CN1031820C - Weak acidic cation exchanging resin producing process - Google Patents
Weak acidic cation exchanging resin producing process Download PDFInfo
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- CN1031820C CN1031820C CN92114550A CN92114550A CN1031820C CN 1031820 C CN1031820 C CN 1031820C CN 92114550 A CN92114550 A CN 92114550A CN 92114550 A CN92114550 A CN 92114550A CN 1031820 C CN1031820 C CN 1031820C
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Abstract
The present invention mainly relates to a producing process of weak acidic cation exchanging resin. Acrylic acid, an olefin containing monomer which has little water solubility, and contains a carboxyl group or can be converted into a carboxyl group, divinylbenzene and an organic solvent (oil phase) are copolymerized in a brine solution, and thus, macroporous ion exchanging resin with uniform crosslinking degree is obtained. The weight exchanging capacity of the resin is from 9.3 to 11.6 mmol/g, the volume exchanging capacity is from 3.5 to 4.6 mmol/ml, the acid-alkali transconformation volume change is from 64 to 85%, and the sphere rate achieves 50 to 85% after the resin is ground.
Description
The invention belongs to the ion exchange resin field.
The traditional mode of production process of acidulous acrylic acid's cation exchanger resin is that methyl acrylate and divinylbenzene carry out the free radical suspending copolymerization, hydrolysis and get (Qian Tingbao under alkali condition then, " ion-exchange application technology ", Tianjin science tech publishing house publishes, and 1984).In the copolymerization of divinylbenzene and methyl acrylate, the former specific activity latter's is big, therefore cause the inhomogeneities of resin crosslinks network, performance to resin produces a series of harmful effects thus: the volume-exchange amount of resin is little, big, the intensity difference of soda acid Volume Changes transition, easily the exchange kinetics of caking, cation exchange groups is inhomogeneous in the use, the work exchange capacity is low etc.
The present invention is directed to the shortcoming of the resin quality difference that above-mentioned technology produces, invented a kind of synthesizing cross-linked structure new method of weak-acid cation-exchange resin relatively uniformly.Compare with methyl acrylate, acrylic acid radical polymerization activity more approaches radical polymerization activity (Brandrup, the J.﹠amp of divinylbenzene; Immergut, E.T., Polymer Handbook, Second ed., John Wiley﹠amp; Sons Inc., 1975, II). so the combined polymerization of acrylic acid and divinylbenzene obtains relatively homogeneous polymer of cross-linked structure.But because acrylic acid is soluble in water, can be infinitely miscible with water, thereby acrylic acid and divinylbenzene are that the suspending copolymerization of medium is difficult for the weak acid resin that preparation can practicality at water.The present invention is with acrylic acid, crosslinking agent (the mixture of divinylbenzene or divinylbenzene and following one or more crosslinking agents: itaconic acid diallyl ester, mesaconic acid diallyl ester, fumaric acid diallyl ester, cyanuric acid triallyl ester, the cyamelide triallyl ester), water-soluble less and contain that carboxyl maybe can be converted into carboxyl one or more contain alkenyl monomer (as alkyl acrylate, the alkyl methacrylate methacrylic acid), pore-foaming agent is (as gasoline, benzene, toluene, dimethylbenzene, many toluene, chlorobenzene, dichloro-benzenes, aromatic hydrocarbons such as bromobenzene, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, alcohols such as phenmethylol, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, palmitic acid, stearic acid, acids such as oleic acid) four components are oil phase, in saline solution, carry out the free radical suspending copolymerization, obtain cross-linked structure macroreticular resin relatively uniformly.The volume ratio of oil phase and water is 1: 1～1: 5, the content of component A is 15-70% in the oil phase, and the content of component B is 2-15% (content that refers to effective crosslinking agent), and the content of component C is 5～50%, the content of component D is 0～60%, and the content of component E is 0.1～2%.Water-soluble less monomer and pore-foaming agent play extraction in the oil phase, acrylic acid is reduced at the meltage of aqueous phase, water uses salting liquid (as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium sulphate, potassium sulfate, magnesium sulfate etc. simultaneously, can use salt-mixture), play salting out, in the resin that above-mentioned polymerization obtains as contain the group (ester group) that can be converted into carboxyl, then can be further with aqueous slkali or acid solution hydrolysis, make it be converted into carboxyl, obtain the macroporous acrylic cation exchanger resin of function admirable.The key technical indexes of the weak acid resin that this technology is synthetic is: weight exchange capacity 9.3-11.6mmol/g, volume-exchange amount 3.5-4.6mmol/ml, soda acid Volume Changes 64-85% transition, mill back garden ball rate 50-85%.
Example 1
Load onto electric mixer, condenser pipe, nitrogen conduit and thermometer on the 250ml four-hole bottle, logical nitrogen adds the aqueous solution (water) 100ml that contains 15% sodium chloride and 1% gelatin.In addition 6g acrylic acid, 5g methyl acrylate, 4g divinylbenzene (contain divinylbenzene 42.4%, down with), 10g200
#Gasoline and 0.15g azodiisobutyronitrile mix (oil phase), and oil phase is added in the bottle, adjust the size to fit that agitation as appropriate speed makes oil droplet, be warmed up to 65 ℃ of polymerizations 4 hours, be warmed up to 80 ℃ of polymerizations 4 hours again, filter, resin is washed, resin adds the sodium hydroxide solution of 100ml20% then, 80 ℃ of following hydrolysis 12 hours, get the macropore weak-acid cation-exchange resin, the weight exchange capacity of resin is 10.82mmol/g, the volume-exchange amount is 4.35mmol/ml, H
+-Na
+The type Volume Changes is 67%, and garden, mill back ball rate is 83%.
Example 2
Used instrument is with example 1, water be 5% sodium chloride, ,-aqueous solution 100ml of % magnesium chloride and 1% gelatin, oil phase is 5g acrylic acid, 5g methacrylic acid, 3g divinylbenzene, 0.5g itaconic acid diene propyl ester, 8g stearic acid, 0.15g benzoyl peroxide.Polymerization temperature be 70 ℃ 4 hours, 80 ℃ 4 hours, other is operated with example 1, the weight exchange capacity of gained resin is 10.03mmol/g, the volume-exchange amount is 4.41mmol/ml, H
+→ Na
+The type Volume Changes is 64.7%, and garden, mill back ball rate is 89%.
Example 3
Used instrument is with example 1, water is the aqueous solution 100ml of 15% calcium chloride and 1% gelatin, oil phase be 6g acrylic acid, 3g methyl methacrylate, 3g methacrylic acid, 6g divinylbenzene, 10g dichloro-benzenes, 0.15g benzoyl peroxide, polymerization temperature be 70 ℃ 4 hours, 85 ℃ 4 hours, other operation is with example 1, the weight exchange capacity of gained resin is 9.38mmol/g, and the volume-exchange amount is 4.40mmol/ml, H
+→ Na
+The type volume becomes 67%, and garden, mill back ball rate is 70%.
Example 4
Used instrument is with example 1, water is the aqueous solution 60ml of 25% magnesium sulfate and 1% gelatin, oil phase is 10g acrylic acid, 10g methyl acrylate, 2.5g divinylbenzene, 0.2g benzoyl peroxide, 70 ℃ of polymerizations 4 hours, 85 ℃ of polymerizations 4 hours, other is operated with example 1, get the gel-type weak acid resin, the weight exchange capacity is 11.23mmol/g, and the volume-exchange amount is 3.52mmol/ml, H
+→ Na
+The type Volume Changes is 82%, and garden, mill back ball rate is 53%.
Claims (9)
1. method for preparing weak-acid cation-exchange resin, it is characterized in that it is by component A (acrylic acid), component B (diene or polyene cross-linking agent), component C (water-soluble less and contain the monomer that can be converted into carboxyl), the oil phase that component D (pore-foaming agent) and component E (initator) are formed, carry out the free radical suspending copolymerization at the aqueous phase that contains salt and dispersant, its poly-temperature is 40-90 ℃, polymerization time is 4-10 hours, be hydrolyzed with sodium hydrate aqueous solution or aqueous sulfuric acid then, the weight exchange capacity of gained resin is 9.3-11.6mmol/g, the volume-exchange amount is 3.5-4.6mmol/ml, H
+→ Na
+The type Volume Changes is 64-86%, wasting the back rate of small round spheres is 50-85%, oil phase is 1: 1～1: 5 with the ratio of water volume, wherein in the oil phase component A contain the reason be 15～70%, the content of component B is 2-15% (content that refers to effective crosslinking agent), the content of component C is 5～50%, and the content of component D is 0-60%, and the content of component E is 0.1～2%.
2. method according to claim 1, the volume ratio that it is characterized in that oil phase and water is 1: 1～1: 5.
3. method according to claim 1, the content that it is characterized in that component A in the oil phase is 15-70%, and the content of component B is 2-15% (content that refers to effective crosslinking agent), and the content of component C is 5-50%, the content of component D is 0-60%, and the content of component E is 0.1-2%.
4. method according to claim 1, it is characterized in that component B in the oil phase is following one or more mix monomer, as divinylbenzene, itaconic acid diallyl ester, mesaconic acid diallyl ester, fumaric acid diallyl ester, maleic acid diallyl ester, cyanuric acid triallyl ester, cyamelide triallyl ester.
5. method according to claim 1 is characterized in that component C is water-soluble less monomer, for following one or more mix monomers, as methyl acrylate, methyl methacrylate, methacrylic acid.
6. method according to claim 1, it is characterized in that component D is following one or more mixture, as gasoline, benzene,toluene,xylene, many toluene, chlorobenzene, dichloro-benzenes, polystream, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, phenmethylol, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, lauric acid, palmitic acid, hard ester acid, oleic acid.
7. method according to claim 1, it is characterized in that component E is the mixture of following one or more initators, as azodiisobutyronitrile, ABVN, benzoyl peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.
8. method according to claim 1 is characterized in that the water used salt is following one or more salt, as sodium chloride, potassium chloride, calcium chloride, magnesium chloride, ammonium chloride, sodium sulphate, potassium sulfate, magnesium sulfate, ammonium sulfate.
9. method according to claim 1, the used naoh concentration of hydrolysis is 5-30%, and hydrolysis temperature is 70-95 ℃, and used sulfuric acid concentration is 40-65%, and hydrolysis temperature is 80-140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114550A CN1031820C (en) | 1992-12-19 | 1992-12-19 | Weak acidic cation exchanging resin producing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92114550A CN1031820C (en) | 1992-12-19 | 1992-12-19 | Weak acidic cation exchanging resin producing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1088486A CN1088486A (en) | 1994-06-29 |
| CN1031820C true CN1031820C (en) | 1996-05-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92114550A Expired - Fee Related CN1031820C (en) | 1992-12-19 | 1992-12-19 | Weak acidic cation exchanging resin producing process |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4265181B2 (en) * | 2002-09-11 | 2009-05-20 | 昭和電工株式会社 | Method for producing weakly acidic cation exchanger and column for cation chromatography |
| CN102190753A (en) * | 2010-03-19 | 2011-09-21 | 周家付 | Preparation method for macroporous weak-acidic cation exchange resin |
| CN103881016B (en) * | 2012-12-20 | 2017-08-25 | 南开大学 | A kind of porous resin as synthesis in solid state carrier |
| CN103694405B (en) * | 2013-12-16 | 2016-01-27 | 无锡济民可信山禾药业股份有限公司 | A kind of preparation method of Macroporous weak acid cation exchange resin |
| CN106190145A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of preparation method of the desulfurated plaster improveing high-basicity salt-soda soil |
| CN106190150A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of organically-modified method of alkaline land improving desulfurated plaster |
| CN106699974A (en) * | 2016-12-16 | 2017-05-24 | 东至绿洲环保化工有限公司 | Macroporous weakly-acidic cation exchange resin used for removing basic salts in wastewater |
| CN115888852A (en) * | 2023-01-06 | 2023-04-04 | 山东德川化工科技有限责任公司 | Preparation process of acrylate weak acid cation exchange resin |
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1992
- 1992-12-19 CN CN92114550A patent/CN1031820C/en not_active Expired - Fee Related
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|---|---|
| CN1088486A (en) | 1994-06-29 |
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