CN111484531A - 一种含有根皮素单元的聚膦腈微球、制备方法及其应用 - Google Patents
一种含有根皮素单元的聚膦腈微球、制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种含有根皮素单元的聚膦腈微球、制备方法及其应用，属于有机‑无机杂化的交联微球材料领域。它解决了现有环交联聚膦腈制备方法复杂等问题，一种含有根皮素单元的聚膦腈微球，其特征在于，其结构式如式(I)所示：
本发明水解无毒等优点。
Description
技术领域
本发明属于有机-无机杂化的交联微球材料领域，特别涉及一种含有根皮素单元的聚膦腈微球、制备方法及其应用。
背景技术
有机-无机杂化的环交联聚膦腈材料具有稳定的化学结构以及热稳定性、良好的生物相容性。聚合物微球的粒径具有可控性，表面积大和易于化学修饰的性质等优点。目前，因其优异性能，聚膦腈材料被广泛的应用于耐火阻燃、生物医药、电化学、催化等领域(谭娟.聚(环三磷腈-co-4,4'-二羟基二苯砜)对钍(Ⅳ)、铀(Ⅵ)的吸附性能研究[D].)。
聚合物材料在生物医药应用中主要问题之一是聚合物材料在生物降解过程中会逐渐释放出对人体有害的小分子单体。根皮素是黄酮类天然化合物，几乎不溶于水。根皮素具有优异的生物活性，广泛的存在于苹果、梨等水果的果皮及根皮中，目前，已发现具有抗氧化抗炎，抗病毒及抗肿瘤等方面的生物活性，此外还发现具有美容功效(杜鹏.根皮素酰腙衍生物的合成及其生物活性研究[D].2013.)。但因其几乎不溶于水的性质，生物利用率低，使其应用范围受到了极大限制。当前，对根皮素的研究主要是在根皮素的提取、结构以及药理活性等方面，对根皮素化学结构修饰的研究报道还不多。
综上所述，有机-无机杂化的环交联聚膦腈微米材料在药物应用方面进展还比较缓慢，而现有一些技术比较大的缺陷是：一，制备方法复杂，过程繁琐；二，单体价格昂贵，不经济；三，所用单体多数对人体有害，导致其在药物应用方面有很大缺陷；四，药物负载步骤复杂。
国专利文献号公开号CN103113410A，在2013-05-22公开了一种有机微纳米领域的耐高温聚膦腈微球及其制备方法，该技术通过将六氯环三膦腈、间苯三酚和三乙胺在超声水浴条件下反应得到。但该技术中的间苯三酚单体，毒性较大，在人体中水解后会对人造成极大的危害，其很难应用于医药方面。
发明内容
本发明的第一个目的是针对现有技术中存在的上述问题，提供了一种含有根皮素单元的聚膦腈微球；本发明的第二个目的是提供一种制备上述含有根皮素单元的聚膦腈微球的制备方法；本发明的第三个目的是提供一种上述含有根皮素单元的聚膦腈微球的应用。
本发明的第一个目的可通过下列技术方案来实现：一种含有根皮素单元的聚膦腈微球，其特征在于，其结构式如式(I)所示：
本发明的第二个目的可通过下列技术方案来实现：一种制备上述含有根皮素单元的聚膦腈微球的制备方法，其特征在于，包括如下步骤：
S01：将六氯环三膦腈、根皮素和缚酸剂溶解于有机溶剂中，往反应容器中充氮气后抽真空，在真空的条件下进行反应；
S02：反应结束后，将有产物生成的溶液进行离心分离得固体，洗涤、干燥后，得含有根皮素单元的交联聚膦腈微球；
步骤S01中，六氯环三膦腈和根皮素的摩尔比为1:3。
优选地，步骤S01中，六氯环三膦腈与有机溶剂的比例为0.2～10g/L。
优选地，步骤S01中，先在常温下，功率为50～100W的超声水浴中反应1～2h，再在50～65℃的油浴中反应时间为3到12小时。
优选地，步骤S01中，所述的有机溶剂为N,N-二甲基甲酰胺、乙腈、乙醇、丙酮中的一种或任意混合。
优选地，所述的缚酸剂为三乙胺。
优选地，步骤S02中，洗涤时，采用有机溶剂和蒸馏水交叉各洗涤三次。
本发明的第三个目的可通过下列技术方案来实现：一种含有根皮素单元的聚膦腈微球在药物的负载和控释，和/或金属离子的分离中的应用。
与现有技术相比，本发明具有以下优点：
1.本发明含有根皮素单元的聚膦腈微球制备成本低廉，方法简单易行，可在工业中大量制备。
2、本发明反应条件温和易于控制，后处理方便；副产物三乙胺盐酸盐水洗即可除去。
3、本发明的根皮素单体成本低廉，对人体无害，微球表面有羟基和酮基，可进一步功能化，可将其应用于药物的负载和控释，金属离子的分离等领域，金属离子例如铀离子或者钍离子。
4、本发明往反应容器中充氮气后抽真空，在真空的条件下进行反应。目的是为了除去氧，防止在反应的过程中，反应物和产物被氧化。
5、本发明先水浴后油浴的目的是，因为所需要超声的温度较高，若直接水浴，到50～65℃时，水会大量蒸发，大量水汽，容易影响反应。
附图说明
图1是制备环交联的聚膦腈微球的合成路线示意图；
图2是实施例1制得的含有根皮素单元的聚磷腈微球的低倍扫描电镜照片；
图3是是实施例1制得的含有根皮素单元的聚磷腈微球的高倍扫描电镜照片；
图4是实施例1制得的含有根皮素单元的聚磷腈微球的高倍透射电镜照片；
图5是实施例1中的根皮素的傅立叶红外图；
图6是实施例1中的HCCP和目标产物的傅立叶红外图；
图7是实施例2制得的含有根皮素单元的聚磷腈微球的低倍扫描电镜照片；
图8是实施例2制得的含有根皮素单元的聚磷腈微球的高倍扫描电镜照片。
具体实施方式
以下是本发明的具体实施例并结合附图，对本发明的技术方案作进一步的描述，但本发明并不限于这些实施例。
图1是以下实施例制备含有根皮素单元的交联聚膦腈微球的合成路线和化学结构。六氯环三膦腈(HCCP)和根皮素(Phloretin)在三乙胺(TEA)作缚酸剂的条件下发生缩聚反应，产生的HCl被三乙胺吸收形成三乙胺盐酸盐。HCl与三乙胺之间的反应同时促进了根皮素的端羟基与六氯环三膦腈的P-Cl的亲核取代反应，随着缩聚反应的进行，便生成交联的聚合物。
实施例1
向100mL圆底烧瓶中加入0.1g(0.2876mmol)六氯环三膦腈，0.2367g(0.863mmol)根皮素，倒入50mL的DMF(N,N-二甲基甲酰胺)溶剂分散溶解后加入2mL(1.44mmol)三乙胺，再通入氮气抽真空，于超声(100W)恒温水浴中反应常温反应(25℃左右)1h后，放入60℃的油浴下反应10h，将有产物生成的溶液进行离心分离得固体，将粗产物用乙醇和蒸馏水交叉洗涤三次，最后于烘箱中干燥24h得交联聚膦腈微球。
图2为所得交联聚膦腈微球的低倍扫描电镜照片，图3是所得交联聚膦腈微球的高倍扫描电镜照片，图4为交联聚膦腈微球的高倍透射扫描电镜照片，由照片可见该微球的直径为500～900nm，微球表面平整，为实心结构。
图5-6是交联聚膦腈微球的傅里叶变换红外谱图:(a)根皮素,(b)HCCP,(c)目标产物。图5(a)中3263.54cm-1处是羟基的共振吸收峰，而在图6(c)图中峰强度变弱，但不完全消失，说明合成的交联聚膦腈微球还含有羟基。图5(a)和图6(c)对比发现，在1611.97cm-1和1511.79cm-1处存在的基本单元酮基和苯环的共振吸收在图6(c)仍存在；1200cm-1和857cm-1分别是P＝N和P-N键的共振吸收；在601cm-1处的P-Cl反应后消失了。因此，从红外谱图5证明了两种单体成功发生了反应，其为根皮素和HCCP的交联缩聚结构,同时其表面还含有未反应完的羟基。
实施例2
采用实施例1所述的设备和制备过程，反应溶剂为乙腈(Acetonitrile)，其中的超声功率为100W，反应时间温度同实施例1，粗产品经丙酮和蒸馏水交叉洗涤3次于烘箱中干燥24h后制样。由SEM测试结果分析表明，微球分散均匀，微球的直径为600nm～900nm，微球表面平整为实心结构(见图7、图8)，其结构为HCCP和根皮素的交联缩合结构。
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
Claims (8)
1.一种含有根皮素单元的聚膦腈微球，其特征在于，其结构式如式(I)所示：
2.一种制备如权利要求1所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，包括如下步骤：
S01：将六氯环三膦腈、根皮素和缚酸剂溶解于有机溶剂中，往反应容器中充氮气后抽真空，在真空的条件下进行反应；
S02：反应结束后，将有产物生成的溶液进行离心分离得固体，洗涤、干燥后，得含有根皮素单元的交联聚膦腈微球；
步骤S01中，六氯环三膦腈和根皮素的摩尔比为1:3。
3.根据权利要求2所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，步骤S01中，六氯环三膦腈与有机溶剂的比例为0.2～10g/L。
4.根据权利要求2所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，步骤S01中，先在常温下，功率为50～100W的超声水浴中反应1～2h，再在50～65℃的油浴中反应时间为3到12小时。
5.根据权利要求2所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，步骤S01中，所述的有机溶剂为N,N-二甲基甲酰胺、乙腈、乙醇、丙酮中的一种或任意混合。
6.根据权利要求2所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，所述的缚酸剂为三乙胺。
7.根据权利要求2所述的一种含有根皮素单元的聚膦腈微球的制备方法，其特征在于，步骤S02中，洗涤时，采用有机溶剂和蒸馏水交叉各洗涤三次。
8.一种如权利要求1所述的一种含有根皮素单元的聚膦腈微球在药物的负载和控释，和/或金属离子的分离中的应用。
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| CN101875728A (zh) * | 2009-11-12 | 2010-11-03 | 上海交通大学 | 聚膦腈微球及其制备方法、用途及其实现方法 |
| CN103626804A (zh) * | 2013-11-25 | 2014-03-12 | 上海交通大学 | 含有白藜芦醇单元的聚膦腈微球及其制备方法 |
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| US5807757A (en) * | 1996-07-02 | 1998-09-15 | Virus Research Institute, Inc. | Preparation of ionically cross-linked polyphosphazene microspheresy by coacervation |
| CN101875728A (zh) * | 2009-11-12 | 2010-11-03 | 上海交通大学 | 聚膦腈微球及其制备方法、用途及其实现方法 |
| CN103626804A (zh) * | 2013-11-25 | 2014-03-12 | 上海交通大学 | 含有白藜芦醇单元的聚膦腈微球及其制备方法 |
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