CN117123195A - 一种改性聚合物微球及其制备方法和应用 - Google Patents
一种改性聚合物微球及其制备方法和应用 Download PDFInfo
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- CN117123195A CN117123195A CN202311185337.XA CN202311185337A CN117123195A CN 117123195 A CN117123195 A CN 117123195A CN 202311185337 A CN202311185337 A CN 202311185337A CN 117123195 A CN117123195 A CN 117123195A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供一种改性聚合物微球的制备方法及应用，是以含活泼氢的多孔聚合物微球材料为基体对微球改性，合成含叔胺的聚合物微球，并将该微球应用于胆红素、肌酐等人体内源性有毒化合物以及黄酮、多酚、生物碱等天然产物的吸附分离。本发明方法合成的材料条件温和、胺基修饰量可调，并且合成过程中不使用有毒致癌试剂如四氯化碳、氯甲醚等，能够高效吸附胆红素、肌酐等人体内源性有毒化合物以及黄酮、多酚以及生物碱等天然产物。
Description
技术领域
本发明属于吸附分离材料制备及应用技术领域，具体涉及一种改性聚合物微球及其制备方法和应用。
背景技术
含氮聚合物微球因其具有极强的化学稳定性、耐热性能和耐酸碱性能、粒径和孔径可调以及表面易修饰等优点，被广泛地应用于天然产物如黄酮、多酚等分离纯化以及胆红素、肌酐的吸附。目前，含氮功能化聚合物微球的合成主要有两种方法：直接合成法和后改性法。其中直接合成法是将带含氮官能基团的可聚合单体直接与聚合单体和交联剂直接聚合，论文Petroleum Science and Technology(2019，37(14)：1691-1703)以4-乙烯基苯胺为功能单体、二乙烯基苯为交联剂合成聚(4-乙烯基苯胺-二乙烯基苯)分子印迹聚合物，用于选择性吸附燃料中的吡啶。此方法能够引入含氮功能基团，但具有含氮功能基团的可聚合单体数量较少，导致含氮功能化聚合物微球的种类少。后改性法首先利用傅-克反应在聚合物微球表面引入氯甲基，然后再将不同的含氮功能基团键合到聚合物微球上。此方法虽能够将不同的含氮基团引入到聚合物微球上，但是在氯甲基化过程中会使用有毒致癌试剂-氯甲醚，污染环境。
发明内容
本发明提供一种改性聚合物微球及其制备方法和应用，以含活泼氢的聚合物微球为基体，在聚合物微球上引入含氮官能团，再将所制备的改性聚合物微球用于胆红素、肌酐等人体内源性有毒化合物以及黄酮、多酚等天然产物吸附分离。
本发明所提供的改性聚合物微球，其制备方法如下：
1)将含活泼氢的聚合物微球加入到溶胀溶液中进行溶胀，调节溶液的pH至酸性；
所含活泼氢的聚合物微球为含羰基、醛基或酯基官能团的聚合物微球，
所述聚合物微球是聚苯乙烯类、聚丙烯酸酯类或天然多糖类微球，
溶胀溶液包括但不限于甲醇、乙醇、乙腈、四氢呋喃、N,N-二甲基甲酰胺等
2)取胺基化合物，调节其pH至酸性；取醛基化合物，调节其pH至酸性；
所述胺基化合物包括但不限于伯胺或者仲胺化合物，如甲胺、二甲胺、二乙胺等；所述醛基化合物包括但不限于甲醛、乙醛等醛基化合物；
所述醛基化合物和胺基化合物的摩尔比为1：1～5；
3)将步骤2)的溶液依次加入到步骤1)的溶液中进行反应，反应后过滤、洗涤、真空干燥得到改性聚合物微球；
所述反应条件是温度20～100℃，反应时间为1～24h。
本发明所获得的改性聚合物微球用于吸附水中的胆红素、肌酐、黄酮、多酚以及生物碱类化合物。
本发明所制备的改性聚合物微球可显著提高氮含量，操作简单，反应条件温和。该改性聚合物微球既可应用于胆红素、肌酐等人体内源性有毒化合物的选择性吸附分离，也可应用于黄酮、多酚以及生物碱等天然产物的吸附分离。
附图说明
图1：改性聚合物微球的XPS图；
图2：改性聚合物微球的FT-IR图；
图3：改性聚合物微球的N2吸/脱附曲线图；
图4：改性聚合物微球的SEM图。
具体实施方式
本发明所提供的改性聚合物微球，其制备方法如下：
1)称取一定量的含活泼氢的聚合物微球于溶液中溶胀，调节溶液的pH至酸性；
所述聚合物微球是聚苯乙烯类、聚丙烯酸酯类、天然多糖类微球，并且所述微球粒径为1～2000μm；含活泼氢的聚合物微球为含羰基、醛基、酯基等官能团的微球，羰基、醛基、酯基等官能团的微球可以是直接聚合到微球，也可以是通过后修饰的方法键合到微球上；溶胀溶液包括但不限于甲醇、乙醇、乙腈、四氢呋喃、N,N-二甲基甲酰胺等。
2)取一定量的胺基化合物，调节其pH至酸性；另取一定量的醛基化合物，调节其pH至酸性；
所述胺基化合物包括但不限于伯胺或者仲胺化合物，如甲胺、二甲胺、二乙胺等；所述醛基化合物包括但不限于甲醛、乙醛等醛基化合物；所述醛基化合物和胺基化合物的摩尔比为1：(1～5)。
3)将步骤2)的溶液依次加入到步骤1)的溶液中，在一定条件下反应，后过滤、洗涤、真空干燥得反应改性聚合物微球；
所述反应条件是温度20～100℃，反应时间为1～24h。
4)取步骤3)所得改性聚合物微球吸附水中的胆红素、肌酐、黄酮、多酚以及生物碱类化合物。
所提供的改性聚合物微球在吸附水溶液中化合物或天然产物中的应用；所述化合物或天然产物为胆红素、肌酐、黄酮、多酚、生物碱等。
下面通过具体实施例和附图对本发明进行详细的描述。
实施例1：改性聚合物微球的合成
(1)称取1g 2μm PS微球加入70mL 0.35％十二烷基磺酸钠水溶液中，超声分散10min，取2g邻苯二甲酸二甲酯于80mL 0.35％十二烷基磺酸钠水溶液中乳化，然后将两溶液混合于500mL三口圆底烧瓶中，室温溶胀；称取10g苯乙烯、10g二乙烯基苯、5g丙烯酸、10g二甲苯和0.9g偶氮二异丁腈超声溶解，再加入到100mL 0.35％十二烷基磺酸钠水溶液中乳化，将此溶液倒入反应器中，室温继续溶胀；加入70mL 5％聚乙烯吡络烷酮水溶液，氮气保护，升温至80℃反应24h；反应结束后，过滤，用水和乙醇反复冲洗数次，用四氢呋喃索氏提取24h后含活泼氢的5μm左右聚合物微球；
(2)取5g含活泼氢的5μm左右聚合物微球用N,N-二甲基甲酰胺溶胀并调节pH至酸性，取0.1mol甲醛溶液调节pH至酸性，取0.2mol二甲胺调节pH至酸性，上述溶液混合后90℃反应8h，反应结束后用碱性溶液、乙醇和去离子水洗涤至中性，真空干燥得改性聚合物微球。
对改性聚合物微球进行检测，图1XPS表征出现N原子峰，说明经过改性之后在微球上引入了N原子；图2FT-IR表征结果可以看到，3448cm-1处为-OH吸收峰，其可能来源于水，1692cm-1处为羰基，1174cm-1处为C-N吸收峰，以上表征结果说明反应改性聚合物微球成功合成。图3的N2吸脱附曲线为Ⅳ型等温线，具有介孔结构，其比表面积为480.60m2/g，平均孔径为6.00nm。从图4(a)的SEM图中看出合成的材料为规则球形且粒径均一，重复性好。
实施例2：改性聚合物微球的合成
(1)称取1g 5μm PS微球加入70mL 0.35％十二烷基磺酸钠水溶液中，超声分散10min，取2g邻苯二甲酸二甲酯于80mL 0.35％十二烷基磺酸钠水溶液中乳化，然后将两溶液混合于500mL三口圆底烧瓶中，室温溶胀；称取10g丙烯酸甲酯、10g乙二醇二甲基丙烯酸酯、10g环己醇和0.9g偶氮二异丁腈超声溶解，再加入到100mL 0.35％十二烷基磺酸钠水溶液中乳化，将此溶液倒入反应器中，室温继续溶胀；加入70mL 5％聚乙烯醇水溶液，氮气保护，升温至80℃反应24h；反应结束后，过滤，用水和乙醇反复冲洗数次，用四氢呋喃索氏提取24h后含活泼氢的10μm左右聚合物微球。
(2)取5g含活泼氢的10μm左右聚合物微球用乙醇溶胀并调节pH至酸性，取0.1mol甲醛溶液调节pH至酸性，取0.2mol二甲胺调节pH至酸性，上述溶液混合后75℃反应10h，反应结束后用碱性溶液、乙醇和去离子水洗涤至中性，真空干燥得反应改性聚合物微球。从图4(b)的SEM图中看出合成的材料为规则球形且粒径均一，重复性好。
实施例3：改性聚合物微球的合成
(1)称取1g 15μm PS微球加入70mL 0.35％十二烷基磺酸钠水溶液中，超声分散10min，取2g邻苯二甲酸二甲酯于80mL 0.35％十二烷基磺酸钠水溶液中乳化，然后将两溶液混合于500mL三口圆底烧瓶中，室温溶胀；称取10g苯乙烯、10g二乙烯基苯、10g二甲苯和0.9g偶氮二异丁腈超声溶解，再加入到100mL 0.35％十二烷基磺酸钠水溶液中乳化，将此溶液倒入反应器中，室温继续溶胀；加入70mL 5％聚乙烯醇水溶液，氮气保护，升温至80℃反应24h；反应结束后，过滤，用水和乙醇反复冲洗数次，用四氢呋喃索氏提取24h后含活泼氢的40μm左右聚合物微球。
(2)取15g聚苯乙烯-二乙烯基苯微球用二氯甲烷溶胀过夜，后加入1.5mol氯化铝和0.5mol氯乙酰氯，室温反应6h，反应结束后，过滤、洗涤、干燥得氯甲基化聚苯乙烯-二乙烯基苯；取10g氯甲基化聚苯乙烯-二乙烯基苯微球用N,N-二甲基甲酰胺溶胀过夜，加入2g吡络烷酮，80℃反应12h，反应结束后过滤、洗涤、干燥得吡络烷酮修饰的聚苯乙烯-二乙烯基苯微球。
(3)取5g吡络烷酮修饰的聚苯乙烯-二乙烯基苯微球用乙腈溶胀并调节pH至酸性，取0.1mol乙醛溶液调节pH至酸性，取0.2mol二乙胺调节pH至酸性，上述溶液混合后70℃反应12h，反应结束后用碱性溶液、乙醇和去离子水洗涤至中性，真空干燥得反应改性聚合物微球。从图4(c)的SEM图中看出合成的材料为规则球形且粒径均一，重复性好。
实施例4化合物吸附
胆红素首先用少量0.1mol/L NaOH溶液和DMSO溶解，再利用pH为7.4的PBS溶液配制成浓度为0.1mg/mL样品溶液，芦丁、杨梅素、褪黑素和阿托品用20％乙腈水溶液配置成浓度为0.2mg/mL的样品溶液。分别取上述实施例中的材料0.05g于锥形瓶中，并加入50mL配制的溶液于摇床(35℃，120r/min)中吸附，其中胆红素吸附过程中避光。吸附完成后测吸附残液的浓度，计算吸附量和吸附率。吸附量和吸附率如下表1所示。
表1：材料对不同化合物的吸附量和吸附率表
实施例5橄榄苦苷分离
取100g油橄榄叶，分别用60％乙醇提取两次后，合并提取液，旋蒸后定容至1000mL(橄榄苦苷含量为11.40％)，取10g材料湿法装柱，上样体积和流速控制为4BV和2BV/h。吸附完成后，用10BV水洗，之后用3BV 60％乙醇解吸附，洗脱流速为2BV/h，解吸附完毕后，测定解吸液中橄榄苦苷的含量(表2)。
表2：材料分离纯化橄榄苦苷
综上，本发明的改性聚合物微球相比于于改性前的微球，能够更高效的吸附水中的胆红素、肌酐、黄酮、多酚以及生物碱类化合物。
Claims (10)
1.一种改性聚合物微球，其特征在于，所述的改性聚合物微球的制备方法如下：
1)将含活泼氢的聚合物微球加入到溶胀溶液中进行溶胀，调节溶液的pH至酸性；
2)取胺基化合物，调节其pH至酸性；取醛基化合物，调节其pH至酸性；
3)将步骤2)的溶液依次加入到步骤1)的溶液中进行反应，反应后过滤、洗涤、真空干燥得到改性聚合物微球。
2.如权利要求1所述的改性聚合物微球，其特征在于，所述的1)中含活泼氢的聚合物微球为含羰基、醛基或酯基官能团的聚合物微球。
3.如权利要求2所述的改性聚合物微球，其特征在于，所述的聚合物微球是聚苯乙烯类、聚丙烯酸酯类或天然多糖类微球。
4.如权利要求1所述的改性聚合物微球，其特征在于，所述的1)中的溶胀溶液为甲醇、乙醇、乙腈、四氢呋喃或N,N-二甲基甲酰胺。
5.如权利要求1所述的改性聚合物微球，其特征在于，所述的2)中的胺基化合物为伯胺或者仲胺化合物。
6.如权利要求1所述的改性聚合物微球，其特征在于，所述的2)中所述醛基化合物为甲醛或乙醛。
7.如权利要求1所述的改性聚合物微球，其特征在于，所述的3)中反应条件是温度20～100℃，反应时间为1～24h。
8.权利要求1所述的改性聚合物微球在制备用于吸附水体中胆红素、肌酐、黄酮、多酚或生物碱类化合物的制品中的应用。
9.权利要求1所述的改性聚合物微球在吸附水体中胆红素、肌酐、黄酮、多酚或生物碱类化合物中的应用。
10.一种用于吸附水体中胆红素、肌酐、黄酮、多酚或生物碱类化合物的制品，其特征在于，所述的制品中包含有权利要求1所述的改性聚合物微球。
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