CN118085164A - 一种基于天然三萜的两亲性聚合物及其制备方法与应用 - Google Patents
一种基于天然三萜的两亲性聚合物及其制备方法与应用 Download PDFInfo
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- MPDGHEJMBKOTSU-UHFFFAOYSA-N Glycyrrhetinsaeure Natural products C12C(=O)C=C3C4CC(C)(C(O)=O)CCC4(C)CCC3(C)C1(C)CCC1C2(C)CCC(O)C1(C)C MPDGHEJMBKOTSU-UHFFFAOYSA-N 0.000 claims abstract description 42
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Abstract
本发明涉及一种基于天然三萜化合物的两亲性聚合物及其制备方法与应用。本发明以天然三萜甘草次酸为原料，先通过酯化反应引入双键，得到甘草次酸疏水单体；再与亲水单体反应，得到基于天然三萜的两亲性聚合物。该系列两亲性聚合物具有良好的耐热性能，且聚合物的玻璃化转变温度可通过改变单体比例实现精准调控。同时，本发明的聚合物自组装形成的胶束可用于疏水农药活性物质的包裹和释放，不仅解决了活性成分水溶性差的难题，提高了农药的负载量与剂量传递效率，而且在一定程度上改善了现有农药载体带来的环境问题。此外，本发明所用原料为天然化合物，制备所得聚合物具有来源广泛、可再生、环境友好等优势，有望在材料、工程、医药、农业等领域发挥重要作用。
Description
技术领域
本发明涉及小分子、聚合物合成以及在农药学应用的技术领域，具体说是一种基于天然三萜的两亲性聚合物及其制备方法与应用。
背景技术
目前人们所使用的聚合物材料大部分是通过石油提炼的烯烃类单体合成得到的。为减少石油基聚合物对不可持续的石化资源的依赖，国内外的研究者逐渐将目光转向以天然化合物为原料构建的生物基聚合物上，以可再生的生物质资源替代传统的化石能源具有越来越重要的环保意义。
生物基聚合物是一类以非石化天然资源为合成原料的聚合物，具有原料来源广、可再生、产物易回收等优势，是一种环境友好的绿色材料。在可持续发展观念逐步深入的今天，生物基聚合物的合成策略和性能应用受到越来越多的关注。
萜类化合物是自然界中一类重要的天然资源，具有多种反应位点，可以在简化合成步骤的同时，根据需求精确地在分子水平上设计结构明确的生物基聚合物。此外，萜类化合物大多具有多手性中心和良好的生物活性，将其引入到聚合物分子的设计当中，可以赋予聚合物独特的立体构型、良好的生物活性和生物相容性等特点，拓展其在表面涂层、生物医药、组织工程等领域中的应用。
发明内容
针对现有技术中存在的缺陷，本发明的目的在于一种提供基于天然三萜的两亲性聚合物。本发明以天然三萜分子甘草次酸为原料，先通过酯化反应对甘草次酸28位进行修饰引入双键，得到甘草次酸疏水单体；再与亲水单体反应，得到基于天然三萜的两亲性聚合物，并系统研究它们的耐热性质及其在农药包覆领域的应用。本发明“一种基于天然三萜的两亲性聚合物及其制备方法与应用”的提出，旨在合成一系列基于天然三萜的生物基两亲性聚合物，在取代部分石油基聚合物的同时，减少对生态环境的影响。同时，该发明的提出可以很好地解决目前农业领域普遍存在的农药水溶性差、负载量低、剂量传递效率低等问题。
为达到以上目的，本发明采取的技术方案是：
1.一种基于天然三萜的两亲性聚合物，其特征在于，其结构式如下所示：
本发明的另外一个目的在于提供基于天然三萜的两亲性聚合物的制备方法。
为达到以上目的，本发明采取的技术方案是：
一种基于天然三萜的两亲性聚合物的制备方法，其特征在于，包括以下步骤：
步骤1，将甘草次酸(GA)与6-溴正己醇混合，加入碳酸钾反应生成甘草次酸己二醇酯(GAH)；
步骤2，将甘草次酸己二醇酯和甲基丙烯酰氯混合，加入缚酸剂反应生成甘草次酸丙烯酸酯单体(MGA)；
步骤3，将甘草次酸丙烯酸酯(MGA)单体与聚(乙二醇)乙醚甲基丙烯酸酯(MOEG)混合，加入引发剂进行反应，得到甘草次酸两亲共聚物(Poly(GA-OEG))。
在上述方案的基础上，
所述步骤1中，甘草次酸与6-溴正己醇、碳酸钾的摩尔比为1:1:1，溶剂为DMF，反应温度为室温，时间为5～8h；
所述步骤2中，甘草次酸己二醇酯与甲基丙烯酰氯的摩尔比为1:1，缚酸剂为三乙胺，三乙胺与甲基丙烯酰氯的摩尔比为1～2:1，反应温度为室温，时间为6～10h；
所述步骤3中，甘草次酸丙烯酸酯单体与聚(乙二醇)乙醚甲基丙烯酸酯的摩尔比为1:0.5～3，引发剂为偶氮二异丁腈(AIBN)，偶氮二异丁腈与聚(乙二醇)乙醚甲基丙烯酸酯的摩尔比为1:100，溶剂为无水DMF，反应温度为70℃，时间为24h。
本发明的又一个目的在于提供基于天然三萜的两亲性聚合物在农药载体方面的应用。
为达到以上目的，本发明采取的技术方案是：
一种基于天然三萜的两亲性聚合物在农药载体方面的应用。
在上述方案的基础上，所述基于天然三萜的两亲性聚合物用于农药活性物质的包裹和释放，上述农药活性物质包括但不限于咪鲜胺、吡虫啉、噻虫嗪或吡唑醚菌酯。
本发明所述的一种基于天然三萜的两亲性聚合物及其制备方法与应用，其有益效果为：
(1)本发明通过对反应条件的筛选，建立了天然三萜两亲性聚合物的合成方法，先通过酯化反应对甘草次酸28位进行修饰引入双键，得到甘草次酸疏水单体；再与亲水单体反应，得到基于天然三萜的两亲性聚合物。该方法步骤简短，操作方便，后处理简单。
(2)本发明制备的两亲性聚合物的亲疏水性可以通过调节疏水单体和亲水单体的投料比而实现，所制得聚合物的分子量为10000～50000之间，PDI指数为1.7～2.2。
(3)本发明制备的天然三萜两亲性聚合物具有良好的耐热性，300℃以上才开始分解，而且聚合物的玻璃化转变温度Tg具有良好的可调控性，通过调节共聚物中亲水单体的含量(0～100％)，Tg从124℃下降到-56℃。
(4)本发明制备的天然三萜两亲性聚合物可用于水溶性较差的农药活性物质的包裹和释放，所述活性物质包括但不限于咪鲜胺、吡虫啉、噻虫嗪、吡唑醚菌酯等原药成分。
(5)该两亲性聚合物的原料为天然产物甘草次酸，符合绿色可持续发展的理念。所制备得到的天然两亲性聚合物具有良好的生物相容性和环境友好性，将其应用于农药的包裹释放，可有效缓解目前农药领域载体材料的环境问题。
附图说明
本发明有如下附图：
图1为天然三萜两亲性聚合物的分子结构。
图2为天然三萜两亲性聚合物的合成路线。
图3为单体及聚合物的核磁共振氢谱。
图4为不同投料比的聚合物的核磁共振氢谱。
图5为不同聚合物的热重(TGA)曲线。
图6为不同聚合物的差示扫描量热(DSC)曲线。
图7为聚合物的玻璃化转变温度(Tg)随聚合物中MOEG单体比例的变化曲线。
图8为天然三萜两亲性聚合物Poly(GA-OEG)1:1负载咪鲜胺的透射电镜图。
图9为三萜两亲性聚合物Poly(GA-OEG)1:1负载吡虫啉的透射电镜图。
具体实施方式
下面结合实施例对本发明作进一步的说明，但实施例并不限制本发明的范围。本发明中所述的各种材料，均可以通过公开的商业途径购得。
实施例1：一种基于天然三萜两亲性聚合物Poly(GA-OEG)2:1的合成
基于天然三萜两亲性聚合物Poly(GA-OEG)2:1的合成路线如图2所示。
(1)甘草次酸己二醇酯(GAH)的合成：将甘草次酸GA(5.09g,10.80mmol)和6-溴正己醇(1.41mL,10.80mmol)溶于35mL DMF中，加入碳酸钾(1.49g,10.80mmol)搅拌，室温下反应6h。停止搅拌，加入20mL稀盐酸淬灭反应，将反应液转移至分液漏斗，采用乙酸乙酯进行萃取、分层，有机相干燥，过滤，旋干得到黄色固体。粗品进行柱层析分离(洗脱剂：石油醚/乙酸乙酯＝5～1:1,v/v)，得到白色固体GAH 5.85g，产率95％。
对合成的GAH结构进行表征，称取适量终产物于核磁管中，用氘代氯仿溶解，采用核磁共振仪在25℃下进行测试。1H NMR(400MHz,CDCl3,δppm):5.63(s,H,12-CH＝C),4.10(m,2H,CO2CH2),3.64(t,2H,HOCH2),3.21(m,1H,3-CH),1.36,1.14,1.11,0.99,0.80,0.79(s,7×3H,7×CH3).
(2)甘草次酸丙烯酸酯单体(MGA)的合成：将GAH(2.00g,3.50mmol)和三乙胺(583mL,4.21mmol)溶于30mL无水二氯甲烷中，冰浴下缓慢滴加甲基丙烯酰氯(340mL，3.50mmol)的无水二氯甲烷稀释液，温度升至室温后反应8h。停止搅拌，加入20mL稀盐酸淬灭反应，将反应液转移至分液漏斗，采用乙酸乙酯进行萃取、分层，有机相干燥，过滤，旋干得到淡黄色固体。粗品进行柱层析分离(洗脱剂：石油醚/乙酸乙酯＝5:1,v/v)，得到白色固体MGA 1.94g，产率87％。
对合成的MGA结构进行表征，称取适量终产物于核磁管中，用氘代氯仿溶解，采用核磁共振仪在25℃下进行测试。1H NMR(400MHz,CDCl3,δppm):6.06(m,1H,C＝CH2),5.61(s,H,12-CH＝C),5.52(m,1H,C＝CH2),4.10(t,2H,,CO2CH2),4.06(t,2H,CO2CH2),3.21(m,1H,3-CH),1.91,1.34,1.11,1.10,1.09,0.97,0.77(s,7×3H,7×CH3)。
(3)甘草次酸两亲共聚物Poly(GA-OEG)2:1的合成：将MGA(1276mg,2.0mmol)、MOEG(300mg,1.0mmol)、AIBN(1.6mg,0.01mmol)溶解于10mL无水DMF中，然后用液氮冷冻该混合物，在真空下去除系统中的空气后，反复冻抽3次后，将反应瓶放入70℃油浴中反应，隔绝氧气反应24h。之后通过浸入冰水中淬灭反应。减压旋蒸除去溶剂DMF，并加入10mL THF重新溶解产物。然后将其将倒入500mL乙醚中后，收集沉淀物。将沉淀物真空干燥，得到投料比为2:1的共聚物Poly(GA-OEG)2:11.5g。
实施例2：一种基于天然三萜两亲性聚合物Poly(GA-OEG)1:1的合成
以与实施例1相同的方式制备投料比为1:1的天然三萜两亲性聚合物Poly(GA-OEG)1:1，不同之处在于第三步的聚合物合成过程中，疏水单体MGA与亲水单体MOEG的摩尔比为1:1，具体为：MGA(638mg,1.0mmol)、MOEG(300mg,1.0mmol)，其余制备条件均与实施例1相同，得到聚合物Poly(GA-OEG)1:10.9g。
实施例3：一种基于天然三萜两亲性聚合物Poly(GA-OEG)1:2的合成
以与实施例1相同的方式制备投料比为1:2的天然三萜两亲性聚合物Poly(GA-OEG)1:2，不同之处在于第三步的聚合物合成过程中，疏水单体MGA与亲水单体MOEG的摩尔比为1:2，具体为：MGA(638mg,1.0mmol)、MOEG(600mg,2.0mmol)，其余制备条件均与实施例1相同，得到聚合物Poly(GA-OEG)1:21.2g。
实施例4：一种基于天然三萜两亲性聚合物Poly(GA-OEG)1:3的合成
以与实施例1相同的方式制备投料比为1:3的天然三萜两亲性聚合物Poly(GA-OEG)1:3，不同之处在于第三步的聚合物合成过程中，疏水单体MGA与亲水单体MOEG的摩尔比为1:3，具体为：MGA(638mg,1.0mmol)、MOEG(900mg,3.0mmol)，其余制备条件均与实施例1相同，得到聚合物Poly(GA-OEG)1:31.5g。
实施例5：一种基于天然三萜甘草次酸聚合物Poly(GA)的合成
以与实施例1相同的方式制备不含聚乙二醇片段的基于天然三萜甘草次酸的均聚物Poly(GA)，不同之处在于第三步的聚合物合成过程中，不添加亲水单体MOEG，具体为：MGA(638mg,1.0mmol)，其余制备条件均与实施例1相同，得到甘草次酸均聚物Poly(GA)0.5g。
实施例6：一种聚合物Poly(OEG)的合成
以与实施例1相同的方式制备不含甘草次酸的亲水性聚合物Poly(OEG)，不同之处在于第三步的聚合物合成过程中，不添加疏水单体MGA，具体为：MOEG(600mg,2.0mmol)，其余制备条件均与实施例1相同，得到亲水性聚合物Poly(OEG)0.53g。
实施例7：聚合物的核磁氢谱表征
采用核磁共振氢谱分别对聚合反应的单体MOEG、MGA，以及所制备得到的聚合物Poly(OEG)、Poly(GA)、Poly(GA-OEG)1:1的结构进行表征，称取适量物质于核磁管中，用氘代氯仿溶解，采用核磁共振仪在25℃下进行测试。从图3各物质的核磁共振谱图可以看出，聚合反应后，单体MOEG分子中的双键H(标记为a)及MGA分子中双键H(标记为1)的峰均消失，各氢的化学位移、积分及耦合裂分情况均与目标分子相符，说明得到了目标产物。
实施例8：聚合物的物理性质表征
采用Waters公司生产的Breeze 2型凝胶色谱工作站测对实施例1～6所制备的共聚物的分子量及分子量分布进行表征。检测条件为：1515型高压恒流泵，2414型示差折光检测器，使用色谱柱，标准样为聚苯乙烯(PS)，流动相为四氢呋喃(THF)，流动相流速为1mL/min，测试温度为25℃。测试结果整理于表1，所制得聚合物的分子量为10000～50000之间，PDI指数为1.7～2.2。同时，对聚合物进行核磁氢谱的表征，并通过对疏水单体和亲水单体上特征氢化学积分的比例进行计算，可得出实际共聚物中单体的比例。图4为不同聚合物的核磁氢谱，甘草次酸12位双键上氢的积分面积(12’)与-OCH2中氢的积分面积(c,5,10)求比例，得出聚合物Poly(GA-OEG)2:1中实际单体比例为1:0.43，聚合物Poly(GA-OEG)1:1中实际单体比例为1:1.03，聚合物Poly(GA-OEG)1:2中实际单体比例为1:2.10，聚合物Poly(GA-OEG)1:3中实际单体比例为1:2.98。
表1聚合物的物理性质
实施例9：耐热性质测试
采用热重(TGA)和差示扫描量热(DSC)对表1中制备得到的6种聚合物的热性质进行分析。
图5为不同聚合物热重分析结果，可以看出所有基于三萜甘草次酸的聚合物都表现出了很好的热稳定性，在300℃以下没有发生降解与质量损失。不含甘草次酸疏水片段的Poly(OEG)热稳定性略差，从264℃开始有所分解。此外，热稳定性随着两亲性聚合物中甘草次酸单体比例的降低也逐渐下降，再次证明了天然三萜甘草次酸结构对聚合物热学性质的重要性。
图6为不同单体比例的聚合物的DSC曲线，可以看出随着温度从-80℃升高到180℃，所有聚合物的热流量曲线都表现出了明显的台阶，可以测量得到其玻璃化转变温度(Tg)。Poly(GA)、Poly(GA-OEG)2:1、Poly(GA-OEG)1:1、Poly(GA-OEG)1:2、Poly(GA-OEG)1:3、Poly(OEG)的Tg分别为124℃、74℃、40℃、9℃、-8℃、-56℃。
图7为聚合物的玻璃化转变温度Tg随聚合物中MOEG单体比例的变化图，可见Tg随聚合物中MOEG单体比例的增加而呈现线性递减的趋势。因此，聚合物的玻璃化转变温度Tg具有良好的可调控性，可以通过调节共聚物中亲水单体的含量(0～100％)，Tg从124℃下降到-56℃。
实施例10：共聚物负载咪鲜胺性质测试
称取聚合物Poly(GA-OEG)1:1溶解于二甲基亚砜溶液(10mg/mL)中，称取5mg咪鲜胺固体溶解于1mL二甲基亚砜中，制得咪鲜胺二甲基亚砜溶液(5mg/mL)。将咪鲜胺二甲基亚砜溶液与聚合物二甲基亚砜溶液混合，置于透析袋内，浸入500mL去离子水中，并以200r/min磁力搅拌，每隔6h更换溶剂一次，累计透析24h，除去有机溶剂和游离农药分子，收集透析袋内的溶液，进行透射电子显微镜表征。
图8为天然三萜两亲性聚合物Poly(GA-OEG)1:1负载咪鲜胺的透射电镜图，可见聚合物负载农药分子后形成直径为10～20nm的球形胶束。其形成机理主要为两亲性聚合物在水中将疏水的甘草次酸基团包裹在内侧，亲水的聚乙二醇片段分散在外侧，疏水的咪鲜胺分子恰好被包裹在三萜片段中间，因而形成球形胶束。
实施例11：共聚物负载吡虫啉性质测试
以与实施例10相同的方式负载杀虫剂吡虫啉。图9为三萜两亲性聚合物Poly(GA-OEG)1:1负载吡虫啉的透射电镜图，可见聚合物负载农药分子后形成直径为25～50nm的球形胶束。
本说明书中未作详细描述的内容属于本领域专业技术人员公知的现有技术。
Claims (5)
1.一种基于天然三萜的两亲性聚合物，其特征在于，其结构式如下所示：
2.如权利要求1所述的一种基于天然三萜的两亲性聚合物的制备方法，其特征在于，包括以下步骤：
步骤1，将甘草次酸与6-溴正己醇混合，加入碳酸钾反应生成甘草次酸己二醇酯；
步骤2，将甘草次酸己二醇酯和甲基丙烯酰氯混合，加入缚酸剂反应生成甘草次酸丙烯酸酯单体；
步骤3，将甘草次酸丙烯酸酯单体与聚(乙二醇)乙醚甲基丙烯酸酯混合，加入引发剂进行反应，得到甘草次酸两亲共聚物。
3.如权利要求2所述的一种基于天然三萜的两亲性聚合物的制备方法，其特征在于：
所述步骤1中，甘草次酸与6-溴正己醇、碳酸钾的摩尔比为1:1:1，溶剂为DMF，反应温度为室温，时间为5～8h；
所述步骤2中，甘草次酸己二醇酯与甲基丙烯酰氯的摩尔比为1:1，缚酸剂为三乙胺，三乙胺与甲基丙烯酰氯的摩尔比为1～2:1，反应温度为室温，时间为6～10h；
所述步骤3中，甘草次酸丙烯酸酯单体与聚(乙二醇)乙醚甲基丙烯酸酯的摩尔比为1:0.5～3，引发剂为偶氮二异丁腈，偶氮二异丁腈与聚(乙二醇)乙醚甲基丙烯酸酯的摩尔比为1:100，溶剂为无水DMF，反应温度为70℃，时间为24h。
4.如权利要求1所述的一种基于天然三萜的两亲性聚合物在农药载体方面的应用。
5.如权利要求4所述的应用，其特征在于，所述基于天然三萜的两亲性聚合物用于农药的包裹和释放，上述农药包括咪鲜胺、吡虫啉、噻虫嗪或吡唑醚菌酯。
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