CN1131112C - Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking - Google Patents
Process for synthesizing weakly alkaline anionic exchange resin with double functions and superhigh cross-linking Download PDFInfo
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- CN1131112C CN1131112C CN 01134143 CN01134143A CN1131112C CN 1131112 C CN1131112 C CN 1131112C CN 01134143 CN01134143 CN 01134143 CN 01134143 A CN01134143 A CN 01134143A CN 1131112 C CN1131112 C CN 1131112C
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Abstract
The present invention discloses a method for preparing superhigh crosslinking weak alkali anion exchange resin with the double functions of adsorption and exchange. In the method, in the process of the crosslinking reaction after the chloromethylation of low crosslinked macroporous polystyrenes, nitrobenzene or substituted nitrobenzene is used as a solvent, lewis acids of zinc chloride, ferric chloride, etc. are used as catalysts, and through controlling residual chlorine content of resin and then using dimethylamine for amination, a series of superhigh crosslinking weak alkali anion exchange resin with different specific surface areas and different exchange capacity is prepared.
Description
Technical field
The present invention relates to a kind of preparation method, belong to ion-exchange and polymeric adsorbent field with superhigh cross-linking weak basic anion exchange resin of absorption and exchange dual-use function.
Background technology
Have absorption and extract at natural drug with the superhigh cross-linking weak basic anion exchange resin that exchanges dual-use function, organic enrichment, separation in the water have important purposes in the fields such as waste water treatment.The document that relevant superhigh cross-linking weak base resin is seen seldom, has only once reported for work performance (the The Purolite Company of the synthetic a kind of superhigh cross-linking weak basic anion exchange resin Hypersol-Macronet MN-300 of the said firm of Purolite international Ltd., 1995, Purolite TechnicalBulletin, Hypersol-Macronet
TMSorbent Resins).Literature search shows, does not see the synthetic method of superhigh cross-linking weak basic anion exchange resin in the existing bibliographical information.
Summary of the invention
Main purpose of the present invention is exactly to propose a kind of synthetic method with superhigh cross-linking weak base anion resins of dual-use function.
Technical scheme of the present invention is as follows:
The present invention utilizes atoleine or 200# gasoline to make the 40%-100% of the pore-foaming agent consumption of suspension copolymerization reaction for monomer, make dispersant with one or more mixtures in magnesium carbonate, gelatin, the polyvinyl alcohol, styrene is monomer, divinylbenzene is made crosslinking agent, benzoyl peroxide is made initator, adopt the suspension copolymerization method, synthetic low crosslinking degree macroporous polystyrene, the degree of cross linking is between 2-10%, with steam distillation or with behind acetone and the lower boiling gasoline extracting pore-foaming agent, pneumatic conveying drying gets low cross-linking macropore styrene-divinylbenzene copolymer Archon pearl body then.Soak Archon pearl body with Archon pearl body weight 4-7 chloromethyl ether doubly, zinc chloride with Archon pearl body weight 30-50% is made catalyst, at 36-42 ℃ of chloromethylation, reach more than 18% until the chlorine ball chlorinity that makes, take out chlorination mother solution, water or organic solvent are washed remaining chlorination mother solution in the most resin, dry chloromethylation low cross-linking polystyrene.Behind chloromethylation low cross-linking polystyrene in the cross-linking reaction process, make solvent with nitrobenzene or substituted-nitrobenzene, consumption is 4-7 a times of chloromethylation low cross-linking polystyrene, use zinc chloride, ferric trichloride, Louis's acid as catalyst such as butter of tin, consumption is the 5-30% of Archon pearl body weight, after chloromethylation low cross-linking polystyrene expanded 2 hours in nitrobenzene or substituted-nitrobenzene, add lewis acid then, stir, be warming up to 80-150 ℃ then, the synthetic final residual chlorine content of superhigh cross-linking resin of control is determined reaction end, take out most reaction mother liquor, use ethanol, dimethoxym ethane, one or more washing superhigh cross-linking resins in the acetone, till nitrobenzene or substituted-nitrobenzene are washed to the greatest extent, directly carry out aminating reaction with dimethylamine as aminating agent then, the dimethylamine consumption is 1-3 a times of chlorine ball, can make a series of different specific areas, the superhigh cross-linking weak basic anion exchange resin of different exchange capacities.
Synthetic technology with superhigh cross-linking weak base anion resins of absorption and exchange dual-use function of the present invention, it be at chloromethylation low cross-linking macroporous polystyrene in cross-linking process after one's death, make reaction dissolvent with nitrobenzene or substituted-nitrobenzene, with Louis's acid as catalyst such as ferric trichloride, zinc chloride, butters of tin, reaction at a certain temperature, by control resin residual chlorine content is that 2-15% determines reaction end, use the dimethylamine amination then, can make a serial specific area is 1000-150m
2/ g, exchange capacity are the superhigh cross-linking weak basic anion exchange resin with dual-use function of 0.5-4.0mmol/g.This resinoid has ion-exchange and adsorption dual function, and the aspect such as extracting, separate in organic wastewater improvement and resource and medicine has good application performance and wide application prospect.
The specific embodiment
Embodiment
With liquid wax is pore-foaming agent, and styrene and divinylbenzene copolymerization form crosslinked network size structure, with low boiling point solvent extract waxes such as acetone.Making large-pore white balls used pearl body carries out the chloromethyl reaction with chloromethyl ether again under zinc chloride catalysis, on making large-pore white balls used, import chloromethyl, after cleaning, dry chloromethylation low cross-linking polystyrene, make solvent with nitrobenzene again, make catalyst with zinc chloride, carry out the back cross-linking reaction, residual chlorine content by control synthetic resin, obtain the superhigh cross-linking resin of the different chlorinities of series, use the dimethylamine amination then, on the superhigh cross-linking resin, import tertiary amine groups again, can make a serial superhigh cross-linking weak basic anion exchange resin.
I. polymerization
(1) gets the raw materials ready
Styrene 213.5g
Divinylbenzene (50%) 26.5g
Liquid wax 140g
Benzoyl peroxide 3.6g
Pure water 600g
Gelatin 6.0g
The blue 0.008g of methine
(2) operation
1. resin column filtration or the diluted sodium hydroxide solution washing of monomer through strong basic anion-exchange resin is housed removes polymerization inhibitor, prepares burden after the passed examination;
2.1000ml there-necked flask washes, and drops into pure water, is warming up to 40 ℃;
3. gelatin soaked 3-4 hour with ten times of pure water in advance, and it is standby to be heated to 50 ℃ of dissolvings again;
4. after the input gelatin reaches the methine orchid mutually, stir, drop into monomer, pore-foaming agent and crosslinking agent mixed liquor then.Make the pore-foaming agent of copolyreaction with liquid wax, the ratio that the pore-foaming agent consumption accounts for monomer is 40%-100%, and the degree of cross linking of low cross-linking macroporous polystyrene is 2-10%;
5. look pearl body situation, regulate rotating speed, heat up gradually after the epigranular;
6. be warming up to 80 ℃ of insulations 4 hours with 1 ℃/6 minutes speed, then 85 ℃ 3 hours, 90 ℃ 2 hours, 95 ℃ 4 hours, discharging, hot wash, filter is done, and comes the extracting polymer pore-foaming agent clean until extracting with a kind of in acetone or alcohol or low boiling point solvent gasoline or the normal heptane, heated-air drying, sieve, classifying screen is got suitable particle size pearl body.
II. chloromethylation
(1) gets the raw materials ready
Archon 300g
Chloromethyl ether 1200g
Zinc chloride 150g
(2) operating process
1. with the oven dry of 2000ml flask, drop into Archon;
2. behind the adding chloromethyl ether, expanded 2 hours down in 20-25 ℃, stir following minute three times and add zinc chloride, each half an hour at interval, when adding zinc chloride, the control temperature is no more than 25 ℃, adds the back and stirs one hour, is warming up to 38 ± 1 ℃, reacted 12-16 hour, look the suitably additional chlorination mother solution of drying regime in the still in the reaction, the control chlorinity can finish reaction more than 18.5%;
3. after reaction finishes, chlorination mother solution is exhausted with vacuum;
4. chloromethylation low cross-linking polystyrene water or organic solvent are washed most residue mother liquor, oven dry.
III. cross-linking reaction behind the chloromethylation macroporous polystyrene
(1) gets the raw materials ready
Chloromethylation low cross-linking polystyrene 300g
Nitrobenzene 1800g
Zinc chloride 45g
Dimethoxym ethane 1000g
(2) operating process
1. in the 2000ml flask, add dry chlorine ball, add chlorine ball weight 4-7 nitrobenzene or substituted-nitrobenzene doubly, stirred 1 hour, at room temperature expanded again 2 hours after adding, add zinc chloride, stirred again after adding 2 hours;
2. slowly be warming up to 110 ℃, carry out the back cross-linking reaction,, determine the length in reaction time according to the requirement of the residual chlorine content that synthesizes superhigh cross-linking;
3. after residual chlorinity reaches the requirement of 2-15%, stop reaction, take out most mother liquor through cooling;
4. with one or more washing extractings in ethanol, dimethoxym ethane, acetone, the methyl alcohol, till nitrobenzene in synthetic superhigh cross-linking resin or substituted-nitrobenzene are washed to the greatest extent;
5. recovery mother liquor, cleaning solution distill recovery.
IV. amination
(1) gets the raw materials ready
Superhigh cross-linking resin resin 300g
Dimethylamine agueous solution (40%) 600g
(2) operating process
1. add in reactor that good superhigh cross-linking resin and the dimethylamine agueous solution of extracting carries out aminating reaction among the Step II I, during with the dimethylamine amination, the consumption of aminating agent be the superhigh cross-linking amount of resin 1-3 doubly.Stirred 1 hour, and be warming up to 45 insulation 10 hours then, reaction finishes;
2. take out most amination mother liquor, washes clean makes product.
V. the processing of reaction mother liquor
The chloromethylation mother liquor reclaims system ethanol or dimethoxym ethane or acetone or methyl alcohol, residue preparing active carbon by distillation; Nitrobenzene or substituted-nitrobenzene mother liquor reclaim nitrobenzene or substituted-nitrobenzene by distillation; The amination mother liquor reclaims dimethylamine by distillation.
The synthetic superhigh cross-linking weak basic anion exchange resin of this technology is the superhigh cross-linking weak basic anion exchange resin that has absorption and exchange dual-use function simultaneously, and exchange capacity is controlled at 0.5-4.0mmol/g, specific area 1000-150m
2/ g.
The key technical indexes such as the following table of the superhigh cross-linking weak basic anion exchange resin that this technology is synthetic:
Superhigh cross-linking macropore weak basic anion exchange resin physical and chemical performance list
| Numbering | Control residual chlorine content (%) | Specific area (m 2/g) | CEC (mmol/g) | Moisture content % | Wet apparent density (g/ml) | Highly basic exchange capacity (mmol/g) |
| A B C | 4.01 6.50 8.39 | 950 800 240 | 1.33 1.89 2.48 | 56.19 56.63 56.92 | 0.75 0.77 0.79 | 0.14 0.07 0.03 |
Claims (10)
1, a kind of synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function is characterized in that:
A) utilize atoleine or 200# solvent naphtha to make pore-foaming agent, make dispersant with one or more mixtures in magnesium carbonate, gelatin, the polyvinyl alcohol, styrene is made monomer, divinylbenzene is made crosslinking agent, benzoyl peroxide is made initator, adopts suspension polymerization, synthetic low crosslinking degree macroporous polystyrene, select steam distillation for use according to pore-foaming agent character then or with acetone, lower boiling gasoline extracting pore-foaming agent, pneumatic conveying drying gets and is called for short Archon pearl body under the low cross-linking macropore polystyrene resin (ps) again;
B) soak Archon pearl body with Archon pearl body weight 4-7 chloromethyl ether doubly, zinc chloride with Archon pearl body weight 30-50% is made catalyst, carry out chloromethylation at 36-42 ℃, reach more than 18% until chlorinity, take out most chlorination mother solution, water or organic solvent are washed remaining chlorination mother solution in the most resin, and be dry then, get dry chloroethyl crosslinked polystyrene, following abbreviation chlorine ball;
C) at chloromethylation low cross-linking polystyrene in cross-linking process after one's death, make solvent with nitrobenzene or substituted-nitrobenzene, make catalyst with zinc chloride, ferric trichloride or butter of tin, consumption is the 5-30% of chlorine ball weight, be warming up to suitable temperature, determine reaction end by control resin residual chlorine content;
D) after the reaction, take out most reaction mother liquor, with one or more organic solvent washing super high cross-linked adsorbing resins in ethanol, dimethoxym ethane, acetone, the methyl alcohol, directly use the dimethylamine amination then, the dimethylamine consumption is 1-3 a times of chlorine ball, makes the superhigh cross-linking weak basic anion exchange resin of a series of different specific areas, different exchange capacities.
2, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, it is characterized in that doing the pore-foaming agent of copolyreaction with liquid wax or 200# industrial naptha, the ratio that the pore-foaming agent consumption accounts for monomer is 40%-100%, and the degree of cross linking of low cross-linking macroporous polystyrene is 2-10%.
3, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, it is characterized in that the used method of extracting polymer pore-foaming agent selects steam distillation for use or use solvent extraction according to the character of pore-foaming agent, is a kind of in acetone, ethanol, low boiling point solvent gasoline, the normal heptane with the solvent extraction solvent for use.
4,, it is characterized in that the used method of extracting polymer pore-foaming agent adopts steam distillation or with acetone and the extracting of low boiling point solvent gasoline according to right 3 described synthetic methods with superhigh cross-linking weak basic anion exchange resin of dual-use function.
5, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, after it is characterized in that low cross-linking macroporous polystyrene chloromethylation, take out most mother liquor after, the processing of residue mother liquor in the resin hole, water or organic solvent are washed to the greatest extent, and be dry then.
6, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, it is characterized in that behind the chloromethylation low cross-linking macroporous polystyrene in the cross-linking process, make solvent with nitrobenzene or substituted-nitrobenzene, consumption is 4-7 a times of chlorine ball weight, and reaction temperature is at 80-150 ℃.
7, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, it is characterized in that chloromethylation macropore low cross-linking polystyrene through after after the cross-linking reaction, take out most mother liquor, use ethanol, dimethoxym ethane, acetone or methanol wash again, till nitrobenzene or substituted-nitrobenzene are washed to the greatest extent.
8, according to right 7 described synthetic methods, it is characterized in that described washing procedure washs with one or more mixtures in ethanol, dimethoxym ethane, the acetone with superhigh cross-linking weak basic anion exchange resin of dual-use function.
9, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, when it is characterized in that with the dimethylamine amination, the consumption of aminating agent is 1-3 a times of chlorine ball.
10, according to right 1 described synthetic method with superhigh cross-linking weak basic anion exchange resin of dual-use function, the residual chlorine content that it is characterized in that resin is controlled at 2-15%, the synthetic superhigh cross-linking weak basic anion exchange resin that has absorption and exchange dual-use function simultaneously, exchange capacity is controlled at 0.5-4.0mmol/g, specific area 1000-150m
2/ g.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9708202B2 (en) | 2012-04-28 | 2017-07-18 | Nanjing University | Electroplating waste water treatment method |
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| US9708202B2 (en) | 2012-04-28 | 2017-07-18 | Nanjing University | Electroplating waste water treatment method |
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