WO2016008396A1 - 一种高交换容量双功能基阴离子交换树脂及其合成方法 - Google Patents

一种高交换容量双功能基阴离子交换树脂及其合成方法 Download PDF

Info

Publication number
WO2016008396A1
WO2016008396A1 PCT/CN2015/083880 CN2015083880W WO2016008396A1 WO 2016008396 A1 WO2016008396 A1 WO 2016008396A1 CN 2015083880 W CN2015083880 W CN 2015083880W WO 2016008396 A1 WO2016008396 A1 WO 2016008396A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
polymer
anion exchange
exchange capacity
exchange resin
Prior art date
Application number
PCT/CN2015/083880
Other languages
English (en)
French (fr)
Inventor
王津南
王钇
杨欣
程澄
陈晨
Original Assignee
南京大学
南京大学盐城环保技术与工程研究院
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 南京大学, 南京大学盐城环保技术与工程研究院 filed Critical 南京大学
Priority to US15/511,184 priority Critical patent/US9950319B2/en
Publication of WO2016008396A1 publication Critical patent/WO2016008396A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C08F12/28—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts

Definitions

  • the invention discloses an anion exchange resin and a synthesis method thereof, and more particularly to a high exchange capacity bifunctional anion exchange resin and a synthesis method thereof, which are based on a chloromethylated polystyrene-divinylbenzene polymer. After the primary amination and quaternization reaction, a high exchange capacity bifunctional anion exchange resin and a synthesis method thereof are prepared.
  • the biochemical process has a longer cycle and the effect is more affected by the season.
  • the chemical reduction method has high requirements on conditions and is difficult to apply on a large scale.
  • the electroosmosis treatment has high cost and cannot be used for a long time.
  • the ion exchange and adsorption method is considered to be an ideal treatment method because of its simple process, fast and efficient, low cost and regenerability.
  • Cao Guoming et al. used a strong base anion exchange resin to treat nitrate-contaminated groundwater, which achieved good results (Cao Guoming, Sheng Mei, Fei Yulei, Meng Kewei, Shi Weiwei, Yu Yifeng. Continuous flow treatment by ion exchange method Nitrate contaminated groundwater. Water purification technology.
  • the organic matter is mainly plant organic matter, which will cause the water body to produce bad color, taste, affect water quality, and will be in the water treatment and disinfection process.
  • the production of disinfection by-products poses a hazard to human health.
  • the effective adsorbent material for removing such natural organic matter is mainly a weak base anion exchange resin.
  • the functional group of the anion exchange resin is an amino group or a quaternary ammonium salt group, and the amount of adsorption of the nitrate ion is controlled by the number of functional groups on the surface of the resin.
  • the chloromethyl group on each polymer can only react to form a quaternary ammonium salt group.
  • the chloromethyl content in the chloromethylated polystyrene-divinylbenzene polymer is fixed (mass fraction 16-20%) and is difficult to increase.
  • the ion exchange resin for removing nitrate ions in water is mainly a strong base anion exchange resin, and the amount of adsorption of nitrate ions depends on the amount of ammonia/ammonium group of the ion exchange resin, because the nitrate ion preferentially
  • the strong base ion exchange group undergoes ion exchange and then ion exchange with the weak base ion exchange group.
  • the traditional polystyrene-divinylbenzene skeleton strong base anion exchange resin can only be connected to each chloromethyl group during the quaternization reaction of the chloromethylated polystyrene-divinylbenzene polymer.
  • a quaternary ammonium salt group on the branch which limits the number of strong base type ion exchange groups on the surface of the resin, and the adsorption capacity of the nitrate ion is difficult to be greatly increased. Therefore, how to increase the number of ion exchange groups of the ion exchange resin is a primary technical problem to be solved.
  • the actual natural water or wastewater generally contains phytic acid natural organic matter (tannic acid, gallic acid), which can not only interact with the ammonia/ammonium group of the anion exchange resin, but also compete with the nitrate ion for adsorption.
  • phytic acid natural organic matter titanium acid, gallic acid
  • the adsorption capacity of the resin to nitrate ions is decreased; and the natural organic matter also produces disinfection by-products during the disinfection process in the later stage of water treatment, which is harmful to human health.
  • the adsorbent materials capable of effectively adsorbing and removing phytic acid organic matter in water are mainly weak base ion exchange resins containing primary, secondary and tertiary amine groups, because phytic acid substances preferentially interact with weak base ion exchange groups. It is then reacted with a strong base ion exchange group. Therefore, a weak base type ion exchange group is simultaneously introduced on the strong base type ion exchange resin, and the phytic acid substance in the water is preferentially adsorbed to ensure that the resin has a sufficient number of strong base type ion exchange groups and nitrate ions, which is Another technical problem that needs to be solved.
  • anion exchange resin chloromethylated polystyrene-divinylbenzene is usually subjected to amination reaction with dimethylamine or quaternization with trimethylamine.
  • the anion exchange resin prepared by this method is difficult to further react to increase the amino group or the quaternary ammonium salt group of the resin, which is also a technical problem to be solved.
  • the present invention provides a bifunctional anion exchange resin having a high exchange capacity and containing both a strong base type and a weak base type ion exchange group, and a synthesis method thereof.
  • the synthesis method is simple and easy to operate, and a weak base type and a strong base type ion exchange group can be simultaneously introduced on the chloromethyl group of the chloromethylated polystyrene-divinylbenzene polymer, and the ion exchange capacity of the resin is remarkably improved.
  • the resin has a significant increase in the adsorption capacity of nitrate ions, but also the weakly basic ion exchange groups can synergistically remove the phytic acid organic matter in the water, and reduce the competition effect of phytic acid on the removal of nitrate ions during the adsorption process.
  • m is a degree of polymerization, and the value is in the range of 3,000 to 5,000, which is determined by gel permeation chromatography.
  • a high exchange capacity bifunctional anion exchange resin with a chloromethylated polystyrene-divinylbenzene polymer as a precursor first introducing a weak base ion exchange group (primary amine group), on the basis of which A strong base type ion exchange group (quaternary ammonium salt group) is introduced to form a novel anion exchange resin having a bifunctional group.
  • the synthesis process is as follows:
  • step 1
  • the chloromethylated polystyrene-divinylbenzene polymer is first swollen in a mixed solution of absolute ethanol and chloroform at 20-25 ° C for 3-4 hours; the chloromethyl group Polystyrene-divinylbenzene polymer g: absolute ethanol ml: chloroform ml: hexamethylenetetramine g is 5:15 to 20:2 to 4:4 to 5.
  • the concentrated hydrochloric acid-anhydrous ethanol mixed acid hydrolysis solution is prepared by mixing a concentrated hydrochloric acid having a mass fraction of 37.5% with anhydrous ethanol to form a mixed acid hydrolysis solution, so that the concentrated hydrochloric acid volume ml: absolute ethanol volume ml is 1 :2-3.
  • the NaOH solution is added to control the pH>14 transformation for 2-3 hours, and the mass percentage of the NaOH solution is 1%.
  • step (2) the concentration of 3-chloro-2-hydroxypropyltrimethylammonium chloride solution is 60%, and the concentration of NaOH solution is 40% by mass, chlorinated according to 3-chloro-2-hydroxypropyltrimethyl Ammonium solution and NaOH solution volume The ratio is 8-10:1 to configure the mixed solution; in step (2), the vacuum is dried for 12-24 hours, and the pressure is -0.09 to -0.08 MPa.
  • the invention provides a preparation method of a high exchange capacity bifunctional anion exchange resin, such that the total exchange capacity is as high as 6.3-7.9 mmol/g, wherein the strong base exchange capacity reaches 3.8-4.7 mmol/g, and the weak base exchange capacity reaches 2.5 to 3.2 mmol/g.
  • the adsorbent prepared by the invention has a weak base anion exchange group and a strong base anion exchange group, and can remove the nitrate organic ions and remove the plant organic matter by using the weak base group, thereby realizing the water treatment use. Achieve dual functionality. It has broad application prospects in the fields of drinking water treatment, groundwater remediation, and urban sewage treatment.
  • Figure 1 is a structural view of a high exchange capacity bifunctional anion exchange resin prepared in Examples 1-12 of the present invention.
  • Example 2 is a FT-IR spectrum of a high exchange capacity bifunctional anion exchange resin (ie, a new resin in the figure) prepared in Example 1 of the present invention, the abscissa of the spectrum is the wave number, and the ordinate is the transmittance, indicating The transmittance of the sample for different wavelengths of infrared light.
  • a high exchange capacity bifunctional anion exchange resin ie, a new resin in the figure
  • Example 3 is a solid nuclear magnetic resonance spectrum of a high exchange capacity bifunctional anion exchange resin prepared in Example 1 of the present invention, and the abscissa is a chemical shift.
  • Example 4 is a scanning electron micrograph of a high exchange capacity bifunctional anion exchange resin prepared in Example 1 of the present invention.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and added with 1% NaOH solution to control pH>14 for 2 hours, washed with water and filtered to obtain polyethylene.
  • a benzene-vinylbenzylamine polymer
  • the maximum adsorption capacity of the new resin for nitrate was 198.5 mg/g
  • the maximum adsorption amount for tannic acid was 493.7 mg/g
  • the maximum adsorption amount for gallic acid was 407.6 mg/g.
  • the total exchange capacity of the resin was 7.9 mmol/g, wherein the strong base exchange capacity was 4.7 mmol/g, the weak base exchange capacity was 3.2 mmol/g, and the average resin particle diameter was 550 ⁇ m.
  • Figure 1 is a structural diagram of a high exchange capacity bifunctional anion exchange resin prepared in the present example.
  • FIG. 2 is a FT-IR spectrum of a high exchange capacity bifunctional anion exchange resin prepared according to an example of the present invention.
  • the corresponding one is -NH 2 .
  • the absorption peak of the N-H bending vibration indicates that the reaction step 1 has successfully inserted the primary amine group; and in the infrared spectrum of the new resin (the high exchange capacity bifunctional anion exchange resin prepared in the embodiment of the present invention),
  • the absorption peak of NH 2 almost disappeared, and a strong absorption peak at 1476 cm -1 was replaced, which corresponds to the bending vibration of N-CH 3 in the trimethylammonium chloride group.
  • FIG. 3 is a solid nuclear magnetic resonance spectrum of a high exchange capacity bifunctional anion exchange resin prepared according to the examples of the present invention. Based on the infrared spectrum analysis of Fig. 2 and the nuclear magnetic resonance analysis of Fig. 3, it can be confirmed that the high exchange capacity bifunctional anion exchange resin is as shown in Fig. 1. 4 is a scanning electron micrograph of a high exchange capacity bifunctional anion exchange resin prepared according to an example of the present invention.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and adjusted to pH > 14 for 2 hours by adding 1% NaOH solution, washed with water, and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • the properties of the new resin are similar to those in Example 1.
  • the maximum adsorption capacity for nitrate is 173.3 mg/g for tannins.
  • the maximum adsorption amount of acid was 466.5 mg/g, and the maximum adsorption amount to gallic acid was 379.2 mg/g.
  • the total exchange capacity of the resin was 6.6 mmol/g, wherein the strong base exchange capacity was 3.9 mmol/g, the weak base exchange capacity was 2.7 mmol/g, and the resin average particle diameter was 600 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and adjusted to pH > 14 for 2 hours by adding 1% NaOH solution, washed with water, and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • the properties of the resin of Example 3 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 175.1 mg/g
  • the maximum adsorption amount for tannic acid was 468.7 mg/g
  • the maximum adsorption amount for gallic acid was 381.4 mg/g.
  • the total exchange capacity of the resin was 6.6 mmol/g, wherein the strong base exchange capacity was 3.8 mmol/g, the weak base exchange capacity was 2.8 mmol/g, and the average resin particle diameter was 580 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the properties of the resin of Example 4 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 185.5 mg/g
  • the maximum adsorption amount for tannic acid was 481.5 mg/g
  • the maximum adsorption amount for gallic acid was 400.4 mg/g.
  • the total exchange capacity of the resin was 7.1 mmol/g, wherein the strong base exchange capacity was 4.2 mmol/g, the weak base exchange capacity was 2.9 mmol/g, and the resin average particle diameter was 590 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the properties of the resin of Example 5 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 187.2 mg/g
  • the maximum adsorption amount for tannic acid was 487.1 mg/g
  • the maximum adsorption amount for gallic acid was 406.7 mg/g.
  • the total exchange capacity of the resin was 7.0 mmol/g, wherein the strong base exchange capacity was 4.2 mmol/g, the weak base exchange capacity was 2.8 mmol/g, and the average resin particle diameter was 600 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the properties of the resin of Example 6 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 184.5 mg/g
  • the maximum adsorption amount for tannic acid was 488.3 mg/g
  • the maximum adsorption amount for gallic acid was 395.6 mg/g.
  • the total exchange capacity of the resin was 7.1 mmol/g, wherein the strong base exchange capacity was 4.1 mmol/g, the weak base exchange capacity was 3.0 mmol/g, and the average resin particle diameter was 630 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and added with a 1% NaOH solution to control pH > 14 for 3 hours, washed with water, and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • a mixed solution of a 60% by mass aqueous solution containing 3-chloro-2-hydroxypropyltrimethylammonium chloride and 40% NaOH solution to prepare a 3-chloro-2-hydroxypropyltrimethylammonium chloride solution
  • the volume ratio to the NaOH solution was 8:1.
  • the product was washed with a 10% by mass HCl solution and deionized water, and dried under vacuum at 40 ° C for 12 h (pressure - 0.09 MPa) to obtain a high exchange capacity bifunctional anion exchange resin.
  • the properties of the resin of Example 7 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 185.5 mg/g
  • the maximum adsorption amount for tannic acid was 480.1 mg/g
  • the maximum adsorption amount for gallic acid was 387.7 mg/g.
  • the total exchange capacity of the resin was 7.3 mmol/g, wherein the strong base exchange capacity was 4.2 mmol/g, the weak base exchange capacity was 3.1 mmol/g, and the resin average particle diameter was 590 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and added with a 1% NaOH solution to control pH > 14 for 3 hours, washed with water, and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • the properties of the resin of Example 8 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 187.2 mg/g
  • the maximum adsorption amount for tannic acid was 478.2 mg/g
  • the maximum adsorption amount for gallic acid was 384.6 mg/g.
  • the total exchange capacity of the resin was 7.3 mmol/g, wherein the strong base exchange capacity was 4.3 mmol/g, the weak base exchange capacity was 3.0 mmol/g, and the resin average particle diameter was 620 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and added with 1% NaOH solution to control pH>14 for 3 hours, washed with water and filtered to obtain polydivinylbenzene-vinylbenzyl. Amine polymer.
  • the volume ratio of ammonium solution to NaOH solution was 10:1.
  • the product was washed with a 30% by mass HCl solution and deionized water, and dried under vacuum at 60 ° C for 24 h (pressure - 0.08 MPa) to obtain a high exchange capacity bifunctional anion exchange resin.
  • the properties of the resin of Example 9 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 184.5 mg/g
  • the maximum adsorption amount for tannic acid was 466.9 mg/g
  • the maximum adsorption amount for gallic acid was 376.7 mg/g.
  • the total exchange capacity of the resin was 7.0 mmol/g, wherein the strong base exchange capacity was 3.9 mmol/g, the weak base exchange capacity was 3.1 mmol/g, and the resin average particle diameter was 610 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, added with 1% NaOH solution to control pH>14 for 2 hours, washed with water and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer;
  • the volume ratio of ammonium solution to NaOH solution was 8:1.
  • the product was washed with a 20% by mass HCl solution and deionized water, and dried under vacuum at 50 ° C for 18 h (pressure) -0.085 MPa) to obtain a high exchange capacity bifunctional anion exchange resin.
  • the properties of the resin of Example 10 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 171.7 mg/g
  • the maximum adsorption amount for tannic acid was 459.6 mg/g
  • the maximum adsorption amount for gallic acid was 375.4 mg/g.
  • the total exchange capacity of the resin was 6.3 mmol/g, wherein the strong base exchange capacity was 3.8 mmol/g, the weak base exchange capacity was 2.5 mmol/g, and the average resin particle diameter was 650 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off and washed with water, added with 1% NaOH solution to control pH > 14 for 2 hours, washed with water and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • the volume ratio of ammonium solution to NaOH solution was 9:1.
  • the product was washed with a 30% by mass HCl solution and deionized water, and dried under vacuum at 60 ° C for 24 h (pressure - 0.08 MPa) to obtain a high exchange capacity bifunctional anion exchange resin.
  • the properties of the resin of Example 11 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 179.1 mg/g
  • the maximum adsorption amount for tannic acid was 466.5 mg/g
  • the maximum adsorption amount for gallic acid was 383.7 mg/g.
  • the total exchange capacity of the resin was 6.5 mmol/g, wherein the strong base exchange capacity was 3.8 mmol/g, the weak base exchange capacity was 2.7 mmol/g, and the average resin particle diameter was 620 ⁇ m.
  • a method for preparing a high exchange capacity bifunctional anion exchange resin the steps of which are:
  • the polymer was filtered off, washed with water, and added with a 1% NaOH solution to control pH > 14 for 2.5 hours, washed with water and filtered to obtain a polydivinylbenzene-vinylbenzylamine polymer.
  • a mixed solution containing 60% by mass of 3-chloro-2-hydroxypropyltrimethylammonium chloride and 40% by mass of NaOH solution is used to chlorinate 3-chloro-2-hydroxypropyltrimethyl
  • the volume ratio of ammonium solution to NaOH solution was 10:1.
  • the product was washed with a 10% by mass HCl solution and deionized water, and dried under vacuum at 40 ° C for 12 h (pressure - 0.09 MPa) to obtain a high exchange capacity bifunctional anion exchange resin.
  • the properties of the resin of Example 12 were similar to those of Example 1.
  • the maximum adsorption amount for nitrate was 189.5 mg/g
  • the maximum adsorption amount for tannic acid was 477.5 mg/g
  • the maximum adsorption amount for gallic acid was 398.8 mg/g.
  • the total exchange capacity of the resin was 7.5 mmol/g, wherein the strong base exchange capacity was 4.3 mmol/g, the weak base exchange capacity was 3.2 mmol/g, and the resin average particle diameter was 610 ⁇ m.

Abstract

本发明公开了一种高交换容量双功能基阴离子交换树脂及其合成方法，属于环境功能材料合成与应用领域。该树脂使用氯甲基化聚苯乙烯-二乙烯苯聚合物为基体，通过伯胺化与季铵化反应，制得同时具有弱碱型和强碱型阴离子基团的双功能基的阴离子交换树脂。该阴离子交换树脂不仅对水中硝酸根离子有较高的吸附容量，还能有效吸附水中植酸类天然有机酸；可同时去除水中硝酸根离子和植酸类有机质，因此在饮用水处理、地下水修复、城市生活污水深度处理领域具有广阔应用前景。

Description

一种高交换容量双功能基阴离子交换树脂及其合成方法 技术领域
本发明公开了阴离子交换树脂及其合成方法，更具体地说是一种高交换容量双功能基阴离子交换树脂及其合成方法，其以氯甲基化聚苯乙烯-二乙烯苯聚合物为基体，经过伯胺化和季铵化反应，制得高交换容量双功能基阴离子交换树脂及其合成方法。
背景技术
近年来水资源尤其是地下水资源受到了严重的污染，对生态环境和人造成了的各种直接或潜在的危害。其中农业氮肥的大量使用，含氮污水的排放等使水体中硝酸根离子浓度不断增加，早已经突破了水体自净能力的极限。而人体摄入过多硝酸根离子摄入，会造成严重的健康问题，如出生缺陷，腹泻腹痛，糖尿病，高血压等。去除水中硝酸根离子意义重大，常用水中硝酸根离子的去除方法主要有生化法，化学还原法，电渗法，吸附法。生化法处理的周期较长，效果受季节的影响较大。化学还原法对条件要求较高，很难大规模应用。而电渗法处理成本较高，无法长期使用。离子交换与吸附法以其工艺简单，快速高效，成本低，可再生等优点，被认为是理想的处理方法。曹国明等利用强碱型阴离子交换树脂处理受硝酸盐污染的地下水，达到了较好的效果(曹国明,盛梅,费宇雷,孟科伟,史伟伟,俞益峰.离子交换法连续流处理受硝酸盐污染的地下水.净水技术.2011,30(5)：90-94.)。另一方面无论是城市生活污水、废水生化尾水还是天然水体，其中的有机质主要是植类有机质，此类物质会使得水体产生不良的色、味，影响水质，且在水处理消毒过程中会产生消毒副产物，对人体健康产生危害。而去除此类天然有机质的有效吸附材料主要是弱碱型阴离子交换树脂。
通常阴离子交换树脂功能基团为氨基或者季铵盐基团，其对硝酸根离子的吸附量受控于树脂表面功能基团数量。而传统的氯甲基化聚苯乙烯-二乙烯苯聚合物进行季铵化反应时，每个聚合物上氯甲基仅能反应生成一个季铵盐基团。而氯甲基化聚苯乙烯-二乙烯苯聚合物中的氯甲基含量是固定的(质量分数16-20％)，难以提高。这就导致树脂表面季铵盐基团数量受限于氯甲基的数量，也难以提高。因此，如何增加氯甲基化聚苯乙烯-二乙烯苯的氯甲基上反应生成的季铵盐基团数量成为一个不易解决的难题。
发明内容
1、发明要解决的技术问题
(1)针对现有去除水中硝酸根离子的离子交换树脂主要为强碱型阴离子交换树脂，其对硝酸根离子的吸附量取决于离子交换树脂的氨/铵基数量，因为硝酸根离子优先与强碱型离子交换基团发生离子交换作用，而后再与弱碱型离子交换基团发生离子交换作用。然而传统聚聚苯乙烯-二乙烯苯骨架的强碱型阴离子交换树脂在合成过程中，氯甲基化聚苯乙烯-二乙烯苯聚合物进行季铵化反应时每个氯甲基仅能接枝上一个季铵盐基团，这使得树脂表面的强碱型离子交换基团数量受到限制，对硝酸根离子的吸附容量难以大幅提高。因此，如何增加离子交换树脂的离子交换基团数量是首要解决的一个技术难题。
(2)实际天然水体或者废水中普遍含有植酸类天然有机质(单宁酸、没食子酸)，这些天然有机质不仅能够与阴离子交换树脂的氨/铵基发生作用，与硝酸根离子产生竞争吸附，导致树脂对硝酸根离子的吸附容量下降；而且天然有机质在水处理后期的消毒过程中还会产生消毒副产物，对人体健康产生危害。目前能够有效吸附去除水中植酸类有机质的吸附材料主要是含有伯胺、仲胺和叔胺基团的弱碱型离子交换树脂，因为植酸类物质优先与弱碱型离子交换基团作用，而后再与强碱型离子交换基团作用。因此，在强碱型离子交换树脂上同时引入弱碱型离子交换基团，优先吸附水中植酸类物质，保证树脂有足够数量的强碱型离子交换基团与硝酸根离子发生作用，这是另一个需要解决的技术难题。
(3)而现有的阴离子交换树脂合成方法，通常用氯甲基化聚苯乙烯-二乙烯苯与二甲胺进行胺化反应，或者与三甲胺进行季铵化反应。通过这一方法制得的阴离子交换树脂难以进一步反应增加树脂的氨基或者季铵盐基团，这也是需要解决的技术难题。
针对上述三个技术难题，本发明提供一种高交换容量，且同时含有强碱型和弱碱型离子交换基团的双功能基阴离子交换树脂及其合成方法。该合成方法简单、易于操作，可在氯甲基化聚苯乙烯-二乙烯苯聚合物的氯甲基上同时引入弱碱型和强碱型离子交换基团，显著提高树脂的离子交换容量，不仅使树脂对硝酸根离子吸附容量显著提高，还能够利用弱碱型离子交换基团协同去除水中植酸类有机质，减少吸附过程中植酸类物质对去除硝酸根离子的竞争作用。
2、技术方案
一种高交换容量双功能基阴离子交换树脂，以氯甲基化聚苯乙烯-二乙烯苯聚合物为母体，合成的高交换容量双功能基阴离子交换树脂的总交换容量为6.3～7.9mmol/g，其中强碱交换容量为3.8～4.7mmol/g，弱碱交换容量为2.5～3.2mmol/g，树脂平均粒径为550～650μm，树脂通过先将伯胺作为弱碱型阴离子交换基团接枝到氯甲基化聚苯乙烯-二乙烯苯聚合物的骨架上，再将3-氯-2-羟丙基三甲基氯化铵作为强碱型阴离子交换基团接枝到伯胺基团上，形成具有弱碱型、强碱型阴离子交换基团的双功能基团的高交换容量阴离子交换树脂，其结构式如下：
Figure PCTCN2015083880-appb-000001
结构式中m为聚合度，数值在3000～5000范围内，用凝胶渗透色谱法测定。参考文献：杨尔思.凝胶渗透色谱法测定高抗冲聚苯乙烯的分子量及其分布.吉化科技,1997,2:26-28.
一种高交换容量双功能基阴离子交换树脂，以氯甲基化聚苯乙烯-二乙烯苯聚合物为母体，先引入弱碱型离子交换基团(伯胺基团)，在此基础上再引入强碱型离子交换基团(季铵盐基团)，成为具有双功能基的新型阴离子交换树脂。合成流程如下：
步骤1：
Figure PCTCN2015083880-appb-000002
步骤2：
Figure PCTCN2015083880-appb-000003
制备的具体步骤为：
(1)伯胺化反应
将氯甲基化聚苯乙烯-二乙烯苯聚合物在无水乙醇和氯仿的混合溶液中溶胀，再加入六次甲基四胺，在35-45℃下搅拌反应6-7小时；将聚合物滤出，用乙醇洗涤，将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物g：混合酸解溶液ml＝1：4-5，在35-45℃反应2-3小时，再次将聚合物滤出，水洗，加NaOH溶液控制pH>14转型2-3小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物；
(2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵的水溶液与的NaOH溶液配制混合溶液，往混合溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量g：混合溶液体积ml＝1-2：50，在70-80℃下搅拌反应2-3个小时，所得到的产物用质量百分比浓度为10-30％的HCl溶液和去离子水洗涤，40-60℃真空干燥，得到高交换容量双功能基阴离子交换树脂。
所述步骤(1)中，先使氯甲基化聚苯乙烯-二乙烯苯聚合物在无水乙醇和氯仿的混合溶液中在20-25℃下溶胀3-4小时；所述氯甲基化聚苯乙烯-二乙烯苯聚合物g：无水乙醇ml：氯仿ml：六次甲基四胺g为5：15～20：2～4：4～5。
所述步骤(1)中浓盐酸-无水乙醇混合酸解溶液为将质量分数37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积ml：无水乙醇体积ml为1：2-3。
所述步骤(1)中，加NaOH溶液控制pH>14转型2-3小时，所述NaOH溶液质量百分比为1％。
步骤(2)中3-氯-2-羟丙基三甲基氯化铵溶液浓度为60％，NaOH溶液质量百分比浓度为40％，按照3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积 比为8-10:1配置混合溶液；步骤(2)中真空干燥12-24h，压力为-0.09～-0.08MPa。
3、有益效果
本发明提供了一种高交换容量双功能基阴离子交换树脂的制备方法，使得其总交换容量高达6.3～7.9mmol/g，其中强碱交换容量达到3.8～4.7mmol/g，弱碱交换容量达到2.5～3.2mmol/g。本发明制备的吸附材料同时具有弱碱型阴离子交换基团和强碱型阴离子交换基团，能够在去除硝酸根离子的同时，利用弱碱基团去除植类有机质，从而在实际水处理用途上实现了双功能化。在饮用水处理、地下水修复、城市生活污水深度处理领域具有广阔应用前景。
附图说明
图1为本发明实施例1-12制备得到的高交换容量双功能基阴离子交换树脂的结构图。
图2为本发明实施例1制备得到的高交换容量双功能基阴离子交换树脂(即图中的新树脂)的FT-IR图谱，图谱横坐标为波数，纵坐标为透过率，表明的是样品对于不同波数的红外光的透过率。
图3为本发明实施例1制备得到的高交换容量双功能基阴离子交换树脂的固体核磁共振图谱，横坐标为化学位移。
图4为本发明实施例1制备得到的高交换容量双功能基阴离子交换树脂扫描电镜图。
具体实施方式
实施例1
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度m为3000)在15毫升无水乙醇和2毫升氯仿的混合溶液中20℃下溶胀3小时，加入4克六次甲基四胺，在35℃下搅拌反应6小时。将聚合物滤出，用乙醇洗涤。将质量分数37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4。35℃反应2小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2小时，水洗、过滤得聚二乙 烯苯-乙烯基苄胺聚合物；
Figure PCTCN2015083880-appb-000004
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为8:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1：50，在70℃下搅拌反应2个小时。产物用质量浓度为10％的HCl溶液和去离子水洗涤，40℃真空干燥12h(压力-0.09MPa)，得到高交换容量双功能基阴离子交换树脂；
Figure PCTCN2015083880-appb-000005
经过测试新树脂对硝酸根的最大吸附量为198.5mg/g，对单宁酸的最大吸附量为493.7mg/g,对没食子酸最大吸附量为407.6mg/g。树脂的总交换容量为7.9mmol/g，其中强碱交换容量为4.7mmol/g，弱碱交换容量为3.2mmol/g，树脂平均粒径为550μm。
如图1为本实例制备得到的高交换容量双功能基阴离子交换树脂的结构图，
Figure PCTCN2015083880-appb-000006
图2为本发明实例制备得到的高交换容量双功能基阴离子交换树脂的FT-IR图谱，聚二乙烯苯-乙烯基苄胺的谱线中，1564cm-1处显示对应的是—NH2中N—H弯曲振动的吸收峰，说明反应步骤1已经成功将伯胺基团接入；而在新树脂(本发明实施例所制备的高交换容量双功能基阴离子交换树脂)的红外图谱中，—NH2的吸收峰几乎消失，取而代之的是1476cm-1处的强吸收峰，而这正对应的是三甲基氯化铵基团中N—CH3的弯曲振动。而在1100cm-1出现的吸收峰，则对应的是C—O的伸缩振动。图3为本发明实例制备得到的高交换容量双功能基阴离子交换树脂的固体核磁共振图谱。综合图2红外光谱分析和图3核磁共振分析，可以证实高交换容量双功能基阴离子交换树脂如图1的结构。图4为本发明实例制备得到的高交换容量双功能基阴离子交换树脂扫描电镜图。
实施例2
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3530)在15毫升无水乙醇和2毫升氯仿的混合溶液中20℃下溶胀3小时，加入4克六次甲基四胺，在35℃下搅拌反应6小时。将聚合物滤出，用乙醇洗涤。将质量分数37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4。35℃反应2小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为9:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1.5：50，在75℃下搅拌反应2.5个小时。产物用质量浓度为20％的HCl溶液和去离子水洗涤，50℃真空干燥18h(压力-0.085MPa)，得到高交换容量双功能基阴离子交换树脂。
新树脂的性状与实例1相似，对硝酸根的最大吸附量为173.3mg/g，对单宁 酸的最大吸附量为466.5mg/g,对没食子酸最大吸附量为379.2mg/g。树脂的总交换容量为6.6mmol/g，其中强碱交换容量为3.9mmol/g，弱碱交换容量为2.7mmol/g，树脂平均粒径为600μm。
实施例3
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3870)在15毫升无水乙醇和2毫升氯仿的混合溶液中20℃下溶胀3小时，加入4克六次甲基四胺，在35℃下搅拌反应6小时。将聚合物滤出，用乙醇洗涤。将质量分数37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4。35℃反应2小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为10:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝2：50，在80℃下搅拌反应3个小时。产物用质量浓度为30％的HCl溶液和去离子水洗涤，60℃真空干燥24h(压力-0.08MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例3树脂的性状与实例1相似，对硝酸根的最大吸附量为175.1mg/g，对单宁酸的最大吸附量为468.7mg/g,对没食子酸最大吸附量为381.4mg/g。树脂的总交换容量为6.6mmol/g，其中强碱交换容量为3.8mmol/g，弱碱交换容量为2.8mmol/g，树脂平均粒径为580μm。
实施例4
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度4600)在17毫升无水乙 醇和3毫升氯仿的混合溶液中22℃下溶胀3.5小时，加入4.5克六次甲基四胺，在40℃下搅拌反应6.5小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2.5。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4.5。40℃反应2.5小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2.5小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为8:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1：50，在70℃下搅拌反应2个小时。产物用质量浓度为10％的HCl溶液和去离子水洗涤，40℃真空干燥12h(压力-0.09MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例4树脂的性状与实例1相似，对硝酸根的最大吸附量为185.5mg/g，对单宁酸的最大吸附量为481.5mg/g,对没食子酸最大吸附量为400.4mg/g。树脂的总交换容量为7.1mmol/g，其中强碱交换容量为4.2mmol/g，弱碱交换容量为2.9mmol/g，树脂平均粒径为590μm。
实施例5
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度4880)在17毫升无水乙醇和3毫升氯仿的混合溶液中22℃下溶胀3.5小时，加入4.5克六次甲基四胺，在40℃下搅拌反应6.5小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2.5。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4.5。40℃反应2.5小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2.5小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为9:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1.5：50，在75℃下搅拌反应2.5个小时。产物用质量浓度为20％的HCl溶液和去离子水洗涤，50℃真空干燥18h(压力-0.085MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例5树脂的性状与实例1相似，对硝酸根的最大吸附量为187.2mg/g，对单宁酸的最大吸附量为487.1mg/g,对没食子酸最大吸附量为406.7mg/g。树脂的总交换容量为7.0mmol/g，其中强碱交换容量为4.2mmol/g，弱碱交换容量为2.8mmol/g，树脂平均粒径为600μm。
实施例6
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度5000)在17毫升无水乙醇和3毫升氯仿的混合溶液中22℃下溶胀3.5小时，加入4.5克六次甲基四胺，在40℃下搅拌反应6.5小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1：2.5。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1：4.5。40℃反应2.5小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2.5小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为10:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝2：50，在80℃下搅拌反应3个小时。产物用质量浓度为30％的HCl溶液和去离子水洗涤，60℃真空干燥24h(压力-0.08MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例6树脂的性状与实例1相似，对硝酸根的最大吸附量为184.5mg/g，对单宁酸的最大吸附量为488.3mg/g,对没食子酸最大吸附量为395.6mg/g。树脂的总交换容量为7.1mmol/g，其中强碱交换容量为4.1mmol/g，弱碱交换容量为3.0mmol/g，树脂平均粒径为630μm。
实施例7
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3300)在20毫升无水乙醇和4毫升氯仿的混合溶液中25℃下溶胀4小时，加入5克六次甲基四胺，在45℃下搅拌反应7小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:3。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:5。45℃反应3小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型3小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％质量分数的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为8:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1：50，在70℃下搅拌反应2个小时。产物用质量浓度为10％的HCl溶液和去离子水洗涤，40℃真空干燥12h(压力-0.09MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例7树脂的性状与实例1相似，对硝酸根的最大吸附量为185.5mg/g，对单宁酸的最大吸附量为480.1mg/g,对没食子酸最大吸附量为387.7mg/g。树脂的总交换容量为7.3mmol/g，其中强碱交换容量为4.2mmol/g，弱碱交换容量为3.1mmol/g，树脂平均粒径为590μm。
实施例8
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度4150)在20毫升无水乙醇和4毫升氯仿的混合溶液中25℃下溶胀4小时，加入5克六次甲基四胺，在45℃下搅拌反应7小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:3。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:5。45℃反应3小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型3小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％的水溶液与40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为9:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1.5：50，在75℃下搅拌反应2.5个小时。产物用质量浓度为20％的HCl溶液和去离子水洗涤，50℃真空干燥18h(压力-0.085MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例8树脂的性状与实例1相似，对硝酸根的最大吸附量为187.2mg/g，对单宁酸的最大吸附量为478.2mg/g,对没食子酸最大吸附量为384.6mg/g。树脂的总交换容量为7.3mmol/g，其中强碱交换容量为4.3mmol/g，弱碱交换容量为3.0mmol/g，树脂平均粒径为620μm。
实施例9
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3740)在20毫升无水乙醇和4毫升氯仿的混合溶液中25℃下溶胀4小时，加入5克六次甲基四胺，在45℃下搅拌反应7小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:3。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:5。45℃反应3小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型3小时，水洗、过滤得聚二乙烯苯-乙烯基苄 胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％质量分数的水溶液与质量分数40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为10:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝2：50，在80℃下搅拌反应3个小时。产物用质量浓度为30％的HCl溶液和去离子水洗涤，60℃真空干燥24h(压力-0.08MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例9树脂的性状与实例1相似，对硝酸根的最大吸附量为184.5mg/g，对单宁酸的最大吸附量为466.9mg/g,对没食子酸最大吸附量为376.7mg/g。树脂的总交换容量为7.0mmol/g，其中强碱交换容量为3.9mmol/g，弱碱交换容量为3.1mmol/g，树脂平均粒径为610μm。
实施例10
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度4560)在15毫升无水乙醇和2毫升氯仿的混合溶液中20℃下溶胀4小时，加入4克六次甲基四胺，在35℃下搅拌反应6小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:2。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:5。45℃反应3小时。将聚合物滤出，水洗，加1％NaOH溶液控制pH>14转型2小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物；
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％质量分数的水溶液与质量分数40％的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为8:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1.5：50，在75℃下搅拌反应2.5个小时。产物用质量浓度为20％的HCl溶液和去离子水洗涤，50℃真空干燥18h(压力 -0.085MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例10树脂的性状与实例1相似，对硝酸根的最大吸附量为171.7mg/g，对单宁酸的最大吸附量为459.6mg/g,对没食子酸最大吸附量为375.4mg/g。树脂的总交换容量为6.3mmol/g，其中强碱交换容量为3.8mmol/g，弱碱交换容量为2.5mmol/g，树脂平均粒径为650μm。
实施例11
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3890)在15毫升无水乙醇和2毫升氯仿的混合溶液中20℃下溶胀4小时，加入4克六次甲基四胺，在35℃下搅拌反应6小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:3。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:4。45℃反应3小时。将聚合物滤出水洗，加1％NaOH溶液控制pH>14转型2小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵60％质量分数的水溶液与40％质量分数的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为9:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝2：50，在80℃下搅拌反应3个小时。产物用质量浓度为30％的HCl溶液和去离子水洗涤，60℃真空干燥24h(压力-0.08MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例11树脂的性状与实例1相似，对硝酸根的最大吸附量为179.1mg/g，对单宁酸的最大吸附量为466.5mg/g,对没食子酸最大吸附量为383.7mg/g。树脂的总交换容量为6.5mmol/g，其中强碱交换容量为3.8mmol/g，弱碱交换容量为2.7mmol/g，树脂平均粒径为620μm。
实施例12
一种高交换容量双功能基阴离子交换树脂制备方法，其步骤为：
1)伯胺化反应
将5g氯甲基化聚苯乙烯-二乙烯苯聚合物(聚合度3470)在17毫升无水乙醇和3毫升氯仿的混合溶液中22℃下溶胀4小时，加入4.5克六次甲基四胺，在40℃下搅拌反应6.5小时。将聚合物滤出，用乙醇洗涤。将37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积(ml)：无水乙醇体积(ml)＝1:2.5。将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物(g)：混合酸解溶液(ml)＝1:5。45℃反应3小时。将聚合物滤出,水洗，加1％NaOH溶液控制pH>14转型2.5小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物。
2)季铵化反应
将含3-氯-2-羟丙基三甲基氯化铵质量分数60％的水溶液与40％质量分数的NaOH溶液配制混合溶液，使3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为10:1。往溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量(g)：混合溶液体积(毫升)＝1：50，在70℃下搅拌反应2个小时。产物用质量浓度为10％的HCl溶液和去离子水洗涤，40℃真空干燥12h(压力-0.09MPa)，得到高交换容量双功能基阴离子交换树脂。
实施例12树脂的性状与实例1相似，对硝酸根的最大吸附量为189.5mg/g，对单宁酸的最大吸附量为477.5mg/g,对没食子酸最大吸附量为398.8mg/g。树脂的总交换容量为7.5mmol/g，其中强碱交换容量为4.3mmol/g，弱碱交换容量为3.2mmol/g，树脂平均粒径为610μm。

Claims (8)

  1. 一种高交换容量双功能基阴离子交换树脂，其特征在于，以氯甲基化聚苯乙烯-二乙烯苯聚合物为基体，通过先将伯胺作为弱碱型阴离子交换基团接枝到氯甲基化聚苯乙烯-二乙烯苯聚合物的骨架上，再将3-氯-2-羟丙基三甲基氯化铵作为强碱型阴离子交换基团接枝到伯胺基团上，形成具有弱碱型、强碱型阴离子交换基团的双功能基团的高交换容量阴离子交换树脂，其结构式如下：
    Figure PCTCN2015083880-appb-100001
    结构式中m为聚合度，数值在3000～5000范围内。
  2. 根据权利要求1所述的高交换容量双功能基阴离子交换树脂，其特征在于，所述的高交换容量双功能基阴离子交换树脂的总交换容量为6.3～7.9mmol/g，其中强碱交换容量为3.8～4.7mmol/g，弱碱交换容量为2.5～3.2mmol/g，树脂平均粒径为550～650μm。
  3. 一种高交换容量双功能基阴离子交换树脂合成方法，其步骤为：
    (1)伯胺化反应
    将氯甲基化聚苯乙烯-二乙烯苯聚合物在无水乙醇和氯仿的混合溶液中溶胀，再加入六次甲基四胺，在35-45℃下搅拌反应6-7小时；将聚合物滤出，用乙醇洗涤，将聚合物加入浓盐酸-无水乙醇混合酸解溶液中，使氯甲基化聚苯乙烯-二乙烯苯聚合物g：混合酸解溶液ml＝1：4-5，在35-45℃反应2-3小时，再次将聚合物滤出，水洗，加NaOH溶液控制pH>14转型2-3小时，水洗、过滤得聚二乙烯苯-乙烯基苄胺聚合物；
    (2)季铵化反应
    将含3-氯-2-羟丙基三甲基氯化铵的水溶液与的NaOH溶液配制混合溶液，往混合溶液中加入步骤(1)中制备聚二乙烯苯-乙烯基苄胺聚合物，聚合物质量 g：混合溶液体积ml＝1-2：50，在70-80℃下搅拌反应2-3个小时，所得到的产物用质量百分比浓度为10-30％的HCl溶液和去离子水洗涤，40-60℃真空干燥，得到高交换容量双功能基阴离子交换树脂。
  4. 根据权利要求3所述的高交换容量双功能基阴离子交换树脂的合成方法，其特征在于，所述步骤(1)中，先使氯甲基化聚苯乙烯-二乙烯苯聚合物在无水乙醇和氯仿的混合溶液中在20-25℃下溶胀3-4小时；所述氯甲基化聚苯乙烯-二乙烯苯聚合物g：无水乙醇ml：氯仿ml：六次甲基四胺g为5：15～20：2～4：4～5。
  5. 根据权利要求3所述的高交换容量双功能基阴离子交换树脂的合成方法，其特征在于，所述步骤(1)中浓盐酸-无水乙醇混合酸解溶液为将质量分数为37.5％的浓盐酸与无水乙醇配成混合酸解溶液，使浓盐酸体积ml：无水乙醇体积ml为1：2-3。
  6. 根据权利要求3所述的高交换容量双功能基阴离子交换树脂的合成方法，其特征在于，所述步骤(1)中，加NaOH溶液控制pH>14转型2-3小时，所述NaOH溶液质量百分比为1％。
  7. 根据权利要求3所述的高交换容量双功能基阴离子交换树脂的合成方法，其特征在于，所述步骤(2)中3-氯-2-羟丙基三甲基氯化铵溶液质量分数为60％，NaOH溶液质量百分比浓度为40％，按照3-氯-2-羟丙基三甲基氯化铵溶液和NaOH溶液体积比为8-10:1配置混合溶液。
  8. 根据权利要求3所述的高交换容量双功能基阴离子交换树脂的合成方法，其特征在于，所述步骤(2)中真空干燥12-24h，压力为-0.09～-0.08MPa。
PCT/CN2015/083880 2014-07-15 2015-07-13 一种高交换容量双功能基阴离子交换树脂及其合成方法 WO2016008396A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/511,184 US9950319B2 (en) 2014-07-15 2015-07-13 High exchange-capacity anion exchange resin with dual functional-groups and method of synthesis thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410335922.8A CN104119466B (zh) 2014-07-15 2014-07-15 一种高交换容量双功能基阴离子交换树脂及其合成方法
CN201410335922.8 2014-07-15

Publications (1)

Publication Number Publication Date
WO2016008396A1 true WO2016008396A1 (zh) 2016-01-21

Family

ID=51765123

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/083880 WO2016008396A1 (zh) 2014-07-15 2015-07-13 一种高交换容量双功能基阴离子交换树脂及其合成方法

Country Status (3)

Country Link
US (1) US9950319B2 (zh)
CN (1) CN104119466B (zh)
WO (1) WO2016008396A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111269339A (zh) * 2020-01-21 2020-06-12 广西大学 一种硅基阴离子交换树脂及其制备方法
CN113443773A (zh) * 2021-07-21 2021-09-28 安徽东至广信农化有限公司 一种邻苯二胺生产废水的处理方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104119466B (zh) * 2014-07-15 2016-07-06 南京大学 一种高交换容量双功能基阴离子交换树脂及其合成方法
CN105254790B (zh) * 2015-11-11 2018-08-14 青岛埃仑色谱科技有限公司 离子交换树脂的制备方法、由该方法制备的离子交换树脂制成的阴离子色谱柱及其应用
CN111003745A (zh) * 2019-12-27 2020-04-14 苏州博睿特环保科技有限公司 一种利用吸附法资源回收乙酸废水的方法
CN111514944B (zh) * 2020-05-08 2022-04-15 南京大学 一种去除水垢的季铵型树脂及其合成方法与应用
CN112125992B (zh) * 2020-09-11 2021-09-14 昌果生物医药科技河北有限公司 一种丙烯酸系树脂的合成方法
CN116943623A (zh) * 2023-08-21 2023-10-27 江苏南大华兴环保科技股份公司 一种深度除氟的树脂吸附剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781381A (zh) * 2009-12-31 2010-07-21 安徽皖东化工有限公司 201×4强碱性苯乙烯系阴离子交换树脂的制备方法
CN103301890A (zh) * 2013-06-26 2013-09-18 东南大学 一种选择性强碱阴离子交换树脂及其制备方法
CN103524657A (zh) * 2013-10-17 2014-01-22 西安建筑科技大学 一种去除水中硝酸盐的大孔强碱性阴离子交换树脂的制备方法
CN104119466A (zh) * 2014-07-15 2014-10-29 南京大学 一种高交换容量双功能基阴离子交换树脂及其合成方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102189008B (zh) * 2011-04-11 2013-05-08 常州大学 一种新型强弱碱阴离子交换树脂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781381A (zh) * 2009-12-31 2010-07-21 安徽皖东化工有限公司 201×4强碱性苯乙烯系阴离子交换树脂的制备方法
CN103301890A (zh) * 2013-06-26 2013-09-18 东南大学 一种选择性强碱阴离子交换树脂及其制备方法
CN103524657A (zh) * 2013-10-17 2014-01-22 西安建筑科技大学 一种去除水中硝酸盐的大孔强碱性阴离子交换树脂的制备方法
CN104119466A (zh) * 2014-07-15 2014-10-29 南京大学 一种高交换容量双功能基阴离子交换树脂及其合成方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111269339A (zh) * 2020-01-21 2020-06-12 广西大学 一种硅基阴离子交换树脂及其制备方法
CN113443773A (zh) * 2021-07-21 2021-09-28 安徽东至广信农化有限公司 一种邻苯二胺生产废水的处理方法
CN113443773B (zh) * 2021-07-21 2022-09-20 安徽东至广信农化有限公司 一种邻苯二胺生产废水的处理方法

Also Published As

Publication number Publication date
CN104119466B (zh) 2016-07-06
US9950319B2 (en) 2018-04-24
CN104119466A (zh) 2014-10-29
US20170259255A1 (en) 2017-09-14

Similar Documents

Publication Publication Date Title
WO2016008396A1 (zh) 一种高交换容量双功能基阴离子交换树脂及其合成方法
Wu et al. Fabrication of carboxymethyl chitosan–hemicellulose resin for adsorptive removal of heavy metals from wastewater
Vakili et al. Novel crosslinked chitosan for enhanced adsorption of hexavalent chromium in acidic solution
Lu et al. Fabrication of cross-linked chitosan beads grafted by polyethylenimine for efficient adsorption of diclofenac sodium from water
d’Halluin et al. Chemically modified cellulose filter paper for heavy metal remediation in water
Dragan et al. Kinetics, equilibrium modeling, and thermodynamics on removal of Cr (VI) ions from aqueous solution using novel composites with strong base anion exchanger microspheres embedded into chitosan/poly (vinyl amine) cryogels
Song et al. Selective removal of nitrate from water by a macroporous strong basic anion exchange resin
Shang et al. Preferable uptake of phosphate by hydrous zirconium oxide nanoparticles embedded in quaternary-ammonium Chinese reed
Hamza et al. As (V) sorption from aqueous solutions using quaternized algal/polyethyleneimine composite beads
CN103910822B (zh) 一种凝胶型强碱性阴离子交换树脂的制备方法
CN106622166B (zh) 一种用于去除重金属离子的聚天冬氨酸膨润土复合材料及其制备方法
WO2021120439A1 (zh) 一种用于染料吸附的壳聚糖-环糊精基海绵的制备方法
CN111068632A (zh) 一种铅离子复合吸附剂及其制备方法
CN109550485A (zh) 一种氨基化磁性壳聚糖的制备方法
CN102489268A (zh) 一种胺修饰的纤维状应急吸附材料及其制备方法
Li et al. Preparation of quaternary ammonium-functionalized metal–organic framework/chitosan composite aerogel with outstanding scavenging of melanoidin
Zhang et al. Precise identification and transport of specific molecules through framework-functionalized membranes with multiple binding sites
CN104117344A (zh) 新型壳聚糖金属离子吸附剂的制备方法
CN109052715B (zh) 一种固态/液态有机污染物去除方法
CN108514870A (zh) 水滑石-聚间苯二胺复合材料及其制备方法和应用
CN109174040B (zh) 一种多官能团金属吸附剂的制备方法
Zhu et al. Polymer brush-grafted cotton fiber for the efficient removal of aromatic halogenated disinfection by-products in drinking water
CN108772038B (zh) 一种脱除水中铅离子的吸附剂及其制备方法和应用
CN111359594B (zh) 一种硼酸吸附材料及制备方法
CN103301890A (zh) 一种选择性强碱阴离子交换树脂及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15821977

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15511184

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 15821977

Country of ref document: EP

Kind code of ref document: A1