CN104448091A - Method for preparing aromatic carboxylic acid adsorption resin - Google Patents
Method for preparing aromatic carboxylic acid adsorption resin Download PDFInfo
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Abstract
The invention discloses a method for preparing an aromatic carboxylic acid adsorption resin. The method comprises the following steps: A, conducting suspension polymerization on a dispersed phase of an aqueous solution of polyvinyl alcohol and sodium chloride, monomers of chloromethyl styrene and styrene and a crosslinking agent divinyl benzene, in the presence of an initiator and a pore forming agent, so as to prepare a polymerization product; B, washing the polymerization product obtained in step A with water and methanol, filtering, then conducting Soxhlet extraction with an solvent, washing with ethanol, and carrying out vacuum drying to obtain chloromethylated polystyrene; and C, completely swelling the chloromethylated polystyrene obtained in the step B with a solvent, removing the solvent after swelling, adding an amination reagent for amination, so as to obtain an aminated product; and washing the aminated product with deionized water and ethanol, and conducting vacuum drying to obtain the resin. The invention eliminates the problem of additional crosslinking of methylene and pollution of metal catalyst, and the obtained resin has high full exchange capacity and adsorption rate of more than 95%.
Description
Technical field
The present invention relates to a kind of preparation method of aromatic carboxylic acid polymeric adsorbent, belong to waste water adsorption treatment field.
Background technology
Resin is a kind of cancellated bead functional high molecule material of porous three-dimensional of synthetic, and in oxygen, heat and chemical reagent, have satisfactory stability, be the new functional macromolecule material that a class has good adsorbent and desorption performance.Resin have adsorption selectivity uniqueness, desorption and regeneration easily, the feature such as can to recycle for a long time, lower concentration and difficult degradation organic chemical waste water field have unique advantage in processes.
As a kind of functional high molecule material of synthetic, resin can carry out molecular designing, synthesis, modification targetedly according to actual needs, has developed many special polymeric adsorbent kinds having single-minded purposes at present.For the aromatic carboxylic acid class waste water of difficult degradation, the phenylethylene resin series adsorption effect containing phenyl ring is best.The synthetic method of current phenylethylene resin series mainly contains four routes: be 1. first polymerized, rear chloromethylation, reamination; 2. be first polymerized, rear acid amides methylates, reamination; 3. be first polymerized, rear halo, reamination; 4. be first polymerized, rear Mannich amination;
In above-mentioned four synthetic routes, chloromethylation process occupies the main positions that polystyrene type anionite is produced for a long time, but owing to using carinogenicity reaction raw materials chloromethyl ether or dichlormethyl ether in this production process, it is eliminated should be trend of the times; Acid amides methylating reagent is somewhat expensive, and reaction conditions is also comparatively harsh, high to the requirement of equipment, energy consumption is high, limits the popularization of acid amides methylation method; Because some halide reagent is toxic, some is too expensive, and halo process is often difficult to control, and therefore halo method is unwell to the production method as commercial resin at present; Owing to needing need to do activation treatment to the aromatic proton of resin before Mannich amination, add the complexity and difficulties of preparation, the cost of resin is significantly improved, therefore Mannich amination method is also unsuitable for producing commercial resin;
Although the method for producing at present phenylethylene resin series is a lot, the adsorption effect of phenylethylene resin series to aromatic carboxylic acid type organic produced is unsatisfactory, therefore to develop a kind of large to aromatic carboxylic acid loading capacity, that stability is strong resin be problem demanding prompt solution.
Summary of the invention
The object of this invention is to provide a kind of preparation method of aromatic carboxylic acid polymeric adsorbent, the chloromethylation process that instant invention overcomes polystyrene in prior art adopts the shortcoming of the chloromethyl ether of strong carinogenicity or the raw material of dichlormethyl ether, provides the aromatic carboxylic acid polymeric adsorbent that a kind of materials safety, reactions steps are simple, can obtain a series of different amine groups content.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A preparation method for aromatic carboxylic acid polymeric adsorbent, is characterized in that: comprise following steps:
A, with the aqueous solution of polyvinyl alcohol and sodium-chlor for disperse phase, with p-chloromethyl styrene and vinylbenzene for monomer, take Vinylstyrene as linking agent, under initiator and pore-creating agent exist, obtain polymerisate by suspension polymerization;
After B, polymerisate steps A obtained use water, methanol wash respectively, filter, then use solvent surname extraction, then use washing with alcohol, vacuum-drying, obtain chloromethylated polystyrene;
C, the chloromethylated polystyrene solvent obtained by step B are fully swelling, except desolventizing after swelling, add amination reagent and carry out amination, and obtained aminate, uses deionized water, washing with alcohol respectively by aminate, vacuum-drying, to obtain final product.
Above-mentioned preparation method adopts the monomer 1-chloro-4-methyl-benzene with chloromethyl active group in suspension polymerization, eliminate chloromethylation step, avoid the chloromethyl ether or the dichlormethyl ether that use and have strong carcinogenesis, eliminate the problem such as the additive-crosslinking of methylene radical and the pollution of metal catalyst; And the distribution of resin function base is more even, simultaneously also to have exchange capacity high for resin, mechanical stability, thermostability and oxidative stability are good, and the feature such as the high and anti-organic contamination of regeneration efficiency is strong, has good adsorption effect to the aromatic substance in waste water.
In order to improve polymerization efficiency, in the disperse phase described in steps A, the mass concentration of polyvinyl alcohol and NaCl is respectively 0.5 ~ 2% and 2 ~ 4%, and polyvinyl alcohol molecule amount is 30000 ~ 50000.
In order to improve the adsorption effect of gained resin to aromatic substance, in the monomer described in steps A, p-chloromethyl styrene and cinnamic volume ratio are 1:(0.5-3).
In order to improve the adsorption effect of gained resin to aromatic substance further, the monomer described in steps A and the volume ratio of linking agent are (2-6): 1.
In order to improve the exchange capacity of gained resin, improve the mechanical stability of gained resin, thermostability and oxidative stability simultaneously, in steps A, initiator is Diisopropyl azodicarboxylate or benzoyl peroxide, initiator amount is 0.5 ~ 2% of oil phase quality, and oil phase comprises monomer, linking agent and pore-creating agent.
In order to improve the adsorption effect of gained resin to aromatic substance further, the pore-creating agent described in steps A is hexalin or toluene, and the volume ratio of monomer and pore-creating agent is (0.5-2): 1.
In order to improve polymerization efficiency, ensure the quality of products obtained therefrom, in steps A, the oil phase be made up of monomer, linking agent and pore-creating agent and the volume ratio of disperse phase are 1:(4-10 simultaneously).
In order to ensure the quality of products obtained therefrom, in steps A, the temperature of suspension polymerization is 60 ~ 85 DEG C, and the time is 6 ~ 12h.
In order to improve the purity of products obtained therefrom, ensure the quality of products obtained therefrom, in step B, surname extraction solvent used is methylene dichloride or acetone simultaneously; In step C, swelling solvent used is toluene or chloroform.
In order to ensure the performance of products obtained therefrom, the amination reagent described in step C is trimethylamine aqueous solution, dimethylamine agueous solution, monomethylamine aqueous solution or the hexamethylenetetramine aqueous solution, amination reagent to be mass concentration be 20 ~ 50% the aqueous solution; The mass ratio of amination reagent and chloromethylated polystyrene is (10 ~ 2): 1; Amination reaction temperature is 15 ~ 45 DEG C, and the reaction times is 8 ~ 12h.
The not specified technology of the present invention is prior art.
The preparation method of aromatic carboxylic acid polymeric adsorbent of the present invention owing to adopting the monomer 1-chloro-4-methyl-benzene with chloromethyl active group in suspension polymerization, eliminate chloromethylation step, avoid the chloromethyl ether or the dichlormethyl ether that use and have strong carcinogenesis, eliminate the problem such as the additive-crosslinking of methylene radical and the pollution of metal catalyst, and the complete exchange capacity of gained polymeric adsorbent is high, adsorption rate is up to more than 95%.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
Polymerization single polymerization monomer 1-chloro-4-methyl-benzene and cinnamic mass ratio are 1:0.5, and the ratio of monomer and cross-linker divinylbenzene is 2:1, and the volume ratio of pore-creating agent toluene and monomer is 1:0.5, mixes rear for subsequent use as oil phase; Disperse phase is the aqueous solution that massfraction is respectively the polyvinyl alcohol (molecular weight is 30000) of 2% and the NaCl of 4%, is warming up to 75 DEG C, is stirred to solid and dissolves be disperse phase completely; With in churned mechanically there-necked flask, the volume ratio of the volume and disperse phase that add oil phase is 1:4, adds the initiator Diisopropyl azodicarboxylate that quality is oil phase quality 0.5% simultaneously, reacts 12h at 60 DEG C.The resin that reaction obtains first washes with water, then uses methanol wash, filters, dries, use methylene dichloride surname extraction, then use washing with alcohol, vacuum-drying, obtain chloromethylated polystyrene (CMPS).
Preparation CMPS toluene swell 2h, the CMPS after swelling is joined in there-necked flask, then add 2 times of CMPS quality 40% trimethylamine aqueous solution, amination reaction 12h at 15 DEG C.Product deionized water, ethanol wash respectively, vacuum-drying, obtain season amine type resin.
The complete exchange capacity that experiment records the quaternary amine type resin that above-mentioned steps obtains is 3.404mmol/g, and adsorbing p-methylbenzoic acid concentration is at normal temperatures the water sample of 400ppm, and when the mass ratio of resin and water is 1:800, adsorption rate is 97%.
Embodiment 2
The step of suspension polymerization is identical with embodiment 1, reaction mass proportioning changes into: 1-chloro-4-methyl-benzene: vinylbenzene mass ratio is 1:0.5, monomer and cross-linker divinylbenzene volume ratio are 4:1, the volume ratio of pore-creating agent hexalin and monomer is 1:1, disperse phase is the aqueous solution that massfraction is respectively the polyvinyl alcohol (molecular weight is 40000) of 1% and the NaCl of 2%, the cumulative volume of oil phase and the volume ratio of disperse phase are 1:5, and initiator Diisopropyl azodicarboxylate is 1% of oil phase quality.Suspension reaction temperature 85 DEG C, reaction times 6h, surname extraction solvent is acetone.
Preparation CMPS toluene swell 2h, the CMPS after swelling is joined in there-necked flask, then add 10 times of CMPS quality 30% dimethylamine agueous solution, amination reaction 8h at 45 DEG C.Product deionized water, ethanol wash respectively, and vacuum-drying obtains tertiary amine resin.
The complete exchange capacity that experiment records the tertiary amine resin resin that above-mentioned steps obtains is 2.642mmol/g, and adsorbing initial terephthalic acid's concentration is at normal temperatures the water sample of 100ppm, and when the mass ratio of resin and water is 1:800, adsorption rate is 96%.
Embodiment 3
The step of suspension polymerization is identical with embodiment 1, reaction mass proportioning changes into: 1-chloro-4-methyl-benzene: vinylbenzene mass ratio is 1:2, monomer and cross-linker divinylbenzene volume ratio are 4:1, the volume ratio of pore-creating agent hexalin and monomer is 1:1, disperse phase is the aqueous solution that massfraction is respectively the polyvinyl alcohol (molecular weight is 35000) of 1.5% and the NaCl of 3.5%, the cumulative volume of oil phase and the volume ratio of disperse phase are 1:7, and initiator benzoyl peroxide is 2% of oil phase quality.Suspension reaction temperature 70 C, reaction times 10h, surname extraction solvent is methylene dichloride.
Amination step is identical with embodiment 2, and amination reagent changes the monomethylamine aqueous solution of 20% into, and finally obtained resin is secondary amine type resin.
The complete exchange capacity that experiment records the secondary amine type resin that above-mentioned steps obtains is 2.378mmol/g, and adsorbing p-carboxybenzaldehyde concentration is at normal temperatures the water sample of 300ppm, and when the mass ratio of resin and water is 1:800, adsorption rate is 96%.
Embodiment 4
The step of suspension polymerization is identical with embodiment 1, reaction mass proportioning changes into: 1-chloro-4-methyl-benzene: vinylbenzene mass ratio is 1:3, monomer and cross-linker divinylbenzene volume ratio are 6:1, the volume ratio of pore-creating agent hexalin and monomer is 1:2, disperse phase is the aqueous solution that massfraction is respectively the polyvinyl alcohol (molecular weight is 50000) of 0.5% and the NaCl of 3%, the cumulative volume of oil phase and the volume ratio of disperse phase are 1:10, and initiator Diisopropyl azodicarboxylate is 2% of oil phase quality.Suspension reaction temperature 75 DEG C, reaction times 8h, surname extraction solvent is methylene dichloride.
Preparation the swelling 2h of CMPS chloroform, the CMPS after swelling is joined in there-necked flask, then add 4 times of CMPS quality 50% the hexamethylenetetramine aqueous solution, amination reaction 10h at 25 DEG C.Product deionized water, ethanol wash respectively, vacuum-drying, obtain uncle's amine type resin.
The complete exchange capacity that experiment records the primary amine type resin that above-mentioned steps obtains is 1.897mmol/g, and adsorbing p-methylbenzoic acid concentration is at normal temperatures the water sample of 300ppm, and when the mass ratio of resin and water is 1:800, adsorption rate is 95%.
Claims (10)
1. a preparation method for aromatic carboxylic acid polymeric adsorbent, is characterized in that: comprise following steps:
A, with the aqueous solution of polyvinyl alcohol and sodium-chlor for disperse phase, with p-chloromethyl styrene and vinylbenzene for monomer, take Vinylstyrene as linking agent, under initiator and pore-creating agent exist, obtain polymerisate by suspension polymerization;
After B, polymerisate steps A obtained use water, methanol wash respectively, filter, then use solvent surname extraction, then use washing with alcohol, vacuum-drying, obtain chloromethylated polystyrene;
C, the chloromethylated polystyrene solvent obtained by step B are fully swelling, except desolventizing after swelling, add amination reagent and carry out amination, and obtained aminate, uses deionized water, washing with alcohol respectively by aminate, vacuum-drying, to obtain final product.
2. the method for claim 1, is characterized in that: in the disperse phase described in steps A, and the mass concentration of polyvinyl alcohol and NaCl is respectively 0.5 ~ 2% and 2 ~ 4%, and polyvinyl alcohol molecule amount is 30000 ~ 50000.
3. method as claimed in claim 1 or 2, it is characterized in that: in the monomer described in steps A, p-chloromethyl styrene and cinnamic volume ratio are 1:(0.5-3).
4. method as claimed in claim 1 or 2, is characterized in that: the monomer described in steps A and the volume ratio of linking agent are (2-6): 1.
5. method as claimed in claim 1 or 2, it is characterized in that: in steps A, initiator is Diisopropyl azodicarboxylate or benzoyl peroxide, and initiator amount is 0.5 ~ 2% of oil phase quality, and oil phase comprises monomer, linking agent and pore-creating agent.
6. method as claimed in claim 1 or 2, it is characterized in that: the pore-creating agent described in steps A is hexalin or toluene, the volume ratio of monomer and pore-creating agent is (0.5-2): 1.
7. method as claimed in claim 1 or 2, it is characterized in that: in steps A, the oil phase be made up of monomer, linking agent and pore-creating agent and the volume ratio of disperse phase are 1:(4-10).
8. method as claimed in claim 1 or 2, it is characterized in that: in steps A, the temperature of suspension polymerization is 60 ~ 85 DEG C, and the time is 6 ~ 12h.
9. method as claimed in claim 1 or 2, is characterized in that: in step B, and surname extraction solvent used is methylene dichloride or acetone; In step C, swelling solvent used is toluene or chloroform.
10. method as claimed in claim 1 or 2, is characterized in that: the amination reagent described in step C is trimethylamine aqueous solution, dimethylamine agueous solution, monomethylamine aqueous solution or the hexamethylenetetramine aqueous solution, amination reagent to be mass concentration be 20 ~ 50% the aqueous solution; The mass ratio of amination reagent and chloromethylated polystyrene is (10 ~ 2): 1; Amination reaction temperature is 15 ~ 45 DEG C, and the reaction times is 8 ~ 12h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107126937A (en) * | 2017-05-09 | 2017-09-05 | 安徽皖东化工有限公司 | A kind of preparation technology of high-adsorption-capacity strong-base anion-exchange resin |
| CN108070048A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of preparation method of the porous organic polymer containing chiral amine ligand |
| CN109336999A (en) * | 2018-10-11 | 2019-02-15 | 万华化学集团股份有限公司 | Acid absorbent and preparation method thereof and the purposes divided for reducing isocyanate products acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
| CN101912770A (en) * | 2010-09-03 | 2010-12-15 | 中国科学院长春应用化学研究所 | Polymeric adsorbent and preparation method thereof |
| CN102002127A (en) * | 2010-10-26 | 2011-04-06 | 东华大学 | Quaternionic random copolymer and synthetic method thereof |
-
2013
- 2013-09-18 CN CN201310426522.3A patent/CN104448091B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865302A (en) * | 2006-04-25 | 2006-11-22 | 南京大学 | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method |
| CN101912770A (en) * | 2010-09-03 | 2010-12-15 | 中国科学院长春应用化学研究所 | Polymeric adsorbent and preparation method thereof |
| CN102002127A (en) * | 2010-10-26 | 2011-04-06 | 东华大学 | Quaternionic random copolymer and synthetic method thereof |
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| CN107126937A (en) * | 2017-05-09 | 2017-09-05 | 安徽皖东化工有限公司 | A kind of preparation technology of high-adsorption-capacity strong-base anion-exchange resin |
| CN109336999A (en) * | 2018-10-11 | 2019-02-15 | 万华化学集团股份有限公司 | Acid absorbent and preparation method thereof and the purposes divided for reducing isocyanate products acid |
| CN109336999B (en) * | 2018-10-11 | 2021-02-02 | 万华化学集团股份有限公司 | Acid absorbent, preparation method thereof and application of acid absorbent for reducing acid content of isocyanate product |
| CN113501901A (en) * | 2021-07-23 | 2021-10-15 | 核工业北京化工冶金研究院 | Preparation method of uranium-adsorbing strongly-basic resin with narrow distribution particle size |
| CN113501901B (en) * | 2021-07-23 | 2023-11-28 | 核工业北京化工冶金研究院 | Preparation method of strong alkaline resin with narrow-distribution particle size for adsorbing uranium |
| CN115785515A (en) * | 2021-09-09 | 2023-03-14 | 佛山市云米电器科技有限公司 | Weak acid resin and preparation method thereof |
| CN115785515B (en) * | 2021-09-09 | 2024-01-26 | 佛山市云米电器科技有限公司 | Weak acid resin and preparation method thereof |
| CN114588953A (en) * | 2022-04-01 | 2022-06-07 | 丹东明珠特种树脂有限公司 | Methanol extraction water deacidification agent in etherification preparation process and preparation method thereof |
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| CN116284512B (en) * | 2023-05-25 | 2023-08-22 | 天津南开和成科技有限公司 | Amino-containing resin and preparation method and application thereof |
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