CN104667893A - Method for improving hydrophily of macroporous adsorption resin - Google Patents
Method for improving hydrophily of macroporous adsorption resin Download PDFInfo
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- CN104667893A CN104667893A CN201510071711.2A CN201510071711A CN104667893A CN 104667893 A CN104667893 A CN 104667893A CN 201510071711 A CN201510071711 A CN 201510071711A CN 104667893 A CN104667893 A CN 104667893A
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- macroporous absorbent
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Abstract
The invention discloses a method for improving the hydrophily of macroporous adsorption resin. The method comprises the following steps: under the effect of a catalyst magnesium chloride, the macroporous adsorption resin and chloromethyl ether have a chloromethylation reaction; the resin with chloromethyl introduced and a solvent DMF solution are uniformly mixed; and KOH is added and hydrolyzation is carried out to generate hydroxylating resin. The adsorption amount of the hydroxylating resin on phenol is researched, and the optimal embodiment hydroxylating resin adsorption amount is 1.648mg/g.
Description
Technical field
The present invention relates to macroporous absorbent resin preparation field, be specifically related to the method for modifying that a kind of hydrophobicity macroporous absorbent resin introduces hydroxyl.
Background technology:
Macroporous absorbent resin is a kind of polymer absorbant with porous three dimensional structure Prof. Du Yucang, main dependence and by the Van der Waals force between binding molecule, carry out physical absorption by its huge specific surface to work, molecule close with its skeleton structure to some in actual applications has very strong adsorption capacity, its absorbing process is easy and simple to handle, cost is lower, resin is reusable, is applicable to industrialization quantity-produced feature and makes it apply widely.
Macroporous absorbent resin is different with selected monomer molecule structure by its polarity size, can be divided into polarity, Semi-polarity and nonpolar three classes.Wherein nonpolar macroporous adsorption resin is obtained by the monomer polymerization that dipole moment is very little, feature is not for be with any function base, the hydrophobicity of hole table is strong, representative is styrene, divinylbenzene polymer, but its adsorption mechanism is more single, mainly interact with hydrophobicity active force and adsorption molecule, in the adsorption process of the aqueous solution, hydrophobic forces is nonspecific adsorption, and this certainly will cause resin adsorption poor selectivity.
Summary of the invention
The object of the present invention is to provide a kind of hydrophilic method of raising macroporous absorbent resin, the method introduces oh group on macroporous absorbent resin, improve the hydrophily of resin, thus improve the adsorptive selectivity of resin, strengthen the effect of mass transmitting of resin and water thus improve its adsorption rate and adsorb saturation capacity.
For achieving the above object, technical scheme provided by the invention is:
A kind of hydrophilic method of raising macroporous absorbent resin, comprising:
Step 1: add macroporous absorbent resin and chloromethyl ether in the there-necked flask that agitator, thermometer and reflux condenser are housed, magnesium chloride powder is slowly added after stirring, the mass ratio of resin and chloromethyl ether, magnesium chloride is 1: 7-10: 0.3-0.8, to be mixed evenly after be warming up to 35-50 DEG C with heating water bath, reaction time is 8-14 hour, and reaction terminates rear cooling decompress filter and goes out chloromethyl resin;
Step 2: add chloromethyl resin in four mouthfuls of tank reactors that agitator, thermometer, funnel and reflux condenser are housed, add the dimethyl formamide (DMF) that concentration is 13-30% afterwards, the resin added and DMF mass ratio are 1: 1-4, and reactant mixes by turn on agitator;
Step 3: when heating water bath constant temperature is to 80-105 DEG C, be that the KOH solution of 5-20% adds within the 3-20min time by concentration in funnel, the mass ratio of resin and KOH is 1: 0.1-0.7, reacting after 2-8 hour and stops reaction, obtaining hydroxylating resin by carrying out decompress filter after cold for mixture going.
Step 4: rinsed well by resin with ethanol, washes off by deionized water afterwards.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, and it is characterized in that, in described step 1, macroreticular resin is XAD-2.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, it is characterized in that, described step 1 before the reaction resin need use soaked in absolute ethyl alcohol 72 hours, cleans ethanol afterwards by deionized water; Reaction terminates rear chloromethyl resin ethanol and cleans residual reactant liquor, and cleans ethanol by deionized water.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, it is characterized in that, add resin and chloromethyl ether in described step 1, the mass ratio of magnesium chloride is 1: 8: 0.7, water bath heating temperature is 45 DEG C, and the reaction time is 12H.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, and it is characterized in that, in described step 2, chloromethyl resin puts into the swelling 12H of ethanol, and fully swelling resin deionized water cleans ethanol.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, and it is characterized in that, in described step 2, resin and DMF mass ratio are 1: 2.5, DMF solution concentration is 25%.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, it is characterized in that, in described step 3, KOH solution concentration is 10%, solution dropping funel at the uniform velocity joined in reactor in 20 minutes, and the mass ratio of resin and KOH is 1: 0.2, and the reaction time is 6 hours.
Preferably, described one improves the hydrophilic method of macroporous absorbent resin, it is characterized in that, the resin alcohol flushing that described step 3 obtains is clean, washes off afterwards by deionized water.
Beneficial effect of the present invention improves the hydrophily of resin, thus improve the adsorptive selectivity of resin, strengthens the effect of mass transmitting of resin and water thus improve its adsorption rate and adsorb saturation capacity.
Detailed description of the invention
Below in conjunction with the present invention preferably specific embodiment the present invention is described in further details.
Embodiment 1
First resin carries out chloromethylation, and the resin of chloromethylation is easy to introduce oh group.
Step 1: resin XAD-2 first uses soaked in absolute ethyl alcohol 72 hours, then clean by deionized water; XAD-2 macroporous absorbent resin 10.0g and chloromethyl ether 80.0g is added in the there-necked flask that agitator, thermometer and reflux condenser are housed, turn on agitator keeps moderate-speed mixer, add 7g magnesium chloride powder after being warming up to 45 DEG C with heating water bath afterwards, react after 12 hours and terminate reaction; Leave standstill reactant mixture and carry out decompress filter to cooling, obtain graininess chloromethyl resin XAD-2L; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Step 2: add XAD-2L resin 10g in four mouthfuls of tank reactors that agitator, thermometer, funnel and reflux condenser are housed, then add concentration be 25% DMF solution 100g be reaction dissolvent, resin mixes with solvent by turn on agitator.
Step 3: with heating water bath to 90 DEG C and constant temperature, at the uniform velocity join in reactor in 20 minutes by the KOH solution that 20g concentration is 10% by dropping funel, stop reaction after 6 hours, carry out decompress filter after leaving standstill reactant mixture to room temperature, obtain hydroxylating resin XAD-2H-1; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Embodiment 2
Step 1: resin XAD-2 first uses soaked in absolute ethyl alcohol 72 hours, then clean by deionized water; XAD-2 macroporous absorbent resin 10.0g and chloromethyl ether 80.0g is added in the there-necked flask that agitator, thermometer and reflux condenser are housed, turn on agitator keeps moderate-speed mixer, add 7g magnesium chloride powder after being warming up to 45 DEG C with heating water bath afterwards, react after 12 hours and terminate reaction; Leave standstill reactant mixture and carry out decompress filter to cooling, obtain graininess chloromethyl resin XAD-2L; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Step 2: add XAD-2L resin 10g in four mouthfuls of tank reactors that agitator, thermometer, funnel and reflux condenser are housed, then the DMF solution 100g adding that solvent strength is 25%, resin mixes with solvent by turn on agitator.
Step 3: with heating water bath to 97 DEG C and constant temperature, at the uniform velocity join in reactor in 20 minutes by the KOH solution that 20g concentration is 10% by dropping funel, stop reaction after 6 hours, carry out decompress filter after leaving standstill reactant mixture to room temperature, obtain hydroxylating resin XAD-2H-2; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Embodiment 3
Step 1: resin XAD-2 first uses soaked in absolute ethyl alcohol 72 hours, then clean by deionized water; XAD-2 macroporous absorbent resin 10.0g and chloromethyl ether 80.0g is added in the there-necked flask that agitator, thermometer and reflux condenser are housed, turn on agitator keeps moderate-speed mixer, add 7g magnesium chloride powder after being warming up to 45 DEG C with heating water bath afterwards, react after 12 hours and terminate reaction; Leave standstill reactant mixture and carry out decompress filter to cooling, obtain graininess chloromethyl resin XAD-2L; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Step 2: add XAD-2L resin 10g in four mouthfuls of tank reactors that agitator, thermometer, funnel and reflux condenser are housed, then the DMF solution 100g adding that solvent strength is 25%, resin mixes with solvent by turn on agitator.
Step 3: with heating water bath to 105 DEG C and constant temperature, at the uniform velocity join in reactor in 20 minutes by the KOH solution that 20g concentration is 10% by dropping funel, stop reaction after 6 hours, carry out decompress filter after leaving standstill reactant mixture to room temperature, obtain hydroxylating resin XAD-2H-3; For ensureing noresidue liquid in resin, using ethanol purge resin, cleaning ethanol by deionized water afterwards.
Embodiment 4
Resin adsorption Performance comparision experiment 1:
Step 1: use soaked in absolute ethyl alcohol XAD-2 macroporous absorbent resin 12 hours, clean ethanol by deionized water afterwards.
Step 2: at ambient temperature, XAD-2 resin 5g is added in the there-necked flask that agitator and 2 sealing-plugs are housed, the phenol solution 100ml that concentration is 120mg/L is added from sealing-plug mouth, start after agitator speed being adjusted to 60r/min to stir, react absorption after 1 hour and reach balance stopping reaction, record phenol solution concentration and reduce to 87.4mg/L.
Embodiment 5
Resin adsorption Performance comparision experiment 2:
Step 1: use soaked in absolute ethyl alcohol XAD-2H-1 macroporous absorbent resin 12 hours, clean ethanol by deionized water afterwards.
Step 2: at ambient temperature, XAD-2H-1 resin 5g is added in the there-necked flask that agitator and 2 sealing-plugs are housed, the phenol solution 100ml that concentration is 120mg/L is added from sealing-plug mouth, start after agitator speed being adjusted to 60r/min to stir, react 15 points afterwards absorption reach balance stop reaction, record phenol solution concentration and reduce to 59.2mg/L.
Embodiment 6
Resin adsorption Performance comparision experiment 3:
Step 1: use soaked in absolute ethyl alcohol XAD-2H-2 macroporous absorbent resin 12 hours, clean ethanol by deionized water afterwards.
Step 2: at ambient temperature, XAD-2H-2 resin 5g is added in the there-necked flask that agitator and 2 sealing-plugs are housed, the phenol solution 100ml that concentration is 120mg/L is added from sealing-plug mouth, start after agitator speed being adjusted to 60r/min to stir, react 15 points afterwards absorption reach balance stop reaction, record phenol solution concentration and reduce to 37.6mg/L.
Embodiment 7
Resin adsorption Performance comparision experiment 4:
Step 1: use soaked in absolute ethyl alcohol XAD-2H-3 macroporous absorbent resin 12 hours, clean ethanol by deionized water afterwards.
Step 2: at ambient temperature, XAD-2H-3 resin 5g is added in the there-necked flask that agitator and 2 sealing-plugs are housed, the phenol solution 100ml that concentration is 120mg/L is added from sealing-plug mouth, start after agitator speed being adjusted to 60r/min to stir, react 15 points afterwards absorption reach balance stop reaction, record phenol solution concentration and reduce to 38.9mg/L.
Table 1
| Resin model | Hydroxyl modification experimental temperature (DEG C) | Resin adsorption amount (mg/g) | Reaction time (min) |
| XAD-2 | / | 0.652 | 60 |
| XAD-2H-1 | 90 | 1.216 | 15 |
| XAD-2H-2 | 97 | 1.648 | 15 |
| XAD-2H-3 | 105 | 1.622 | 15 |
As seen from Table 1, macroporous absorbent resin XAD-2 is increased dramatically to the phenol ability being slightly soluble in water after hydroxyl modification, adsorption time also shortens 45 minutes, illustrate that the macroporous absorbent resin hydrophily through modification strengthens, the effect of mass transmitting of resin and water strengthens, indirectly making the phenol being slightly soluble in water can enter resin micropore by better mass transfer, is directly that the adsorbance of resin Pyrogentisinic Acid increases; Temperature through comparing hydroxyl modification experiment is known, and when temperature is 97 DEG C, modified resin Pyrogentisinic Acid adsorption effect is best, and when temperature is 105 DEG C, the capacity of returns of solvent DMF increases, and temperature of reaction system cannot raise and cause resin modified effect not compared with 97 DEG C of differences.
Beneficial effect of the present invention improves the hydrophily of resin, thus improve the adsorptive selectivity of resin, strengthens the effect of mass transmitting of resin and water thus improve its adsorption rate and adsorb saturation capacity.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (8)
1. improve the hydrophilic method of macroporous absorbent resin, it is characterized in that, comprising:
Step 1: add macroporous absorbent resin and chloromethyl ether in the there-necked flask that agitator, thermometer and reflux condenser are housed, magnesium chloride powder is slowly added after stirring, the mass ratio of resin and chloromethyl ether, magnesium chloride is 1:7-10:0.3-0.8, to be mixed evenly after be warming up to 35-50 DEG C with heating water bath, reaction time is 8-14 hour, and reaction terminates rear cooling decompress filter and goes out chloromethyl resin;
Step 2: add chloromethyl resin in four mouthfuls of tank reactors that agitator, thermometer, funnel and reflux condenser are housed, add the dimethyl formamide (DMF) that concentration is 13-30% afterwards, the resin added and DMF mass ratio are 1:1-4, and reactant mixes by turn on agitator;
Step 3: when heating water bath constant temperature is to 80-105 DEG C, be that the KOH solution of 5-20% adds within the 3-20min time by concentration in funnel, the mass ratio of resin and KOH is 1:0.1-0.7, reacting after 2-8 hour and stops reaction, obtaining hydroxylating resin by carrying out decompress filter after cold for mixture going.
Step 4: rinsed well by resin with ethanol, washes off by deionized water afterwards.
2. the hydrophilic method of a kind of raising macroporous absorbent resin as claimed in claim 1, it is characterized in that, in described step 1, macroreticular resin is XAD-2.
3. the hydrophilic method of a kind of raising macroporous absorbent resin as claimed in claim 1 or 2, is characterized in that, described step 1 before the reaction resin need use soaked in absolute ethyl alcohol 72 hours, cleans ethanol afterwards by deionized water; Reaction terminates rear chloromethyl resin ethanol and cleans residual reactant liquor, and cleans ethanol by deionized water.
4. as claimed in claim 1 a kind of improve the hydrophilic method of macroporous absorbent resin, it is characterized in that, add resin and chloromethyl ether in described step 1, the mass ratio of magnesium chloride is 1:8:0.7, water bath heating temperature is 45 DEG C, and the reaction time is 12H.
5. the hydrophilic method of a kind of raising macroporous absorbent resin as claimed in claim 1, it is characterized in that, in described step 2, chloromethyl resin puts into the swelling 12H of ethanol, and fully swelling resin deionized water cleans ethanol.
6. the one as described in claim 1 or 5 improves the hydrophilic method of macroporous absorbent resin, and it is characterized in that, in described step 2, resin and DMF mass ratio are 1:2.5, DMF solution concentration is 25%.
7. the hydrophilic method of a kind of raising macroporous absorbent resin as claimed in claim 1, it is characterized in that, in described step 3, KOH solution concentration is 10%, solution dropping funel at the uniform velocity joined in reactor in 20 minutes, the mass ratio of resin and KOH is 1:0.2, and the reaction time is 6 hours.
8. the hydrophilic method of a kind of raising macroporous absorbent resin as claimed in claim 1, is characterized in that, the resin alcohol flushing that described step 3 obtains is clean, washes off afterwards by deionized water.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001147A (en) * | 1975-03-03 | 1977-01-04 | The Dow Chemical Company | Oxazoline and/or oxazine-modified polymers |
| JP2000331693A (en) * | 1999-05-19 | 2000-11-30 | Asahi Glass Co Ltd | Solid polymer type fuel cell |
| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
-
2015
- 2015-02-11 CN CN201510071711.2A patent/CN104667893A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001147A (en) * | 1975-03-03 | 1977-01-04 | The Dow Chemical Company | Oxazoline and/or oxazine-modified polymers |
| JP2000331693A (en) * | 1999-05-19 | 2000-11-30 | Asahi Glass Co Ltd | Solid polymer type fuel cell |
| CN102815765A (en) * | 2012-08-30 | 2012-12-12 | 中国石油天然气股份有限公司 | Deep softening method of thick oil sewage |
Non-Patent Citations (3)
| Title |
|---|
| 何炳林等: "合成聚乙烯基苯甲酸树脂的研究（Ⅱ）-由氯甲基化交联聚苯乙烯树脂按二步法合成", 《高等学校化学学报》 * |
| 王津南等: "酚羟基修饰的超高交联聚苯乙烯树脂对苯酚吸附及脱附性能的研究", 《离子交换与吸附》 * |
| 蒋永生等: "聚苯乙烯树脂的间接氯甲基化反应", 《渝州大学学报》 * |
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Application publication date: 20150603 |