CN101974848B - Preparation method of cellulose-based ion exchange fiber - Google Patents
Preparation method of cellulose-based ion exchange fiber Download PDFInfo
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- CN101974848B CN101974848B CN2010102660826A CN201010266082A CN101974848B CN 101974848 B CN101974848 B CN 101974848B CN 2010102660826 A CN2010102660826 A CN 2010102660826A CN 201010266082 A CN201010266082 A CN 201010266082A CN 101974848 B CN101974848 B CN 101974848B
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- 239000000835 fiber Substances 0.000 title claims abstract description 52
- 238000005342 ion exchange Methods 0.000 title claims abstract description 41
- 239000001913 cellulose Substances 0.000 title claims abstract description 32
- 229920002678 cellulose Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 4
- 239000007795 chemical reaction product Substances 0.000 abstract 3
- 238000007334 copolymerization reaction Methods 0.000 abstract 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000008234 soft water Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- -1 phenolic aldehyde Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The invention discloses a preparation method of cellulose-based ion exchange fiber, which comprises the following steps: (1) dipping dried cellulose fiber dried with constant weight into acidic potassium permanganate solution, stirring the mixture, washing the cellulose fiber with water, and removing moisture to obtain cellulose fiber carried with MnO2; (2) putting the cellulose fiber carried with the MnO2 in acrylamide solution, adding a reducing agent, carrying out graft copolymerization in thermostatic shaking water bath for 3-5h, washing the obtained reaction product with water, removing the residual manganese ions after copolymerization, washing the reaction product with water again, and drying the reaction product until being in a constant weight state to obtain a graft polymer; and (3) adding the graft polymer to mixed solution of NaOH and NaClO, carrying out degradation reaction in the thermostatic shaking water bath for 0.5-2h, performing acid-washing on the graft polymer to remove the residual chlorine after reaction, washing the obtained graft polymer with water and drying the washed graft polymer until being in a constant weight state to obtain the cellulose-based ion exchange fiber.
Description
Technical field
The present invention relates to the ionic exchange fibre technology field, relate in particular to a kind of preparation method of cellulose base ion-exchange fibre.
Background technology
Ion-exchange fibre is a kind of fibrous ion exchange sorbing material, and it is made up of the monofilament of many even thickness, and diameter range is between 20～300um.The structure of ion-exchange fibre is made up of with the cation exchange groups two parts on being connected it matrix fiber.Wherein matrix fiber has polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride-acrylonitrile copolymer, gathers phenolic aldehyde, gathers phthalein amine, polyolefin etc., and cation exchange groups has strong acid, weak acid, highly basic, weak base, amphiprotic group etc.
The preparation of ion-exchange fibre starts from the forties in 20th century, and people have at first prepared the yin, yang ion-exchange fibre of phosphorous acidic group and amido.Since the seventies, the former Soviet Union, the U.S., Japan successfully develop all types of ion-exchange fibres in succession, and have realized industrialization, are successfully used to the recovery field of environmental improvement and resource.Along with to the structure of ion-exchange fibre and deepening continuously of performance scheduling theory Study on Problems, the Application Areas of ion-exchange fibre is also widened gradually.
Though the research about ion-exchange fibre is more, its preparation method basically all is that matrix material carries out graft modification with synthetic fiber, and does not see that cellulose fibre is the research report of the ion-exchange fibre of matrix material.The alkalinous ion-exchange fibre absorbent of introducing like Chinese patent 03115872.2 is the acrylonitrile-methymethacrylate-itaconic ester trimer of amino-contained functional group.Chinese patent 02125204.1 is that raw material makes the core-skin layered material respectively with the high impact polystyrene of certain prescription, polystyrene, polypropylene, polyethylene etc., and then steps such as compound silk, fiber are crosslinked, fiber functionalization make corresponding ion-exchange fibre through making.Also have Chinese patent 92111328.5,01142191.6,01100437.1,200710054239.7,200410060275.0 etc., all belong to this type of, just do not give unnecessary details one by one at this.
Summary of the invention
Technical problem to be solved by this invention is: the preparation method of the cellulose base ion-exchange fibre of to the deficiency that prior art exists, provide that a kind of technology is simple, flow process short, absorption and desorption rate are fast.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of preparation method of cellulose base ion-exchange fibre may further comprise the steps:
(1) adhering to of initator: will dry to the cellulose fibre of constant weight and be immersed in the acid permanganate soln, stir 10～60 minutes, water flushing then separates and removes moisture, obtains being attached with MnO
2Cellulose fibre.
(2) graft polymerization reaction: will be attached with MnO
2Cellulose fibre put into propylene phthalein amine aqueous solution, add reductant, in 50 ± 10 ℃ constant-temperature shaking water-bath; Behind the graft polymerization reaction 3～5 hours; With the flushing of product water and except that the remaining manganese ion of dereaction, water washes and is dried to constant weight again, obtains the glycerol polymerization product.
(3) degradation reaction: the glycerol polymerization product is joined in the mixed solution of NaOH and NaClO; In 20 ± 10 ℃ constant-temperature shaking water-bath; Demote reaction after 0.5～2 hour; With the remaining chlorine of pickling dereaction, water washes and is dried to constant weight then, obtains the cellulose base ion-exchange fibre.Wherein, described degradation reaction is the reaction of Hofmann degradation.Said water is preferably when washing and uses the soft water flushing.
Wherein, said acid permanganate soln is potassium permanganate-sulfuric acid solution, and sulfuric acid concentration is 0.010～0.015mol/L in the said acid permanganate soln, and potassium permanganate concentration is 0.012～0.020mol/L.
Wherein, the concentration of said propylene phthalein amine aqueous solution is 1～2mol/L.
In the step (2), the reductant of said adding is a sulfuric acid solution, and the concentration of said reductant sulfuric acid solution in reaction solution is 0.006～0.010mol/L.
In the step (2), the product water is washed, and remove the remaining manganese ion of dereaction with oxalic acid solution.
In the mixed solution of said NaOH and NaClO, the concentration of NaOH is 0.3～0.5mol/L, and the concentration of NaCIO is 0.01～0.02mol/L.
In the step (3), when removing unnecessary chlorine with pickling, said acid is sulfuric acid solution.
Said cellulose fibre can be a natural fabric, also can be regenerated celulose fibre, and natural fabric can be used cotton fiber, and cotton or absorbent gauze, regenerated celulose fibre can be viscose, fabric, nonwoven fabric etc.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the preparation of ion-exchange fibre of the present invention is to be base material with the cellulose fibre, and this cellulose fibre matrix can be a native cellulose both, like cotton, also can be regenerated cellulose, like viscose etc.Broad like this raw material sources, having avoided is that the raw material of feedstock production ion-exchange fibre reduces day by day with synthetic fiber, supplies shortcoming hard to carry on.Simultaneously, the Application Areas and the scope of cellulose fibre have further been expanded again.
2, act as chemisorbed between the cellulose base ion-exchange fibre of the present invention preparation and solute, or be referred to as ion exchange.Compare with granular ion exchange material of the prior art, absorption and desorption rate are arranged faster, its adsorption rate granular ion exchange material of comparing can exceed several times to tens times.
3, another outstanding feature of cellulose base ion-exchange fibre is can be to SO
2, HF, HCI, Cl
2, F
2, NH
3Adsorb etc. harmful sour gas, adsorption rate is fast, and exchange capacity is big; And granular ion exchange resin is difficult to and gas generation ion-exchange reactions owing to shrinkage cavity or closed pore under drying regime.
4, because non-stripping active groups such as organic amine are contained on cellulose base ion-exchange fibre surface; Can change the skin microenvironment when contacting, reach and press down Bactericidal purpose, simultaneously with human body skin; Also can absorb peculiar smell such as hydrogen sulfide that human body discharges and ammonia; Effect with deodorizing adds the superior wearability that cellulose fibre itself has, and therefore can be used for making house spins articles for use, underwear, sweat shirt etc.
The specific embodiment
Come further to set forth the present invention below in conjunction with concrete embodiment.Should be understood that these embodiment only to be used to the present invention is described and be not used in restriction protection scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) adhering to of initator: extracting degreasing gauze 15g, in vacuum drying oven, dry to constant weight, be immersed in potassium permanganate-sulfuric acid solution; Wherein potassium permanganate concentration is 0.015mol/L; Sulfuric acid concentration is 0.011mol/L, and stirring reaction 30 minutes is rinsed well with soft water then; Separate and remove redundant moisture, obtain being attached with MnO
2Cellulose fibre.
(2) graft polymerization reaction: will be attached with MnO
2Cellulose fibre put into graft polymerization reaction solution, the concentration of propylene phthalein amine is 1.2mol/L in this solution, the concentration of reductant sulfuric acid is 0.008mol/L; In 50 ℃ constant-temperature shaking water-bath, graft polymerization reaction washed product after 4 hours with soft water; Remove the remaining manganese ion of dereaction with rare oxalic acid solution; Extremely neutral with the soft water flushing again, and be dried to constant weight, obtain the glycerol polymerization product.
(3) Hofmann degradation reaction: it is that 0.45mol/L and NaClO concentration are in the mixed solution of 0.012mol/L that the glycerol polymerization product is joined NaOH concentration; In 25 ℃ constant-temperature shaking water-bath; Carry out the reaction of Hofmann degradation after 1.5 hours; With the remaining chlorine of dilute sulfuric acid dip dereaction,, obtain the cellulose base ion-exchange fibre then with soft water flushing and be dried to constant weight.The percent grafting of gained cellulose base ion-exchange fibre is 72%, and the exchange capacity of fiber is 2.5-3.8mmol/g.
Embodiment 2
(1) adhering to of initator: get 1.67dtex * 38mm viscose short-thread 10g, in vacuum drying oven, dry, be immersed in potassium permanganate-sulfuric acid solution to constant weight; Wherein potassium permanganate concentration is 0.012mol/L; Sulfuric acid concentration is 0.013mol/L, and stirring reaction 20 minutes is rinsed well with soft water then; Separate and remove redundant moisture, obtain being attached with MnO
2Cellulose fibre.
(2) graft polymerization reaction: will be attached with MnO
2Cellulose fibre put into graft polymerization reaction solution, the concentration of propylene phthalein amine is 1.5mol/L in this solution, the concentration of reductant sulfuric acid is 0.007mol/L; In 50 ℃ constant-temperature shaking water-bath, graft polymerization reaction washed product after 3 hours with soft water; Remove the remaining manganese ion of dereaction with rare oxalic acid solution; Extremely neutral with the soft water flushing again, and be dried to constant weight, obtain the glycerol polymerization product.
(3) Hofmann degradation reaction: it is that 0.375mol/L and NaClO concentration are in the mixed solution of 0.015mol/L that the glycerol polymerization product is joined NaOH concentration; In 30 ℃ constant-temperature shaking water-bath; Carry out the reaction of Hofmann degradation after 1 hour; With the remaining chlorine of dilute sulfuric acid dip dereaction,, obtain the cellulose base ion-exchange fibre then with soft water flushing and be dried to constant weight.The percent grafting of gained cellulose base ion-exchange fibre is 75%, and the exchange capacity of fiber is 4.0-5.2mmol/g.
Claims (7)
1. the preparation method of a cellulose base ion-exchange fibre is characterized in that may further comprise the steps:
(1) adhering to of initator: the cellulose fibre that will be dried to constant weight is immersed in the acid permanganate soln, stirs 10～60 minutes, and water flushing then separates and removes moisture, obtains being attached with MnO
2Cellulose fibre;
(2) graft polymerization reaction: will be attached with MnO
2Cellulose fibre put into propylene phthalein amine aqueous solution, add reductant, in 50 ± 10 ℃ constant-temperature shaking water-bath; Graft polymerization reaction 3～5 hours; With the flushing of product water and except that the remaining manganese ion of dereaction, water washes and is dried to constant weight again, obtains the glycerol polymerization product;
(3) degradation reaction: the glycerol polymerization product is joined in the mixed solution of NaOH and NaClO; In 20 ± 10 ℃ constant-temperature shaking water-bath, the reaction 0.5～2 hour of demoting is with the remaining chlorine of pickling dereaction; Water washes and is dried to constant weight then, obtains the cellulose base ion-exchange fibre.
2. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1; It is characterized in that: said acid permanganate soln is potassium permanganate-sulfuric acid solution; Sulfuric acid concentration is 0.010～0.015mol/L in the said acid permanganate soln, and potassium permanganate concentration is 0.012～0.020mol/L.
3. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1 is characterized in that: the concentration of said propylene phthalein amine aqueous solution is 1～2mol/L.
4. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1 is characterized in that: in the step (2), the reductant of said adding is a sulfuric acid solution, and the concentration of said reductant sulfuric acid solution in reaction solution is 0.006～0.010mol/L.
5. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1 is characterized in that: in the step (2), the product water is washed, and remove the remaining manganese ion of dereaction with oxalic acid solution.
6. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1 is characterized in that: in the mixed solution of said NaOH and NaClO, the concentration of NaOH is 0.3～0.5mol/L, and the concentration of NaClO is 0.01～0.02mo l/L.
7. the preparation method of cellulose base ion-exchange fibre as claimed in claim 1 is characterized in that: in the step (3), when removing unnecessary chlorine with pickling, said acid is sulfuric acid solution.
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| CN2010102660826A CN101974848B (en) | 2010-08-27 | 2010-08-27 | Preparation method of cellulose-based ion exchange fiber |
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| CN101974848B true CN101974848B (en) | 2012-07-04 |
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| CN103790010B (en) * | 2013-10-30 | 2015-12-02 | 青岛大学 | A kind of side chain contains the preparation of the chelate fibre of triazole heterocycle |
| CN103668946B (en) * | 2013-11-25 | 2015-12-30 | 恒天海龙股份有限公司 | A kind of blending method prepares the method for ion-exchange viscose and the ion-exchange viscose of preparation thereof |
| CN104876455B (en) * | 2015-05-15 | 2017-04-19 | 济南大学 | Preparation method of manganese dioxide modified glass fibers |
| CN106000340A (en) * | 2016-06-13 | 2016-10-12 | 石狮市三小福服饰有限公司 | Preparation method of manganese dioxide cellulose nanofiber mixed compound |
| CN112981951B (en) * | 2021-03-01 | 2022-12-16 | 上海正家牛奶丝科技有限公司 | Instant deodorizing fiber and preparation method thereof |
| CN114709556A (en) * | 2022-04-22 | 2022-07-05 | 河北工业大学 | Zinc ion battery diaphragm for inhibiting dendritic crystal growth and preparation method thereof |
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