CN114014966B - 一种酰胺基团改性超高交联吸附树脂及其制备方法和应用 - Google Patents
一种酰胺基团改性超高交联吸附树脂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种酰胺基团改性超高交联吸附树脂的制备方法,包括如下步骤:将亲水网络单体、疏水网络单体和引发剂混合后进行自由基聚合反应,即可获得酰胺基团改性超高交联吸附树脂;其中上述亲水网络单体为N,N′‑(4,4′‑亚甲基二苯基)双马来酰亚胺和/或N,N′‑1,3‑苯撑双马来酰亚胺;疏水网络单体为苯乙烯和/或二乙烯苯;亲水网络单体与疏水网络单体的摩尔比为1:(0.11~1.5);聚合反应温度为70~90℃,时间为4~24h。由上述方法制备的交联吸附树脂应用于吸附分离5‑羟甲基糠醛时,其吸附容量最高可达67.2mg/g湿树脂,对5‑羟甲基糠醛的洗脱率≥99.5%,实现对5‑羟甲基糠醛的高效分离。
Description
技术领域
本发明涉及高分子材料技术领域,更具体地,涉及一种酰胺基团改性超高交联吸附树脂及其制备方法和应用。
背景技术
5-羟甲基糠醛(5-hydroxymethylfurfural,简称5-HMF)是木质纤维素类生物质在高温稀酸水解过程中的一种重要中间产物,其分子中含有一个呋喃环、一个醛基和一个羟甲基,可以通过加氢、氧化脱氢、酯化、卤化、聚合水解等反应转化成其他目标分子,制备多种高附加值化学品和能源燃料,广泛应用在精细化工、医药、燃料添加剂等行业。5-羟甲基糠醛的制备主要通过生物质转换的单糖或多糖在酸催化剂的作用下脱水得到,然而由于其本身在酸性环境中化学性质不稳定,易进一步水合生成乙酰丙酸和甲酸等副产物,从而影响了5-羟甲基糠醛的收率。目前,5-羟甲基糠醛的分离纯化方法主要有减压蒸馏法、溶液萃取法、重结晶法、膜分离法以及吸附法。其中,吸附分离法具有节能环保、成本较低、操作容易且吸附剂容易再生回收等特点,在经济效益和能耗方面具有显著的优势。
交联吸附树脂因其具有较高的比表面积、稳定的物理化学性质、可调的孔径结构和表面极性、良好的吸附/脱附性能等优点,成为一类可替代活性炭和离子交换树脂的新型吸附材料。例如CN109847715A公开了一种酰胺基团改性聚苯乙烯系交联吸附树脂的制备方法,该方法通过在苯乙烯系树脂中引入含双键的酯类单体和胺化试剂,但该方法合成路线复杂,不仅需要额外的胺化剂、致孔剂,还需要含卤素催化剂,所产生的含氯离子废水难以处理,污染环境。
发明内容
本发明的目的是克服现有酰胺基团改性聚苯乙烯系交联吸附树脂合成路线复杂,不仅需要额外的胺化剂、致孔剂,还需要含卤素催化剂的缺陷和不足,在保持交联吸附树脂吸附性能的基础上提供一种酰胺基团改性超高交联吸附树脂的制备方法,该方法采用自由基聚合反应一步制备酰胺基团改性超高交联吸附树脂,亲水网络单体本身就是胺化试剂,形成交联吸附树脂的同时即引入大量酰胺基团,实现酰胺基团改性的目的。
本发明的另一目的是提供一种酰胺基团改性超高交联吸附树脂。
本发明的又一目的是由上述方法制备的酰胺基团改性超高交联吸附树脂在吸附分离5-羟甲基糠醛中的应用。
本发明上述目的通过以下技术方案实现:
一种酰胺基团改性超高交联吸附树脂的制备方法,包括如下步骤:
将亲水网络单体和疏水网络单体在反应溶剂中混合均匀并加入引发剂,进行自由基聚合反应,反应完全即可获得酰胺基团改性超高交联吸附树脂;
其中,所述亲水网络单体为N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺和/或N,N′-1,3-苯撑双马来酰亚胺;所述疏水网络单体为苯乙烯和/或二乙烯苯;所述亲水网络单体与疏水网络单体的摩尔比为1:(0.11~1.5);所述自由基聚合反应的温度为70~90℃,反应时间为4~24h。
优选地,亲水网络单体与疏水网络单体的摩尔比为1:(0.33~1)。更优选的亲水网络单体与疏水网络单体的摩尔比为1:1。
本发明采用交替自由基共聚策略一步制备酰胺基团改性超高交联吸附树脂,交联吸附树脂中的苯环在吸附时与5-羟甲基糠醛中呋喃环形成疏水-疏水作用,而酰胺基团和羰基与5-羟甲基糠醛中羟甲基形成氢键作用,通过疏水-疏水作用和氢键协同作用提高树脂对5-羟甲基糠醛的吸附性能。
与其他酰胺基团改性相比,本发明所采用的N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺和N,N′-1,3-苯撑双马来酰亚胺中含有强吸电子基团,可直接参与交联反应,不过其本身难以均聚,但可以与极性相反的二乙烯苯或苯乙烯类疏水单体发生共聚,而且两种单体相反的极化结构还可以发生交替自由基共聚,使引入的酰胺基团均匀分布在交联吸附树脂中,进而促进吸附容量的提升。
当亲水网络单体过多时,由于其本身难以发生聚合反应,只能与疏水网络单体聚合,因此将会导致酰胺基团改性超高交联吸附树脂产率的下降;同时酰胺基团改性超高交联吸附树脂中过多的亲水网络分子链段会使其过度溶胀,进而使树脂颗粒破裂;当亲水网络单体过少时,难以有效改善树脂的亲水性。综合考虑酰胺基团改性超高交联吸附树脂的吸附性能和产率及吸附过程中的溶胀性能,优选的亲水网络单体与疏水网络单体的摩尔比为1:(0.33~1),更优选的亲水网络单体与疏水网络单体的摩尔比为1:1。
优选地,亲水网络单体为N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺。
优选地,疏水网络单体为二乙烯苯。
优选地,亲水网络单体为N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺,疏水网络单体为二乙烯苯,亲水网络单体与疏水网络单体的摩尔比为1:1。
需要说明的是本发明中引发剂为偶氮二异丁腈、过氧化苯甲酰和过氧化十二酰中一种或多种,其中偶氮二异丁腈的引发温度为65~85℃、过氧化苯甲酰的引发温度为80~110℃、过氧化十二酰的引发温度为50~70℃;反应溶剂为二甲胺、二甲基甲酰胺和1,2-二氯乙烷中一种或多种;
反应生成的酰胺基团改性超高交联吸附树脂需要进行提纯、干燥处理,提纯为索氏抽提,抽提时间为6~48h,抽提温度为80~120℃,再用清水冲洗浸泡直至无味;抽提溶剂为乙醇、丙酮和四氢呋喃中一种或多种;干燥处理的温度为50~80℃,干燥时间为24~72h。
一种由上述制备方法制备的酰胺基团改性超高交联吸附树脂也在本发明的保护范围内。
优选地,酰胺基团改性超高交联吸附树脂的比表面积为650~750m2/g,孔容为0.2~0.8cm3/g,平均孔径为1~5nm。
本发明中所制备的酰胺基团改性超高交联吸附树脂在吸附分离5-羟甲基糠醛中的应用。
优选地,酰胺基团改性超高交联吸附树脂与5-羟甲基糠醛溶液的固液比为1:10~150g/mL,更优选的固液比为1:10~100g/mL。
优选地,吸附分离的pH值为1~12。
优选地,吸附分离的pH值为7~12。
生物质水解液体系除5-羟甲基糠醛外,还含有乙酰丙酸、甲酸和葡萄糖。乙酰丙酸和甲酸分子中含有-COOH基团,在溶液中会解离成H+和COO-离子,解离程度越大,溶液中的乙酰丙酸和甲酸分子越少,树脂吸附的乙酰丙酸和甲酸就越少,越容易使5-羟甲基糠醛与副产物分离。因此,调节吸附分离体系的pH值有利于提高吸附分离效率。
优选地,5-羟甲基糠醛的浓度≤30g/L。
优选地,吸附分离平衡时间为12min。当吸附时间为12min时,酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的吸附基本达到饱和状态。
与现有技术相比,本发明的有益效果是:
本发明提供一种酰胺基团改性超高交联吸附树脂的制备方法,通过自由基聚合反应一步制备酰胺基团改性超高交联吸附树脂,该制备方法不需要额外的胺化试剂,亲水网络单体本身就是胺化试剂,形成交联吸附树脂的同时即引入大量酰胺基团,实现酰胺基团改性。
本发明所制备的酰胺基团改性超高交联吸附树脂在在吸附分离5-羟甲基糠醛中的应用中,对5-羟甲基糠醛吸附容量最高可达67.2mg/g湿树脂,洗脱率大于99.5%,实现对5-羟甲基糠醛的高效分离,同时实现对5-羟甲基糠醛的高吸附选择性。
附图说明
图1为实施例1中酰胺基团改性超高交联吸附树脂的红外表征图;
图2为实施例1中酰胺基团改性超高交联吸附树脂的SEM图;
图3为实施例1中酰胺基团改性超高交联吸附树脂的N2吸附脱附图;
图4为实施例1中酰胺基团改性超高交联吸附树脂的吸附等温线。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明,但实施例并不对本发明做任何形式的限定。除非另有说明,本发明实施例采用的原料试剂为常规购买的原料试剂。
实施例1
一种酰胺基团改性超高交联吸附树脂的制备方法,包括以下步骤:
首先,在150mL三口烧瓶中加入摩尔比为1:1的亲水网络单体N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺和疏水网络单体二乙烯苯,以及适量引发剂偶氮二异丁腈;然后往三口烧瓶中加入100mL二甲基甲酰胺,在室温下搅拌溶解,氮气鼓泡去氧0.5h后升温至80℃,保温反应24h,得到反应产物;
然后,将上述反应产物用四氢呋喃进行索氏抽提24h,再用清水冲洗浸泡12h直至无味;最后在80℃条件下下真空干燥24h,即可获得酰胺基团改性超高交联吸附树脂,其产率为99.3%。
由上述制备方法制备的酰胺基团改性超高交联吸附树脂的比表面积为709.56m2/g、孔容为0.550cm3/g、平均孔径为3.719nm。
实施例2~4
实施例2中亲水网络单体与疏水网络单体的摩尔比为1:1.5,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为85.6%。
实施例3中亲水网络单体与疏水网络单体的摩尔比为1:0.33,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为76.2%。
实施例4中亲水网络单体与疏水网络单体的摩尔比为1:0.11,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为68.4%。
实施例5~7
实施例5中亲水网络单体为N,N′-1,3-苯撑双马来酰亚胺,疏水网络单体为二乙烯苯,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为87.0%。
实施例6中亲水网络单体为N,N′-(4,4′-亚甲基二苯基)双马来酰亚胺,疏水网络单体为苯乙烯,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为90.9%。
实施例7中亲水网络单体为N,N′-1,3-苯撑双马来酰亚胺,疏水网络单体为苯乙烯,其他同实施例1;所制得的酰胺基团改性超高交联吸附树脂的产率为82.8%。
实施例8
一种酰胺基团改性超高交联吸附树脂在吸附分离5-羟甲基糠醛中的应用,包括以下步骤:
将实施例1中所制得的酰胺基团改性超高交联吸附树脂放入95%乙醇溶液中溶胀24h,然后用去离子水洗涤至无味,抽滤即可得到湿树脂;称取0.1g湿树脂加入10mL生物质水解液(pH=2.78)体系中,然后置于25℃的振荡培养器中振荡240min,转速为120rpm,达到吸附平衡后,再将酰胺基团改性超高交联吸附树脂与溶液分离。
其中,生物质水解液体系中5-羟甲基糠醛的浓度为5.0g/L,乙酰丙酸的浓度为2.5g/L,甲酸的浓度为1.0g/L,葡萄糖的浓度为1.0g/L。
实施例9~11
实施例9中用0.5mol/L的盐酸将生物质水解液体系溶液调至pH=1,其他同实施例8。
实施例10中用0.4mol/L的氢氧化钠将生物质水解液体系的溶液pH=7,其他同实施例8。
实施例11中用0.4mol/L的氢氧化钠将生物质水解液体系的溶液pH=12,其他同实施例8。
对比例1~2
对比例1中亲水网络单体与疏水网络单体的摩尔比为1:9,其他同实施例1。
对比例2中亲水网络单体与疏水网络单体的摩尔比为1:3,其他同实施例1。
结果检测
(1)红外测试
图1为实施例1中的酰胺基改性交联吸附树脂的红外表征图谱,由图1可知,在3087~3105cm-1处出现的=C-H吸收峰与1601~1629cm-1处出现的C=C吸收峰较弱,这是由于N,N′-4,4′-二苯基甲烷-双马来酰亚胺与二乙烯苯自由基聚合反应发生交联引起的;在2927cm-1处出现的吸收峰是由二乙烯苯中C-H伸展为-CH2-引起的;在1708cm-1和1384cm-1处出现的吸收峰是由N,N′-4,4′-二苯基甲烷-双马来酰亚胺单体中C=O键和C-N-C键伸缩振动引起的。综上表明,N,N′-4,4′-二苯基甲烷-双马来酰亚胺单体与二乙烯苯单体成功交联生成酰胺基团改性超高交联吸附树脂。
(2)SEM测试
图2为实施例1中的酰胺基改性交联吸附树脂的SEM图,由图2可知树脂表面十分粗糙,分布着很多孔洞且存在一定程度的塌陷;这可能是由于酰胺基的引入使得孔洞塌陷造成树脂表面粗糙,并且使得孔洞形状不规则。
(2)N2吸附脱测试
具体测试方法:采用QUADRASORB SI型全自动比表面积及孔径分析仪,测试树脂在77K温度下的N2吸附脱附等温线。测试之前,将实施例1中所制得的酰胺基团改性超高交联吸附树脂(约0.05g)在363K下真空脱气15h以除去吸附的气体和其他杂质。
图3为实施例1提供的酰胺基团改性超高交联吸附树脂的N2吸附脱附图,由图3可知,当P/P0<0.05时,酰胺基团改性超高交联吸附树脂对N2的吸附容量快速增加,表明树脂存在微孔;在0.05<P/P0<0.95时,吸附和脱附等温线之间存在着明显的毛细凝聚现象和滞后现象,表明酰胺基团改性超高交联吸附树脂具有丰富的介孔结构;在较高的相对压力下(P/P0>0.95),滞后曲线的存在表明酰胺基团改性超高交联吸附树脂中含有大孔结构。
(3)吸附平衡测试
具体测试方法:将实施例1中所制得的酰胺基团改性超高交联吸附树脂放入95%乙醇溶液中溶胀24h,然后用去离子水洗涤至无味,抽滤后即可获得湿树脂。称取0.25g湿树脂加入25mL 5-羟甲基糠醛溶液中,将样品分别放置于15℃、25℃、35℃、45℃的振荡培养器中振荡240min,转速设置为120rpm,达到吸附平衡后,再将酰胺基团改性超高交联吸附树脂与溶液分离,经测定后绘制吸附等温线。
图4为实施例1提供的酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的单组分吸附等温线。由图4可知,在同一温度条件下,酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的平衡吸附容量随着平衡浓度的增大而增大,呈非线性等温线;随着温度的升高,酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的平衡吸附容量逐渐减小,表明5-羟甲基糠醛在树脂上的吸附过程为放热过程。利用Langmuir模型和Freundlich模型对静态平衡吸附结果进行拟合发现,酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的吸附更加符合Langmuir模型。
(4)吸附性能测试
具体测试方法:将实施例1~7和对比例1~2中所制得的酰胺基团改性超高交联吸附树脂放入95%乙醇溶液中溶胀24h,然后用去离子水洗涤至无味,抽滤即可获得湿树脂。分别称取0.25g湿树脂加入25mL生物质水解液体系中,将样品置于振荡培养器中25℃条件下振荡240min,转速为120rpm,达到吸附平衡后,再将酰胺基团改性超高交联吸附树脂与溶液分离;其中,生物质水解液体系中5-羟甲基糠醛的浓度为5.0g/L,乙酰丙酸的浓度为2.5g/L,甲酸的浓度为1.0g/L,葡萄糖的浓度为1.0g/L。
吸附容量的检测方法为高效液相色谱检测法,具体测试条件为:测试所用流动相为5mM稀硫酸溶液,流量为0.5mL/min;色谱柱为HPX-87H;测试温度为55℃;进样量为10μL。
表1实施例1~8和对比例1~2中酰胺基团改性超高交联吸附树脂的吸附性能测试
从实施例1~7和对比例1~2可看出,本发明制备的酰胺基团改性超高交联吸附树脂对5-羟甲基糠醛的吸附容量最高可达67.2mg/g湿树脂,洗脱率均≥99.5%,实现了对5-羟甲基糠醛的高效吸附分离。
表2实施例1中酰胺基团改性超高交联吸附树脂不同条件下的吸附性能测试
从实施例8~11可看出,本发明所制备的酰胺基团改性超高交联吸附树脂应用于吸附分离5-羟甲基糠醛时,通过调节溶液pH值,可以有效提高5-羟甲基糠醛和乙酰丙酸、甲酸、葡萄糖的分离因子。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (7)
1.一种酰胺基团改性超高交联吸附树脂在吸附分离5-羟甲基糠醛中的应用,其特征在于,所述酰胺基团改性超高交联吸附树脂由以下制备方法制得:
将亲水网络单体和疏水网络单体在反应溶剂中混合均匀并加入引发剂,进行自由基聚合反应,反应完全即获得酰胺基团改性超高交联吸附树脂;
其中,所述亲水网络单体为N,N′- (4,4′-亚甲基二苯基)双马来酰亚胺和/或N,N′-1,3-苯撑双马来酰亚胺;所述疏水网络单体为苯乙烯和/或二乙烯苯;所述亲水网络单体与疏水网络单体的摩尔比为1:(0.11 ~1.5);所述自由基聚合反应的温度为70~90℃,反应时间为4~24h;
所述酰胺基团改性超高交联吸附树脂的比表面积为650~750m2/g,孔容为0.2~0.8cm3/g,平均孔径为1~5nm。
2.如权利要求1所述应用,其特征在于,所述亲水网络单体与疏水网络单体的摩尔比为1:(0.33~1)。
3. 如权利要求1所述应用,其特征在于,所述亲水网络单体为N,N′- (4,4′-亚甲基二苯基)双马来酰亚胺。
4.如权利要求1所述应用,其特征在于,所述疏水网络单体为二乙烯苯。
5. 如权利要求1所述应用,其特征在于,所述亲水网络单体为N,N′- (4,4′-亚甲基二苯基)双马来酰亚胺,疏水网络单体为二乙烯苯,亲水网络单体与疏水网络单体的摩尔比为1:1。
6.如权利要求1所述应用,其特征在于,所述应用中吸附分离的pH值为1~12。
7.如权利要求6所述应用,其特征在于,所述应用中吸附分离的pH值为7~12。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010866A (en) * | 1977-11-15 | 1979-07-04 | Rhone Poulenc Ind | Styrene polymers having improved heat properties |
CN105218730A (zh) * | 2015-09-14 | 2016-01-06 | 清华大学深圳研究生院 | 吸附树脂及其制备方法和用途 |
CN106397652A (zh) * | 2016-09-14 | 2017-02-15 | 济南大学 | 一种制备超大孔高比表面积聚合物的方法 |
CN109847715A (zh) * | 2018-12-05 | 2019-06-07 | 广东工业大学 | 一种酰胺基团改性聚苯乙烯系超高交联吸附树脂的制备方法 |
CN109999762A (zh) * | 2019-03-14 | 2019-07-12 | 广东工业大学 | 一种酰胺基团改性聚苯乙烯系超高交联吸附树脂及其应用 |
CN110527019A (zh) * | 2019-08-07 | 2019-12-03 | 北京化工大学 | 一种双马来酰亚胺树脂微球及其制备方法 |
-
2021
- 2021-09-28 CN CN202111146687.6A patent/CN114014966B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2010866A (en) * | 1977-11-15 | 1979-07-04 | Rhone Poulenc Ind | Styrene polymers having improved heat properties |
CN105218730A (zh) * | 2015-09-14 | 2016-01-06 | 清华大学深圳研究生院 | 吸附树脂及其制备方法和用途 |
CN106397652A (zh) * | 2016-09-14 | 2017-02-15 | 济南大学 | 一种制备超大孔高比表面积聚合物的方法 |
CN109847715A (zh) * | 2018-12-05 | 2019-06-07 | 广东工业大学 | 一种酰胺基团改性聚苯乙烯系超高交联吸附树脂的制备方法 |
CN109999762A (zh) * | 2019-03-14 | 2019-07-12 | 广东工业大学 | 一种酰胺基团改性聚苯乙烯系超高交联吸附树脂及其应用 |
CN110527019A (zh) * | 2019-08-07 | 2019-12-03 | 北京化工大学 | 一种双马来酰亚胺树脂微球及其制备方法 |
Non-Patent Citations (1)
Title |
---|
Hui Gao et al..Hyper-Cross-Linked Organic Microporous Polymers Based on Alternating Copolymerization of Bismaleimide.ACS Macro Lett..2016,第5卷第377-381页. * |
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