技术领域technical field
本发明涉及一种乙酰胺基修饰的超高交联型吸附树脂的制备方法及其应用，属于高分子改性领域。The invention relates to a preparation method and application of an acetamide-modified ultra-high cross-linking adsorption resin, which belongs to the field of polymer modification.
背景技术Background technique
20世纪70年代初，Davankov等通过Friedel-Crafts反应将线型聚苯乙烯交联或将低交联聚苯乙烯再交联合成了一类结构独特、性能优良的多孔聚合物。根据其制备方式，这类反应称为超高交联反应(又称为Davankov超高交联反应)。由超高交联反应制备的多孔聚合物称为超高交联型吸附树脂。超高交联型吸附树脂被认为是继凝胶型、大孔型吸附树脂后的第三代吸附树脂。超高交联吸附树脂通常具有比表面积大、平均孔径小、孔径分布窄、机械强度好等结构特征，目前在有毒有机废水的治理、中草药与抗生素的提取、气体的储存分离等领域显示了广阔的应用前景。In the early 1970s, Davankov et al crosslinked linear polystyrene or recrosslinked low crosslinked polystyrene through Friedel-Crafts reaction to form a class of porous polymers with unique structure and excellent performance. According to its preparation method, this type of reaction is called hypercrosslinking reaction (also known as Davankov hypercrosslinking reaction). The porous polymer prepared by ultra-high cross-linking reaction is called ultra-high cross-linked adsorption resin. Ultra-high cross-linked adsorbent resins are considered to be the third generation of adsorbent resins after gel-type and macroporous adsorbent resins. Ultra-high cross-linked adsorption resins usually have structural characteristics such as large specific surface area, small average pore size, narrow pore size distribution, and good mechanical strength. At present, they have shown great potential in the treatment of toxic organic wastewater, the extraction of Chinese herbal medicines and antibiotics, and the storage and separation of gases. application prospects.
然而，超高交联型吸附树脂的骨架结构都是疏水性的聚苯乙烯，其强疏水性一方面使得其在使用前需用极性试剂(如：甲醇)预处理，增加了操作的复杂性；另一方面使得其对水溶液中溶解度大的极性物质(如：苯酚、水杨酸、对氨基苯磺酸等)的吸附量小，选择性差。为了提高这类树脂对在水溶液中溶解度大的极性物质的吸附量，开发出一类具有合适孔结构和一定极性的新型超高交联型吸附树脂显得尤为重要。专利(授权公告号ZL201110179667.9)公开了一种N-甲基乙酰胺基修饰的超高交联型吸附树脂的制备方法。N-甲基乙酰胺基修饰的超高交联型吸附树脂的吸附性能结果表明，这类树脂对弱极性或极性物质(如：苯酚、水杨酸)具有一定的吸附能力，但是吸附效果并不十分理想。However, the skeleton structure of ultra-highly cross-linked adsorption resins is hydrophobic polystyrene. On the one hand, its strong hydrophobicity requires pretreatment with polar reagents (such as: methanol) before use, which increases the complexity of the operation. On the other hand, it has a small adsorption capacity and poor selectivity to polar substances with high solubility in aqueous solution (such as: phenol, salicylic acid, p-aminobenzenesulfonic acid, etc.). In order to increase the adsorption capacity of such resins for polar substances with high solubility in aqueous solution, it is particularly important to develop a new type of ultra-high cross-linked adsorption resin with suitable pore structure and certain polarity. The patent (authorized announcement number ZL201110179667.9) discloses a preparation method of an N-methylacetamide modified ultra-high cross-linked adsorption resin. The adsorption performance results of N-methylacetamide-modified ultra-high cross-linked adsorption resins show that this type of resin has a certain adsorption capacity for weakly polar or polar substances (such as: phenol, salicylic acid), but the adsorption The effect is not very ideal.
发明内容Contents of the invention
针对现有技术中的改性交联聚苯乙烯存在对水中的极性有机物质(如：弱极性的苯酚、极性强的水杨酸)吸附效果不理想的缺陷，使其应用受到局限，本发明的目的是在于提供一种过程简单、低成本制备比表面积高和孔容大，且具有适宜孔径和极性孔结构的乙酰胺基修饰的超高交联型吸附树脂的方法。In view of the defect that the modified cross-linked polystyrene in the prior art has an unsatisfactory adsorption effect on polar organic substances in water (such as: weakly polar phenol, highly polar salicylic acid), its application is limited. The purpose of the present invention is to provide a method for preparing acetamide-modified ultra-high cross-linked adsorption resin with simple process and low cost, which has high specific surface area and large pore volume, and has suitable pore diameter and polar pore structure.
本发明的另一个目的是在于提供所述乙酰胺基修饰的超高交联型吸附树脂在选择性吸附水溶液中的极性吸附质方面的应用，特别是对苯酚和/或水杨酸具有选择性吸收效果，且吸附后容易洗脱，树脂可以重复使用，重复使用效果好。Another object of the present invention is to provide the application of the acetamide-modified ultra-high cross-linked adsorption resin in the selective adsorption of polar adsorbates in aqueous solution, especially for phenol and/or salicylic acid. Non-toxic absorption effect, and easy to wash off after adsorption, the resin can be reused, and the repeated use effect is good.
本发明提供了一种乙酰胺基修饰的超高交联型吸附树脂的制备方法，该制备方法是将氯甲基化聚苯乙烯通过溶剂溶胀后，以路易斯酸作为催化剂，在80～85℃的温度条件下，进行Friedel-Crafts反应5～8h，反应完成后，得到超高交联型树脂；将所述的超高交联型树脂溶胀在溶有六次甲基四胺和碘化钾的溶剂中，在95～105℃的温度条件下，进行Delépine反应8～12h，Delépine反应完成后，得到胺基修饰的超高交联型树脂；所得胺基修饰的超高交联型树脂采用苯类溶剂溶胀后，再加入乙酰化试剂，回流，进行乙酰化反应10～12h，即得到乙酰胺基修饰的超高交联型吸附树脂；其中，六次甲基四胺的摩尔用量为超高交联型树脂中残余氯摩尔量的2.0～3.0倍，碘化钾与六次甲基四胺等摩尔量。The invention provides a method for preparing an acetamide-modified ultra-high cross-linked adsorption resin. The preparation method is to swell chloromethylated polystyrene through a solvent, use Lewis acid as a catalyst, and heat the resin at 80-85°C Under the temperature condition, carry out Friedel-Crafts reaction 5～8h, after reaction is finished, obtain ultra-high cross-linking type resin; Said ultra-high cross-linking type resin is swollen in the solvent that dissolves hexamethylenetetramine and potassium iodide In the process, at a temperature of 95-105°C, the Delépine reaction is carried out for 8-12 hours. After the Delépine reaction is completed, an amine-modified ultra-high cross-linked resin is obtained; the obtained amine-modified ultra-high cross-linked resin is made of benzene After the solvent is swollen, add an acetylation reagent, reflux, and carry out the acetylation reaction for 10-12 hours to obtain an acetamide-modified ultra-high cross-linked adsorption resin; wherein, the molar amount of hexamethylenetetramine is the ultra-high cross-linked adsorption resin. 2.0 to 3.0 times the molar amount of residual chlorine in the joint resin, and the molar amount of potassium iodide and hexamethylenetetramine is equal.
本发明还包括以下进一步优选的方案：The present invention also includes following further preferred schemes:
所述的Delépine反应得到的胺基修饰的超高交联型树脂残余氯的质量分数为1.25％～2.25％，弱碱交换容量为0.8～1.5mmol/g。The mass fraction of residual chlorine in the amine-modified ultra-high cross-linked resin obtained by the Delépine reaction is 1.25%-2.25%, and the weak base exchange capacity is 0.8-1.5mmol/g.
所述的制备方法中加入的乙酰化试剂中活性乙酰基的摩尔量为胺基修饰的超高交联型树脂的弱碱交换容量的1.5～3.0倍。The molar amount of the active acetyl group in the acetylation reagent added in the preparation method is 1.5-3.0 times of the weak base exchange capacity of the amine-modified ultra-high cross-linked resin.
所述的乙酰化试剂为乙酸酐、乙酰氯或乙酸。The acetylating reagent is acetic anhydride, acetyl chloride or acetic acid.
所述的超高交联型树脂中残余氯的质量百分数为3.35～6.24％。The mass percentage of residual chlorine in the ultra-high cross-linking resin is 3.35-6.24%.
所述的制备方法中溶胀氯甲基化聚苯乙烯采用的溶剂为二氯乙烷、对二氯苯、二氯乙烷中一种，或二氯乙烷与对二氯苯的任意比混合。The solvent used for swelling chloromethylated polystyrene in the preparation method is one of dichloroethane, p-dichlorobenzene, dichloroethane, or a mixture of dichloroethane and p-dichlorobenzene in any ratio .
所述的制备方法中溶胀超高交联型树脂采用的溶剂为N,N’-二甲基甲酰胺；In the described preparation method, the solvent used for swelling the ultra-high cross-linked resin is N,N'-dimethylformamide;
所述的制备方法中溶胀胺基修饰的超高交联型树脂采用的苯类溶剂为甲苯、二甲苯或苯；优选为苯。The benzene solvent used in the swollen amine-modified ultra-high cross-linked resin in the preparation method is toluene, xylene or benzene; preferably benzene.
所述的路易斯酸为FeCl3、AlCl3或SnCl4；路易斯酸的用量为氯甲基化聚苯乙烯质量的20～40％。The Lewis acid is FeCl3 , AlCl3 or SnCl4 ; the amount of the Lewis acid is 20-40% of the mass of chloromethylated polystyrene.
所述的乙酰胺基修饰的超高交联型吸附树脂比表面积为650～950m2/g，孔容为0.38～0.64cm3/g。The specific surface area of the acetamide-modified ultra-high cross-linked adsorption resin is 650-950m2 /g, and the pore volume is 0.38-0.64cm3 /g.
所述的氯甲基化聚苯乙烯通过溶剂溶胀后，在45～55℃下加入路易斯酸催化剂，再升温到80～85℃进行Friedel-Crafts反应。After the chloromethylated polystyrene is swelled by a solvent, a Lewis acid catalyst is added at 45-55° C., and the temperature is raised to 80-85° C. to carry out Friedel-Crafts reaction.
所述的原料氯甲基化聚苯乙烯的氯含量为17.3wt％，交联度为6％。The chlorine content of the raw material chloromethylated polystyrene is 17.3wt%, and the degree of crosslinking is 6%.
本发明还提供了一种所述的制备方法制得的乙酰胺基修饰的超高交联型吸附树脂的应用，该应用是将所述的乙酰胺基修饰的超高交联型吸附树脂应用于选择性吸附水中的极性有机质。The present invention also provides an application of the acetamide-modified ultra-high cross-linking adsorption resin prepared by the preparation method, the application is to apply the acetamide-modified ultra-high cross-linking adsorption resin In the selective adsorption of polar organic matter in water.
所述的极性有机质为苯酚和/或水杨酸。The polar organic matter is phenol and/or salicylic acid.
所述的乙酰胺基修饰的超高交联型吸附树脂中接枝的乙酰胺基越多，越有利于趋向吸附极性较高的极性有机质(如：水杨酸)，接枝乙酰胺基越少，越有利于趋向吸附极性较低的有机质(如：苯酚)。The more acetamide groups grafted in the acetamide-modified ultra-high cross-linked adsorption resin, the more favorable the tendency to adsorb polar organic matter with higher polarity (such as: salicylic acid). Grafting acetamide The fewer groups, the more favorable the tendency to adsorb organic matter with lower polarity (such as: phenol).
所述的乙酰胺基修饰的超高交联型吸附树脂对苯酚类化合物的吸附原理：所述树脂的酰胺基氮原子上有一个氢原子，可与酚类化合物(如：苯酚)的酚羟基通过双重氢键作用形成如下表达式中的六元环结构，可增加树脂对酚类化合物的吸附量和吸附焓。The adsorption principle of the ultra-high cross-linked adsorption resin modified by acetamide group to phenolic compounds: there is a hydrogen atom on the amido nitrogen atom of the resin, which can be combined with the phenolic hydroxyl group of phenolic compounds (such as: phenol) The six-membered ring structure in the following expression is formed through double hydrogen bonding, which can increase the adsorption capacity and adsorption enthalpy of the resin on phenolic compounds.
本发明乙酰胺基修饰的超高交联型吸附树脂的制备方法，其合成的具体制备包括以下步骤：The preparation method of the ultra-high cross-linked adsorption resin modified by acetamide group of the present invention, the concrete preparation of its synthesis comprises the following steps:
1)氯甲基化聚苯乙烯的Friedel-Crafts反应：1) Friedel-Crafts reaction of chloromethylated polystyrene:
将氯甲基化聚苯乙烯加入到溶剂(如：二氯乙烷、对二氯苯、或二氯乙烷与对二氯苯的任意比混合)中浸泡直到溶胀，再升温至45～55℃，加入路易斯酸(如：FeCl3、AlCl3或SnCl4)作为催化剂(路易斯酸的加入量为氯甲基化聚苯乙烯质量的20～40％)，搅拌至完全溶解后，缓慢升温至80～85℃，并在此温度下进行Friedel～Crafts反应5～8h；倾出反应母液，用质量分数为1.0％的盐酸水溶液和无水乙醇交替洗涤，并用无水乙醇抽提树脂8～16h，得到超高交联型树脂；Add chloromethylated polystyrene to a solvent (such as: dichloroethane, p-dichlorobenzene, or a mixture of dichloroethane and p-dichlorobenzene in any ratio) and soak until it swells, then raise the temperature to 45-55 ℃, add a Lewis acid (such as: FeCl3 , AlCl3 or SnCl4 ) as a catalyst (the amount of Lewis acid added is 20-40% of the mass of chloromethylated polystyrene), stir until completely dissolved, then slowly heat up to 80～85℃, and carry out Friedel～Crafts reaction at this temperature for 5～8h; pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid aqueous solution and absolute ethanol, and extract the resin with absolute ethanol for 8～16h , to obtain ultra-high cross-linked resin;
2)胺化反应2) Amination reaction
步骤1)所得的超高交联型树脂用溶有六次甲基四胺(六次甲基四胺摩尔用量为超高交联型树脂中残余氯摩尔量的2.0～3.0倍)和碘化钾(碘化钾的用量与六次甲基四胺等摩尔量)的N,N’-二甲基甲酰胺进行溶胀后，在油浴中升温至95～105℃反应8～12h，倾出母液，依次用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，再用乙醇抽提树脂8～16h，干燥后得到胺基修饰的超高交联型树脂；Step 1) the super-high cross-linking type resin of gained is dissolved with hexamethylenetetramine (the molar consumption of hexamethylenetetramine is 2.0～3.0 times of the residual chlorine molar weight in the super-high cross-linking type resin) and potassium iodide ( The amount of potassium iodide and the molar amount of hexamethylenetetramine) N,N'-dimethylformamide is swollen, and the temperature is raised to 95-105°C in an oil bath to react for 8-12 hours, and the mother liquor is poured out. Wash with 6mol/L hydrochloric acid, water, 10% sodium hydroxide and water for 3 times respectively, then extract the resin with ethanol for 8-16 hours, and obtain an amino-modified ultra-high cross-linked resin after drying;
3)乙酰化反应3) Acetylation reaction
步骤2)所得胺基修饰的超高交联型树脂用苯类溶剂溶胀后，加入乙酰化试剂(乙酰化试剂中的活性乙酰基摩尔量为胺基修饰的超高交联型树脂的弱碱交换容量的1.5～3.0倍)，回流反应10～12h；倾出反应母液，用水冲洗数次，用乙醇抽提12h，干燥后得到乙酰胺基修饰的超高交联型吸附树脂。Step 2) After the amine-modified ultra-high cross-linked resin is swollen with a benzene solvent, add an acetylation reagent (the molar amount of active acetyl groups in the acetylation reagent is the weak base of the amino-modified ultra-high cross-linked resin 1.5 to 3.0 times the exchange capacity), reflux reaction for 10 to 12 hours; pour out the reaction mother liquor, rinse with water several times, extract with ethanol for 12 hours, and dry to obtain acetamide-modified ultra-high cross-linked adsorption resin.
本发明的有益效果：本发明首次通过Friedel-Crafts反应结合Delépine反应和酰胺化反应制得一种具有高比表面积和孔容，且孔径和极性大小适宜的乙酰胺基修饰的超高交联型吸附树脂，将其应用于吸附水溶液中的极性有机质，能对水中溶解度较大的极性有机化合物(如：较弱极性的苯酚和/或较强极性的水杨酸)进行高效选择性吸附效果。本发明先严格控制Friedel-Crafts反应的时间调控超高交联型树脂中残余的氯质量百分含量于3.35～6.24％之间，一方面能将孔结构调节到合适的大小，另一方面为可以控制接枝酰胺基的量；再进一步通过控制Delépine反应条件，接枝引入适量的位阻小的氨基，能对树脂的孔结构(孔径和孔容)进行微调，同时将树脂转换成极性，并有利于下一步酰胺化反应；再此基础上进一步乙酰胺化，不但对孔结构(孔径和孔容)和极性进一步进行精确调控到合适大小，而生成的酰胺基中的仲氨基和羰基能和含羟基的有机质形成相对稳定的六元环的氢键结构，有效增加树脂对含羟基有机质的吸附焓，大大增加了对有机质的吸附量和吸附能力，特别酚类化合物作用明显。本发明的制备方法通过胺化和乙酰化两步修饰，一方面可将树脂极性吸附的吸附位点转移到酰胺基的羰基氧原子上，降低了吸附空间位阻；另一方面通过乙酰胺基的修饰，树脂极性也不强，大大提高了树脂对水溶液中溶解度大的弱极性或极性物质选择吸附的能力。本发明制备方法通过Friedel-Crafts反应，并结合Delépine反应和酰胺化反应获得不同交联程度及接枝程度，可以调控制得的树脂孔结构和极性大小，得到不同孔结构和不同极性的一系列乙酰胺基修饰的超高交联型吸附树脂，调控乙酰胺基含量较多时，对水杨酸等极性较大的物质有较好的吸附性能，调控乙酰胺基含量较少时，对苯酚等极性较弱的有机质有较好的吸附性能。本发明制备方法制得的乙酰胺基修饰的超高交联型吸附树脂吸附后洗脱容易，可重复使用，重复使用效果好，且制备方法操作简单、成本较低，可以工业化生产。Beneficial effects of the present invention: for the first time, the present invention combines the Delépine reaction and the amidation reaction to obtain an ultra-high cross-linked acetamide modified with high specific surface area and pore volume, and suitable pore diameter and polarity. Type adsorption resin, which is applied to adsorb polar organic matter in aqueous solution, can efficiently carry out polar organic compounds with high solubility in water (such as: weaker polar phenol and/or stronger polar salicylic acid) Selective adsorption effect. The present invention first strictly controls the time of the Friedel-Crafts reaction to adjust the mass percentage of residual chlorine in the ultra-high cross-linked resin to be between 3.35% and 6.24%. On the one hand, the pore structure can be adjusted to a suitable size; The amount of grafted amide groups can be controlled; further by controlling the Delépine reaction conditions, grafting introduces an appropriate amount of amino groups with small steric hindrances, which can fine-tune the pore structure (pore size and pore volume) of the resin, and at the same time convert the resin into polarity , and is conducive to the next amidation reaction; further acetamidation on this basis, not only the pore structure (pore size and pore volume) and polarity are further precisely regulated to a suitable size, but the secondary amino groups and The carbonyl group can form a relatively stable six-membered ring hydrogen bond structure with the hydroxyl-containing organic matter, effectively increasing the adsorption enthalpy of the resin on the hydroxyl-containing organic matter, and greatly increasing the adsorption capacity and adsorption capacity of the organic matter, especially the phenolic compounds. The preparation method of the present invention is modified by two steps of amination and acetylation. On the one hand, the adsorption site for polar adsorption of the resin can be transferred to the carbonyl oxygen atom of the amide group, which reduces the steric hindrance of the adsorption; The modification of the base, the polarity of the resin is not strong, which greatly improves the ability of the resin to selectively adsorb weakly polar or polar substances with high solubility in aqueous solution. The preparation method of the present invention obtains different cross-linking degrees and grafting degrees through the Friedel-Crafts reaction, combined with the Delépine reaction and amidation reaction, can adjust the obtained resin pore structure and polarity, and obtain different pore structures and different polarities. A series of ultra-high cross-linked adsorption resins modified by acetamide groups. When the content of acetamide groups is adjusted to be large, it has good adsorption performance for highly polar substances such as salicylic acid. When the content of acetamide groups is adjusted to be small, It has good adsorption performance for organic substances with weak polarity such as phenol. The acetamide-modified ultra-high cross-linked adsorption resin prepared by the preparation method of the invention is easy to elute after adsorption, can be reused, has good repeated use effect, and the preparation method has simple operation, low cost and can be industrialized.
附图说明Description of drawings
【图1】为本发明实施例1中原料氯甲基化聚苯乙烯、中间体超高交联型树脂、胺基修饰的超高交联型树脂及制得的乙酰胺基修饰的超高交联型吸附树脂的红外光谱图；Chloromethylated PS为氯甲基化聚苯乙烯，HP99为超高交联型树脂，HP09为胺基修饰的超高交联型树脂，HP-Y09为乙酰胺基修饰的超高交联型吸附树脂。[Figure 1] is the raw material chloromethylated polystyrene in Example 1 of the present invention, the intermediate ultra-high cross-linked resin, the amino-modified ultra-high cross-linked resin and the obtained acetamide-modified ultra-high cross-linked resin Infrared spectrum of cross-linked adsorption resin; Chloromethylated PS is chloromethylated polystyrene, HP99 is ultra-high cross-linked resin, HP09 is amino-modified ultra-high cross-linked resin, HP-Y09 is acetamide Modified ultra-high cross-linked adsorption resin.
【图2】为本发明实施例1中的中间体超高交联型树脂、胺基修饰的超高交联型树脂及制得的乙酰胺基修饰的超高交联型吸附树脂的孔径分布图：(1)为超高交联型树脂，(2)为胺基修饰的超高交联型树脂，(3)为乙酰胺基修饰的超高交联型吸附树脂。[Figure 2] shows the pore size distribution of the intermediate ultra-high cross-linked resin, amine-modified ultra-high cross-linked resin and the prepared acetamide-modified ultra-high cross-linked adsorption resin in Example 1 of the present invention Figure: (1) is ultra-high cross-linked resin, (2) is amino-modified ultra-high cross-linked resin, (3) is acetamide-modified ultra-high cross-linked adsorption resin.
【图3】为本发明实施例1中原料氯甲基化聚苯乙烯、中间体超高交联型树脂、胺基修饰的超高交联型树脂及制得的乙酰胺基修饰的超高交联型吸附树脂的比表面积、孔容变化趋势图：(1)为氯甲基化聚苯乙烯，(2)为超高交联型树脂，(3)为胺基修饰的超高交联型树脂，(4)为乙酰胺基修饰的超高交联型吸附树脂。[Figure 3] is the raw material chloromethylated polystyrene in Example 1 of the present invention, the intermediate ultra-high cross-linked resin, the amino-modified ultra-high cross-linked resin and the obtained acetamide-modified ultra-high cross-linked resin Trend chart of specific surface area and pore volume of cross-linked adsorption resin: (1) is chloromethylated polystyrene, (2) is ultra-high cross-linked resin, (3) is amino-modified ultra-high cross-linked resin type resin, (4) is an ultra-high cross-linked adsorption resin modified by acetamide groups.
【图4】为本发明实施例1中的中间体超高交联型树脂、胺基修饰的超高交联型树脂及制得的乙酰胺基修饰的超高交联型吸附树脂对苯酚的吸附量比较图：(1)为超高交联型树脂，(2)为胺基修饰的超高交联型树脂，(3)为乙酰胺基修饰的超高交联型吸附树脂。[Fig. 4] is the intermediate ultra-high cross-linked resin in Example 1 of the present invention, the ultra-high cross-linked resin modified by amine groups and the obtained acetamide modified ultra-high cross-linked adsorption resin to phenol Comparison chart of adsorption capacity: (1) is ultra-high cross-linked resin, (2) is amino-modified ultra-high cross-linked resin, (3) is acetamide-modified ultra-high cross-linked adsorption resin.
【图5】为不同脱附剂对吸附了苯酚的本发明实施例1制备的乙酰氨基修饰的超高交联型吸附树脂的静态解吸结果图。[ FIG. 5 ] is a graph showing the static desorption results of different desorbents on the acetamido-modified ultra-high cross-linked adsorption resin prepared in Example 1 of the present invention that adsorbed phenol.
【图6】为本发明实施例1制备的乙酰胺基修饰的超高交联型吸附树脂对苯酚的动态吸附-脱附曲线。[ Fig. 6 ] is the dynamic adsorption-desorption curve of the acetamide-modified ultra-high cross-linked adsorption resin for phenol prepared in Example 1 of the present invention.
【图7】为本发明实施例1制备的乙酰胺基修饰的超高交联型吸附树脂对苯酚的重复吸附脱附使用率结果。[ Fig. 7 ] shows the results of repeated adsorption and desorption of phenol by the acetamide-modified ultra-high cross-linked adsorption resin prepared in Example 1 of the present invention.
具体实施方式Detailed ways
以下实施例旨在说明本发明内容，而不是对本发明保护范围的进一步限定。实施例1The following examples are intended to illustrate the content of the present invention, rather than to further limit the protection scope of the present invention. Example 1
Friedel-Crafts反应：在250mL三口瓶中加入20.0g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入120mL二氯乙烷溶胀剂溶胀过夜；升温至50℃，加入4.0g FeCl3并搅拌直至FeCl3完全溶解后升温至80℃，并在此温度下反应8h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为3.35％，树脂的比表面积为1032.6m2/g，孔容为0.6729cm3/g。Friedel-Crafts reaction: add 20.0g dry chloromethylated polystyrene (chlorine content is 17.3%, crosslinking degree is 6%) in 250mL there-necked flask, then add 120mL dichloroethane swelling agent to swell overnight; Raise the temperature to 50°C, add 4.0g FeCl3 and stir until the FeCl3 is completely dissolved, then raise the temperature to 80°C, and react at this temperature for 8h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 3.35%, the specific surface area of the resin is 1032.6m2 /g, and the pore volume is 0.6729cm3 /g.
胺化反应：在250mL三口瓶中用适量的N,N-二甲基甲酰胺溶解5.3g六次甲基四胺和6.3g碘化钾，加入到20.1g超高交联型树脂中溶胀过夜，在油浴中升温至95℃反应8h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为1.25％，树脂的弱碱交换量为0.8mmol/g，树脂的比表面积为921.3m2/g，孔容为0.5673cm3/g。Amination reaction: Dissolve 5.3g of hexamethylenetetramine and 6.3g of potassium iodide in a 250mL three-necked flask with an appropriate amount of N,N-dimethylformamide, add to 20.1g of ultra-high cross-linked resin to swell overnight, and Heat up to 95°C in an oil bath and react for 8 hours. After the reaction, pour out the mother liquor, wash with 6mol/L hydrochloric acid, water, 10% sodium hydroxide and water for 3 times, extract with ethanol for 12 hours, and transfer out the resin , and vacuum-dried to obtain an amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 1.25%, the weak base exchange capacity of the resin is 0.8mmol/g, the specific surface area of the resin is 921.3m2 /g, and the pore volume is 0.5673cm3 /g.
乙酰化反应：用苯溶胀20.2g胺基修饰的超高交联型树脂过夜，加入25.5mL乙酸酐回流反应10h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为650.8m2/g，孔容为0.3758cm3/g。Acetylation reaction: Swell 20.2 g of amino-modified ultra-high cross-linked resin with benzene overnight, add 25.5 mL of acetic anhydride to reflux for 10 h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 650.8m2 /g, and the pore volume is 0.3758cm3 /g.
从红外图谱(如图1)可以看出，经Friedel-Crafts反应后，氯甲基化聚苯乙烯的红外光谱在1265cm～1处的CH2Cl特征峰大大减弱；经胺化反应后，在3928～3246cm～1处出现较宽的N-H伸缩振动峰，可能与NH2或NH-的N-H拉伸振动有关；在1662cm～1处出现了酰胺基的羰基振动吸收。It can be seen from the infrared spectrum (as shown in Figure 1) that after the Friedel-Crafts reaction, the characteristic peak of CH2 Cl in the infrared spectrum of chloromethylated polystyrene at 1265 cm~ 1 is greatly weakened; after the amination reaction, at A broad NH stretching vibration peak appeared at 3928-3246cm～1 , which may be related to the NH stretching vibration of NH2 or NH-; at 1662cm～1 , the carbonyl vibration absorption of amide group appeared.
从孔径分布图(如图2)中可以看出，乙酰胺基修饰的超高交联型吸附树脂及Friedel-Crafts反应后得到的超高交联型树脂以2～5nm的介孔为主，也有部分大孔，而氯甲基化聚苯乙烯以2～18nm的中孔为主，说明树脂孔结构的变化树脂性能改善的一个重要因素。It can be seen from the pore size distribution diagram (as shown in Figure 2) that the ultra-high cross-linked adsorption resin modified by acetamide group and the ultra-high cross-linked resin obtained after Friedel-Crafts reaction mainly have mesopores of 2-5nm. There are also some macropores, while chloromethylated polystyrene is dominated by mesopores of 2-18nm, which shows that the change of resin pore structure is an important factor for the improvement of resin performance.
从比表面积、孔容变化趋势图(如图3)中可以看出：氯甲基化聚苯乙烯经步骤1)反应后，比表面积由原来的18.02m2/g增加到800～1200m2/g，孔容由原来的几乎为0增加到0.5～0.8cm3/g，之后经步骤2)和3)功能化反应后，比表面和孔容略有减少(比表面积的减少幅度在100～200m2/g，孔容的减少幅度在0.1～0.2cm3/g)。It can be seen from the trend diagram of specific surface area and pore volume (as shown in Figure 3) that after the reaction of chloromethylated polystyrene in step 1), the specific surface area increases from the original 18.02m2 /g to 800-1200m2 /g g, the pore volume increased from almost 0 to 0.5-0.8 cm3 /g, and then after the functionalization reaction in steps 2) and 3), the specific surface and pore volume decreased slightly (the decrease in the specific surface area was between 100 and 200m2 /g, the decrease of pore volume is 0.1～0.2cm3 /g).
实施例2Example 2
Friedel-Crafts反应：在250mL三口瓶中加入20.3g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入120mL对二氯苯溶胀剂溶胀过夜；升温至50℃，加入8.0g AlCl3并搅拌直至AlCl3完全溶解后逐步升温至85℃，并在此温度下反应5h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为6.24％，树脂的比表面积为1045.6m2/g，孔容为0.7929cm3/g。Friedel-Crafts reaction: add 20.3g dry chloromethylated polystyrene (chlorine content is 17.3%, cross-linking degree is 6%) in 250mL there-necked flask, then add 120mL p-dichlorobenzene swelling agent to swell overnight; Raise the temperature to 50°C, add 8.0g AlCl3 and stir until the AlCl3 is completely dissolved, then gradually raise the temperature to 85°C, and react at this temperature for 5h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 6.24%, the specific surface area of the resin is 1045.6m2 /g, and the pore volume is 0.7929cm3 /g.
胺化反应：在250mL三口瓶中加入用适量的N,N-二甲基甲酰胺溶解10.2g六次甲基四胺和12.0g碘化钾，加入到20.5g超高交联型树脂中溶胀过夜，在油浴中升温至105℃反应12h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为2.25％，树脂的弱碱交换量为1.5mmol/g，树脂的比表面积为936.3m2/g，孔容为0.6873cm3/g。Amination reaction: Dissolve 10.2g of hexamethylenetetramine and 12.0g of potassium iodide in a 250mL three-necked flask with an appropriate amount of N,N-dimethylformamide, add to 20.5g of ultra-high cross-linked resin to swell overnight, Heat up to 105°C in an oil bath and react for 12 hours. After the reaction, pour out the mother liquor, wash with 6mol/L hydrochloric acid, water, 10% sodium hydroxide and water for 3 times, extract with ethanol for 12 hours, and transfer out The resin is vacuum-dried to obtain an amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 2.25%, the weak base exchange capacity of the resin is 1.5mmol/g, the specific surface area of the resin is 936.3m2 /g, and the pore volume is 0.6873cm3 /g.
乙酰化反应：用苯溶胀20.0g胺基修饰的超高交联型树脂过夜，加入45.5mL乙酸回流反应10h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为950.8m2/g，孔容为0.5769cm3/g。Acetylation reaction: Swell 20.0 g of amine-modified ultra-high cross-linked resin with benzene overnight, add 45.5 mL of acetic acid to reflux for 10 h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 950.8m2 /g, and the pore volume is 0.5769cm3 /g.
实施例3Example 3
Friedel-Crafts反应：在250mL三口瓶中加入20.0g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入120mL二氯乙烷溶胀剂溶胀过夜；升温至50℃，加入7.0g SnCl4并搅拌直至SnCl4完全溶解后逐步升温至80℃，并在此温度下反应5h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为4.75％，树脂的比表面积为976.5m2/g，孔容为0.6485cm3/g。Friedel-Crafts reaction: add 20.0g dry chloromethylated polystyrene (chlorine content is 17.3%, crosslinking degree is 6%) in 250mL there-necked flask, then add 120mL dichloroethane swelling agent to swell overnight; Raise the temperature to 50°C, add 7.0g SnCl4 and stir until the SnCl4 is completely dissolved, then gradually raise the temperature to 80°C, and react at this temperature for 5h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 4.75%, the specific surface area of the resin is 976.5m2 /g, and the pore volume is 0.6485cm3 /g.
胺化反应：在250mL三口瓶中用适量的N,N-二甲基甲酰胺溶解10.5g六次甲基四胺和11.8g碘化钾，加入到21.0g超高交联型树脂中溶胀过夜，在油浴中升温至100℃反应10h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为2.75％，树脂的弱碱交换量为1.0mmol/g，树脂的比表面积为876.3m2/g，孔容为0.5134cm3/g。Amination reaction: dissolve 10.5g of hexamethylenetetramine and 11.8g of potassium iodide in a 250mL three-necked flask with an appropriate amount of N,N-dimethylformamide, add them to 21.0g of ultra-high cross-linked resin to swell overnight, and Heat up to 100°C in an oil bath and react for 10 hours. After the reaction, pour out the mother liquor, wash with 6mol/L hydrochloric acid, water, 10% sodium hydroxide and water for 3 times, extract with ethanol for 12 hours, and transfer out the resin , and vacuum-dried to obtain an amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 2.75%, the weak base exchange capacity of the resin is 1.0mmol/g, the specific surface area of the resin is 876.3m2 /g, and the pore volume is 0.5134cm3 /g.
乙酰化反应：用苯溶胀20.0g胺基修饰的超高交联型树脂过夜，加入30.5乙酰氯回流反应10h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为760.8m2/g，孔容为0.4138cm3/g。Acetylation reaction: Swell 20.0 g of amine-modified ultra-high cross-linked resin with benzene overnight, add 30.5 acetyl chloride to reflux for 10 h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 760.8m2 /g, and the pore volume is 0.4138cm3 /g.
实施例4Example 4
Friedel-Crafts反应：在250mL三口瓶中加入21.5g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入129mL对二氯苯溶胀剂溶胀过夜；升温至50℃，加入5.0g AlCl3并搅拌直至AlCl3完全溶解后逐步升温至80℃，并在此温度下反应6h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为6.15％，树脂的比表面积为912.6m2/g，孔容为0.5624cm3/g。Friedel-Crafts reaction: add 21.5g dry chloromethylated polystyrene (chlorine content is 17.3%, crosslinking degree is 6%) in 250mL there-necked flask, then add 129mL p-dichlorobenzene swelling agent to swell overnight; Raise the temperature to 50°C, add 5.0g AlCl3 and stir until the AlCl3 is completely dissolved, then gradually raise the temperature to 80°C, and react at this temperature for 6h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 6.15%, the specific surface area of the resin is 912.6m2 /g, and the pore volume is 0.5624cm3 /g.
胺化反应：在250mL三口瓶中适量的N,N-二甲基甲酰胺溶解9.8g六次甲基四胺和11.5g碘化钾，加入到19.9g超高交联型树脂中溶胀过夜，在油浴中升温至95℃反应8h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为1.74％，树脂的弱碱交换量为1.2mmol/g，树脂的比表面积为917.3m2/g，孔容为0.5553cm3/g。Amination reaction: Dissolve 9.8g of hexamethylenetetramine and 11.5g of potassium iodide in an appropriate amount of N,N-dimethylformamide in a 250mL three-necked flask, add to 19.9g of ultra-high cross-linked resin to swell overnight, and dissolve in oil In the bath, the temperature was raised to 95° C. to react for 8 hours. After the reaction, the mother liquor was poured out, washed three times with 6 mol/L hydrochloric acid, water, 10% sodium hydroxide and water respectively, extracted with ethanol for 12 hours, and the resin was transferred out. Vacuum drying to obtain amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 1.74%, the weak base exchange capacity of the resin is 1.2mmol/g, the specific surface area of the resin is 917.3m2 /g, and the pore volume is 0.5553cm3 /g.
乙酰化反应：用苯溶胀20.2g胺基修饰的超高交联型树脂过夜，加入36.0mL乙酸酐回流反应10h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为650.8m2/g，孔容为0.3758cm3/g。Acetylation reaction: Swell 20.2 g of amino-modified ultra-high cross-linked resin with benzene overnight, add 36.0 mL of acetic anhydride to reflux for 10 h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 650.8m2 /g, and the pore volume is 0.3758cm3 /g.
实施例5Example 5
Friedel-Crafts反应：在250mL三口瓶中加入20.0g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入120mL二氯乙烷与对二氯苯的混合溶液(体积比1:1)胀剂溶胀过夜；升温至50℃，加入4.0g SnCl4并搅拌直至SnCl4完全溶解后逐步升温至80℃，并在此温度下反应5h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为5.35％，树脂的比表面积为916.6m2/g，孔容为0.5749cm3/g。Friedel-Crafts reaction: add 20.0g dry chloromethylated polystyrene (chlorine content is 17.3%, cross-linking degree is 6%) in 250mL there-necked flask, then add 120mL dichloroethane and p-dichlorobenzene The mixed solution (volume ratio 1:1) was swollen overnight; the temperature was raised to 50°C, 4.0g of SnCl4 was added and stirred until the SnCl4 was completely dissolved, then the temperature was gradually raised to 80°C, and the reaction was carried out at this temperature for 5h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 5.35%, the specific surface area of the resin is 916.6m2 /g, and the pore volume is 0.5749cm3 /g.
胺化反应：在250mL三口瓶中适量的N,N-二甲基甲酰胺溶解8.6g六次甲基四胺和10.2g碘化钾，加入到20.3g超高交联型树脂中溶胀过夜，在油浴中升温至95℃反应8h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为1.85％，树脂的弱碱交换量为1.4mmol/g，树脂的比表面积为869.3m2/g，孔容为0.4693cm3/g。Amination reaction: Dissolve 8.6g of hexamethylenetetramine and 10.2g of potassium iodide in an appropriate amount of N,N-dimethylformamide in a 250mL three-necked flask, add to 20.3g of ultra-high cross-linked resin to swell overnight, and dissolve in oil In the bath, the temperature was raised to 95° C. to react for 8 hours. After the reaction, the mother liquor was poured out, washed three times with 6 mol/L hydrochloric acid, water, 10% sodium hydroxide and water respectively, extracted with ethanol for 12 hours, and the resin was transferred out. Vacuum drying to obtain amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 1.85%, the weak base exchange capacity of the resin is 1.4mmol/g, the specific surface area of the resin is 869.3m2 /g, and the pore volume is 0.4693cm3 /g.
乙酰化反应：用苯溶胀20.0g胺基修饰的超高交联型树脂过夜，加入42.5mL乙酸酐回流反应11h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为871.6m2/g，孔容为0.4377cm3/g。Acetylation reaction: Swell 20.0 g of amine-modified ultra-high cross-linked resin with benzene overnight, add 42.5 mL of acetic anhydride to reflux for 11 h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 871.6m2 /g, and the pore volume is 0.4377cm3 /g.
实施例6Example 6
Friedel-Crafts反应：在250mL三口瓶中加入21.0g干燥的氯甲基化聚苯乙烯(含氯量为17.3％，交联度为6％)，然后加入126mL二氯乙烷溶胀剂溶胀过夜；升温至50℃，加入6.0g FeCl3并搅拌直至FeCl3完全溶解后逐步升温至82℃，并在此温度下反应7h。反应完成后，倾出反应母液，用质量分数1.0％的盐酸溶液和无水乙醇交替洗涤，直至洗出液澄清，再转移至索氏提取器中，用无水乙醇抽提12h，干燥后得到超高交联型树脂。树脂的残余氯含量为4.55％，树脂的比表面积为932.5m2/g，孔容为0.5879cm3/g。Friedel-Crafts reaction: add 21.0g dry chloromethylated polystyrene (chlorine content is 17.3%, cross-linking degree is 6%) in 250mL there-necked flask, then add 126mL dichloroethane swelling agent to swell overnight; Raise the temperature to 50°C, add 6.0g FeCl3 and stir until the FeCl3 is completely dissolved, then gradually raise the temperature to 82°C, and react at this temperature for 7h. After the reaction is completed, pour out the reaction mother liquor, alternately wash with 1.0% hydrochloric acid solution and absolute ethanol until the eluate is clear, then transfer to a Soxhlet extractor, extract with absolute ethanol for 12 hours, and dry to obtain Super high cross-linked resin. The residual chlorine content of the resin is 4.55%, the specific surface area of the resin is 932.5m2 /g, and the pore volume is 0.5879cm3 /g.
胺化反应：在250mL三口瓶中加入适量的N,N-二甲基甲酰胺溶解7.2g六次甲基四胺和8.5g碘化钾，加入到19.8g超高交联型树脂中溶胀过夜，在油浴中升温至95℃反应8h，反应结束后，倾出母液，用6mol/L盐酸、水、质量分数10％的氢氧化钠、水分别洗涤3遍，用乙醇抽提12h，转出树脂，真空干燥得到胺基修饰的超高交联型树脂。树脂的残余氯含量为1.75％，树脂的弱碱交换量为0.9mmol/g，树脂的比表面积为908.3m2/g，孔容为0.4872cm3/g。Amination reaction: Add appropriate amount of N,N-dimethylformamide to dissolve 7.2g of hexamethylenetetramine and 8.5g of potassium iodide in a 250mL three-necked flask, add to 19.8g of ultra-high cross-linked resin to swell overnight, and Heat up to 95°C in an oil bath and react for 8 hours. After the reaction, pour out the mother liquor, wash with 6mol/L hydrochloric acid, water, 10% sodium hydroxide and water for 3 times, extract with ethanol for 12 hours, and transfer out the resin , and vacuum-dried to obtain an amino-modified ultra-high cross-linked resin. The residual chlorine content of the resin is 1.75%, the weak base exchange capacity of the resin is 0.9mmol/g, the specific surface area of the resin is 908.3m2 /g, and the pore volume is 0.4872cm3 /g.
乙酰化反应：用苯溶胀20.5g胺基修饰的超高交联型树脂过夜，加入50.5mL乙酸酐回流反应12h。倾出反应母液，用水洗涤3遍，最后用无水乙醇抽提12h，真空干燥后得到乙酰胺基修饰的超高交联型吸附树脂。树脂的比表面积为721.8m2/g，孔容为0.4633cm3/g。Acetylation reaction: Swell 20.5g of amino-modified ultra-high cross-linked resin with benzene overnight, add 50.5mL of acetic anhydride to reflux for 12h. The reaction mother liquor was poured out, washed with water for 3 times, and finally extracted with absolute ethanol for 12 hours, and vacuum-dried to obtain an acetamide-modified ultra-high cross-linked adsorption resin. The specific surface area of the resin is 721.8m2 /g, and the pore volume is 0.4633cm3 /g.
实施例7Example 7
静态吸附脱附实验：取一组6个具塞锥形瓶，向其中分别加入0.10g实施例1制备的树脂和50.00mL相同浓度的苯酚溶液。将它们置于旋转水浴振荡器中，于298K下恒温振荡6h，使吸附达到平衡。用紫外可见光谱仪在苯酚的最大吸收波长处测定吸附后残液的吸光度值，转化为吸附达到平衡后的苯酚的浓度，得到平衡吸附量。Static adsorption-desorption experiment: Take a group of 6 Erlenmeyer flasks with stoppers, and add 0.10 g of the resin prepared in Example 1 and 50.00 mL of phenol solution of the same concentration into them respectively. They were placed in a rotating water bath shaker and oscillated at a constant temperature of 298K for 6h to allow the adsorption to reach equilibrium. Measure the absorbance value of the raffinate after adsorption at the maximum absorption wavelength of phenol with a UV-visible spectrometer, convert it into the concentration of phenol after the adsorption reaches equilibrium, and obtain the equilibrium adsorption amount.
将吸附后的残液倒掉，并加入10mL蒸馏水洗涤，浆水倒净后加入不同乙醇和NaOH组成的脱附剂，置于298K恒温振荡器中振荡6h，使脱附达到平衡。测定洗脱液中苯酚的含量，计算各洗脱液在298K下的洗脱率(％)，得到图5所示的静态解析图。Pour off the residual liquid after adsorption, and add 10 mL of distilled water to wash, pour out the slurry, add desorbents composed of different ethanol and NaOH, place in a 298K constant temperature oscillator and shake for 6 hours to make the desorption reach equilibrium. The content of phenol in the eluents was measured, and the elution rate (%) of each eluent at 298K was calculated to obtain the static analysis diagram shown in FIG. 5 .
动态吸附-脱附实验：量取9.8mL干燥的实施例1制得的树脂，置于乙醇水溶液中浸泡，过夜。之后量取10mL浸泡好的树脂转移到玻璃柱中，敲紧装实。将一定浓度的苯酚溶液流过交换柱进行吸附，控制管口流速不变，用自动部份收集器收集流出液，测定其吸光度。当流出液中苯酚的浓度与原液的浓度相同后，停止吸附。以床体积数为横坐标，流出液吸光度与原液吸光度之比为横坐标，绘制动态吸附曲线。用静态解析效果最好的洗脱剂洗涤已吸附饱和的树脂，直至流出液中几乎无苯酚检出为止。同样定时测定流出液的吸光度，以床体积为横坐标、流出液浓度为纵坐标绘制动态脱附曲线。Dynamic adsorption-desorption experiment: Measure 9.8 mL of the dried resin prepared in Example 1, soak in ethanol aqueous solution overnight. Then measure 10mL of soaked resin and transfer it to a glass column, tap it tightly and pack it firmly. Flow a certain concentration of phenol solution through the exchange column for adsorption, control the flow rate of the nozzle to remain constant, collect the effluent with an automatic partial collector, and measure its absorbance. When the concentration of phenol in the effluent is the same as that of the stock solution, the adsorption is stopped. Take the bed volume as the abscissa, and the ratio of the absorbance of the effluent to the absorbance of the stock solution as the abscissa, and draw the dynamic adsorption curve. Wash the saturated resin with the eluent with the best static analysis effect until almost no phenol is detected in the effluent. The absorbance of the effluent is also measured regularly, and the dynamic desorption curve is drawn with the bed volume as the abscissa and the effluent concentration as the ordinate.
重复吸附脱附使用率实验：在具塞锥形瓶加入0.10g实施例1制备的树脂和50.00mL一定浓度的苯酚溶液，重复五次静态吸附脱附的实验，测定实验苯酚的吸附和脱附能力，得到图7所示的重复吸附脱附使用率图。Repeated adsorption and desorption utilization rate experiment: add 0.10g of the resin prepared in Example 1 and 50.00mL of a certain concentration of phenol solution to a conical flask with a stopper, repeat the experiment of static adsorption and desorption for five times, and measure the adsorption and desorption of experimental phenol Capacity, get the repeated adsorption and desorption utilization rate diagram shown in Figure 7.
从图5可以看出，随着乙醇体积分数的增大或NaOH浓度的增大，乙酰氨基修饰的超高交联型吸附树脂对苯酚静态解吸率增大。NaOH和乙醇的混合溶液解吸效果优于单独的乙醇或NaOH。当NaOH浓度为0.1mol/L、乙醇体积分数为50％的溶液作为脱附剂时，解吸率可达99.33％。It can be seen from Figure 5 that with the increase of the volume fraction of ethanol or the concentration of NaOH, the static desorption rate of phenol by the acetamido-modified ultra-high cross-linked adsorption resin increases. The desorption effect of the mixed solution of NaOH and ethanol is better than ethanol or NaOH alone. When the solution with NaOH concentration of 0.1mol/L and ethanol volume fraction of 50% was used as the desorption agent, the desorption rate could reach 99.33%.
从图6中可以看出：苯酚初始浓度1000mg/L，流速4.8BV/h，在90.2BV处泄露，在122.0BV处吸附饱和，表现出很好的吸附性能。而且吸附了苯酚的树脂可用0.01mol/L的NaOH、50％的乙醇溶液脱附，在8.0BV时洗脱基本完全，在装柱使用过程中，树脂机械强度良好，未出现破损，可重复使用。It can be seen from Figure 6 that: the initial concentration of phenol is 1000mg/L, the flow rate is 4.8BV/h, the leakage is at 90.2BV, and the adsorption is saturated at 122.0BV, showing good adsorption performance. Moreover, the resin that has adsorbed phenol can be desorbed with 0.01mol/L NaOH and 50% ethanol solution, and the elution is basically complete at 8.0BV. During the use of the column, the resin has good mechanical strength and no damage, and can be reused .
该树脂对苯酚经过吸附-脱附-再吸附-再脱附循环使用后，树脂呈现良好的再生和重复使用性能。After the resin is recycled to phenol through adsorption-desorption-re-adsorption-re-desorption, the resin exhibits good regeneration and reuse performance.
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