CN85104153A - The synthetic method of acrylate type weakly basic anionic ionexchange resin - Google Patents
The synthetic method of acrylate type weakly basic anionic ionexchange resin Download PDFInfo
- Publication number
- CN85104153A CN85104153A CN198585104153A CN85104153A CN85104153A CN 85104153 A CN85104153 A CN 85104153A CN 198585104153 A CN198585104153 A CN 198585104153A CN 85104153 A CN85104153 A CN 85104153A CN 85104153 A CN85104153 A CN 85104153A
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- CN
- China
- Prior art keywords
- resin
- temperature
- pore
- exchange resin
- weak 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.)
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- 125000000129 anionic group Chemical group 0.000 title claims abstract description 9
- 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 title claims abstract description 8
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229920000768 polyamine Polymers 0.000 claims abstract description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 10
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000007098 aminolysis reaction Methods 0.000 claims description 7
- 230000002862 amidating effect Effects 0.000 claims description 5
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 5
- YTLYLLTVENPWFT-UPHRSURJSA-N (Z)-3-aminoacrylic acid Chemical compound N\C=C/C(O)=O YTLYLLTVENPWFT-UPHRSURJSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- 239000011733 molybdenum Substances 0.000 abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 abstract description 9
- 239000010937 tungsten Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000008961 swelling Effects 0.000 abstract description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002500 ions Chemical group 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract description 2
- 238000005194 fractionation Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940059260 amidate Drugs 0.000 description 2
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of acrylate type weakly basic anionic ionexchange resin is characterized in that, in the presence of various ester classes and gasoline, methyl acrylate and divinylbenzene is made the pearl macroporous copolymer.With the mixture of quadrol and various fat polyamines, obtain containing amino weakly base resin then by low-temp reaction.Swelling agent toluene in the building-up process or dimethylbenzene and mixed amine can return repeated use respectively through fractionation by distillation.This resin has special adsorptive power to polymeric heavy ion group in acidic medium, can reach 2200 milligrams/gram as the loading capacity to tungsten and do, and can reach 600 milligrams/gram to the loading capacity of molybdenum and do.
Description
The present invention relates to a kind of synthetic method of macromolecular compound, particularly a kind of synthetic method that contains amino acrylate type weakly basic anionic ionexchange resin.
Synthesizing of acrylate type weakly basic anionic ionexchange resin, general methyl acrylate and the linking agent divinylbenzene copolymerization of adopting prepares bead-like copolymer, the multipolymer that obtains macroporous structure in the presence of the pore-creating agent is being arranged, containing amino acrylate type weakly basic anionic ionexchange resin through making behind the polyethylene polyamine amidate action again.This method is because high temperature (160～180 ℃) carries out amidate action, and it is crosslinked to cause serious pair of resin generation to add, and resin structure is become closely, only limits to adsorb the small ion group, and polymeric heavy ion group is then shown as very low exchange capacity.Soviet Union X И М И Я И X И М И Ч Е С К А Я TEXHO Л О Г И Я TOM XXV21982 synthetic AH-80 π resin, use the octane-iso pore, as amidating agent, the low temperature aminolysis has improved the pore structure of resin effectively with quadrol.But this resin is still lower to the loading capacity of polymer ions groups such as tungsten, molybdenum.
Task of the present invention is synthetic a kind of amino acrylate type weakly basic anionic ionexchange resin that contains, and this resin is adsorpting polymerization thing ionic group effectively, can adsorb tungsten and molybdenum especially from solution such as high-load tungsten, molybdenum.
Implementing main points of the present invention is, when methyl acrylate and divinylbenzene low-temperature suspension polymerization prepare the macropore dropwise multipolymer, use two pore-creating agent pores, multipolymer swelling agent swelling, with the blended fat polyamine as amidating agent, the low temperature aminolysis, introduce amino, generation has the poly-dielectric medium of three-dimensional polymeric molecule of weakly alkaline group, this poly-dielectric medium can swelling in the aqueous solution, and not dissolved, the weakly alkaline group that it had can be from solution anionic group such as the tungsten of adsorpting polymerization and molybdenum.
We know that tungsten and molybdenum etc. easily form polymer in acidic medium, freely enter the resin duct for making these polymerization physical efficiencys, require resin that certain specific surface area and aperture are arranged.For this reason, the present invention adopts low temperature polymerization in the presence of two pore-creating agents, be to become the macropore dropwise multipolymer through suspension polymerization under 60～85 ℃ in temperature promptly.Said pair of pore-creating agent, i.e. mixed solvent, wherein a kind of is good solvent, plays a part swelling and unfolds back bone network, another kind is a poor solvent, plays a part to form macropore.These two kinds of solvents are mixed use by a certain percentage, not only can improve the kinetics of adsorption performance of resin, and help of the diffusion of heavy ion group in resin inside.Two pore-creating agents can be the mixtures of various ester classes and gasoline, and the preferential ester of selecting is a rutgers, and its consumption ester is 3～30%(weight percent, down together), gasoline is 40～70%.
Macropore dropwise multipolymer swelling agent toluene or dimethylbenzene swelling, carry out aminolysis reaction with the blended fat polyamine as amidating agent, temperature of reaction can be controlled at 100～130 ℃ and adopt the mixed amine aminolysis reaction, can reduce paying in the reaction and add crosslinked phenomenon, the structure of resin is unfolded, the distribution uniform of cation exchange groups helps the absorption of heavy ion group, particularly tungsten and molybdenum etc. is had higher exchange capacity.Mixed amine used in the present invention can be the mixture of quadrol and other various fat polyamines, and selected fat polyamine is diethylenetriamine or triethylene tetramine or tetraethylene pentamine or polyethylene polyamine.Quadrol is 1 to 0.5 to 1.5 with the blending ratio of other fat polyamines.
Following Example is used for further specifying the present invention, also is concrete enforcement of the present invention.
In 2000 milliliters of reaction flasks that agitator, thermometer, reflux exchanger are housed, add 1000 milliliters of entry, gelatin 3 grams, sodium-chlor 100 grams, stirring and dissolving.In a beaker, take by weighing divinylbenzene 75 grams, benzoyl peroxide 3 grams, methyl acrylate 225 grams, gasoline 120 grams, rutgers 10 grams mix the back and add in the reaction flask, stir into pearl, reacted 14 hours down in 80 ℃, cool off then, filter, washing, drying.Take by weighing macroporous copolymer 100 grams, add and have in 1000 milliliters of reaction flasks of agitator, reflux exchanger, thermometer, add toluene 300 grams, add quadrol 200 grams after 2 hours, tetraethylene pentamine 100 grams reacted 10 hours down in 100 ℃, steam toluene, washed resin is used hcl acidifying, obtains the resin finished product after washing with water again.
In implementation process of the present invention, toluene or dimethylbenzene and mixed amine can pass through fractionation by distillation, and can return repeated use respectively, can save starting material like this, and also unlikely effluxing pollutes.The present invention does not produce to pay in implementation process and adds crosslinking reaction, by institute of the present invention synthetic resin, the aperture is stable, chlorine type exchange capacity can reach 3.5～4.5 milligramequivalent/grams to be done, and have good kinetics of adsorption performance, be specially adapted to from the ore leach liquor, reclaim tungsten and molybdenum in the crystalline mother solution, can reach 2200 milligrams/gram to the dynamic adsorption capacity of tungsten and do, can reach 600 milligrams/gram to the dynamic adsorption capacity of molybdenum and do.
Claims (5)
1, a kind of synthetic method that contains amino acrylate type weakly basic anionic ionexchange resin adopts methyl acrylate, in the presence of octane-iso, becomes macroporous copolymer with divinylbenzene suspension polymerization after the polyethylene polyamine aminolysis, and feature of the present invention is:
(1) in the presence of two pore-creating agents, low-temperature suspension polymerization becomes macroporous copolymer, and said pair of pore-creating agent is the mixture of gasoline and various ester classes, and the consumption of two pore-creating agents, gasoline are 40～70% (weight percents, down together), and ester is 3～30%.
(2) macroporous copolymer is with mixing the amidating agent aminolysis, and said mixing amidating agent is the mixture of quadrol and other fat polyamines.The blending ratio of quadrol and other fat polyamines is 1 to 0.5 to 1.5.
2, weak base anion-exchange resin according to claim 1, the temperature that it is characterized in that low-temperature suspension polymerization are 60～85 ℃.
3, weak base anion-exchange resin according to claim 1, the temperature that it is characterized in that the low temperature aminolysis is 95～130 ℃.
4, weak base anion-exchange resin according to claim 1 is characterized in that said other fat polyamines are diethylenetriamines, or triethylene tetramine, or tetraethylene pentamine, or polyethylene polyamine.
5, weak base anion-exchange resin according to claim 1 is characterized in that the preferential ester of selecting is a rutgers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104153A CN85104153B (en) | 1985-06-03 | 1985-06-03 | Synthesis method of acrylic acid type weak-base anion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104153A CN85104153B (en) | 1985-06-03 | 1985-06-03 | Synthesis method of acrylic acid type weak-base anion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104153A true CN85104153A (en) | 1986-12-03 |
| CN85104153B CN85104153B (en) | 1987-08-19 |
Family
ID=4793664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85104153A Expired CN85104153B (en) | 1985-06-03 | 1985-06-03 | Synthesis method of acrylic acid type weak-base anion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85104153B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101804331A (en) * | 2010-03-02 | 2010-08-18 | 江苏工业学院 | Dendritic polyamine adsorptive resin and preparation method thereof |
| CN101781437B (en) * | 2010-01-12 | 2012-07-04 | 南京大学 | Magnetic acrylic acid series strongly basic anion exchange microballoon resin and preparation method thereof |
| CN102585076A (en) * | 2011-12-27 | 2012-07-18 | 深圳清华大学研究院 | Macroporous resin microspheres and preparation method and application thereof |
| CN103012656A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin |
| CN103008029A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin |
| CN103826744A (en) * | 2011-03-01 | 2014-05-28 | 通用汽车环球科技运作有限责任公司 | Synthesis of nanosized metal carbides on graphitized carbon as supporting materials for electrocatalysts |
| CN104387517A (en) * | 2014-11-19 | 2015-03-04 | 辽宁大学 | Preparation method of modified methyl methacrylate-based microspheres |
| CN104910313A (en) * | 2015-06-24 | 2015-09-16 | 中南大学 | Method for preparing polar modified ultrahighly-crosslinked resin and application of resin |
| CN105037663A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for inorganic modified macroporous weakly basic anion exchange resin |
| CN105949354A (en) * | 2016-07-07 | 2016-09-21 | 宁波争光树脂有限公司 | Preparation method of weak basic anion exchange resin, product of preparation method and application of product |
| CN102585076B (en) * | 2011-12-27 | 2016-12-14 | 深圳清华大学研究院 | A kind of macroporous resin microspheres, its preparation method and application |
-
1985
- 1985-06-03 CN CN85104153A patent/CN85104153B/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781437B (en) * | 2010-01-12 | 2012-07-04 | 南京大学 | Magnetic acrylic acid series strongly basic anion exchange microballoon resin and preparation method thereof |
| CN101804331A (en) * | 2010-03-02 | 2010-08-18 | 江苏工业学院 | Dendritic polyamine adsorptive resin and preparation method thereof |
| CN101804331B (en) * | 2010-03-02 | 2013-05-08 | 江苏工业学院 | Dendritic polyamine adsorptive resin and preparation method thereof |
| CN103826744A (en) * | 2011-03-01 | 2014-05-28 | 通用汽车环球科技运作有限责任公司 | Synthesis of nanosized metal carbides on graphitized carbon as supporting materials for electrocatalysts |
| CN102585076A (en) * | 2011-12-27 | 2012-07-18 | 深圳清华大学研究院 | Macroporous resin microspheres and preparation method and application thereof |
| CN102585076B (en) * | 2011-12-27 | 2016-12-14 | 深圳清华大学研究院 | A kind of macroporous resin microspheres, its preparation method and application |
| CN103012656A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin |
| CN103008029B (en) * | 2012-11-27 | 2016-02-24 | 安徽皖东化工有限公司 | The preparation method of macroreticular weakly base composite acrylic acid series anion exchange resin |
| CN103008029A (en) * | 2012-11-27 | 2013-04-03 | 安徽皖东化工有限公司 | Preparation method of macroporous weak-alkaline compound acrylic anion exchange resin |
| CN104387517A (en) * | 2014-11-19 | 2015-03-04 | 辽宁大学 | Preparation method of modified methyl methacrylate-based microspheres |
| CN104910313A (en) * | 2015-06-24 | 2015-09-16 | 中南大学 | Method for preparing polar modified ultrahighly-crosslinked resin and application of resin |
| CN104910313B (en) * | 2015-06-24 | 2017-10-17 | 中南大学 | Prepare method and the application of Modified with Polar Monomer hypercrosslinked polymeric resin |
| CN105037663A (en) * | 2015-07-09 | 2015-11-11 | 安徽皖东化工有限公司 | Preparation method for inorganic modified macroporous weakly basic anion exchange resin |
| CN105949354A (en) * | 2016-07-07 | 2016-09-21 | 宁波争光树脂有限公司 | Preparation method of weak basic anion exchange resin, product of preparation method and application of product |
| CN105949354B (en) * | 2016-07-07 | 2018-08-14 | 宁波争光树脂有限公司 | A kind of preparation method of weak-base anion-exchange resin and products thereof and purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104153B (en) | 1987-08-19 |
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