CN101899132B - Preparation method of polyacrylonitrile adsorbing materials - Google Patents
Preparation method of polyacrylonitrile adsorbing materials Download PDFInfo
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- CN101899132B CN101899132B CN2010102451110A CN201010245111A CN101899132B CN 101899132 B CN101899132 B CN 101899132B CN 2010102451110 A CN2010102451110 A CN 2010102451110A CN 201010245111 A CN201010245111 A CN 201010245111A CN 101899132 B CN101899132 B CN 101899132B
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- vinyl cyanide
- polyacrylonitrile
- ferric chloride
- modification
- macromole evocating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of polyacrylonitrile adsorbing materials, which is characterized by grafting polyacrylonitrile with chain length being basically consistent on the surface of a modifying macroinitiator by utilizing atom transfer radical polymerization initiated by an electron transfer regenerated catalyst and then modifying the grafted product with hydroxylamine hydrochloride to obtain the adsorbing materials with good adsorbing performance to the metal ions.
Description
Technical field
The present invention relates to a kind of preparation method of sorbing material, especially a kind of atom transferred free radical living polymerization that adopts the transfer transport regenerated catalyst to cause prepares the method for sorbing material at modification macromole evocating agent surface grafting polyacrylonitrile.
Background technology
In recent years; Along with the continuous quickening of urbanization process and the rapid raising of industrialized level; The trade effluent of heavy metal ion such as that industry such as smelting, electrolysis, plating, medicine, dyestuff is all discharged every year is mercurous in a large number, silver; Life brings serious harm, wastewater treatment to become the hot research problem to human being's production.
Existing sewage water treatment method comprises the physics method, chemical method and biological process at present.The physics method can only treating water in insoluble suspended matter and can not handle colloidalmaterial and the dissolved matter that dissolves in the water; And biological process since to environmental requirement relatively harshness limited its range of application, this makes chemical method become the main path of WWT.The chemiadsorption most critical issue is the preparation high-efficiency absorption material.Polyacrylonitrile is the important presoma of macromolecular material, can be used as sorbing material behind the nitrile-group modification in the molecular chain.The preparation polyacrylonitrile adsorbing materials has direct function method and grafting functional method.Direct function method itrile group transformation efficiency and functional group content are not high.The grafting functional method is graft polypropylene nitrile on other matrixes at first, afterwards itrile group again with other function reagent reacts, obtain sorbing material.In addition, the polyacrylonitrile chain length that traditional grafting method prepares is different in size, and MWD is wide, influences the absorption property of final sorbing material.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, and the preparation method of the polyacrylonitrile adsorbing materials of a kind of grafting chain length basically identical, good adsorption performance is provided.
The object of the invention can reach through following measure: at first synthetic through silane coupler modified silica gel macromole evocating agent with through chlorsulfonic acid, Tri N-Propyl Amine, Youxiaolin polystyrene modified microballoon macromole evocating agent, then catalyzer FERRIC CHLORIDE ANHYDROUS, part iminodiethanoic acid are dissolved into solvent N, in the dinethylformamide; In the monomer vinyl cyanide, wherein, the mol ratio of vinyl cyanide and modification macromole evocating agent is 200: (0.5～1.5) with modification macromole evocating agent, reductive agent dissolution of ascorbic acid; The mol ratio of vinyl cyanide and FERRIC CHLORIDE ANHYDROUS is 200: (0.005～0.015), the mol ratio of FERRIC CHLORIDE ANHYDROUS and iminodiethanoic acid are 1: (5～15), the mol ratio of FERRIC CHLORIDE ANHYDROUS and xitix are 1: (5～15); Vinyl cyanide and N; The volume ratio of dinethylformamide is 1: 2～2: 3, and the volumetric molar concentration of vinyl cyanide is 5～8 mol, and polymeric reaction temperature is 55～70 degrees centigrade; Fill nitrogen deoxygenation at least 1 time repeatedly; Carry out the atom transferred free radical living polymerization at least 12 hours that the transfer transport regenerated catalyst causes, product washs through concentrated hydrochloric acid, deposition; Suction filtration; Drying is carried out modification with products therefrom with oxammonium hydrochloride at last, obtains sorbing material of the present invention.
Compared with present technology the present invention has following advantage: the present invention adopts the transfer transport regenerated catalyst to cause atom transferred free radical living polymerization graft polypropylene nitrile on matrix, and reaction conditions is gentle, and easy and simple to handle, the product that obtains is pure.The present invention can prepare the polyacrylonitrile of different chain length and different percentage of grafting through the ratio of control monomer and macromole evocating agent, the sorbing material stable performance that modification obtains, and adsorptive capacity is big.
Embodiment
Specify the present invention below and provide several embodiment:
Embodiment one:
(1). the synthesized silicon rubber macromole evocating agent.Will be in the CPTS of 100 milliliters of dry toluenes and 270 mmoles through the silica gel behind nitric acid and the hydrochloric acid activation, nitrogen protection refluxed 12 hours, and the extracting drying obtains silica gel modification macromole evocating agent.
(2). 0.0024 gram FERRIC CHLORIDE ANHYDROUS, 0.0264 gram iminodiethanoic acid are dissolved into 30 milliliters of N; In the dinethylformamide; 0.5 gram silica gel modification macromole evocating agent, 0.0312 gram dissolution of ascorbic acid are in 26 milliliters of vinyl cyanide; Join successively and fill nitrogen deoxygenation at least 1 time in the reaction flask, reaction flask is put into 65 degrees centigrade constant temperature oil bath polymerization.Reacted 48 hours, product washs through concentrated hydrochloric acid, deposition, suction filtration, drying.
(3). with 5 grams of products therefrom in (2) in pH is 9 35 ml methanol, 70 degrees centigrade down with 7.5 gram oxammonium hydrochlorides reactions 20 hours, absolute ethyl alcohol extracting 24 hours, 50 degrees centigrade of following vacuum-dryings obtain sorbing material according to the invention.
The synthetic silica gel graft polypropylene nitrile sorbing material that obtains is 3.2 mmole/grams to the adsorptive capacity of mercury ion.
Embodiment two:
Present embodiment and embodiment one are basic identical, and different is: the amount of silica gel macromole evocating agent is 0.4 gram, and the amount of FERRIC CHLORIDE ANHYDROUS is 0.0029 gram, and the amount of iminodiethanoic acid is 0.0317 gram, and the amount of xitix is 0.025 gram.Be reflected at and carried out under 55 degrees centigrade 32 hours.
The synthetic silica gel graft polypropylene nitrile sorbing material that obtains is 2.6 mmole/grams to the adsorptive capacity of mercury ion.
Embodiment three:
(1). synthetic polystyrene microballoon initiator.25.3 the gram polystyrene microsphere is put into 50 milliliters chlorsulfonic acid and is reacted 72h; 0 degree centigrade of the Tri N-Propyl Amine solution that the polystyrene microsphere of chlorosulphonation is put into 15 milliliters of 2-SL 1332s and 12 milliliters reaction 10 hours down; Get the amidated polymer microballoon of 10 grams and put into 50 milliliters, contain in the commodity SYNTHETIC OPTICAL WHITNER of 26% reactive chlorine, reaction is 3 days in the refrigerator; Product drying at room temperature 24 hours after washing, subsequent use.
(2). 0.0024 gram FERRIC CHLORIDE ANHYDROUS, 0.0264 gram iminodiethanoic acid are dissolved into 30 milliliters of N; In the dinethylformamide; 0.74 gram polystyrene microsphere modification macromole evocating agent, 0.0312 gram dissolution of ascorbic acid are in 26 milliliters of vinyl cyanide; Join successively and fill nitrogen deoxygenation at least 1 time in the reaction flask, reaction flask is put into 65 degrees centigrade constant temperature oil bath polymerization.Reacted 60 hours, product washs through concentrated hydrochloric acid, deposition, suction filtration, drying.Modification procedure is identical with instance one.
The synthetic polystyrene microsphere graft polypropylene nitrile sorbing material that obtains is 3.0 mmole/grams to the adsorptive capacity of mercury ion.
Embodiment four:
Present embodiment and embodiment three are basic identical, and different is: macromole evocating agent MPS microballoon is 0.5 gram, and FERRIC CHLORIDE ANHYDROUS is 0.0019 gram, and the amount of iminodiethanoic acid is 0.022 gram, and the amount of xitix is 0.0466 gram.Be reflected at and carried out under 70 degrees centigrade 48 hours.Modification procedure is identical with instance one.
The synthetic polystyrene microsphere graft polypropylene nitrile sorbing material that obtains is 2.3 mmole/grams to the adsorptive capacity of mercury ion.
Claims (1)
1. the preparation method of a polyacrylonitrile adsorbing materials is characterized in that: to be the modification macromole evocating agent through silane coupler modified silica gel or through chlorsulfonic acid, Tri N-Propyl Amine, Youxiaolin polystyrene modified microballoon, catalyzer FERRIC CHLORIDE ANHYDROUS and part iminodiethanoic acid are dissolved into solvent N; In the dinethylformamide, with modification macromole evocating agent, reductive agent dissolution of ascorbic acid in the monomer vinyl cyanide, wherein; The mol ratio of vinyl cyanide and modification macromole evocating agent is 200: 0.5～200: 1.5, and the mol ratio of vinyl cyanide and FERRIC CHLORIDE ANHYDROUS is 200: 0.005～200: 0.015, and the mol ratio of FERRIC CHLORIDE ANHYDROUS and iminodiethanoic acid is 1: 5～1: 15; The mol ratio of FERRIC CHLORIDE ANHYDROUS and xitix is 1: 5～1: 15, vinyl cyanide and N, and the volume ratio of dinethylformamide is 1: 2～2: 3; The volumetric molar concentration of vinyl cyanide is 5～8 mol, and polymeric reaction temperature is 55～70 degrees centigrade, fills nitrogen deoxygenation at least 1 time repeatedly; The atom transferred free radical living polymerization that adopts the initiation of transfer transport regenerated catalyst is at modification macromole evocating agent surface grafting polyacrylonitrile; In at least 12 hours reaction times, product washs through concentrated hydrochloric acid, deposition; Suction filtration; Drying is carried out modification with products therefrom with oxammonium hydrochloride at last, obtains polyacrylonitrile adsorbing materials.
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| CN102060962A (en) * | 2010-12-06 | 2011-05-18 | 鲁东大学 | Method for preparing high oil absorption resin |
| CN103641190A (en) * | 2013-11-30 | 2014-03-19 | 常熟市华宇针织印染有限公司 | Treating agent for printing and dyeing wastewater |
| CN103966851B (en) * | 2014-05-22 | 2016-08-24 | 安徽工程大学 | A kind of functional AOPAN nanofiber and preparation method thereof |
| CN104028238B (en) * | 2014-06-16 | 2015-12-02 | 鲁东大学 | A kind of preparation method based on polyacrylonitrile-itaconic acid arsenic-removing adsorption agent |
| CN104667886B (en) * | 2015-01-22 | 2017-05-17 | 鲁东大学 | Preparation method and application of amidoxime group modified p-aramid adsorption material, and application of amidoxime group modified p-aramid adsorption material |
| CN105152303A (en) * | 2015-10-20 | 2015-12-16 | 鲁东大学 | Hydroxylamine modified polyacrylonitrile-iron complex hydrogen peroxide oxidation arsenic removal method |
| CN106268699A (en) * | 2016-09-24 | 2017-01-04 | 北京益净环保设备科技有限公司 | For granule adsorbent adsorbing furan and preparation method thereof |
| CN110449141B (en) * | 2019-09-10 | 2022-04-19 | 江苏中科睿赛环境工程有限公司 | Preparation method of polyacrylonitrile fiber organic waste gas adsorbent, adsorption device using polyacrylonitrile fiber organic waste gas adsorbent and adsorption method |
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| CN101348950B (en) * | 2008-06-06 | 2010-07-21 | 天津工业大学 | Preparation of adsorption function modified polyacrylonitrile fibre |
| CN101519501B (en) * | 2009-02-24 | 2011-05-04 | 上海大学 | Method for preparing polypropylene ion chelating membrane by radiation grafting method |
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