CN106632920A - 一种含二茂铁基两亲性三嵌段共聚物及其检测、制备方法 - Google Patents
一种含二茂铁基两亲性三嵌段共聚物及其检测、制备方法 Download PDFInfo
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- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 14
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims abstract description 13
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Abstract
一种含二茂铁基两亲性三嵌段共聚物及其检测、制备方法,以Br‑PEO‑Br为大分子引发剂,CuBr/PMDETA为催化剂,通过ATRP法合成结构明确的PFCn‑b‑PEO‑b‑PFCn三嵌段共聚物,其中,n为嵌段共聚物,b为嵌段,PFC为聚甲基丙烯酸二茂铁十一烷基酯),PEO为聚乙二醇。
Description
技术领域
本申请涉及一种三嵌段共聚物及其检测、制备方法,特别涉及一种含二茂铁基两亲性三嵌段共聚物及其检测、制备方法。
背景技术
嵌段共聚物是由两段或多段化学性质不同的聚合物链段通过化学键相连接而组成的大分子。在水中可以溶解或溶胀的高分子通称为水溶性高分子。水溶性嵌段共聚物是一类特殊的水溶性高分子,根据它们在水中的溶解性的不同可以简单的归为两大类:双亲水嵌段共聚物(Double hydrophilic block copolymers,DHBCs)和两亲性嵌段共聚物(Amphiphilic block copolymers)。两亲性嵌段共聚物(Amphiphilic block copolymers)是指同一大分子中同时具有对两相都有亲和性的聚合物,一般是指同时具有亲水链段和疏水链段的聚合物。当大分子链中亲水链段较长而疏水链段较短时,两亲性嵌段共聚物主要表现为亲水性,可以分散在水介质中形成稳定的胶束或其他聚集体,这类水溶性的两亲性嵌段共聚物又被称之为亲水-疏水嵌段共聚物[3]。由于两亲性嵌段共聚物具有良好的结构可调性和丰富的自组装形态,其自组装制备纳米胶束和粒子可以在水体系中进行,因而双亲水嵌段共聚物的合成及其自组装行为的研究近几年来成为大分子自组装领域的研究热点之一,其独特的溶液性质和自组装行为使得它们具有广阔的潜在应用价值,如药物装载和基因治疗、矿化模板、结晶生长修饰剂、金属胶体粒子合成的纳米反应器等。
近几年,通过氧化或者氧化还原调控方式制备刺激响应型组装体的报道开始引起了人们的关注。主要原理是将含硫、含硒、紫精、二茂铁等氧化还原敏感基团引入到大分子自组装体系中,通过这些基团在不同的氧化还原环境中亲疏水性的变化调控大分子组装体的聚集形态,从而制备出新型氧化或者氧化还原响应型组装体。
发明内容
本申请通过直接在疏水嵌段中引入二茂铁基功能基团,制备出一种含二茂铁基两亲性三嵌段共聚物,该两亲性嵌段共聚物具有氧化还原响应性,在药物控释等领域具有潜在的应用价值。
为解决上述技术问题:本申请提出1.一种含二茂铁基两亲性三嵌段共聚物,其特征在于:以Br-PEO-Br为大分子引发剂,CuBr/PMDETA为催化剂,通过ATRP法合成结构明确的PFCn-b-PEO-b-PFCn三嵌段共聚物,其中,n为本案件中共合成出三种不同n值的嵌段共聚物,即10,17,28,也可以通过改变单体的量进行调控,b为block的简写,嵌段的意思,PFC为聚甲基丙烯酸二茂铁十一烷基酯,PEO为聚乙二醇。
可优选的是,所述Br-PEO-Br具体为两端为2-溴代异丁酰溴的Br-PEO20000-Br大分子引发剂,所述Br-PEO20000-Br大分子引发剂通过分子量为20000的PEO的两端羟基与2-溴代异丁酰溴的酰化或酯化反应得到。
可优选的是,所述2-溴代异丁酰溴选用的浓度大于98%,所述CuBr使用前用冰醋酸洗至无色,再分别用无水甲醇、无水乙醚洗三次,真空干燥,氮气气氛中保存;所述PMDETA选用的浓度约为99%。
一种上述任一项所述的含二茂铁基两亲性三嵌段共聚物的检测方法,其特征在于,包括如下步骤:
(1)将所述三嵌段共聚物溶于CDCl3中,测定三嵌段共聚物的HNMR谱图;
(2)根据HNMR谱图,判断PEO链段和二茂铁嵌段的质子振动情况;如果为强峰,则确定聚合物中同时含有PEO和二茂铁嵌段;否则,则不同时含有;
(3)计算二茂铁侧链的聚合度DPFc和三嵌段共聚物的分子量Mn(NMR);
(4)通过GPC曲线测定聚合物的分子量及分子量分布。
可优选的是,所述步骤(3)具体为:通过公式(1-1)和(1-2)计算出二茂铁侧链的聚合度DPFc和三嵌段共聚物的分子量Mn(NMR):
DPFc=(I2.3/2)/[I3.65/(4×452)] (1-1)
Mn(NMR)=DPFc×MFc+MBr-PEO20000-Br (1-2)
式中I2.3和I3.65分别为2.3ppm和3.65ppm处的核磁峰积分面积。
可优选的是,所述步骤(4)中测定具体为:采用Waters GPC测定,采用三根Styragel色谱柱串联(HR3、HR4、HR6),Waters 515泵,717自动进样器,2414型RI监测器,用一系列单分散的聚苯乙烯标样校准,THF为流动相,流速为1.0mL/min,柱温35℃。
可优选的是,比较Br-PEO-Br和PFCn-b-PEO-b-PFCn三嵌段共聚物的GPC曲线,PFCn-b-PEO-b-PFCn在比Br-PEO20000-Br大分子引发剂流出时间更短的位置呈现了一个对称的单峰。
所述制备方法,包括如下步骤:
(1)在室温下,将一定量的大分子引发剂Br-PEO20000-Br和催化剂CuBr加入到充氩气的5mL Schlenk瓶中;
(2)用翻口胶塞密封,抽真空除氧,用氩气清洗过的注射器加入脱气的甲苯2mL溶解大分子引发剂;
(3)加入按设计聚合度计量比的经脱气的单体甲基丙烯酸二茂铁十一烷基酯,液氮冷冻-抽真空-充氩气解冻,循环三次除氧,用氩气清洗过的注射器加入一定量的配体PMDETA;
(4)浸入预先加热至80℃的油浴中,反应6h,液氮冷冻快速终止反应;
(5)将反应体系浓缩,加入石油醚:乙酸乙酯=4:1的混合溶剂溶解,过柱,将未反应单体洗出后,然后用THF+5%三乙胺混合溶剂洗脱出粗产品;
(6)将粗产品溶解于少量二氯甲烷中,在大量正己烷中反复沉淀,得到纯净的三嵌段共聚物PFCn-b-PEO-b-PFCn,真空干燥至恒重。
可优选的是,所述步骤(1)中的所述大分子引发剂Br-PEO20000-Br和催化剂CuBr按1:2的摩尔比加入到充氩气的5mL Schlenk瓶中。
可优选的是,所述步骤(3)中配体PMDETA加入的计量为大分子引发剂计的2倍。
附图说明
图1为PFCn-b-PEO-b-PFCn三嵌段共聚物示意图。
图2为PFCn-b-PEO-b-PFCn三嵌段共聚物的合成路线示意图。
图3为M28-b-E454-b-M28三嵌段共聚物的核磁谱图。
图4为Br-PEO2000-Br和PFCn-b-PEO-b-PFCn的GPC曲线。
具体实施方式
下面结合附图对本申请作进一步详细描述,有必要在此指出的是,以下具体实施方式只用于对本发明进行进一步的说明,不能理解为对本发明保护范围的限制,该领域的技术人员可以根据下述内容对本申请作出一些非本质的改进和调整。
图1为PFCn-b-PEO-b-PFCn三嵌段共聚物示意图。
试剂:聚乙二醇(PEO):分子量为20,000,中国医药集团,试剂中痕量的水分通过与甲苯减压共沸蒸馏除去。
2-溴代异丁酰溴(>98%):购自Adlrich,直接使用。
N,N,N’,N”,N”-五甲基二乙烯基三胺(PMDETA,99%):购自Adlrich,直接使用。
溴化亚铜(CuBr):分析纯,广州化学试剂一厂,使用前用冰醋酸洗至无色,再分别用无水甲醇、无水乙醚洗三次,真空干燥,氮气气氛中保存。
三乙胺(TEA):分析纯,广州化学试剂一厂,与对甲苯磺酸酰氯回流,蒸馏,CaH2存在下储存。
二氯甲烷:分析纯,天津化学试剂一厂,用5%碳酸钠溶液洗涤,再用水洗涤,然后用无水氯化钙干燥,蒸馏收集40~41℃的馏分,保存在棕色瓶中。
甲苯,分析纯,使用前用钠丝回流除水,常压蒸馏。
其他试剂均为分析纯,使用前干燥、蒸馏。
所有实验用水均为高纯水,Millipore净化装置处理,电阻率≥18.2MΩ。
图2所示为PFCn-b-PEO-b-PFCn三嵌段共聚物的合成路线。
聚合反应具体过程:在室温下,将一定量的大分子引发剂Br-PEO20000-Br和催化剂CuBr(按1:2的摩尔比)加入到充氩气的5mL Schlenk瓶中,用翻口胶塞密封,抽真空除氧,用氩气清洗过的注射器加入脱气的甲苯2mL溶解大分子引发剂,加入按设计聚合度计量比的经脱气的单体甲基丙烯酸二茂铁十一烷基酯,液氮冷冻-抽真空-充氩气解冻,循环三次除氧,用氩气清洗过的注射器加入一定量的配体PMDETA(加入计量为大分子引发剂计2倍)。浸入预先加热至80℃的油浴中,反应6h,液氮冷冻快速终止反应。将反应体系浓缩,加入石油醚:乙酸乙酯=4:1的混合溶剂溶解,过柱(洗脱和展开剂:油醚/乙酸乙酯=4/1),将未反应单体洗出后,然后用THF+5%三乙胺混合溶剂洗脱出粗产品。将粗产品溶解于少量二氯甲烷中,在大量正己烷中反复沉淀,得到纯净的三嵌段共聚物PFCn-b-PEO-b-PFCn,真空干燥至恒重。
测试与表征,傅立叶变换红外光谱(FT-IR)采用Bruker Vertor 33傅立叶变换红外光谱仪测试,均采用室温下KBr压片法。
采用Bruker Avance Digital 400MHz核磁共振仪在CDCl3中测定Br-PEO-Br、Fcn-b-PEO-b-Fcn三嵌段共聚物的1H NMR谱图。
聚合物分子量及分子量分布采用Waters GPC测定,采用三根Styragel色谱柱串联(HR3、HR4、HR6),Waters 515泵,717自动进样器,2414型RI监测器。用一系列单分散的聚苯乙烯标样校准,THF为流动相,流速为1.0mL/min,柱温35℃。
三嵌段共聚物PFCn-b-PEO-b-PFCn的合成,以Br-PEO-Br为大分子引发剂,CuBr/PMDETA为催化剂,通过ATRP法合成了结构明确的PFCn-b-PEO-b-PFCn三嵌段共聚物。
PFCn-b-PEO-b-PFCn(具体可以描述成Mn-b-E454-b-Mn)三嵌段共聚物的结构用1HNMR和GPC表征。以M28-b-E454-b-M28为例,其在CDCl3中的1H NMR谱图如图3所示。对比图3,在图3可以发现:源于PEO链段的3.65ppm处的(-CH2CH2O-)重复结构单元上质子的振动吸收可以清晰的观察到,在4.1处出现的强峰为二茂铁质子振动的特征峰,证明得到的聚合物中同时含有PEO和二茂铁嵌段。通过测定2.3ppm二茂铁基团相邻的质子的特征峰的积分面积和3.65ppm处PEO链中重复结构单元质子的振动峰积分面积,通过公式(5-1)和(5-2)计算出二茂铁侧链的聚合度DPFc和三嵌段共聚物的分子量Mn(NMR):
DPFc=(I2.3/2)/[I3.65/(4×452)] (1-1)
Mn(NMR)=DPFc×MFc+MBr-PEO20000-Br (1-2)
式中I2.3和I3.65分别为2.3ppm和3.65ppm处的核磁峰积分面积。
图4为Br-PEO-Br和PFCn-b-PEO-b-PFCn三嵌段共聚物的GPC曲线。图中可以看到,PFCn-b-PEO-b-PFCn在比Br-PEO20000-Br大分子引发剂流出时间更短(也就是分子量较大)的位置呈现了一个对称的单峰,说明所得的是三嵌段共聚物而不是PFCn和PEO两种均聚物的混合物。Br-PEO-Br和PFCn-b-PEO-b-PFCn三嵌段共聚物的GPC和1H NMR表征结果列于表1-1,表中缩写M和E分别代表PFC和PEO链段,下标10,17和28是三嵌段共聚物大分子链两端的PFC的聚合度,454是PEO链段的聚合度,DP是指PFC链段的聚合度。
表1-1.Br-PEO2000-Br和PFCn-b-PEO-b-PFCn的分子特性参数
Table 1-1.Characterization of PEO macroinitiator and PFCn-b-PEO-b-PFCntriblock copolymers
Sample | Mn a | Mw a | Mn/Mn a | Mn,NMR b | DPb |
Br-E454-Br | 18243 | 19885 | 1.09 | 20273 | |
M10-b-E454-b-M10 | 20236 | 26299 | 1.30 | 28761 | 20 |
M17-b-E454-b-M17 | 23794 | 31381 | 1.32 | 34703 | 34 |
M28-b-E454-b-M28 | 25392 | 33312 | 1.31 | 44464 | 56 |
a:Determined by GPC in THF at 1.0mL/min using PS standard;
b:Determined by 1H NMR。
通过分子量为20000的PEO的两端羟基与2-溴代异丁酰溴的酰化反应,成功合成了两端为2-溴代异丁酰溴的Br-PEO20000-Br大分子引发剂。用这种大分子引发,CuBr/PMDETA为催化剂,通过ATRP法合成了结构明确的两亲性PFCn-b-PEO-b-PFCn三嵌段共聚物。通过1HNMR和GPC等测试分析,证实了其分子结构及分布。
Claims (10)
1.一种含二茂铁基两亲性三嵌段共聚物,其特征在于:以Br-PEO-Br为大分子引发剂,CuBr/PMDETA为催化剂,通过ATRP法合成结构明确的PFCn-b-PEO-b-PFCn三嵌段共聚物,其中,n为嵌段共聚物,b为嵌段,PFC为聚甲基丙烯酸二茂铁十一烷基酯,PEO为聚乙二醇。
2.如权利要求1所述的共聚物,其特征在于:所述Br-PEO-Br具体为两端为2-溴代异丁酰溴的Br-PEO20000-Br大分子引发剂,所述Br-PEO20000-Br大分子引发剂通过分子量为20000的PEO的两端羟基与2-溴代异丁酰溴的酰化或酯化反应得到。
3.如权利要求2所述的共聚物,其特征在于:所述2-溴代异丁酰溴选用的浓度大于98%,所述CuBr使用前用冰醋酸洗至无色,再分别用无水甲醇、无水乙醚洗三次,真空干燥,氮气气氛中保存;所述PMDETA选用的浓度约为99%。
4.一种如权利要求1-3任一项所述的含二茂铁基两亲性三嵌段共聚物的检测方法,其特征在于:包括如下步骤:
(1)将所述三嵌段共聚物溶于CDCl3中,测定三嵌段共聚物的HNMR谱图;
(2)根据HNMR谱图,判断PEO链段和二茂铁嵌段的质子振动情况;如果为强峰,则确定聚合物中同时含有PEO和二茂铁嵌段;否则,则不同时含有;
(3)计算二茂铁侧链的聚合度DPFc和三嵌段共聚物的分子量Mn(NMR);
(4)通过GPC曲线测定聚合物的分子量及分子量分布。
5.如权利要求4所述的检测方法,其特征在于:所述步骤(3)具体为:通过公式(1-1)和(1-2)计算出二茂铁侧链的聚合度DPFc和三嵌段共聚物的分子量Mn(NMR):
DPFc=(I2.3/2)/[I3.65/(4×452)] (1-1)
Mn(NMR)=DPFc×MFc+MBr-PEO20000-Br (1-2)
式中I2.3和I3.65分别为2.3ppm和3.65ppm处的核磁峰积分面积。
6.如权利要求4所述的检测方法,其特征在于:所述步骤(4)中测定具体为:采用WatersGPC测定,采用三根Styragel色谱柱串联(HR3、HR4、HR6),Waters 515泵,717自动进样器,2414型RI监测器,用一系列单分散的聚苯乙烯标样校准,THF为流动相,流速为1.0mL/min,柱温35℃。
7.如权利要求4所述的检测方法,其特征在于:比较Br-PEO-Br和PFCn-b-PEO-b-PFCn三嵌段共聚物的GPC曲线,PFCn-b-PEO-b-PFCn在比Br-PEO20000-Br大分子引发剂流出时间更短的位置呈现了一个对称的单峰。
8.一种如权利要求1-3任一项所述的含二茂铁基两亲性三嵌段共聚物的制备方法,其特征在于:包括如下步骤:
(1)在室温下,将一定量的大分子引发剂Br-PEO20000-Br和催化剂CuBr加入到充氩气的5mL Schlenk瓶中;
(2)用翻口胶塞密封,抽真空除氧,用氩气清洗过的注射器加入脱气的甲苯2mL溶解大分子引发剂,(3)加入按设计聚合度计量比的经脱气的单体甲基丙烯酸二茂铁十一烷基酯,液氮冷冻-抽真空-充氩气解冻,循环三次除氧,用氩气清洗过的注射器加入一定量的配体PMDETA;
(4)浸入预先加热至80℃的油浴中,反应6h,液氮冷冻快速终止反应;
(5)将反应体系浓缩,加入石油醚:乙酸乙酯=4:1的混合溶剂溶解,过柱,将未反应单体洗出后,然后用THF+5%三乙胺混合溶剂洗脱出粗产品;
(6)将粗产品溶解于少量二氯甲烷中,在大量正己烷中反复沉淀,得到纯净的三嵌段共聚物PFCn-b-PEO-b-PFCn,真空干燥至恒重。
9.一种如权利要求8所述制备方法,其特征在于:所述步骤(1)中的所述大分子引发剂Br-PEO20000-Br和催化剂CuBr按1:2的摩尔比加入到充氩气的5mL Schlenk瓶中。
10.一种如权利要求8所述制备方法,其特征在于:所述步骤(3)中配体PMDETA加入的计量为大分子引发剂计的2倍。
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