CN101450330A - Ion exchange fiber material one-step preparation method - Google Patents
Ion exchange fiber material one-step preparation method Download PDFInfo
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- CN101450330A CN101450330A CNA2008102202233A CN200810220223A CN101450330A CN 101450330 A CN101450330 A CN 101450330A CN A2008102202233 A CNA2008102202233 A CN A2008102202233A CN 200810220223 A CN200810220223 A CN 200810220223A CN 101450330 A CN101450330 A CN 101450330A
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- 238000005342 ion exchange Methods 0.000 title claims abstract description 40
- 239000002657 fibrous material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 239000002253 acid Substances 0.000 claims abstract description 45
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 32
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000004743 Polypropylene Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000012190 activator Substances 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical group [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 229920002994 synthetic fiber Polymers 0.000 claims description 5
- 239000012209 synthetic fiber Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000002131 composite material Substances 0.000 claims 2
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000003068 static effect Effects 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000006277 sulfonation reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 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 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- 239000012445 acidic reagent Substances 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 22
- 238000012545 processing Methods 0.000 description 20
- 238000001291 vacuum drying Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 230000005855 radiation Effects 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
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- 238000005292 vacuum distillation Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
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- 230000008901 benefit Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical class OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 238000007385 chemical modification Methods 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a method for preparing ion exchange fiber materials. The method takes fibers such as polytetrafluoroethylene, polypropylene, polyacrylonitrile and polyvinyl alcohol which still have good stability and integrity in an extreme environment as a substrate, prepares the strong-acid and weak-acid bifunctional ion exchange fiber materials by pre-irradiation grafting, and provides products with more superior performance for application (such as purification of strong acid reagent and strong alkali reagent) of the ion exchange fiber materials under harsh conditions. The static adsorption capacity of the products can be controlled to be between 3.0 and 4.98 mmol/g, wherein the static adsorption capacity of strong acid parts is between 1.85 and 2.57 mmol/g. The method has high pre-irradiation grafting efficiency, avoids huge waste of monomers in mutual irradiation, can make the grafting ratio realize controllable operation, avoid utilization of strong corrosive materials such as concentrated sulfuric acid and chlorosulfonic acid for sulfonation reaction, avoid environmental pollution and equipment corrosion, has simple process and easy operation, and provides favorable conditions for industrialization of the ion exchange fiber materials.
Description
Technical field
The present invention relates to a class is matrix with fibers such as polytetrafluoroethylene (PTFE), polypropylene, polyacrylonitrile and polyvinyl alcohol, prepares preparation method's technology of novel ion exchange fiber material by pre-irradiation grafting, belongs to functional high polymer material field.
Background technology
Along with the progress of science and technology, the development of society, people have proposed new requirement to parting material.Ion-exchange fibre is referred to as the functional material of 21 century by scientific and technological circle, industrial circle, is class novel environmental consciousness material.This type of material has been obtained widely in industries such as medical components purification, nuclear waste water and trade effluent processing, the processing of waste gas poison gas, air and drink water purifying, food and medicine decolouring, precious metal enrichment and organic solvent recovery, biological substance raising yields and has been used.Expansionary good, function of fine quality is ion-exchange fibre and Application and Development technology thereof efficiently, is a focus of global parting material research and development always.
With the native cellulose is that the ion-exchange fibre of matrix preparation is because its hydrophily is strong, effective ratio area is big, to advantage such as the absorption that is adsorbed separate substance and desorption rate be fast, but because therefore mechanical performance, heat endurance, the corrosion-resistant of such material have limited their scope of application.Synthetic fibers such as polytetrafluoroethylene (PTFE), polypropylene have very excellent chemical stability, if with it is matrix, will obtain the novel ion exchange fiber material of function admirable, this material has very excellent decay resistance, can relatively use under the rigorous environment.
The preparation method of ion-exchange fibre can be divided into two kinds: a kind of be blend, be copolymerized into fine functionalization method, will have the monomer that maybe can be transformed into ion-exchange group or polymer and carry out copolymerization or blend, spinned fiber then with becoming fine monomer or polymer.The ion-exchange fibre of this method preparation, its functional group is evenly distributed on skeleton, and the functional group content height, but the technology complexity; Another kind is the graft modification method of finished fiber, by the modification to natural fiber or synthetic fibers, comprises that active group etc. is introduced in the chemical transformation, graft copolymerization of functional group.Wherein can be divided into chemical method and high-energy physics method again, the major advantage of this method is that macromolecular scaffold is ready-made, and alternative matrix material is many, and chemical fibre is cheap, and raw material sources are convenient, and the preparation method is simple, is the focus of studying at present.
Because the chemical stability of fibers such as tetrafluoroethene adopts common chemical method, be difficult to realize to its surperficial chemical modification.For example patent CN 1608734A discloses a kind of polytetrafluoroethylene fibre and styrene monomer mutual radiation, graft fibres prepare the method for strong acid ion exchange fiber through the sulfonation of chlorosulfonic acid method, but the grafting efficiency of this method is very low, cause a large amount of wastes of monomer, percent grafting can not be realized controllable operating; And produce acid waste liquid in the sulfonation process, and cause environmental pollution, equipment corrosion, make that the industrialization of this product is very difficult.The present invention is a matrix with fibers such as polytetrafluoroethylene (PTFE), by pre-irradiation grafting have can transform the functional group to styrene monomer, then graft fibres being carried out acidifying modifies, preparation strong acid, the novel high-exchange-capacity of weak acid difunctionality, high mechanical properties, high thermal stability, corrosion-resistant, oxidation resistant ion exchange fiber material are for the application (as the purifying of strong acid, highly basic reagent) of ion exchange fiber material under harsh conditions provides a class performance excellent more product.Simultaneously, preparation process has been avoided the use of sulfonating reaction to strong corrosive materials such as the concentrated sulfuric acid, chlorosulfonic acids, solved thorny difficult problems such as the environmental pollution that conventional method is brought, equipment corrosion, simple, the processing ease of process is for the industrialization of ion exchange fiber material provides advantage.
Summary of the invention
The object of the present invention is to provide a kind of novel ion exchange fiber material and preparation method thereof.
Ion-exchange fibre of the present invention is the ion exchange fiber material that a class contains strong acid, weak acid double functional group.
The preparation method of ion-exchange fibre of the present invention is to be the pre-irradiation method of the high-energy physics method of matrix with synthetic fibers, and irradiation bomb is cobalt 60 gamma rays.
Matrix fiber of the present invention is the synthetic fibers such as polytetrafluoroethylene (PTFE), polypropylene, polyacrylonitrile and polyvinyl alcohol that still have good stable and integrality in extreme environment.
The method that the present invention prepares novel ion exchange fiber material comprises the steps:
(1) preliminary treatment: fibers such as polytetrafluoroethylene (PTFE), polypropylene, polyacrylonitrile and polyvinyl alcohol were soaked 2 days vacuum drying under filtration, the uniform temperature in acetone (can be alkali lye in the industry).
(2) pre-irradiation: fibers such as packaged polytetrafluoroethylene (PTFE), polypropylene, polyacrylonitrile and polyvinyl alcohol are carried out irradiation with cobalt 60 gamma rays to it, control dose of radiation 20-150KGy, exposure time is 24-168 hour.To preserve at low temperature below 4 ℃ through fiber behind the pre-irradiation.
(3) grafting: the fiber through radiation treatment mixes with grafted monomers, acrylic acid), the reaction time is that 2～10h, reaction temperature are 50～100 ℃ and add activators such as Mohr's salt, formaldehyde, hydrazine hydrate, urea or nanometer Mg powder, makes fiber carry out graft reaction the weight of control reaction system solution and the part by weight (to call bath raio in the following text) of fiber are that the concentration of 1:10～1:50, grafted monomers is 10～80%, two monomer ratio 1:1～1:6 (sodium p styrene sulfonates:.After reaction finished, the grafting system was removed organic solvent and unconverted monomer by vacuum distillation; Soaked 1-2 days with organic solvent then, suction filtration is removed homopolymers, with precipitating reagent washing, vacuum drying.The pre-irradiation fiber with to obtaining strong acid, weak acid difunctionality ion-exchange fibre after vinylbenzenesulfonic acid monomer, the acrylic monomers grafting.
(4) handle transition: handle strong acid, the weak acid difunctionality ion-exchange fibre that obtains with the 10-25% aqueous slkali, can make it change into the Na type; Handle with the 10-25% acid solution, can change into the H type.Processing time is 0.5-2 hour.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, Weak-acid cation difunctionality exchanging fiber material.
Description of drawings
The sem photograph of Fig. 1 difunctionality ion-exchange fibre
The infrared spectrogram of Fig. 2 difunctionality ion-exchange fibre
The specific embodiment
The present invention will be described in detail below in conjunction with drawings and Examples.
Embodiment 1
The pretreated polytetrafluoroethylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio is 1:3) and carrene by volume percentage are mixed with even mixed solution at 60: 40, by 1: 30 bath raio (weight: the polytetrafluoroethylene fibre behind adding 3.5g pre-irradiation volume), add the activator Mohr's salt by 5%, reaction is 6 hours under 80 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 95%, soaked 2 days with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 167%, grafting efficiency 10.4%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.92mmol/g, wherein strong acid part 2.40mmol/g.
Embodiment 2
The pretreated polytetrafluoroethylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio is 1:3) and N, dinethylformamide by volume percentage is mixed with even mixed solution at 60: 40, by 1: 30 bath raio (weight: the polytetrafluoroethylene fibre behind adding 3.5g pre-irradiation volume), add the activator Mohr's salt by 5%, 75 ℃ of reaction temperatures, 8 hours reaction time.Postorder is handled with embodiment 1, obtains ion exchange fiber material of the same type, and monomer conversion is 98%, and percent grafting is 120%, grafting efficiency 7.5%.Maximum static exchange capacity is 3.0mmol/g, wherein strong acid part 1.85mmol/g.
Embodiment 3
The pretreated polyacrylonitrile fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio is 1:5) and carrene by volume percentage are mixed with even mixed solution at 50: 50, by 1: 30 bath raio (weight: the polyacrylonitrile fibre behind adding 3.5g pre-irradiation volume), add the activator nanometer Mg powder by 5%, reaction is 6 hours under 80 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 96%, soaked 2 days with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 133%, grafting efficiency 9.79%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.53mmol/g, wherein strong acid part 2.85mmol/g.
Perhaps activator changes formaldehyde into, and the maximum static exchange capacity that obtains material is 4.03mmol/g, wherein strong acid part 1.95mmol/g.
Embodiment 4
The pretreated vinal that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio is 1:5) and N, dinethylformamide by volume percentage is mixed with even mixed solution at 50: 50, by 1: 30 bath raio (weight: the vinal behind adding 3.5g pre-irradiation volume), add the activator Mohr's salt by 5%, reaction is 8 hours under 75 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 97%, soaked 2 days with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 127%, grafting efficiency 11.4%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.95mmol/g, wherein strong acid part 2.48mmol/g.
Perhaps activator changes urea into, and the maximum static exchange capacity that obtains material is 4.38mmol/g, wherein strong acid part 1.62mmol/g.
Embodiment 5
The pretreated polypropylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 40KGy, exposure time is 46 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:1) and toluene by volume percentage are mixed with even mixed solution at 80: 20, by 1: 10 bath raio (weight: the polypropylene fibre behind adding 2.5g pre-irradiation volume), add the activator Mohr's salt by 5%, reaction is 2 hours under 100 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 98%, soaked 1 day with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 87%, grafting efficiency 11.09%.To the fibrous material processing that makes the transition, the processing time is 0.5 hour with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.88mmol/g, wherein strong acid part 2.47mmol/g.
Embodiment 6
The pretreated polypropylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 20KGy, exposure time is 24 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:3) and N, dinethylformamide by volume percentage is mixed with even mixed solution at 60: 40, by 1: 40 bath raio (weight: the polypropylene fibre behind adding 2.5g pre-irradiation volume), add the activator Mohr's salt by 5%, 80 ℃ of reaction temperatures, 6 hours reaction time.Postorder is handled with embodiment 5, obtains ion exchange fiber material of the same type, and monomer conversion is 95%, and percent grafting is 102%, grafting efficiency 13.42%.Maximum static exchange capacity is 4.90mmol/g, wherein strong acid part 2.24mmol/g.
Embodiment 7
The pretreated polypropylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 40KGy, exposure time is 46 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:5) and toluene by volume percentage are mixed with even mixed solution at 50: 50, by 1: 40 bath raio (weight: the polypropylene fibre behind adding 2.5g pre-irradiation volume), add the activator nanometer Mg powder by 5%, reaction is 8 hours under 75 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 96%, soaked 1 day with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 114%, grafting efficiency 17.81%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.70mmol/g, wherein strong acid part 2.07mmol/g.
Perhaps activator changes formaldehyde into, and the maximum static exchange capacity that obtains material is 3.53mmol/g, wherein strong acid part 1.25mmol/g.
Embodiment 8
The pretreated polypropylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 40KGy, exposure time is 46 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:5) and toluene by volume percentage be mixed with even mixed solution at 50: 50, by 1: 40 bath raio (weight: the polypropylene fibre behind adding 2.5g pre-irradiation volume), add activator magnesium powder by 5%, reaction is 6 hours under 80 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 97%, soaked 1 day with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying is calculated percent grafting and is 125%, grafting efficiency 20.0%.To the fibrous material processing that makes the transition, the processing time is 0.5 hour with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.75mmol/g, wherein strong acid part 2.2.18mmol/g.
Perhaps activator changes urea into, and the maximum static exchange capacity that obtains material is 4.43mmol/g, wherein strong acid part 1.47mmol/g.
Embodiment 9
The pretreated polytetrafluoroethylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 150KGy, exposure time is 168 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:3) and carrene by volume percentage are mixed with even mixed solution at 10: 90, by 1: 50 bath raio (weight: the polytetrafluoroethylene fibre behind adding 3.0g pre-irradiation volume), add the activator Mohr's salt by 5%, reaction is 10 hours under 50 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 99%, soaked 2 days with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 86%, grafting efficiency 13.0%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.67mmol/g, wherein strong acid part 2.00mmol/g.
Embodiment 10
The pretreated polypropylene fibre that takes by weighing certain mass seals with pellosil in tool plug conical flask.With cobalt 60 gamma rays it is carried out irradiation, control dose of radiation 48KGy, exposure time is 55 hours.With p-sulfonic acid sodium base styrene, acrylic monomers (monomer ratio 1:6) and carrene by volume percentage are mixed with even mixed solution at 50: 50, by 1: 40 bath raio (weight: the polytetrafluoroethylene fibre behind adding 3.0g pre-irradiation volume), add the activator Mohr's salt by 5%, reaction is 9 hours under 70 ℃ of temperature, the vacuum distillation of back grafting system be will react and organic solvent and unconverted monomer removed, calculating monomer conversion is 94%, soaked 2 days with toluene, suction filtration is removed homopolymers, use methanol wash, vacuum drying, calculating percent grafting is 104%, grafting efficiency 19.91%.To the fibrous material processing that makes the transition, the processing time is 2 hours with the 1M hydrochloric acid solution.Use deionized water rinsing then, until being neutral, vacuum drying obtains strong acid, weak-type difunctionality ion exchange fiber material, and maximum static exchange capacity is 4.98mmol/g, wherein strong acid part 2.57mmol/g.
Perhaps activator changes hydrazine hydrate into, and the maximum static exchange capacity that obtains material is 4.03mmol/g, wherein strong acid part 1.19mmol/g.
Claims (5)
1. the preparation method of a class ion exchange fiber material: with the composite fibre materials is matrix, by pre-irradiation grafting one step preparation strong acid, weak acid difunctionality ion exchange fiber material.
2. by the preparation method of the described strong acid of claim 1, weak acid difunctionality ion exchange fiber material, it is characterized by:
Under nitrogen protection, carry out pre-irradiation through pretreated fibrous material with cobalt 60; irradiation dose 20-150KGy; exposure time is 24-168 hour; grafting in the presence of organic solvent and activator prepares target product with sodium p styrene sulfonate monomer and acrylic monomers then; monomer concentration 10～80%, and two monomer ratio 1:1～1:6 (sodium p styrene sulfonate: acrylic acid), bath raio 1:10～1:50; the grafting temperature is 50～100 ℃, and the grafting time is 2-10 hour.Monomer conversion 〉=94%, percent grafting〉85%, grafting efficiency 7.5%～20%, total exchange capacity reaches 3.0～4.98mmol/g, wherein, strong acid part 1.85～2.57mmol/g.
3. be synthetic fibers such as polytetrafluoroethylene (PTFE), polypropylene, polyacrylonitrile and polyvinyl alcohol by the described composite fibre materials of claim 1.
4. by the described method of claim 2, organic solvent is carrene, N, one or more in dinethylformamide and the toluene.
5. by the described method of claim 2, activator can be Mohr's salt, formaldehyde, hydrazine hydrate, urea and nanometer Mg powder etc.
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| CN101603271B (en) * | 2009-07-01 | 2011-06-15 | 河南省科学院化学研究所有限公司 | Fiber material containing sulfonic groups, and synthesis method thereof |
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| CN102989509A (en) * | 2012-12-18 | 2013-03-27 | 天津工业大学 | Catalyst of sulfonated polystyrene grafted polytetrafluoroethylene fiber metal complex and preparation method thereof |
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| CN110026160A (en) * | 2019-04-03 | 2019-07-19 | 山东师范大学 | A kind of preparation method of weak base type ion exchange fiber |
| CN110026160B (en) * | 2019-04-03 | 2022-04-15 | 山东师范大学 | Preparation method of weak base type ion exchange fiber |
| CN117358321A (en) * | 2023-12-04 | 2024-01-09 | 赛普(杭州)过滤科技有限公司 | Chromatography medium and preparation method thereof |
| CN117358321B (en) * | 2023-12-04 | 2024-03-19 | 赛普(杭州)过滤科技有限公司 | Chromatography medium and preparation method thereof |
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Assignee: Zhuhai WSM Costume Co., Ltd. Assignor: Sun Yat-sen University Contract record no.: 2011440001112 Denomination of invention: Ion exchange fiber material one-step preparation method Granted publication date: 20110810 License type: Exclusive License Open date: 20090610 Record date: 20111229 |
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