CN114703661A - Strong base type ion exchange fiber and preparation method thereof - Google Patents
Strong base type ion exchange fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114703661A CN114703661A CN202210278548.7A CN202210278548A CN114703661A CN 114703661 A CN114703661 A CN 114703661A CN 202210278548 A CN202210278548 A CN 202210278548A CN 114703661 A CN114703661 A CN 114703661A
- Authority
- CN
- China
- Prior art keywords
- fiber
- reaction
- solution
- groups
- strong base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 98
- 238000005342 ion exchange Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 10
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 56
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 38
- 239000002585 base Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 19
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 7
- 150000003512 tertiary amines Chemical group 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 small molecule compound Chemical class 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 4
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 4
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 3
- 230000010933 acylation Effects 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- BPNUQXPIQBZCMR-IBGZPJMESA-N (2s)-1-{[5-(3-methyl-1h-indazol-5-yl)pyridin-3-yl]oxy}-3-phenylpropan-2-amine Chemical compound C([C@H](N)COC=1C=NC=C(C=1)C1=CC=C2NN=C(C2=C1)C)C1=CC=CC=C1 BPNUQXPIQBZCMR-IBGZPJMESA-N 0.000 claims description 2
- WAPNOHKVXSQRPX-SSDOTTSWSA-N (R)-1-phenylethanol Chemical compound C[C@@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-SSDOTTSWSA-N 0.000 claims description 2
- 125000002668 chloroacetyl group Chemical group ClCC(=O)* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000002657 fibrous material Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000126 substance Substances 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
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
- D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/17—Halides of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a strong base type ion exchange fiber containing two or more quaternary ammonium salt groups and a preparation method thereof, belonging to the technical field of high polymer materials. The invention takes PP-ST-DVB graft fiber as an initial raw material, reacts with a micromolecule compound containing two or more tertiary amine structures after chloroacetylation reaction, and further performs quaternization reaction with methyl iodide or ethyl bromide to obtain the functional fiber containing two or more than two quaternary ammonium groups with a novel structure. The preparation method has the advantages of simple process, mild conditions and easy control, and the adopted raw materials are nontoxic or low-toxicity raw materials, so the preparation method is an environment-friendly preparation method.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a fiber material and a synthesis method thereof, and particularly relates to a strong base type ion exchange fiber containing two or more quaternary ammonium salt groups and a preparation method thereof.
Background
The Ion Exchange Fiber (IEF) has good chemical stability and high mechanical strength, and can be widely applied to many fields. Compared with ion exchange resin, the ion exchange fiber has the advantages of large specific surface area, small diameter, easy regeneration, obvious dynamic performance, such as short migration distance, high adsorption rate, high ion removal rate and the like. According to the functional group, the fiber can be divided into cation exchange fiber, anion exchange fiber and amphoteric ion exchange fiber.
The anion exchange fiber is divided into strong base ion exchange fiber and weak base ion exchange fiber, and the fiber containing quaternary ammonium group is strong base type ion exchange fiber. The strong base ion exchange fiber is usually obtained by respectively performing chloromethylation reaction and quaternization reaction on a base fiber. When trimethylamine is used as a reactant to perform quaternization reaction to prepare the strong alkali type ion exchange fiber, the strong fishy smell and the foul smell are also generated even under low concentration in the reaction process or after treatment. In the course of earlier research work (technological research for preparing strong base ion exchange fiber by chloroacetylation, Zhang Benshang et al, Henan science, 2018,36(1), pages 49-53), chloroacetyl chloride is used as an acylation reagent, aluminum trichloride is used as a catalyst, and a Friedel-crafts acylation reaction method is adopted, so that carcinogenic chloromethyl ether is prevented from being used in the preparation process of the strong base fiber. In order to further optimize a reaction route and avoid using trimethylamine with fishy smell and foul smell, the invention introduces a quaternary ammonium group by using a small molecular compound containing two or more tertiary amine groups as a quaternizing reagent, and further performs quaternization reaction with methyl iodide or ethyl bromide to obtain the strong base type ion exchange fiber with a novel structure and containing two or more quaternary ammonium groups.
Disclosure of Invention
The invention provides a strong base type ion exchange fiber containing two or more quaternary ammonium salt groups and a preparation method thereof, aiming at replacing the prior trimethylamine with strong fishy and foul smell when preparing the strong base type ion exchange fiber and simultaneously improving the content of quaternary ammonium functional groups in the fiber. The preparation method has the advantages of simple process, mild conditions and easy control, and the adopted raw materials are nontoxic or low-toxicity raw materials, so the preparation method is an environment-friendly preparation method.
In order to achieve the technical purpose, the technical scheme provided by the invention is as follows:
a method for preparing strong base type ion exchange fiber containing two or more quaternary ammonium salt groups is characterized by at least comprising the following steps:
SS1, taking PP-ST-DVB grafted fiber as an initial raw material, taking chloroacetyl chloride as an acylation reagent, taking aluminum trichloride as a catalyst, taking dichloromethane or dichloroethane as a solvent to prepare chloroacetylation reaction solution, adding the chloroacetylation reaction solution in at least two batches at intervals for chloroacetylation reaction, introducing chloroacetyl groups on the PP-ST-DVB grafted fiber after the reaction is finished, leaching with dilute hydrochloric acid, leaching with distilled water, filtering until no chloride ion is detected in a silver nitrate solution measuring solution, and drying to constant weight to obtain chloroacetylated PP-ST-DVB grafted fiber;
SS2, reacting the chloroacetylated PP-ST-DVB grafted fiber obtained in the step SS1 with an aqueous solution or an alcohol solution of a micromolecule compound containing a plurality of tertiary amino groups under the conditions of water bath and nitrogen atmosphere, filtering and washing the product to be neutral by using distilled water after the reaction is finished, detecting no chloride ion in a silver nitrate solution detection solution, and drying the product until the weight is constant to obtain a functional fiber simultaneously containing strong base and weak base groups;
and SS3, performing quaternization reaction on the functional fiber containing the strong base and the weak base groups obtained in the step SS2 and methyl iodide or ethyl bromide under the conditions of normal temperature and light resistance, soaking the functional fiber in saturated saline solution for a plurality of times after the reaction is finished, converting the functional fiber into chlorine type strong base fiber, filtering, washing the fiber with distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, and finally drying the fiber to constant weight to obtain the ion exchange fiber containing a plurality of quaternary ammonium groups.
Preferably, in step SS2, the small molecule compound containing a plurality of tertiary amine groups is a small molecule compound containing two or more tertiary amine groups, such as pentamethyldiethylenetriamine (cas: 3030-47-5), tetramethylethylenediamine (cas: 110-18-9), triethylenediamine (cas: 280-57-9), N '-diethyl-N, N' -dimethylethane-1, 2-diamine (cas: 106-66-1), tetraethylethylenediamine (cas: 150-77-6), and the like.
Preferably, in step SS2, preparing a small molecule compound containing a plurality of tertiary amine groups into an aqueous solution or an ethanol solution with a volume fraction of 30% -50%, adding chloroacetylated PP-ST-DVB fibers under the protection of nitrogen at a bath ratio of 20-40, reacting at 50-90 ℃ for 12-48 hours, filtering after the reaction is finished, washing with distilled water until the mixture is neutral, detecting no chloride ion in a silver nitrate solution detection solution, and finally drying to constant weight to obtain the functional fiber containing both strong base and weak base groups.
Preferably, in step SS3, methyl iodide or ethyl bromide is used as the quaternizing agent, the bath ratio is 15 to 40, and the bath ratio is preferably 25 to 35.
Further, when methyl iodide is used as a quaternizing agent, the reaction conditions are room temperature and light shielding, and the reaction time is 8-12 d; or introducing nitrogen and heating and refluxing for reaction for 48-96 hours under the condition of keeping out of the sun.
And further, when bromoethane is used as a quaternizing agent, introducing nitrogen, and heating and refluxing for reaction for 25-40 hours under the condition of keeping out of the sun.
It is another object of the present invention to provide a strong base ion exchange fiber containing two or more quaternary ammonium salt groups prepared by the above method of the present invention.
Compared with the prior art, the strong base type ion exchange fiber and the preparation method thereof have the advantages that: (1) the strong base fiber material prepared by the invention is a functional fiber with a novel structure, so that the content of ion exchange or adsorption groups on the fiber is improved, and carcinogenic chloromethyl ether and fishy and malodorous trimethylamine are prevented from being used; (2) the chemical raw materials adopted by the invention are nontoxic or low-toxicity raw materials, the consumption of the raw materials is less in the reaction process, no toxic by-product is generated, the reaction liquid can be recycled, and the preparation method is an environment-friendly preparation method.
Detailed Description
In order to make the implementation objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention are described in more detail below. The described embodiments, which are part of the present invention, are not all embodiments, and are intended to be illustrative of the present invention and should not be construed as limiting the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the strong base type ion exchange fiber containing two or more quaternary ammonium salt groups and the preparation method thereof provided by the following embodiments, the content of the strong base group is determined by the measuring method of method II in GB/T11992-2008 chlorine type strong base anion exchange resin exchange capacity determining method.
Example 1
Adding 60mL of dried dichloromethane into a 250mL cylindrical reaction bottle, adding 3g of PP-ST-DVB grafted fiber with the grafting rate of 200%, placing the cylindrical reaction bottle in a water bath at 35 ℃ for swelling for 5h, preparing 45mL of reaction liquid containing chloroacetyl chloride and aluminum trichloride by using anhydrous dichloromethane as a solvent (wherein the mass ratio of styrene to chloroacetyl chloride to aluminum trichloride in the PP-ST-DVB grafted fiber is 1: 1.1: 1.2), adding 15mL of chloroacetyl chloride and aluminum trichloride for 3 times at an interval of 50 minutes every time, continuing to react for 100 minutes after the 3 rd addition, and finishing the reaction, then filtering and respectively soaking and washing with dilute hydrochloric acid (5%) for 2 times, washing with distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, and finally drying in a vacuum drying oven at the temperature of 50 ℃ until the weight is constant to obtain the chloroacetylated PP-ST-DVB fiber.
2g of the chloroacetylated PP-ST-DVB fiber is weighed and put into a 250mL cylindrical reaction bottle, 60mL of pentamethyl divinyl triamine (cas: 3030-47-5) water solution with the mass fraction of 30 percent is added, and nitrogen is introducedPlacing the reaction bottle in a water bath at 50 ℃ for reaction for 12h, filtering, washing with distilled water until the reaction bottle is neutral, detecting no chloride ion in a silver nitrate solution detection solution, placing the reaction bottle in a vacuum drying oven for drying at 50 ℃ to constant weight, placing the reaction bottle in a single-mouth bottle containing 60mL of iodomethane, sealing, reacting in the dark for 10d at normal temperature, further soaking with saturated saline solution for 3 times after filtering, converting the obtained product into chlorine type strong base fiber, filtering, washing with distilled water until no chloride ion is detected in a silver nitrate solution detection solution, finally drying to constant weight, and detecting that the content of the quaternary ammonium group in the fiber prepared in the embodiment is 5.46 mmol/g-1。
Example 2
Adding 60mL of dried dichloromethane into a 250mL cylindrical reaction bottle, adding 3g of PP-ST-DVB grafted fiber with the grafting rate of 185%, placing the cylindrical reaction bottle in a water bath at 35 ℃ for swelling for 5h, preparing 45mL of reaction liquid containing chloroacetyl chloride and aluminum trichloride by using anhydrous dichloromethane as a solvent (wherein the mass ratio of styrene to chloroacetyl chloride to aluminum trichloride in the PP-ST-DVB grafted fiber is 1: 1.1: 1.2), adding 15mL of chloroacetyl chloride and aluminum trichloride for 3 times at an interval of 50 minutes every time, continuing to react for 100 minutes after the 3 rd addition, and finishing the reaction, then filtering and respectively soaking and washing with dilute hydrochloric acid (5%) for 2 times, washing with distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, and finally drying in a vacuum drying oven at the temperature of 50 ℃ until the weight is constant to obtain the chloroacetylated PP-ST-DVB fiber.
Weighing 2g of the chloroacetylated PP-ST-DVB fiber, putting the chloroacetylated PP-ST-DVB fiber into a 250mL cylindrical reaction bottle, adding 60mL of pentamethyl divinyl triamine (cas: 3030-47-5) aqueous solution with the mass fraction of 30%, introducing nitrogen, placing the reaction bottle in a water bath at 50 ℃ for reaction for 12h, filtering, washing with distilled water until the reaction bottle is neutral, detecting no chloride ion in a silver nitrate solution detection solution, and putting the reaction bottle in a vacuum drying oven for drying at 50 ℃ until the weight is constant; then putting the mixture into a three-neck flask containing 60mL of bromoethane, introducing nitrogen, sealing, heating, refluxing and reacting for 30h, further soaking for 3 times by using saturated saline solution after filtering, converting the mixture into chlorine type strong alkali fiber, filtering, washing by using distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, finally drying to constant weight, and measuring that the content of quaternary ammonium group in the fiber prepared in the embodiment is 5.18mmolg-1。
Example 3
Adding 60mL of dried dichloromethane into a 250mL cylindrical reaction bottle, adding 3g of PP-ST-DVB grafted fiber with the grafting rate of 170%, placing the cylindrical reaction bottle in a water bath at 35 ℃ for swelling for 5h, preparing 30mL of reaction liquid containing chloroacetyl chloride and aluminum trichloride by using anhydrous dichloromethane as a solvent (wherein the mass ratio of styrene to chloroacetyl chloride to aluminum trichloride in the PP-ST-DVB grafted fiber is 1: 1.1: 1.2), adding 15mL of chloroacetyl chloride and aluminum trichloride for 3 times at an interval of 50 minutes every time, continuing to react for 100 minutes after the 3 rd addition, and finishing the reaction, then filtering and respectively soaking and washing the fiber with dilute hydrochloric acid (5%) for 2 times, washing the fiber with distilled water until no chloride ion is detected in a silver nitrate solution detection solution, and finally drying the fiber in a vacuum drying oven at the temperature of 50 ℃ until the weight is constant to obtain the chloroacetylated PP-ST-DVB fiber.
Weighing 2g of the chloroacetylated PP-ST-DVB fiber, putting the chloroacetylated PP-ST-DVB fiber into a 250mL cylindrical reaction bottle, adding 60mL of tetramethylethylenediamine (cas: 110-18-9) aqueous solution with the mass fraction of 30%, introducing nitrogen, placing the reaction bottle in a water bath at 50 ℃ for reaction for 12h, filtering, washing with distilled water to be neutral, putting the reaction bottle into a vacuum drying oven at 50 ℃ for drying to constant weight, then putting the reaction bottle into a three-neck flask containing 60mL of iodomethane, introducing nitrogen, sealing, heating and refluxing for 72h, further soaking with saturated salt solution for 3 times after filtering, converting into chlorine type strong alkali fiber, filtering, washing with distilled water until no chloride ion is detected in a silver nitrate solution determination solution, finally drying to constant weight, and determining that the content of quaternary ammonium group in the fiber prepared in the embodiment is 4.53 mmol/g-1。
Example 4
Adding 60mL of anhydrous dichloroethane into a 250mL cylindrical reaction bottle, adding 3g of PP-ST-DVB grafted fiber with the grafting rate of 165%, placing the cylindrical reaction bottle in a water bath at 35 ℃ for swelling for 5h, preparing 45mL of reaction liquid containing chloroacetyl chloride and aluminum trichloride by using dichloroethane as a solvent (wherein the mass ratio of styrene to chloroacetyl chloride to aluminum trichloride in the PP-ST-DVB grafted fiber is 1: 1.1: 1.2), adding 15mL of the mixture every time, adding the mixture in 3 times at an interval of 50 minutes, continuing to react for 100 minutes after the 3-time addition, then filtering and respectively soaking and washing the mixture for 2 times by using dilute hydrochloric acid (5%), washing the mixture by using distilled water until no chloride ion is detected in a silver nitrate solution detection liquid, and finally drying the mixture in a vacuum drying oven at 50 ℃ until the constant weight is achieved to obtain the chloroethylene PP-ST-DVB fiber.
Weighing 2g of the chloroacetylated PP-ST-DVB fiber, putting the chloroacetylated PP-ST-DVB fiber into a 250mL cylindrical reaction bottle, adding 60mL of 30 mass percent pentamethyl divinyl triamine (cas: 3030-47-5) ethanol solution, introducing nitrogen, placing the reaction bottle in a water bath at 80 ℃ for reaction for 24 hours, then filtering, washing with distilled water until the washing solution is neutral, detecting no chloride ion in a silver nitrate solution detection solution, and finally drying to constant weight; then putting the fiber into a three-neck flask containing 60mL of bromoethane, introducing nitrogen, carrying out reflux reaction for 28h, filtering, soaking for 3 times by using saturated saline solution, converting the fiber into chlorine type strong alkali fiber, filtering, washing by using distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, finally drying to constant weight, and measuring that the content of quaternary ammonium group in the fiber prepared in the embodiment is 4.42 mmol-g-1。
Application example 1
0.0562g of alkali fiber prepared in example 1 is weighed and put into 150mL of the solution with the concentration of 160.6 mg.L-1Adjusting the pH value of the Cr (VI) aqueous solution to 2-5, oscillating and adsorbing the solution at 25 ℃ for 6 hours, and measuring that the concentration of the Cr (VI) in the solution is reduced to 77.2 mg.L-1In this case, the amount of Cr (VI) adsorbed by the fibers was 223mg g-1The application example shows that the strong base fiber material prepared by the method has good adsorption performance on Cr (VI).
Application example 2
0.0512g of the alkali fiber material prepared in example 3 was weighed and charged into 150mL of 160.6 mg. L-1Adjusting the pH value of the Cr (VI) aqueous solution to 2-5, oscillating and adsorbing the solution at 25 ℃ for 6 hours, and measuring that the concentration of the Cr (VI) in the solution is reduced to 97.5 mg.L-1In this case, the amount of Cr (VI) adsorbed by the fibers was 185mg g-1A fiber.
The object of the present invention is fully effectively achieved by the above embodiments. Those skilled in the art will appreciate that the present invention includes, but is not limited to, what has been described in the foregoing detailed description. While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications within the spirit and scope of the appended claims.
The invention has not been described in detail and is within the knowledge of a person skilled in the art.
Claims (7)
1. A method for preparing strong base type ion exchange fiber containing two or more quaternary ammonium salt groups is characterized by at least comprising the following steps:
SS1, taking PP-ST-DVB grafted fiber as an initial raw material, taking chloroacetyl chloride as an acylation reagent, taking aluminum trichloride as a catalyst, taking dichloromethane or dichloroethane as a solvent to prepare chloroacetylation reaction solution, adding the chloroacetylation reaction solution in at least two batches at intervals for chloroacetylation reaction, introducing chloroacetyl groups on the PP-ST-DVB grafted fiber after the reaction is finished, leaching with dilute hydrochloric acid, leaching with distilled water, filtering until no chloride ion is detected in a silver nitrate solution measuring solution, and drying to constant weight to obtain chloroacetylated PP-ST-DVB grafted fiber;
SS2, reacting the chloroacetylated PP-ST-DVB grafted fiber obtained in the step SS1 with an aqueous solution or an alcohol solution of a small molecular compound containing a plurality of tertiary amino groups under a water bath condition and a nitrogen atmosphere, filtering and washing with distilled water to be neutral after the reaction is finished, detecting no chloride ion in a silver nitrate solution detection solution, and drying to constant weight to obtain a functional fiber simultaneously containing strong base and weak base groups;
and SS3, performing quaternization reaction on the functional fiber containing the strong base and the weak base groups obtained in the step SS2 and methyl iodide or ethyl bromide under the conditions of normal temperature and light resistance, soaking the functional fiber in saturated saline solution for a plurality of times after the reaction is finished, converting the functional fiber into chlorine type strong base fiber, filtering, washing the fiber with distilled water until no chloride ion is detected in a silver nitrate solution measuring solution, and finally drying the fiber to constant weight to obtain the ion exchange fiber containing a plurality of quaternary ammonium groups.
2. The preparation method according to the preceding claim, wherein in step SS2, the small molecule compound having a plurality of tertiary amine groups is a small molecule compound having two or more tertiary amine groups, such as pentamethyldiethylenetriamine (cas: 3030-47-5), tetramethylethylenediamine (cas: 110-18-9), triethylenediamine (cas: 280-57-9), N '-diethyl-N, N' -dimethylethane-1, 2-diamine (cas: 106-66-1), tetraethylethylenediamine (cas: 150-77-6), and the like.
3. The preparation method of the claim, wherein in the step SS2, the micromolecular compound containing a plurality of tertiary amine groups is prepared into 30-50% volume fraction aqueous solution or ethanol solution, the bath ratio is 20-40, under the protection of nitrogen, chloroacetylated PP-ST-DVB fiber is added, the reaction is carried out for 12-48 hours at 50-90 ℃, after the reaction is finished, the solution is filtered and washed by distilled water to be neutral, no chloride ion is detected in the silver nitrate solution, and finally the solution is dried to constant weight, so that the functional fiber containing both strong base and weak base groups is obtained.
4. The method according to the preceding claim, wherein in step SS3, iodomethane or bromoethane is used as the quaternizing agent, the bath ratio is 15 to 40, and the bath ratio is preferably 25 to 35.
5. The process according to claim 4, wherein, when methyl iodide is used as the quaternizing agent, the reaction conditions are room temperature, light shielding and the reaction time is 8-12 d; or introducing nitrogen and heating and refluxing for reaction for 48-96 hours under the condition of keeping out of the sun.
6. The preparation method according to claim 4, wherein when bromoethane is used as the quaternizing agent, nitrogen is introduced, and the mixture is heated and refluxed for reaction for 25-40 hours under the condition of keeping out of the light.
7. A strong base ion exchange fiber containing two or more quaternary ammonium salt groups prepared according to the method of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210278548.7A CN114703661A (en) | 2022-03-17 | 2022-03-17 | Strong base type ion exchange fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210278548.7A CN114703661A (en) | 2022-03-17 | 2022-03-17 | Strong base type ion exchange fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114703661A true CN114703661A (en) | 2022-07-05 |
Family
ID=82169303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210278548.7A Pending CN114703661A (en) | 2022-03-17 | 2022-03-17 | Strong base type ion exchange fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114703661A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB779994A (en) * | 1954-05-20 | 1957-07-24 | Rohm & Haas | Quaternary ammonium anion-exchange resins |
| CN102720057A (en) * | 2012-07-03 | 2012-10-10 | 河南省科学院化学研究所有限公司 | Fibre material containing quaternary ammonium groups and synthetic method thereof |
| CN104941588A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Recyclable fiber material capable of quickly removing heavy metal anions |
| CN106397817A (en) * | 2016-08-31 | 2017-02-15 | 深圳前海中盛环保科技有限公司 | Preparation method of strong alkali ion permutation fiber |
| CN111790359A (en) * | 2020-06-18 | 2020-10-20 | 济南大学 | Adsorbent for treating hexavalent chromium in wastewater |
-
2022
- 2022-03-17 CN CN202210278548.7A patent/CN114703661A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB779994A (en) * | 1954-05-20 | 1957-07-24 | Rohm & Haas | Quaternary ammonium anion-exchange resins |
| CN102720057A (en) * | 2012-07-03 | 2012-10-10 | 河南省科学院化学研究所有限公司 | Fibre material containing quaternary ammonium groups and synthetic method thereof |
| CN104941588A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Recyclable fiber material capable of quickly removing heavy metal anions |
| CN106397817A (en) * | 2016-08-31 | 2017-02-15 | 深圳前海中盛环保科技有限公司 | Preparation method of strong alkali ion permutation fiber |
| CN111790359A (en) * | 2020-06-18 | 2020-10-20 | 济南大学 | Adsorbent for treating hexavalent chromium in wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 张本尚 等: "氯乙酰化制备强碱离子交换纤维的工艺研究", 河南科学, vol. 36, no. 01, pages 49 - 53 * |
| 范云鸽;史作清;: "聚苯乙烯型双季铵树脂的制备及性能研究", 离子交换与吸附, no. 06, pages 512 - 518 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sruthi et al. | An overview of synthetic modification of nitrile group in polymers and applications | |
| Zhang et al. | Radiation synthesis and Cr (VI) removal of cellulose microsphere adsorbent | |
| Egawa et al. | Recovery of uranium from seawater. XII. Preparation and characterization of lightly crosslinked highly porous chelating resins containing amidoxime groups | |
| CN106861658A (en) | A kind of preparation method and application of the imine modified porous adsorbing material of high-efficiency polyethylene | |
| CN108912269B (en) | Polyimidazole ionic liquid-based copolymer and preparation method and application thereof | |
| CN102051811B (en) | Method for preparing polyphenylene sulfide-based strong basic ion exchange fibers | |
| CN107226507A (en) | A kind of preparation method of the cysteine-modifying celluloses of L for removal of heavy metal ions | |
| CN102773081A (en) | Preparation method of polyacrylonitrile chelating resin adsorbent | |
| CN1054168C (en) | Multi-dentate ion exchange chelating fibre and its synthetic method | |
| CN106700088B (en) | A kind of preparation method and applications of Pd ion blotting silica gel absorber | |
| CN114703661A (en) | Strong base type ion exchange fiber and preparation method thereof | |
| Trochimczuk et al. | Novel chelating resins with aminothiophosphonate ligands | |
| CN105294890B (en) | A kind of method that chelating resin reclaims silver ion from the mud of cloaca | |
| CN107904939B (en) | Preparation method of strong base ion exchange fiber | |
| CN117050339B (en) | Synthesis process and application of functionalized polystyrene hydrogel | |
| CN101636422A (en) | Material comprising polyazacycloalkanes grafted onto polypropylene fibres method for production thereof and method for removal of metal cations from a liquid | |
| CN108586648B (en) | Chelate resin and preparation method and application thereof | |
| Kise et al. | Synthesis of a new chelate resin for uranium adsorption from seawater. Polystyrene resin containing two amide oxime functions in the repeating unit | |
| CN101190974A (en) | Pyrrolidone-base modified composite function absorption resin and preparation method thereof | |
| CN112111060A (en) | Porous organic framework material, preparation method thereof and application of porous organic framework material in selective separation of perrhenate | |
| CN104877090B (en) | A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer | |
| CN114836980B (en) | Functional fiber containing strong base and weak base groups and preparation method thereof | |
| CN105413651B (en) | A kind of method that chelating resin reclaims silver ion from tantalum electrolytic capacitor | |
| CN115403767A (en) | Preparation method of cationic organic polymer and application of cationic organic polymer to adsorption of perrhenate | |
| CN1049264C (en) | Method for synthesizing multi-functional radical chelate fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220705 |