CN103483474B - Preparation method for macroporous weak-base anion resin - Google Patents
Preparation method for macroporous weak-base anion resin Download PDFInfo
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- CN103483474B CN103483474B CN201310427235.4A CN201310427235A CN103483474B CN 103483474 B CN103483474 B CN 103483474B CN 201310427235 A CN201310427235 A CN 201310427235A CN 103483474 B CN103483474 B CN 103483474B
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- base anion
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- 239000011347 resin Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 150000001450 anions Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- 239000011592 zinc chloride Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000005576 amination reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 241001566735 Archon Species 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- -1 TXB Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- BEVGWNKCJKXLQC-UHFFFAOYSA-N n-methylmethanamine;hydrate Chemical compound [OH-].C[NH2+]C BEVGWNKCJKXLQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920000570 polyether Polymers 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
A preparation method for macroporous weak-base anion resin belongs to the field of high polymer chemistry, and comprises the following steps: the polymerization reaction stage: preparing materials, stirring, heating and reacting to obtain white spheres; the chlorination reaction stage: placing the white spheres into a chlorination reaction kettle, adding chlorinated polyether , zinc chloride and the like, and reacting to obtain chlorinated spheres; the amination reaction stage: performing amination reaction between the chlorinated spheres and a dimethylamine aqueous solution to obtain the macroporous weak-base anion resin. According to the macroporous weak-base anion resin prepared through the method disclosed by the invention, the mechanical strength of the resin is improved, the service life of the resin is prolonged, the specific surface area is larger, the pore diameter is uniform, the exchange capacity and the anti-pollution capacity of the resin are improved, the production cost is lowered, and the economic efficiency is improved.
Description
Technical field
The present invention relates to technical field of polymer chemistry, be specifically related to a kind of preparation method of macropore weak base anion resins.
Background technology
Macropore weak base anion resins is widely used in water softening, de-salted water, pure water preparation, and hydrometallurgy, rare elements separation, pharmacy, sugar industry, the fields such as amino acid absorption.Widespread use D301 in the market.This product value-rising is high, but it can produce a large amount of toxic gases in process of production, easily cause workman and the periphery masses carcinogenic and unhealthful, so, many enterprises cannot normally produce or hide and produce in the mode of frequently changing workman in mountain area, have therefore greatly affected production and the application of macropore weak base anion resins.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of macropore weak base anion resins, has not only improved the intensity of product, and the specific surface area that makes resin is larger, aperture is even, improves exchange capacity and the contamination resistance of resin.
Technical problem to be solved by this invention realizes by the following technical solutions:
A preparation method for macropore weak base anion resins, is characterized in that: its preparation method comprises the steps:
First step 1: polyreaction: a. puts into raw materials vinylbenzene, TXB, initiator and pore-creating agent the still of getting the raw materials ready, and to stir 30min for subsequent use; Dispersion agent and water are dropped in reactor, temperature is risen to 50 DEG C, and stir 1 hour;
B. the raw material stirring in the still of getting the raw materials ready is joined in reactor, temperature is warming up to 80 DEG C, be incubated after 2 hours and again temperature risen between 85 DEG C-95 DEG C, and be incubated four hours; Again temperature is risen to more than 95 DEG C, be incubated cooling after 6 hours, cool the temperature to below 45 DEG C, obtain Archon;
C. the Archon in reactor is put into wash in material still and cleans, until water outlet is limpid;
D. the Archon having washed is sent in drying machine and dried, after oven dry, filter out the Archon that granularity is qualified;
Step 2: chlorination reaction: qualified Archon and chlorinated ether are put into chlorination reaction still and carry out chlorination reaction, temperature is controlled at 30 DEG C, and the time is 2 hours; After 2 hours, in chlorination reaction still, add zinc chloride, temperature is warming up between 45 DEG C-48 DEG C, react and after 15 hours, cool the temperature to 30 DEG C and can obtain below chlorine ball;
Step 3: amination reaction: dimethylamine water is splashed in chlorine ball fast, stablize after 30min and start to stir, temperature is risen to 43 DEG C after being stirred, be incubated sampling survey moisture after 8 hours, water content is greater than 53% can obtain qualified macropore weak base anion resins.
Described initiator, pore-creating agent and dispersion agent are respectively isopropylcarbinol, TXA and polyvinyl alcohol.
In embodiment further of the present invention, in step 1, in described raw materials, the mass ratio of vinylbenzene, TXB, initiator and pore-creating agent is 10:1.4～1.8:4～5:0.15～0.3, is preferably 10:1.6:4.5:0.2; The mass ratio of described raw materials, dispersion agent and water is 10:0.1～0.3:20～30, is preferably 10:0.2:25; Be incubated 2 hours in step 1b after, temperature rises to and is preferably 90 DEG C.
In step 2, the mass volume ratio of described Archon, chloromethyl ether and zinc chloride is 1kg:2～3L:0.2～0.3kg, is preferably 1kg:2.5L:0.25kg; Described temperature rises to and is preferably 46 DEG C.
In step 3, the mass volume ratio of described chlorine ball, dimethylamine and water is 1kg:4～5L:0.8～1.0kg, is preferably 1kg:4.5L:0.9kg.
In the present invention, unless stated otherwise, described TXB refers to the TRIGONOX B that Akzo Nobel N.V. (Holland) produces, and its chemical composition is ditertiary butyl peroxide (DTBP); Described TXA refers to the TRIGONOX A80 that Akzo Nobel N.V. (Holland) produces, and its chemical composition is tertbutanol peroxide (TBHP); Described chlorinated ether refers to chloromethyl methyl ether, is called for short chloromethyl ether.
The invention has the beneficial effects as follows:
1, adopt novel material TXB to replace divinylbenzene of the prior art, greatly improved the physical strength of resin, extended the work-ing life of resin;
2, adopting novel material TXA is pore-creating agent, makes that resin specific surface area is larger, aperture is even, improves the exchange capacity of resin, and contamination resistance strengthens;
3, reduce production cost, improved the economic benefit of product.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, further set forth the present invention.
Embodiment 1
A preparation method for macropore weak base anion resins, is characterized in that: its preparation method comprises the steps:
First step 1: polyreaction: a. puts into the initiator isopropylcarbinol of the TXB of the vinylbenzene of raw materials 10kg, 1.4kg, 4kg and 0.15kg pore-creating agent TXA the still of getting the raw materials ready, and to stir 30min for subsequent use; Dispersion agent 1.55kg polyvinyl alcohol and 31.1kg water are dropped in reactor, temperature is risen to 50 DEG C, and stir 1 hour;
B. the raw material stirring in the still of getting the raw materials ready is joined in reactor, temperature is warming up to 80 DEG C, be incubated and temperature risen to 85 DEG C again after 2 hours, and be incubated four hours; Temperature is risen to 98 DEG C again, be incubated cooling after 6 hours, cool the temperature to 40 DEG C, obtain Archon;
C. the Archon in reactor is put into wash in material still and cleans, until water outlet is limpid;
D. the Archon having washed is sent in drying machine and dried, after oven dry, filter out the Archon that granularity is qualified;
Step 2: chlorination reaction: the chloromethyl ether of the Archon of qualified 10kg and 20L is put into chlorination reaction still and carry out chlorination reaction, temperature is controlled at 30 DEG C, and the time is 2 hours; After 2 hours, in chlorination reaction still, add the zinc chloride of 2kg, temperature is warming up to 45 DEG C, react and after 15 hours, cool the temperature to 25 DEG C and can obtain chlorine ball;
Step 3: amination reaction: the mixing solutions of the water of the dimethylamine of 40L and 8kg is splashed into fast in the chlorine ball of 10kg, after stablizing 30min, start to stir, after being stirred, temperature is risen to 43 DEG C, be incubated sampling after 8 hours and survey moisture, water content is greater than 53% can obtain qualified macropore weak base anion resins.
Embodiment 2-5
Except following table parameter, other are all with embodiment 1, and design parameter is as follows:
The performance index of macropore weak base anion resins prepared by embodiment 1-5 are as follows:
The detection method of described performance index is referring to national standard HG/T2165-1997
Simultaneous test:
For the superiority of the every technical parameter of explanation the present invention, the present invention has carried out simultaneous test, and comparative example parameter in following table is different from embodiment 1, other are all identical with embodiment 1.
The performance index of macropore weak base anion resins prepared by comparative example 1-4 are as follows:
As can be seen from the above table, in the time that the proportioning in preparation method of the present invention exceeds scope of the present invention, the performance index of comparative example 1-4 occur significantly declining compared with embodiment of the present invention 1-5.Also it is pointed out that comparative example 1-4 of the present invention is only the superiority for proving proportioning of the present invention, the present invention also exists a large amount of correlation datas to show the superiority (data are not listed one by one at this) of proportioning of the present invention.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. a preparation method for macropore weak base anion resins, is characterized in that: its preparation method comprises the steps:
First step 1: polyreaction: a. puts into raw materials vinylbenzene, TXB, initiator and pore-creating agent the still of getting the raw materials ready, and to stir 30min for subsequent use; Dispersion agent and water are dropped in reactor, temperature is risen to 50 DEG C, and stir 1 hour; In described raw materials, the mass ratio of vinylbenzene, TXB, initiator and pore-creating agent is 10:1.4～1.8:4～5:0.15～0.3; The mass ratio of described raw materials, dispersion agent and water is 10:0.1～0.3:20～30;
B. the raw material stirring in the still of getting the raw materials ready is joined in reactor, temperature is warming up to 80 DEG C, insulation 2 as a child rose to temperature between 85 DEG C-95 DEG C again, and was incubated four hours; Again temperature is risen to more than 95 DEG C, be incubated cooling after 6 hours, cool the temperature to below 45 DEG C, obtain Archon;
C. the Archon in reactor is put into wash in material still and cleans, until water outlet is limpid;
D. the Archon having washed is sent in drying machine and dried, after oven dry, filter out the Archon that granularity is qualified;
Step 2: chlorination reaction: qualified Archon and chlorinated ether are put into chlorination reaction still and carry out chlorination reaction, temperature is controlled at 30 DEG C, and the time is 2 hours; After 2 hours, in chlorination reaction still, add zinc chloride, temperature is warming up between 45 DEG C-48 DEG C, react and after 15 hours, cool the temperature to 30 DEG C and can obtain below chlorine ball; The mass volume ratio of described Archon, chlorinated ether and zinc chloride is 1kg:2～3L:0.2～0.3kg;
Step 3: amination reaction: dimethylamine water is splashed in chlorine ball fast, stablize after 30min and start to stir, temperature is risen to 43 DEG C after being stirred, be incubated sampling survey moisture after 8 hours, water content is greater than 53% can obtain qualified macropore weak base anion resins; The mass volume ratio of described chlorine ball, dimethylamine and water is 1kg:4～5L:0.8～1.0kg.
2. a kind of preparation method of macropore weak base anion resins according to claim 1, is characterized in that: described initiator, pore-creating agent and dispersion agent are respectively isopropylcarbinol, TXA and polyvinyl alcohol.
3. a kind of preparation method of macropore weak base anion resins according to claim 1, is characterized in that: in described raw materials, the mass ratio of vinylbenzene, TXB, initiator and pore-creating agent is preferably 10:1.6:4.5:0.2.
4. a kind of preparation method of macropore weak base anion resins according to claim 1, is characterized in that: the mass ratio of described raw materials, dispersion agent and water is preferably 10:0.2:25.
5. a kind of preparation method of macropore weak base anion resins according to claim 1, is characterized in that: the mass volume ratio of described Archon, chlorinated ether and zinc chloride is preferably 1kg:2.5L:0.25kg.
6. a kind of preparation method of macropore weak base anion resins according to claim 1, is characterized in that: the mass volume ratio of described chlorine ball, dimethylamine and water is preferably 1kg:4.5L:0.9kg.
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| CN201310427235.4A CN103483474B (en) | 2013-09-18 | 2013-09-18 | Preparation method for macroporous weak-base anion resin |
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| CN201310427235.4A CN103483474B (en) | 2013-09-18 | 2013-09-18 | Preparation method for macroporous weak-base anion resin |
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| CN103483474B true CN103483474B (en) | 2014-06-11 |
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| CN105153344A (en) * | 2015-10-23 | 2015-12-16 | 蓝星（成都）新材料有限公司 | Diethylamine anion exchange resin and preparation method thereof |
| CN106854683A (en) * | 2016-12-05 | 2017-06-16 | 浙江海洋大学 | A kind of cation saccharified liquid discoloration method |
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| CN101954299A (en) * | 2009-07-15 | 2011-01-26 | 中国船舶重工集团公司第七一八研究所 | Method for preparing anion exchange resin |
| CN101703950A (en) * | 2009-11-16 | 2010-05-12 | 江苏苏青水处理工程集团有限公司 | Dedicated ion exchange resin for condensed water precision processing and preparation method thereof |
| CN101781379B (en) * | 2009-12-31 | 2014-08-13 | 安徽皖东化工有限公司 | Preparation method of D301 macroporous weekly acidic styrene type anion exchange resin |
| CN103183755A (en) * | 2013-03-12 | 2013-07-03 | 蚌埠市天星树脂有限责任公司 | Method for preparing macroporous weak-base anion resin |
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Denomination of invention: A preparation method of macroporous weakly alkaline anion resin Granted publication date: 20140611 Pledgee: Agricultural Bank of China Limited Guzhen County Branch Pledgor: BENGBU TIANXING ION-RESIN CO.,LTD. Registration number: Y2024980010243 |
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