CN102516988A - 一类可聚合荧光染料、其制备方法及应用 - Google Patents

一类可聚合荧光染料、其制备方法及应用 Download PDF

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CN102516988A
CN102516988A CN2011103871458A CN201110387145A CN102516988A CN 102516988 A CN102516988 A CN 102516988A CN 2011103871458 A CN2011103871458 A CN 2011103871458A CN 201110387145 A CN201110387145 A CN 201110387145A CN 102516988 A CN102516988 A CN 102516988A
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彭孝军
强新新
樊江莉
宋锋玲
孙世国
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DALIAN FUSIDA SPECIAL CHEMICAL Co Ltd
Dalian University of Technology
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Abstract

一类可聚合荧光染料、其制备方法及应用,所述的可聚合荧光染料具有下述通式的结构:

Description

一类可聚合荧光染料、其制备方法及应用
技术领域
本发明属于有机聚合物材料领域,尤其涉及一类可聚合荧光染料及其应用。
背景技术
功能聚合物纳米微球由于其在材料、荧光传感器、生物医学检测方面的极具潜力的应用而引起人们广泛的研究兴趣。与分子状态的荧光染料相比,荧光微球具有稳定性好、发光效率高的优点;与无机荧光颗粒相比,荧光聚合物微球具有单分散性好、粒度均一、球形度好等特点。因此在标准、计量、免疫医学、生物化学、分析化学、生物医学领域的应用具有良好的前景。
常规方法的荧光微球制备,将荧光染料吸附在载体上[Z.L.Zhang,Y.Long,J.B.Pan and X.M.Yan,Journal of Materials Chemistry 20(2010)1179-1185],这种方法方便快捷,但是吸附的染料分子容易受到外界环境的干扰而脱落,难以功能化,限制了其使用。
另一种方法是硅无机聚合物包埋或单体聚合的方法制备荧光微球[F.Enrichi,G.Canton,R.Ricco,F.Marinello and S.Carmignato,Journal of Nanoparticle Research 13(2011)4349-4356;G.Bosma,C.Pathmamanoharan,E.H.A.de Hoog,W.K.Kegel,A.van Blaaderen and H.N.W.Lekkerkerker,Journal of Colloid and Interface Science 245(2002)292-300],具有无毒的特点,得到了广泛关注,但不耐酸碱,在功能化(如官能团化学交联)时受到了反应条件的限制。
随着荧光微球的应用发展,微球的功能化,如在微球上使用引入羧基、氨基、氯甲基等活性基团满足连接生物分子的要求。但如何在含有荧光的球上同时具有可反应基团,成为难点。
聚苯乙烯和聚丙烯酸作为廉价的聚合体系,可以提供乳化聚合制备微球等有利技术手段,也易于在聚合物上带有可交联的潜在位点。但荧光母体在烯烃自由基聚合过程中,容易对自由基淬灭,起到阻聚剂的终止作用,从而使聚合过程缓慢[Y.J.He andH.Tian,Acta Polymerica Sinica(2000)379-381;潘祖仁.高分子化学[M].化学工业出版社,2007:108]。因此目前报道的体系较少,成为本领域的难点之一。
发明内容
本发明旨在提供一种制备方法简单、可方便地嵌入高分子聚合物中、并且不易脱落的可聚合荧光染料。
本发明首先提供一类可聚合荧光染料,具有通式I的结构:
Figure BDA0000113256800000021
其中:
D是荧光染料母体;
Z为含有可聚合的官能团的连接基团;
n是1或2。
本发明所述的可聚合荧光染料中所述的Z选自Z1、Z2、Z3和Z4
Figure BDA0000113256800000022
其中,虚线键,即X的游离键,为与D连接的键,R1为氢原子或CH3;X为氧原子、CH2或NH。
上述本发明所述的可聚合荧光染料,其特征在于所述的D选自1,8-萘酰亚胺类染料、蒽吡啶酮类染料和苝酰亚胺类染料。
优选的技术方案中,上述本发明的可聚合荧光染料中所述的D选自D1、D2、D3和D4
Figure BDA0000113256800000023
其中,虚线键为与Z连接的键,R2为C1-10的直连烷烃、支链烷烃或环烷烃。
进一步优选,所述的D选自下述化合物:
所述及的D为D1、D2或D3时,本发明所述及的可聚合荧光染料可以通过酰化反应、N烷基化反应或成醚反应制备。本领域的技术人员应当能够从现有技术中得到启示,准确地设计所需反应并确定反应条件。
所述及的D为D4时,本发明所述及的可聚合荧光染料通过化合物i和化合物ii的取代反应得到:
Figure BDA0000113256800000032
所述的化合物i和化合物ii的取代反应体系中,有缚酸剂存在,其选自碳酸钾、碳酸钠、碳酸氢钠或三乙胺。所述反应体系中还有阻聚剂存在,其选自一价铜盐、二价铜盐或碘盐。
本发明再一方面提供一种荧光纳米微球,所述的荧光纳米微球是由上文所述的本发明的可聚合荧光染料与苯乙烯或其衍生物、丙烯酸或其衍生物、甲基丙烯酸或其衍生物中的一种或几种聚合而成。
本发明进一步提供上述荧光纳米微球的制备方法,是乳液聚合的方法,聚合反应以Triton X-100、SDS或二者的混合物为乳化剂,以氧化还原反应体系作为引发体系,反应温度30~55℃,反应时间5~78小时;
其中,乳化剂的用量为聚合单体总质量的1~50%。其中可聚合荧光染料的用量可由本领域技术人员根据对聚合目的产物的荧光当量等具体要求确定,本发明不加以限定。
通过上述本发明的方法制备得到的荧光纳米微球粒径大小为15~300纳米,优选于20~200纳米。
本发明所述的可聚合荧光染料具有光稳定性高、荧光量子产率高的优点,可在激光读取、激光扫描、霓虹灯照射、户外等苛刻条件下使用。所制备得到的荧光纳米微球可广泛应用于生物检测、发光材料、印刷或涂料领域的应用。乳液聚合的制备方法利用烯烃双键自由基聚合反应,可以方便地将荧光染料化学嵌入聚合物中,不脱落,同时引入带有氯化苄乙烯的单体,可以进行形成化学交联位点,通过乳化聚合制备可功能化的荧光纳米微球,可以满足上述需求。
附图说明
本发明附图6幅:
图1是可聚合荧光染料11溶液聚合后的核磁谱图
图2是实施例8制备的纳米聚合物荧光微球的透射电镜图;
图3是实施例8制备的荧光纳米微球的粒径分布;
图4是可聚合荧光染料3及实施例8中制备的荧光纳米微球的光谱图;
图5是实施例10制备的纳米聚合物荧光微球的透射电镜图;
图6是乙醇中可聚合荧光染料3和罗丹明B光降解对比曲线。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
实施例1
可聚合荧光染料3的合成:
Figure BDA0000113256800000051
中间体2的合成:将4-溴-N-甲基蒽吡啶酮(1,4.9g,14.4mmol),无水硫酸铜(0.2g,10mol%)和1,6-己二胺(2g,17.2mmol)溶于100mL乙二醇单甲醚中,加入无水碳酸钾(3g,21.6mmol)作为缚酸剂。回流反应24h后过滤除去碳酸钾及硫酸铜。滤液使用旋转蒸发除去溶剂,得到红色固体。固体用乙醇洗涤,以除去过量的1,6-己二胺。硅胶柱分离(乙酸乙酯∶甲醇=10∶1为洗脱液),产率51%。
1H-NMR(400MHz,CDCl3)δ10.49(m,1H,NH),8.46(d,J=7.7Hz,1H,ArH,),8.30(d,J=7.9Hz,1H,ArH),8.20(d,J=7.9Hz,1H,ArH),7.83-7.62(m,4H,ArH,CH2),3.86(s,3H,CH3),1.71-1.60(nb,12H,CH2).MS(TOF MS ES+)calculated for[C23H26N3O2]+:376.2020,measured:376.2022.
中间体2(1g,2.7mmol),甲基丙烯酰氯(2g,19mmol)和5mL三乙胺作为缚酸剂溶于20mL无水THF中0℃反应8h。反应结束后,将反应液倒入饱和食盐水中,过滤并用水洗涤滤饼,干燥后硅胶柱分离(乙酸乙酯作为洗脱液)可得到0.5g红黑色可聚合荧光染料3产品,产率50%。
1H-NMR(400MHz,CDCl3)δ10.45(s,1H,NH),8.46(d,J=7.7Hz,1H,ArH,),8.18(d,J=7.9Hz,1H,ArH),7.80-7.57(m,4H,ArH,CH2),7.14(d,J=9.5Hz,1H,ArH),5.93(s,1H,NH),5.68(s,1H,CH),5.31(s,1H,CH),3.83(s,3H,CH3),3.46-3.25(m,4H,CH2),1.97(s,3H,CH3),1.80(m,2H,CH2),1.59(m,4H,CH2),1.50-1.39(m,2H,CH2).MS(TOF MS ES+)calculated for[C27H30N3O3]+:444.2282,measured:444.2286。
实施例2
可聚合荧光染料5的合成:
以4-溴-1,8-萘酐为起始原料制备可聚合的萘酰亚胺类荧光染料。
Figure BDA0000113256800000061
中间体4的合成:4-溴-1,8-萘酐(5.5g,19.9mmol)和1,6-己二胺(4.6g,39.7mmol)溶于200mL乙二醇单甲醚中,回流5h,有大量黄色固体析出。反应结束后将反应液倒入500mL水中,过滤,滤饼用冷的乙醇洗涤以除去残留的1,6-己二胺。干燥后得到黄色固体5.1g,产率63%,无需进一步提纯可用于染料5的合成。
将中间体4酰胺化可得到染料5,反应步骤参考合成染料3的过程。
1H-NMR(400MHz,CDCl3)δ8.57(d,1H,J=4.0,ArH),8.45(d,1H,J=8.0,ArH),8.29(d,1H,J=8.0,ArH),7.63(t,1H,J=8.0,ArH),6.71(d,1H,J=8.0,ArH),6.03(s,1H,NH),5.83(s,1H,NH),5.71(d,3H,J=4.0,CH,NH),5.34(d,2H,J=12.0,CH),4.18(t,2H,CH),3.42(m,4H,CH),3.32(m,2H,CH),1.98(s,6H,CH),1.82(6H,m,CH),1.68(m,6H,CH),1.43(s,4H,CH).MS(TOF MS ES+)calculated for[C32H43N4O4]+:547.3279,measured:547.32870.
实施例3
可聚合荧光染料8的合成:
中间体6的合成:4-溴-1,8-萘酐(2.7g,10mmol)和3-辛胺(1.5g,12mmol)溶于100mL乙醇溶液中,加热回流反应10h后,TLC检测无原料4-溴-1,8-萘酐,冷却至室温,有大量土黄色固体析出。过滤反应液,滤饼用少量冷的乙醇溶液洗涤至滤液无黄色,干燥后得到土黄色产品3.0g,粗产率88%。
中间体7的合成:中间体6(3.0g,7.7mmol)和无水哌嗪(5.0g,58mmol)溶于100mL乙二醇单甲醚中,升温至100℃,反应液变成黄褐色,继续反应6h后,冷却至室温。将反应液倒入400mL冷水中,乙酸乙酯萃取(3×100mL),合并有机相,蒸出溶剂得黄色固体2.8g,粗产率93%。
取中间体7(0.6g,1.5mmol)、4-氯甲基苯乙烯(0.3g,2.0mmol)和无水碳酸钾(0.5g,3.6mmol)溶于50mL乙腈中回流反应4h,TLC检测物原料点,反应液倒入冰水中,有黄色固体析出,过滤,滤饼干燥后用碱性氧化铝柱分离后(石油醚∶二氯甲烷=1∶1.5~2为洗脱液)得目标产物为黄色固体0.5g,产率65%。
1H-NMR(400MHz,CDCl3)δ8.57(d,1H,ArH,J=8Hz),8.51(d,1H,ArH,J=18Hz),8.40(d,1H,ArH,J=4Hz,),7.685(t,1H,ArH,J=8.4Hz,),7.413(d,2H,ArH,J=8Hz,),7.350(d,2H,ArH,J=8Hz,),7.205(d,1H,ArH,J=8Hz,),6.760(m,1H,CH),5.778(d,1H,CH,J=17.6Hz),5.257(d,1H,CH,J=10.8Hz,),3.648(s,2H,CH2),3.289(s,4H,CH2),2.773(s,4H,CH2)1.949-0.854(m,15H CH,CH2,CH3).MS(TOF MS ES+)calculated for[C33H40N3O2]+:510.3115,measured:510.3117.
实施例4
可聚合荧光染料11的合成:
Figure BDA0000113256800000081
中间体10的合成:对苯二酚(8.8g,80mmol)、4-氯甲基苯乙烯(3.0g,20mmol)、碳酸钾(2.8g,20mmol)溶于75mL丙酮中,回流反应24h后,冷却至室温,过滤,滤饼用丙酮洗涤(3×5mL),合并滤液后蒸出溶剂,加50mL氯仿至残留物中,充分溶解过滤以除去残留的对苯二酚,蒸干滤液,硅胶柱分离(乙酸乙酯∶石油醚=1∶10为洗脱液),得白色固体1.9g,产率43%。
1H-NMR(400MHz,CDCl3)δ7.404(d,2H,ArH,J=10Hz),7.376(d,1H,ArH,J=10Hz),6.834(d,2H,ArH,J=16Hz,),6.756(d,2H,ArH,J=16Hz,),6.708(m,1H,CH),5.778(d,1H,CH,J=21Hz),5.262(d,1H,CH,J=16Hz,),4.988(s,2H,CH2).
取染料9(0.135g,0.19mmol,合成方法参考L.Fan,Y.Xu and H.Tian,TetrahedronLett,46(2005)4443-4447;B.A.Jones,M.J.Ahrens,M.-H.Yoon,A.Facchetti,T.J.Marksand M.R.Wasielewski,Angewandte Chemie International Edition,43(2004)6363-6366)、中间体10(0.175g,0.77mmol)、碳酸铯(0.1g,0.3mmol)和碘化亚铜(0.1g,0.5mmol)溶于15mL甲苯中,回流反应20h后,蒸出溶剂,加二氯甲烷50mL洗涤残留物,过滤,蒸出溶剂后,硅胶柱分离(石油醚∶二氯甲烷=1∶1~1.5为洗脱液),得目标产物为暗红色固体60mg,产率32%。
1H NMR(400MHz,CDCl3):δ9.54(d,2H,ArH,J=8.0Hz),8.55(d,2H,ArH,J=8.4Hz,),8.21(s,ArH,2H),7.41-7.48(m,ArH,8H),7.03-7.12(m,ArH,2H),6.71(m,CH,2H),5.81(d,2H,CH,J=17.6Hz),5.29(d,2H,CH,J=13.2Hz),5.09(s,CH2,4H),4.98(m,CH,2H),2.52(m,4H,CH2),1.89(d,4H,CH2,J=7.2Hz),1.72(d,4H,CH2,J=12.0Hz)1.23-1.57(m,8H,CH,CH2).MS(TOF MS ES+)calculated for[C66H55N2O8]+:1003.3953,measured:1003.3949.
实施例5
可聚合荧光染料13的合成:
Figure BDA0000113256800000091
中间体12的合成:将对苯二酚(2.5g,22.7mmol)、烯丙基溴(1.4mL,5.7mmol)、无水碳酸钾(0.8g,5.8mmol)加至50mL无水乙腈中,回流反应12h后冷却至室温,过滤后,蒸干滤液,加水100mL,乙醚(3×50mL)萃取,有机相无水硫酸钠干燥后减压蒸干,硅胶柱分离(乙酸乙酯∶石油醚=1∶10为洗脱液)得褐色油状物2.7g,产率79%。
荧光染料13的合成步骤与染料11的合成步骤类似。
产率:53%。1H NMR(400MHz,CDCl3):δ9.60(d,2H,ArH,J=8.0Hz),8.64(d,2H,ArH,J=8.0Hz,),8.24(s,2H,ArH),7.10(d,4H,ArH,J=8.8),7.01(d,4H,ArH,J=9.2Hz),6.09(m,2H,CH),5.49(d,2H,CH,J=17.6Hz),5.36(d,2H,CH,J=10.4Hz),4.98(m,2H,CH),4.59(d,4H,CH2,J=8.0Hz),2.52(m,4H,CH),1.90(d,4H,CH2,J=12.0Hz),1.75(d,8H,CH,J=12.0Hz),1.56(s,2H),1.44-1.25(m,2H).MS(TOF MS ES+)calculated for C54H47N2O8:851.3327,measured:851.3329.
实施例6
可聚合荧光染料14的合成:
Figure BDA0000113256800000101
合成方法与实施例1类似,使用丙烯酸作为酰胺化试剂即可得到染料14。
产率:66%。1H-NMR(400MHz,CDCl3)δ10.40(s,1H,NH),8.43(d,J=8.0Hz,1H,ArH),8.19(d,J=12.0Hz,1H,ArH),7.73-7.55(m,4H,ArH,CH2),7.10(d,J=12.0Hz,1H,ArH),6.31(d,J=16.0Hz,1H,CH),6.16(m,1H,CH),5.95(b,1H,NH),5.63(d,J=16.0Hz,1H,CH),3.79(s,3H,CH3),3.40-3.35(m,4H,CH2),1.80-1.46(m,8H,CH2).MS(TOF MS ES+)calculated for[C26H28N3O3]+:430.2125,measured:430.2123.
实施例7
可聚合荧光染料11的溶剂聚合:
可聚合荧光染料11(50mg,0.05mmol),偶氮二异丁腈(5mg,0.03mmol)溶于10mL环己酮中,70℃反应3h,冷却至室温,将反应液倒入100mL甲醇中,有暗红色固体析出,过滤,并用50mL甲醇洗涤,干燥后得聚合物35mg。
聚合物的核磁表征见图1。
实施例8
较小粒径荧光纳米微球的微乳液制备过程:
单体4-氯甲基苯乙烯(0.5g,4.8mmol)、甲基丙烯酸甲酯(1.5g,15mmol)和实施例1所制备的可聚合荧光染料3(5mg,11.3μmol)的微乳液聚合反应在带三口圆底烧瓶中进行。Triton X-100(0.4g,0.62mmol)作为乳化剂溶解于45mL双蒸水中,随后以上混合在一起的单体加入三口瓶中超声波震荡乳化5min,通氮气除氧10min,匀速磁力搅拌。亚硫酸氢钠(10mg,97.1μmol)和过硫酸钾(45mg,0.17mmol)分别溶在5mL双蒸水中依次加入反应瓶中。聚合反应在40℃引发,反应24h。透射电镜测试在JEM-2000EX(JEOL,Tokyo,Japan)上进行,制得的纳米微球透射电镜图片见图2,纳米微球的粒径分布通过Malvern ZS-90激光纳米粒度仪测试获得,其平均粒径为22nm,见图3。
实施例9
光谱性能测试:
取实施例8所制备的纳米微球乳液,配制成一定浓度的水溶液,测定其荧光性能。同时,将实施例4所制备的可聚合荧光染料11配制成6×10-6M,测定其吸收和荧光光谱性能。归一化的谱图见图4。
实施例10
较大粒径荧光纳米微球的合成步骤:
单体苯乙烯(2.5g,24.0mmol)和实施例4所制备的可聚合荧光染料11(5mg,5.0μmol)的乳液聚合反应在带三口圆底烧瓶中进行。十二烷基磺酸钠(SDS,50mg,0.17mmol)作为乳化剂溶解于45mL双蒸水中,随后以上混合在一起的单体加入三口瓶中超声波震荡乳化5min,通氮气除氧10min,匀速磁力搅拌。过硫酸钾(45mg,0.17mmol)分别溶在5mL双蒸水中滴加至反应瓶中。聚合反应在75℃引发,反应7h。透射电镜测试在JEM-2000EX(JEOL,Tokyo,Japan)上进行,制得的纳米微球透射电镜图片见图5,其平均粒径约为150nm。
实施例11
实施例1所制备的可聚合荧光染料3和商品化染料罗丹明B的光稳定性对比:
罗丹明B是一个广泛应用的商品化染料,我们比较了染料3和罗丹明B在乙醇中光稳定性(如图6)。可见,经过500W碘钨灯照射7h后,在各自最大吸收处的百分比染料3比罗丹明B高约10%,说明染料3比商品化的荧光染料罗丹明B有更高的光稳定性。

Claims (7)

1.一类可聚合荧光染料,具有通式I的结构:
Figure FDA0000113256790000011
其中:
D是荧光染料母体;
Z为含有可聚合的官能团的连接基团;
n是1或2。
2.权利要求1所述的可聚合荧光染料,其特征在于所述的Z选自Z1、Z2、Z3和Z4
其中,虚线键为与D连接的键,R1为氢原子或CH3;X为氧原子、CH2或NH。
3.权利要求1或2所述的可聚合荧光染料,其特征在于所述的D选自1,8-萘酰亚胺类染料、蒽吡啶酮类染料和苝酰亚胺类染料。
4.权利要求3所述的可聚合荧光染料,其特征在于所述的D选自D1、D2、D3和D4
Figure FDA0000113256790000013
其中,虚线键为与Z连接的键,R1为甲基或氢原子;R2为C1-10的直连烷烃、支链烷烃或环烷烃。
5.权利要求4所述的可聚合荧光染料,其特征在于所述的D选自下述化合物:
6.一种荧光纳米微球,其特征在于是由权利要求1所述的可聚合荧光染料与苯乙烯或其衍生物、丙烯酸或其衍生物、甲基丙烯酸或其衍生物中的一种或几种聚合而成。
7.权利要求6所述的荧光纳米微球的制备方法,是乳液聚合的方法,聚合反应以Triton X-100、SDS或二者的混合物为乳化剂,以氧化还原反应体系作为引发体系,反应温度30~55℃,反应时间5~78小时;
其中,乳化剂的用量为聚合单体总质量的1~50%。
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