CN111072876A - 一种表面载有苯硼酸基团的聚合物微球及其制备方法和应用 - Google Patents
一种表面载有苯硼酸基团的聚合物微球及其制备方法和应用 Download PDFInfo
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- CN111072876A CN111072876A CN201911103161.2A CN201911103161A CN111072876A CN 111072876 A CN111072876 A CN 111072876A CN 201911103161 A CN201911103161 A CN 201911103161A CN 111072876 A CN111072876 A CN 111072876A
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- phenylboronic acid
- vpba
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- polymer
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Abstract
本发明公开了一种表面载有苯硼酸基团的聚合物微球及其制备方法和应用。首先用4‑乙烯基苯硼酸(4‑VPBA)和丙烯酸(AA)通过RAFT溶液聚合，制备嵌段型的大分子RAFT试剂P(4‑VPBA)m‑b‑AAn，并以该种大分子RAFT试剂作为稳定剂，与聚合单体、光引发剂通过RAFT光分散聚合方法，成功将苯硼酸基团引入到微球表面，一步简单、高效的制备表面载有苯硼酸基团的聚合物微球。本发明所述聚合物微球范围在100nm～1μm之间，单分散性好。所述苯硼酸聚合物微球对含有邻位羟基结构的化合物，如茜红素染料(ARs)，具有特异吸附作用，在植物成分分离、染料吸附、分析检测等领域具有很广泛应用。
Description
技术领域
本发明涉及高分子材料技术领域，更具体地，涉及一种表面载有苯硼酸基团聚合物微球的制备方法和应用。
背景技术
硼酸及其衍生物种类繁多、应用广泛，其水溶液中有带电荷与不带电荷两种形式，碱性条件下带电荷的形式可以与具有1,2-或1,3-二醇基团的多羟基化合物形成可逆的五元或六元环酯，并且该过程是可逆的。在自然界中，有大量这样的多羟基化合物，如糖蛋白、多糖、黄酮等、多巴胺等物质，它们对于生物体的生命活动有重要影响。由于硼酸具有这种独特的性质，含有硼酸或硼酸衍生物的材料目前被越来越多地用作分子识别单元，在很多领域都有广泛的应用，包括动态共价修复材料，糖敏感型水凝胶，传感器和纳米材料等。尤其是在生物医药领域，硼酸与糖类结合的特性，使其成为糖尿病治疗、检测相关的理想材料。此外，含有硼酸的材料在其他生物医学领域同样有着重要的应用，如用作药物释放载体、细胞捕获和培养、酶抑制技术等等。
目前，关于苯硼酸衍生物材料的一个非常热点的研究方向。利用硼酸对顺式二醇类物质进行色谱的检测与分离，主要是糖类分子、邻羟基黄酮类以及多巴胺等物质。硼酸亲和配体，在碱性条件下，可以与顺式二醇类物质结合；而在较为酸性的条件下，可逆地释放出目标物分子。相对于其他色谱方法，具有简单、可操作性强的明显优势。苯硼酸在各个领域的应用往往都需要借助一定的材料载体。单分散聚合物微球具有稳定性好、尺寸均匀、易分离的优点，将硼酸与聚合物微球结合，制备表面含有丰富硼酸基团的聚合物微球材料，与目标物质吸附后，能够很方便从介质中分离出来，并且在适当的解吸液作用下将目标物质释放出来，再次获得循环利用。这种新型的载体材料特别适合于药物分析检测、蛋白质组学和代谢组学等对高通量、快速、集成化分离分析的要求。然而现有的表面含硼酸基团的聚合物微球的制备方法过于繁琐，且得到的微球分散不均匀。
发明内容
本发明的目的在于克服现有技术中存在的上述缺陷和不足，提供一种表面载有苯硼酸基团的聚合物微球的制备方法。
本发明的另一目的在于提供所述制备方法制备得到的表面载有苯硼酸基团的聚合物微球。
本发明的再一目的在于所述表面载有苯硼酸基团的聚合物微球的应用。
本发明的上述目的是通过以下技术方案给予实现的：
一种表面载有苯硼酸基团的聚合物微球的制备方法，包括如下步骤：
S1.将含有4-乙烯基苯硼酸(4-VPBA)、丙烯酸(简称AA)与RAFT试剂，通过可逆加成-断裂链转移溶液聚合制备到嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn；
S2.将步骤S1得到嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn作为稳定剂，与聚合单体、光引发剂加入到反应容器中，通入氮气，以乙醇/水混合液作为溶剂，光源照射引发聚合反应，反应结束后除去分散介质，得到表面载有苯硼酸基团的聚合物微球。
本发明首先以含有苯硼酸基团的单体的4-乙烯基苯硼酸和丙烯酸在可逆加成-断裂链转移剂的调控下进行RAFT聚合，得到嵌段共聚物P(4-VPBA)-b-AA，称为大分子RAFT试剂；然后将获得的大分子RAFT试剂作为稳定剂与聚合单体、光引发剂通过光引发分散聚合与后修饰结合的方法，制备了表面带有苯硼酸功能基团的聚合物微球，可简单快速的得到单分散的苯硼酸功能聚合物微球。
优选地，所述RAFT试剂为S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)，但不限于此，原理上其余的RAFT试剂都有可能适用于这一合成体系。
优选地，所述大分子RAFT试剂P(4-VPBA)m-b-AAn的结构式如式下所示：
具体地，当RAFT试剂为DDMAT时，所述嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn的制备过程如下反应方程式所示：
首先，4-乙烯基苯硼酸与S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯聚合得到均聚物P(4-VPBA)m-TTC，P(4-VPBA)m-TTC再与丙烯酸聚合得到嵌段共聚物P(4-VPBA)m-b-AAn。
优选地，所述嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn的聚合度m和n分别为50～150和100～300，嵌段大分子的分子量为15000～45000。
优选地，所述嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn的聚合度m和n分别为53和142，即P(4-VPBA)53-b-AA142，其嵌段大分子的分子量为18000。
优选地，聚合物单体浓度为5～20wt％(相对于反应体系)，光引发剂为0.5～10wt％(相对于聚合物单体)，大分子RAFT试剂为0.1～15wt％(相对于聚合单体)，反应时间为0.5～6h。
优选地，所述聚合单体为丙烯酸类或甲基丙烯酸类单体，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯。
优选地，所采用的光引发剂为普通的商品化自由基光引发剂，例如α,α-二甲氧基-α-苯基苯乙酮(又称α,α-二甲基苯偶酰缩酮，Ciba公司商品名为Irgacure651)，2-羟基-2-甲基-1-苯基丙酮-1(Ciba公司商品名为Darocur 1173)，1-羟基-环己基苯酮(Ciba公司商品名为Irgacure 184)，2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1(Ciba公司商品名为Irgacure 907)，2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1(Ciba公司商品名为Irgacure 369)，2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)，苯基双(2,4,6-三甲基苯甲酰基)氧化膦(BAPO)等。原理上来说，现有的已商品化自由基光引发剂都适用于本发明，光引发剂的用量不受特别限制，可根据实际情况选用合适的用量，例如，对于Darocur 1173，其用量相对于单体的重量百分含量可以是0.5～5％，更优选是1～3％。除此之外，还可以采用适用于(甲基)丙烯酰氧基的交联反应的其他公知的光引发剂。
优选地，所述引发光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源，辐射波长为365nm，光强为0.2～100mW/cm2。
优选地，所述的乙醇/混合溶剂中乙醇与水的重量比为20:80～80:20。
本发明还请求保护上述任一所述制备方法制备得到的表面载有苯硼酸基团的聚合物微球，所述苯硼酸功能性聚合物微球均匀分散，其粒径范围在100nm～1μm之间；所述微球对含有邻位羟基结构的化合物，例如茜红素具有特异吸附作用。
因此，本发明还请求保护所述表面载有苯硼酸基团的聚合物微球在分离、吸附、分析检测含邻位羟基结构的化合物中应用。
与现有技术相比，本发明具有以下有益效果：
本发明提供了一种简单快速的合成表面载有苯硼酸基团的聚合物微球的方法，首先用4-乙烯基苯硼酸(4-VPBA)和丙烯酸(AA)通过RAFT溶液聚合，制备嵌段型的大分子RAFT试剂P(4-VPBA)m-b-AAn，并以该种大分子RAFT试剂作为稳定剂，与聚合单体、光引发剂通过RAFT光分散聚合方法，成功将苯硼酸基团引入到微球表面，一步简单、高效的制备表面载有苯硼酸基团的单分散聚合物微球。本发明制备得到的聚合物微球的径范围在100nm～1μm之间，单分散性好，微球表面含有苯硼酸基团。所述苯硼酸聚合物微球对含有邻位羟基结构的化合物，如茜红素染料(ARs)，具有特异吸附作用，在植物成分分离、染料吸附、分析检测等领域具有很广泛应用。
附图说明
图1为本发明大分子RAFT试剂P(4-VPBA)-b-AA的合成路线图。
图2为本发明大分子RAFT试剂P(4-VPBA)-b-AA核磁氢谱(氘代DMSO为溶剂)。
图3为以P(4-VPBA)53-b-AA142为稳定剂制备的PMMA微球的SEM图。
图4为以P(4-VPBA)53-b-AA142为稳定剂制备的PMMA微球的XPS元素分析图。
图5为本发明苯硼酸聚合物微球对茜红素吸附效果图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，以下实施例所用试剂和材料均为市购。
实施例1分子RAFT试剂P(4-VPBA)m-b-AAn的合成
1、合成均聚物P(4-VPBA)53-TTC
将4-乙烯基苯硼酸(4-VPBA)(7.4g，50mmol)，S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯(DDMAT)(0.183g，0.5mmol)和偶氮二异丁腈(AIBN)(0.083g，0.05mmol)，加入到25毫升的烧瓶中，溶解于20m L N,N-二甲基甲酰胺和水的混合溶剂(95/5v/v)，溶液通氮气进行30分钟的脱气，然后浸在70摄氏度的预热油浴中6小时，冷却，暴露在空气，用无水乙醚沉淀，在真空下的室温下干燥后，得到了淡黄色P(4-VPBA)聚合物粉末P(4-VPBA)53-TTC。
2、合成嵌段聚合物
将P(4-VPBA)53-TTC(1.55g，0.20mmol)，丙烯酸(AA)(2.93g，40.70mmol)和偶氮二异丁腈(AIBN)(6.56mg，0.04mmol)，加入到25毫升的烧瓶中，溶解于15g乙醇/水混合溶剂中(95/5w/w)。混合溶液通氮气进行30分钟的脱气，然后浸在70摄氏度的预热的油浴中反应4小时，冷却，暴露在空气，用石油醚沉淀，在真空下的室温下干燥后获得了淡黄色固体P(4-VPBA)53-b-AA142。其合成过程如图1所述，所述嵌段聚合物核磁氢谱如图2所示。
实施例2表面含有苯硼酸基团的聚合物微球的制备
1、以P(4-VPBA)53-b-AA142-TTC为稳定分散剂的聚甲基丙烯酸甲酯(PMMA)微球的合成：在乙醇/水(50/50，w/w)体系中进行：
将重量比40/60(7.2g+10.8g)的乙醇/水混合物的引入25mL的圆底烧瓶中作为溶剂，然后加入2.0g甲基丙烯酸甲酯(MMA)单体(10wt％相对于体系)，0.30g的稳定分散剂P(4-VPBA)53-b-AA142-TTC(15％相对于单体)，0.005g的DDMAT(0.25％相对于单体)和0.06g的光引发剂Darocur 1173(3％相对于单体)，磁力搅拌溶解。反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到聚合物纳米微球(A)；同时使用不同比例的乙醇/水(45:55，w/w)、(50:50，w/w)为溶剂分别制备得到聚合物纳米微球(B)、(C)。
2、聚合物纳米微球的表征
(1)将上述聚合物纳米微球经过扫描电镜测试，且SEM结果如图3所示：所得微球粒径在200nm左右，呈单分散性。
(2)以P(4-VPBA)53-b-AA142-TTC为稳定剂制备的PMMA微球的XPS元素分析如图4所示，有明显的硼元素的峰，表明PMMA微球表面已经成功载上了苯硼酸基团。
实施例3表面含有苯硼酸基团的聚合物微球的制备
1、以P(4-VPBA)53-b-AA142-TTC为稳定分散剂的聚丙烯酸甲酯(PMA)微球的合成：在乙醇/水(50/50，w/w)体系中进行：
将重量比40/60(7.6g+11.4g)的乙醇/水混合物的引入25mL的圆底烧瓶中作为溶剂，然后加入1.0g丙烯酸甲酯(MA)单体(5wt％相对于体系)，0.10g的稳定分散剂P(4-VPBA)53-b-AA142-TTC(10％相对于单体)，0.0025g的DDMAT(0.25％相对于单体)和0.01g的光引发剂Darocur 1173(1％相对于单体)，磁力搅拌溶解。反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到单分散聚合物纳米微球；所述单分散聚合物纳米微球的粒径为200nm，呈单分散性。
实施例4表面含有苯硼酸基团的聚合物微球的制备
1、以P(4-VPBA)53-b-AA142为稳定分散剂的聚甲基丙烯酸丁酯(PBMA)微球的合成：在乙醇/水(50/50，w/w)体系中进行：
将重量比40/60(6.4g+9.6g)的乙醇/水混合物的引入25mL的圆底烧瓶中作为溶剂，然后加入4.0g甲基丙烯酸丁酯(BMA)单体(20wt％相对于体系)，0.04g的稳定分散剂P(4-VPBA)53-b-AA142(1％相对于单体)，0.01g的DDMAT(0.25％相对于单体)和0.2g的光引发剂Darocur 1173(5％相对于单体)，磁力搅拌溶解。反应混合物用氮气除氧30分钟，用带有石英玻璃片的玻璃塞密封，然后在持续搅拌下以365nm波长的LED灯(光强度2.5mW/cm2)从圆底烧瓶顶部照射3小时。产物采用离心法分离，用乙醇/水(50/50，w/w)清洗，反复离心洗涤2～3次，得到单分散聚合物纳米微球。
应用例1
将实施例2制备得到的表面载有苯硼酸基团的微球对染料茜红素ARS的吸附：
取1mL苯硼酸聚合物微球(固含量5％)，用PBS缓冲溶液(pH＝8.2)洗涤两次后，离心去除上清液待用。取0.034g茜红素溶于20mL的缓冲溶液中，配置成浓度为0.5μmol/mL的溶液，取适量加入到上述处理好的苯硼酸聚合物微球中，在磁力搅拌下反应2小时，离心分离上清液。分别在272nm波长处测定茜红素原溶液和与苯硼酸聚合物微球反应后的上清液的吸光度。各种不同的硼酸微球对茜红素ARS染料的吸附作用如图5所示，苯硼酸聚合物微球反应后的茜红素溶液颜色变浅，在278nm处的吸收强度明显减弱、甚至消失，这是由于聚合物微球表面载有的苯硼酸基团，吸收了茜红素，使其在溶液中浓度变低，从而紫外吸光度明显下降。
Claims (9)
1.一种表面载有苯硼酸基团的聚合物微球的制备方法，其特征在于，包括如下步骤：
S1.将4-乙烯基苯硼酸、丙烯酸与RAFT试剂，通过可逆加成-断裂链转移溶液聚合制备到嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn-TTC；
S2.将步骤S1得到嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn作为稳定剂，与聚合单体、光引发剂加入到反应容器中，通入氮气，以乙醇/水混合液作为溶剂，光源照射引发聚合反应，反应结束后除去分散介质，得到表面载有苯硼酸基团的聚合物微球。
2.根据权利要求1所述的制备方法，其特征在于，所述RAFT试剂为S-1-十二烷基-S′-(α,α′-二甲基-α″-乙酸)三硫代碳酸酯，所述大分子RAFT试剂P(4-VPBA)m-b-AAn的结构式如式下所示：
3.根据权利1或2所述的制备方法，其特征在于，所述嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn的聚合度m和n分别为50～150和100～300，嵌段大分子的分子量为15000～45000。
4.根据权利要求3所述的制备方法，其特征在于，所述嵌段型大分子RAFT试剂P(4-VPBA)m-b-AAn的聚合度m和n分别为53和142，嵌段大分子的分子量为18000。
5.根据权利要求1所述的制备方法，其特征在于，聚合物单体浓度为反应体系的5～20wt％，光引发剂浓度为聚合物单体的0.5～10wt％，大分子RAFT试剂为聚合物单体的0.1～15wt％，反应时间为0.5～6h。
6.根据权利要求1所述的制备方法，其特征在于，所述的聚合单体为丙烯酸类或甲基丙烯酸类单体。
7.根据权利要求1所述的制备方法，其特征在于，所述光引发剂为α,α-二甲氧基-α-苯基苯乙酮，2-羟基-2-甲基-1-苯基丙酮-1，1-羟基-环己基苯酮，2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1，2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1，2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)或苯基双(2,4,6-三甲基苯甲酰基)氧化膦(BAPO)。
8.权利要求1～7任一所述制备方法制备得到的表面载有苯硼酸基团的聚合物微球。
9.权利要求8所述的表面载有苯硼酸基团的聚合物微球在分离、吸附、分析检测含邻位羟基结构的化合物中应用。
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| CN110129030A (zh) * | 2019-05-06 | 2019-08-16 | 福建师范大学 | 一种具有刺激响应性嵌段聚合物纳米材料荧光探针的制备与应用 |
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| CN110129030A (zh) * | 2019-05-06 | 2019-08-16 | 福建师范大学 | 一种具有刺激响应性嵌段聚合物纳米材料荧光探针的制备与应用 |
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