CN110681416B - 一种含磺酸基磁性聚合物微球及其制备方法与应用 - Google Patents
一种含磺酸基磁性聚合物微球及其制备方法与应用 Download PDFInfo
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Abstract
一种含磺酸聚合物磁性微球及其制备方法与应用,所述含磺酸聚合物磁性微球以Fe3O4磁簇为核,共价键连接磺酸基的交联聚合物为壳,酸密度≥1.94mmol·g‑1,且磁饱和强度≥18emu·g‑1。本发明还提供所述含磺酸聚合物磁性微球的制备方法与应用。本发明之含磺酸基磁性聚合物微球的制备方法简单、耗时短,所制得含磺酸基磁性聚合物微球酸密度高、磁饱和强度大且稳定性好,作为固体酸催化剂,具有环境友好、催化活性高及可磁分离循环使用等优点,可广泛应用于生物柴油合成和平台化合物制备等领域。
Description
技术领域
本发明涉及一种含磺酸基磁性聚合物微球及其制备方法与应用。
背景技术
固体酸催化具有反应条件温和,设备腐蚀较少,产生废液少等优点。但是,随着固体酸催化剂逐渐向纳米尺度发展,传统的分离手段(如离心、过滤等)已经很难实现催化剂的快速分离回收。磁性粒子负载固体酸催化剂后,在保持其酸催化活性的同时赋予其磁分离性,既降低了催化成本,又简化了催化反应的后处理工艺,在提高催化效率和产品纯度方面具有明显的优势。申请号为201310226222.0的专利申请以废弃的生物质材料为原料,通过吸附铁离子,再经过热解制备磁性多孔碳前体,然后再进行磺化,从而制备出磁性固体酸。申请号为201810204038.9的专利申请采用“一锅法”制备了硅基磁性固体磺酸负载二元胺的复合催化剂。但是,磁性碳基或硅基固体酸的制备工艺复杂、成本较高;而且,碳基固体酸的酸密度较低、且容易脱落,二氧化硅水热稳定性和耐碱较差。申请号为201810648588.X的专利申请将磺化氧化石墨烯和磁性四氧化三铁纳米颗粒均匀分散于纤维素基体中,再通过反向悬浮法固定化成球,制备得到磁性纤维素基固体酸催化剂;申请号为201810454430.9专利申请采用悬浮法制备了一种磺酸基修饰的均粒磁性微球;使用了表面活性剂作为稳定剂,微球洁净度较差;且制备过程复杂,成本较高。
交联聚合物包覆磁性粒子而成的聚合物磁性固体酸,可克服上述缺陷;且聚合物易于修饰。Feyen等通过对包裹四氧化三铁的聚苯乙烯纳米球进行磺化,制备的磁性固体酸的酸强度为2.2-2.5mmol H+/g(Feyen et al.,Chemistry of Materials,2010,22(9),2955-2961);Zillillah等对含有纳米磁性核的多种聚合物微球进行磺化,合成了一系列的磁性固体酸(Zillillah et al.,Green Chemistry,2012,14,3077-3086)。这些聚合物磁性固体酸表现出较高的催化性能和良好的分离能力;但是需要经过聚合、磺化等多个步骤,制备过程复杂,酸腐蚀难以避免,导致难以大规模生产和商业化应用。
发明内容
本发明所要解决的技术问题是,提供一种酸密度高、稳定性好和磁分离性好的含磺酸基磁性聚合物微球。
进一步,本发明所要解决的技术问题是,提供一种不需要酸化或磺化、反应条件温和的含磺酸基磁性聚合物微球的制备方法。
进一步,本发明所要解决的技术问题是,所述含磺酸基磁性聚合物微球在制备生物柴油和平台化合物中的应用,催化活性高,且可磁分离回收循环使用。
本发明解决其技术问题所采用的技术方案是:
一种含磺酸聚合物磁性微球,以Fe3O4磁簇为核,共价键连接磺酸基的交联聚合物为壳,酸密度≥1.94mmol·g-1,且磁饱和强度≥18emu·g-1。
所述含磺酸聚合物磁性微球的制备方法,包括如下步骤:
将含磺酸烯类单体、基体单体、交联单体和改性Fe3O4磁簇加入溶剂中,配制单体混合溶液;在单体混合溶液中加入引发剂,机械搅拌并加热至回流,回流开始后体系逐渐泛白,反应一定时间后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并回收处理,在下层固体物中加入无水乙醇超声分散、洗涤,再磁分离,如此反复洗涤,干燥得到含磺酸聚合物磁性微球。
需要进一步说明的是,所述上清液采用蒸馏回收,可减少废液污染,降低原料成本;所述机械搅拌转速约为300r/min;所述加热采用油浴加热;所述干燥包括冷冻干燥和真空干燥。
进一步,所述含磺酸烯类单体为2-丙烯酰氨基-2-甲基-1-丙烷磺酸(AMPS)、2-丙烯酰胺基十六烷磺酸(AMC16S)、2-丙烯酰胺基十二烷磺酸(AMC12S)和2-丙烯酰胺基十四烷磺酸(AMC14S)中至少一种。
进一步,所述基体单体为苯乙烯、丙烯酸、甲基丙烯酸中至少一种。
进一步,所述交联单体为二乙烯基苯。
进一步,所述改性Fe3O4磁簇是用含乙烯基的硅烷偶联剂对Fe3O4磁簇进行表面改性。
进一步,所述溶剂为单一溶剂或混合溶剂。单一溶剂为乙醇、乙腈、苯或甲苯;混合溶剂为不同比例的乙腈-乙醇、乙醇-苯、乙腈-甲苯、乙醇-甲苯的组合物。
进一步,所述引发剂为偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈和过氧化二苯甲酰中至少一种。
进一步,所述含磺酸烯类单体、交联单体、基体单体的质量比为20~50:20~40:10~60。
进一步,所述含磺酸烯类单体、交联单体、基体单体的总浓度为0.1wt%~5wt%。
进一步,所述改性Fe3O4磁簇的用量为单体总用量的5wt%~40wt%。
进一步,所述引发剂的用量为单体总用量的0.5wt%~5wt%。
进一步,加热的温度为60~120℃,回流反应的时间为0.5~5h。
本发明还提供了所述含磺酸聚合物磁性微球的应用,该应用是将含磺酸聚合物磁性微球作为磁性固体酸催化剂,应用于生物柴油制备、生物质转化和平台化合物合成。
本发明的有益效果:
(1)本发明将含磺酸烯类单体直接在磁簇表面共聚,包裹形成含磺酸基磁性聚合物微球,磺酸基含量高,且通过共价键连接、不易脱落、稳定性好;
(2)本发明采用的简单的一步回流沉淀聚合,不需要经过酸化或磺化,避免了酸腐蚀,反应简单易控制;
(3)本发明所得到的含磺酸基磁性聚合物微球可以作为固体酸催化剂,对反应器腐蚀少,易磁分离回收,可循环利用;
(4)本发明的产品可广泛应用于生物柴油制备、生物质转化和平台化合物合成等领域。
附图说明
图1为实施例1中含磺酸基磁性聚合物微球的TEM照片;
图2为实施例2中含磺酸基磁性聚合物微球的FT-IR光谱;
图3为实施例3中含磺酸基磁性聚合物微球的VSM曲线。
具体实施方式
以下结合附图及实施例对本发明作进一步说明。
实施例1
将0.135g改性Fe3O4磁簇、0.300g 2-丙烯酰氨基-2-甲基-1-丙烷磺酸、0.800g丙烯酸、0.250g二乙烯基苯加入40mL乙腈-乙醇(4:1,v)中,超声分散溶解2分钟,配制单体混合溶液;在单体混合溶液中加入0.0270g偶氮二异丁腈,机械搅拌(300r/min),并用油浴加热至80℃,回流开始后体系逐渐泛白,反应3h后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并蒸馏收集乙醇和乙腈;在下层固体物中加入无水乙醇,超声分散,再磁分离,如此反复洗涤三次,真空干燥得到含磺酸基磁性聚合物微球。
测试该含磺酸基磁性聚合物微球的粒径为560nm,比表面积为240m2·g-1,酸密度为2.19mmol·g-1,磁饱和强度为19emu·g-1,TEM照片如图1所示。
将制备的含磺酸基磁性聚合物微球用于催化油酸和甲醇酯化制备生物柴油,具体步骤如下:
在带机械搅拌和回流冷凝管的100mL三口烧瓶中,加入10g油酸,11.34g甲醇和0.4g上述制备的含磺酸基磁性聚合物微球,超声分散5min,形成均匀的悬浮液;搅拌(350r/min)并升温至80℃,反应8h后停止反应,取样测定酸值,并计算得到油酸的转化率;将反应产物进行磁分离,收集固体物,并用乙醇洗涤三次,再次作为催化剂,按照上述步骤进行催化反应。
含磺酸基磁性聚合物微球循环使用三次的油酸转化率(C)分别为94.1%,92.5%和92.3%。
将制备的含磺酸基磁性聚合物微球用于催化果糖脱水制备5-羟甲基糠醛(5-HMF),具体步骤如下:
在带机械搅拌、回流冷凝管和氮气导管的100mL三口瓶中加入0.3g果糖,14mLDMSO和0.1g上述制备的含磺酸基磁性聚合物微球,在130℃下搅拌(200r/min)反应2h;待反应液冷却至室温,将反应混合物进行磁分离;取一定量反应液,用去离子水稀释一定倍数后,用高效液相色谱分析并计算5-HMF的收率;固体酸催化剂通过磁分离回收,并用乙醇和石油醚洗涤交替洗涤三次,再次作为催化剂,按照上述步骤进行催化反应。
该含磺酸基磁性聚合物微球循环使用三次所得5-HMF的收率分别为90.6%,89.1%和88.7%。
实施例2
将0.200g改性Fe3O4磁簇、0.450g 2-丙烯酰氨基-2-甲基-1-丙烷磺酸、0.250g苯乙烯、0.300g二乙烯基苯加入40mL乙腈中,超声分散溶解2分钟,配制单体混合溶液;在单体混合溶液中加入0.0150g偶氮二异戊腈,机械搅拌(300r/min),并用油浴加热至95℃,回流开始后体系逐渐泛白,反应2h后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并蒸馏收集乙腈;在下层固体物中加入无水乙醇,超声分散,再磁分离,如此反复洗涤三次,真空干燥得到含磺酸基磁性聚合物微球。
测试该含磺酸基磁性聚合物微球的粒径为640nm,比表面积为225m2·g-1,酸密度为2.23mmol·g-1,磁饱和强度为21emu·g-1,FT-IR光谱如图2所示。
将制备的含磺酸基磁性聚合物微球用于催化油酸和甲醇酯化制备生物柴油,具体步骤同
实施例1。
该含磺酸基聚合物微球循环使用三次的油酸转化率(C)分别为95.3%,94.1%和93.8%。
将制备的含磺酸基磁性聚合物微球用于催化果糖脱水制备5-羟甲基糠醛(5-HMF),具体步骤同实施例1。
该含磺酸基聚合物微球循环使用三次所得5-HMF的收率分别为91.1%,90.7%和90.6%。
实施例3
将0.170g改性Fe3O4磁簇、0.500g 2-丙烯酰胺基十六烷磺酸、0.450g甲基丙烯酸、0.200g二乙烯基苯加入40mL乙腈-甲苯(4:1,v)中,超声分散溶解2分钟,配制单体混合溶液;在单体混合溶液中加入0.0115g过氧化二苯甲酰,机械搅拌(300r/min),并用油浴加热至95℃,回流开始后体系逐渐泛白,反应1h后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并蒸馏收集乙腈和甲苯;在下层固体物中加入无水乙醇,超声分散,再磁分离,如此反复洗涤三次,真空干燥得到含磺酸基磁性聚合物微球。
测试该含磺酸基磁性聚合物微球的粒径为770nm,比表面积为209m2·g-1,酸密度为2.01mmol·g-1,磁饱和强度为18emu·g-1,VSM曲线如图3所示。
将制备的含磺酸基磁性聚合物微球用于催化油酸和甲醇酯化制备生物柴油,具体步骤同
实施例1。
该含磺酸基聚合物微球循环使用三次的油酸转化率(C)分别为95.8%,95.1%和94.8%。
将制备的含磺酸基磁性聚合物微球用于催化果糖脱水制备5-羟甲基糠醛(5-HMF),具体步骤同实施例1。
该含磺酸基聚合物微球循环使用三次所得5-HMF的收率分别为91.6%,90.9%和90.5%。
实施例4
将0.310g改性Fe3O4磁簇、0.400g 2-丙烯酰胺基十二烷磺酸、0.350g苯乙烯、0.300g二乙烯基苯加入40mL乙醇/苯(4:1,v)中,超声分散溶解2分钟,配制单体混合溶液;在单体混合溶液中加入0.0315g过氧化二苯甲酰,机械搅拌(300r/min),并用油浴加热至90℃,回流开始后体系逐渐泛白,反应1h后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并蒸馏收集乙醇和苯;在下层固体物中加入无水乙醇,超声分散,再磁分离,如此反复洗涤三次,真空干燥得到含磺酸基磁性聚合物微球。
测试该含磺酸基磁性聚合物微球的粒径为720nm,比表面积为236m2·g-1,酸密度为1.94mmol·g-1,磁饱和强度为24emu·g-1。
将制备的含磺酸基磁性聚合物微球用于催化油酸和甲醇酯化制备生物柴油,具体步骤同
实施例1。
该含磺酸基聚合物微球循环使用三次的油酸转化率(C)分别为93.9%,93.3%和92.8%。
将制备的含磺酸基磁性聚合物微球用于催化果糖脱水制备5-羟甲基糠醛(5-HMF),具体步骤同实施例1。
该含磺酸基聚合物微球循环使用三次所得5-HMF的收率分别为90.5%,89.9%和89.6%。
实施例5
将0.240g改性Fe3O4磁簇、0.350g 2-丙烯酰氨基-2-甲基-1-丙烷磺酸、0.450g甲基丙烯酸、0.400g二乙烯基苯加入40mL乙腈/甲苯(4:1,v)中,超声分散溶解2分钟,配制单体混合溶液;在单体混合溶液中加入0.0120g偶氮二异丁腈,机械搅拌(300r/min),并用油浴加热至95℃,回流开始后体系泛白,反应2.5h后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并蒸馏收集乙腈和甲苯;在下层固体物中加入无水乙醇,超声分散,再磁分离,如此反复洗涤三次,真空干燥得到含磺酸基磁性聚合物微球。
测试该含磺酸基磁性聚合物微球的粒径为840nm,比表面积为187m2·g-1,酸密度为2.21mmol·g-1,磁饱和强度为22emu·g-1。
将制备的含磺酸基磁性聚合物微球用于催化油酸和甲醇酯化制备生物柴油,具体步骤同实施例1。
该含磺酸基聚合物微球循环使用三次的油酸转化率(C)分别为94.2%,93.6%和92.4%。
将制备的含磺酸基磁性聚合物微球用于催化果糖脱水制备5-羟甲基糠醛(5-HMF),具体步骤同实施例1。
该含磺酸基聚合物微球循环使用三次所得5-HMF的收率分别为91.9%,90.9%和90.6%。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (6)
1.一种含磺酸聚合物磁性微球的制备方法,所述含磺酸聚合物磁性微球以Fe3O4磁簇为核,共价键连接磺酸基的交联聚合物为壳,酸密度≥1.94 mmol·g-1,且磁饱和强度≥18emu·g-1;其特征在于,包括如下步骤:
将含磺酸烯类单体、基体单体、交联单体和改性Fe3O4磁簇加入溶剂中,配制单体混合溶液;在单体混合溶液中加入引发剂,机械搅拌并加热至回流,回流开始后体系逐渐泛白,反应一定时间后停止;待反应液冷却至室温后,倒出并磁分离,将上层清液收集并回收处理,在下层固体物中加入无水乙醇超声分散、洗涤,再磁分离,如此反复洗涤,干燥得到含磺酸聚合物磁性微球;
所述含磺酸烯类单体、交联单体、基体单体的质量比为20~50:20~40:10~60;
所述含磺酸烯类单体、交联单体、基体单体的总浓度为0.1wt%~5wt%;
所述改性Fe3O4磁簇的用量为单体总用量的5wt%~40wt%;
所述引发剂的用量为单体总用量的0.5wt%~5wt%;
所述含磺酸烯类单体为2-丙烯酰氨基-2-甲基-1-丙烷磺酸、2-丙烯酰胺基十六烷磺酸、2-丙烯酰胺基十二烷磺酸和2-丙烯酰胺基十四烷磺酸中至少一种。
2.根据权利要求1所述的含磺酸基磁性聚合物微球的制备方法,其特征在于:所述基体单体为苯乙烯、丙烯酸、甲基丙烯酸中至少一种。
3.根据权利要求1所述的含磺酸基磁性聚合物微球的制备方法,其特征在于:所述交联单体为二乙烯基苯。
4.根据权利要求1所述的含磺酸基磁性聚合物微球的制备方法,其特征在于:所述改性Fe3O4磁簇是用含乙烯基的硅烷偶联剂对Fe3O4磁簇进行表面改性。
5.根据权利要求1所述的含磺酸基磁性聚合物微球的制备方法,其特征在于:所述的溶剂为乙醇、乙腈、苯和甲苯的单一溶剂或混合溶剂。
6.根据权利要求1所述的含磺酸基磁性聚合物微球的制备方法,其特征在于:所述引发剂为偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈和过氧化二苯甲酰中至少一种。
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