-isobutyl cyanide, under nitrogen atmosphere, at 100 ℃, react 0.5h, after repeatedly cleaning, vacuum-drying, obtains graft modification Mierocrystalline cellulose.
Embodiment 2
First with polymerization single polymerization monomer allylamine and etoh solvent, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 10mol/L allylamine-ethanol.
10mol/L allylamine-ethanol polymerization single polymerization monomer reaction soln of the rhodia of 10g and 200ml is added in there-necked flask, add again catalyzer 0.1g Sodium Persulfate, under nitrogen atmosphere, 30 ℃ of reaction 48h, repeatedly, after cleaning-drying, obtain the rhodia of graft modification.
Embodiment 3
First by polymerization single polymerization monomer acrylamide and aqueous solvent, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 0.5mol/L acrylamide-water.
0.5mol/L acrylamide-water polymerization single polymerization monomer reaction soln of 20g cellulose acetate propionate and 200ml is added in there-necked flask, add again catalyzer 1.62g iron(ic) chloride, under nitrogen atmosphere, 50 ℃ of reaction 8h, repeatedly, after cleaning-drying, obtain the cellulose acetate propionate of graft modification.
Embodiment 4
First by polymerization single polymerization monomer methyl methacrylate and solvents tetrahydrofurane, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 1mol/L methyl methacrylate-tetrahydrofuran (THF).
Methyl methacrylate-tetrahydrofuran by polymerization monomer reaction solution of the 1mol/L of 1g cellulose acetate butyrate and 1000ml is added in there-necked flask, add again catalyzer 0.0158g potassium permanganate, under nitrogen atmosphere, 45 ℃ of reaction 6h, repeatedly, after cleaning-drying, obtain the cellulose acetate butyrate of graft modification.
Embodiment 5
First with polymerization single polymerization monomer vinylbenzene and solvent toluene, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 2mol/L vinylbenzene-toluene.
Vinylbenzene-toluene polymerization single polymerization monomer reaction soln of the 2mol/L of 10g cellulose nitrate and 1000ml is added in there-necked flask, add again catalyzer 0.5g ceric ammonium nitrate, under nitrogen atmosphere, 55 ℃ of reaction 3h, repeatedly, after cleaning-drying, obtain the cellulose nitrate of graft modification.
Embodiment 6
First with polymerization single polymerization monomer styracin and solvent acetonitrile, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 1mol/L styracin-acetonitrile.
Styracin-acetonitrile polymerization single polymerization monomer reaction soln of the 1mol/L of 10g methylcellulose gum and 1000ml is added in there-necked flask, add again catalyzer 0.4g benzoyl peroxide, under nitrogen atmosphere, 80 ℃ of reaction 12h, repeatedly, after cleaning-drying, obtain the methylcellulose gum of graft modification.
Embodiment 7
First with polymerization single polymerization monomer glycidyl methacrylate and solvent trichloromethane, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 2mol/L glycidyl methacrylate-trichloromethane.
Glycidyl methacrylate-trichloromethane polymerization single polymerization monomer reaction soln of the 2mol/L of 10g ethyl cellulose and 1000ml is added in there-necked flask, add again catalyzer 0.5g methylethyl ketone peroxide, under nitrogen atmosphere, 50 ℃ of reaction 5h, repeatedly, after cleaning-drying, obtain the ethyl cellulose of graft modification.
Embodiment 8
First with polymerization single polymerization monomer methacrylic acid-2-hydroxy methacrylate and solvent ether, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 0.5mol/L methacrylic acid-2-hydroxy methacrylate-ether.
The methacrylic acid of the 0.5mol/L of 10g carboxymethyl cellulose and 1000ml-2-hydroxy methacrylate-ether polymerization single polymerization monomer reaction soln is added in there-necked flask, add again catalyzer 0.6g ammonium persulphate, under nitrogen atmosphere, 60 ℃ of reaction 3h, repeatedly, after cleaning-drying, obtain the carboxymethyl cellulose of graft modification.
Embodiment 9
First by polymerization single polymerization monomer 2-acrylamide-2-methyl propane sulfonic and solvent dimethyl sulfoxide (DMSO), be mixed with the polymerization single polymerization monomer reaction soln that concentration is 0.8mol/L2-acrylamide-2-methyl propane sulfonic-dimethyl sulfoxide (DMSO).
2-acrylamide-2-methyl propane sulfonic-dimethyl sulfoxide (DMSO) polymerization single polymerization monomer reaction soln of the 0.8mol/L of 10g Walocel MT 20.000PV and 1000ml is added in there-necked flask, add again catalyzer 0.5g potassium bichromate, under nitrogen atmosphere, 85 ℃ of reaction 10h, repeatedly, after cleaning-drying, obtain the Walocel MT 20.000PV of graft modification.
Embodiment 10
First with polymerization single polymerization monomer toxilic acid and solvent pyridine, be mixed with the polymerization single polymerization monomer reaction soln that concentration is 0.5mol/L toxilic acid-pyridine.
Toxilic acid-pyridine polymerization single polymerization monomer reaction soln of the 0.5mol/L of 10g rhodia and 1000ml is added in there-necked flask, add again catalyzer 1g 2,2'-Azobis(2,4-dimethylvaleronitrile), under nitrogen atmosphere, 55 ℃ of reaction 7h, repeatedly, after cleaning-drying, obtain the rhodia of graft modification.
In order to prove preparation method's of the present invention superiority, contriver has done following application simultaneous test:
Diacetate fiber in cigarette is extracted, by in above-mentioned unmodified acetate silk, embodiment 1-10 between resulting polymer-modified filling filter tip and cigarette, again the diacetate fiber of originally extracting is put into cigarette, clip the filter tip part that exceeds tipping paper, make through improved cigarette filter.Main absorption property is according to GB: GB/T5606.1-2004, GB/T16447-2004, and GB/T19069-2004, GB/T 23355-2009, GB/T23203.1-2008, GB/T 23356-2009, detects.
Detected result is as follows:
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Unit |
| Benzo [a] pyrene | 9.1 | 7.7 | 8.6 | 8.8 | 8.1 | Nanogram/ |
| Carbon monoxide | 14.4 | 12.9 | 13.2 | 13.9 | 12.4 | Milligram/ |
| Prussic acid | 166.2 | 157.6 | 165.8 | 156.7 | 172.3 | Microgram/ |
| NNK | 5.9 | 4.9 | 4.3 | 4.6 | 3.9 | Nanogram/ |
| Phenol | 13.8 | 12.7 | 10.8 | 11.6 | 12.3 | Microgram/ |
| Ammonia | 5.0 | 3.9 | 3．3 | 4.1 | 3.7 | Microgram/ |
| Nicotine | 1.8 | 1.5 | 1.5 | 1.9 | 1.7 | Milligram/ |
| Tar | 11．3 | 10.9 | 9.8 | 10.1 | 11.9 | Milligram/ |
| ? | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Unit |
| Benzo [a] pyrene | 9.7 | 8．6 | 9.4 | 8.3 | 10.2 | Nanogram/ |
| Carbon monoxide | 13.8 | 13.2 | 13.9 | 13.9 | 12.6 | Milligram/ |
| Prussic acid | 176.1 | 146．5 | 167.2 | 166.6 | 152.8 | Microgram/ |
| NNK | 5.1 | 4.5 | 5.2 | 5.1 | 3.5 | Nanogram/ |
| Phenol | 12.4 | 12.2 | 11.7 | 13.6 | 11.4 | Microgram/ |
| Ammonia | 5.6 | 4.9 | 3.9 | 4.3 | 4.1 | Microgram/ |
| Nicotine | 1.6 | 1.7 | 1.5 | 1.7 | 1.5 | Milligram/ |
| Tar | 12．2 | 11.3 | 11.1 | 11.4 | 12.6 | Milligram/ |
Claims (4)
1. the preparation method of the graft-modification method modification cellulose acetate of a Mierocrystalline cellulose and derivative thereof, it is characterized in that concrete reaction is by carry out as follows: by Mierocrystalline cellulose or derivatived cellulose, the polymerization single polymerization monomer reaction soln of polymerization single polymerization monomer and solvent adds in there-necked flask, add again catalyzer, under nitrogen atmosphere, temperature of reaction is 30-100 ℃, reaction times is 0.5-48h, react the complete modified-cellulose sill that obtains, the mass ratio of Mierocrystalline cellulose or derivatived cellulose and catalyzer is 5-100:1, polymerization single polymerization monomer reaction soln concentration is 0.1mol/L-10 mol/L, the mass volume ratio of Mierocrystalline cellulose or derivatived cellulose and polymerization single polymerization monomer reaction soln is 1:10-1000 g/ml,
Described catalyzer is a kind of in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Sodium Persulfate, benzoyl peroxide, methylethyl ketone peroxide, potassium permanganate, ceric ammonium nitrate, potassium bichromate, iron(ic) chloride.
2. the graft-modification method of Mierocrystalline cellulose according to claim 1 and derivatived cellulose, is characterized in that described derivatived cellulose is a kind of in rhodia, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, methylcellulose gum, ethyl cellulose, carboxymethyl cellulose.
3. the graft-modification method of Mierocrystalline cellulose according to claim 1 and derivatived cellulose, is characterized in that described polymerization single polymerization monomer is a kind of in methyl methacrylate, vinylbenzene, glycidyl methacrylate, allylamine, acrylamide, vinylformic acid, styracin, toxilic acid, 2-acrylamide-2-methyl propane sulfonic.
4. the graft-modification method of Mierocrystalline cellulose according to claim 1 and derivatived cellulose, it is characterized in that described solvent is water, ethanol, benzene, toluene, trichloromethane, acetonitrile, tetrahydrofuran (THF), pyridine, dimethyl sulfoxide (DMSO), a kind of in DMF.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834133A (en) * | 2014-03-05 | 2014-06-04 | 湖南工业大学 | Porous membrane based on ethyl cellulose-grafted polymethyl methacrylate copolymer and preparation method thereof |
| CN104001478A (en) * | 2014-06-19 | 2014-08-27 | 云南中烟工业有限责任公司 | Iron acetate crosslinking montmorillonite filter tip additive and application thereof |
| CN104126870A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Manufacturing method and application of anionic polymer modified cellulose acetate |
| CN104130355A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Preparation method and use of hydrophobic polymer-modified cellulose acetate |
| CN104130354A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Preparation method and use of cationic polymer-modified cellulose acetate |
| CN106621713A (en) * | 2016-12-27 | 2017-05-10 | 兰州理工大学 | Method for treating pollutants of waste gas in glass industry |
| CN108824760A (en) * | 2018-08-01 | 2018-11-16 | 北京启顺京腾科技有限责任公司 | A kind of foamed cement composite floor board and preparation method thereof of modified fibre enhancing |
| CN113699786A (en) * | 2021-10-14 | 2021-11-26 | 陈小琴 | Cotton fiber-based lasting antibacterial fiber fabric and preparation method thereof |
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| CN101787101A (en) * | 2010-01-25 | 2010-07-28 | 陕西科技大学 | Preparation method of nanometer resin with high hygroscopy |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834133A (en) * | 2014-03-05 | 2014-06-04 | 湖南工业大学 | Porous membrane based on ethyl cellulose-grafted polymethyl methacrylate copolymer and preparation method thereof |
| CN103834133B (en) * | 2014-03-05 | 2019-02-22 | 湖南工业大学 | A kind of perforated membrane and preparation method thereof based on ethyl cellulose grafting polymethyl methacrylate copolymer |
| CN104001478A (en) * | 2014-06-19 | 2014-08-27 | 云南中烟工业有限责任公司 | Iron acetate crosslinking montmorillonite filter tip additive and application thereof |
| CN104001478B (en) * | 2014-06-19 | 2016-02-03 | 云南中烟工业有限责任公司 | A kind of ferric acetate cross linked montmorillonite additives of filter tip and application thereof |
| CN104126870A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Manufacturing method and application of anionic polymer modified cellulose acetate |
| CN104130355A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Preparation method and use of hydrophobic polymer-modified cellulose acetate |
| CN104130354A (en) * | 2014-07-18 | 2014-11-05 | 云南中烟工业有限责任公司 | Preparation method and use of cationic polymer-modified cellulose acetate |
| CN104126870B (en) * | 2014-07-18 | 2018-01-30 | 云南中烟工业有限责任公司 | A kind of anionic polymer is modified the preparation method and applications of cellulose acetate |
| CN106621713A (en) * | 2016-12-27 | 2017-05-10 | 兰州理工大学 | Method for treating pollutants of waste gas in glass industry |
| CN108824760A (en) * | 2018-08-01 | 2018-11-16 | 北京启顺京腾科技有限责任公司 | A kind of foamed cement composite floor board and preparation method thereof of modified fibre enhancing |
| CN113699786A (en) * | 2021-10-14 | 2021-11-26 | 陈小琴 | Cotton fiber-based lasting antibacterial fiber fabric and preparation method thereof |
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Application publication date: 20140226 |