CN109320691A - 一种聚异氰的合成方法和应用 - Google Patents
一种聚异氰的合成方法和应用 Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002527 isonitriles Chemical class 0.000 claims abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
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Abstract
在本发明中，我们通过钯催化的溴代芳烃、异腈和炔烃的三组分聚合反应合成具有聚集诱导发光性质的聚异氰。该合成方法具有反应条件温和、效率高、原料简单易得、单体范围广等优点。合成的聚合物均具有良好的溶解性、优异的热稳定性和高的折射率。具有聚集诱导发光性质的聚异氰，通过紫外光照射可以光刻产生具有良好分辨率的荧光图案，并且它们还可以作为灵敏的荧光化学传感器用于氯化氢气体的检测。
Description
技术领域
本发明涉及高分子材料合成技术领域，更具体地说，涉及一种聚异氰的合成方法和应用。
背景技术
新型聚合方法的开发在高分子领域不断地发挥着重要的作用。高效和具有选择性的聚合反应可以使化学家合成结构规整的功能性高分子材料，这不仅可以解决化学方面的广泛科学问题，还可以解决其他领域的相关问题。在过去的几十年中，单组分或两组分聚合反应广泛用于聚合物的合成。然而，由于所生成产物的结构缺乏多样性，大多数聚合反应不适合用于构建具有复杂官能团的聚合物主链结构。近年来，多组分反应(multicomponentreactions)已被应用于高分子的合成领域，并且有望用于合成结构明确且含有复杂官能团结构的聚合物。一些比较有名的多组分反应，例如，Passerini反应、Mannich反应、Ugi反应、Hantzsch反应和Biginelli反应，已被应用于合成各种具有独特性质的新型高分子材料。然而这些方法仍然存在单体的合成路线繁琐、所得聚合物的溶解性差等缺点，因此发展合适的多组分聚合反应用于制备结构明确和分子量高的功能性高分子材料，仍然是具有重要挑战意义的课题。
基于炔烃的多组分聚合反应最近引起了广泛的关注。由于炔烃具有丰富的化学性质，由炔烃单体出发可以合成结构多样化且含有杂环官能团的聚合物，例如，由炔烃、磺酰叠氮和胺(或醇)的多组分聚合反应合成poly(N-sulfonylamidines)或poly(N-sulfonylimidates)；由炔烃、醛和胺的多组分聚合反应制备poly(dipropargylamine)；由炔烃、酰氯和巯基乙酸盐(或肼)的多组分串联聚合反应合成具有共轭结构的聚噻吩或聚吡唑聚合物。含亚胺结构的聚合物(聚异氰)因其在信息储存、化学传感、催化剂等领域具有潜在应用价值而备受关注。然而，目前它们的制备方法仅限于单组分聚合反应。因此，多组分聚合反应将为合成具有亚胺结构的功能性高分子材料提供一种高效的合成方法。
发明内容
在本发明中，提供一种新型的三组分聚合反应用于合成具有聚集诱导发光(AIE)特性的聚合物。该聚合反应是由醋酸钯催化的溴代芳烃、异腈和炔烃的偶联反应，反应在氮气保护下，以四氢呋喃作溶剂，在100℃下进行，可以以较高产率(高达93％)生成具有高分子量(高达38200)的聚异氰高分子。参与聚合的三类单体均简单易得，且稳定存在。生成的聚合物在绝大多数的有机溶剂中具有良好的溶解性，并且具有显著的热稳定性，TGA温度(5％的重量损失)可高达300℃。聚异氰薄膜在400-893nm的波长范围内表现出较高的折射率(1.5922-1.8453)。由于部分聚异氰聚合物具有聚集诱导发光的性质，因此它们可以在紫外光辐射下形成具有良好分辨率的荧光图案，并且还可以作为荧光化学传感器用于氯化氢气体的检测。
附图说明
图1为模型化合物4的高分辨质谱；
图2为红外图谱：(A)1a；(B)2a；(C)3a；(D)4和(E)P1a/2a/3a；
图3为氢谱：(A)1a；(B)2a；(C)3a；(D)4和(E)P1a/2a/3a；
图4为碳谱：(A)1a；(B)2a；(C)3a；(D)4和(E)P1a/2a/3a；
图5为聚合物P1/2/3的热重曲线；
图6为聚合物P1/2/3的差示扫描量热曲线；
图7为聚合物P1/2/3在四氢呋喃溶液中的吸收光谱，浓度为10μM；
图8为：(A)聚合物P1a/2a/3a在不同比例四氢呋喃/水混合溶液中的荧光光谱，浓度为10μM，激发波长为370nm；(B)相对荧光强度(I/I0)与水的百分含量关系图，其中I是在混合溶液中测得的荧光强度，I0在纯四氢呋喃中测得的荧光强度.，嵌入B中的照片是聚合物P1a/2a/3a在纯四氢呋喃和80％水含量的四氢呋喃溶液的荧光照片；
图9为聚合物薄膜P1/2/3在不同波长下的折光率；
图10为聚合物膜的二维荧光图案：(A)P1a/2a/3a和(B)P1c/2a/3a，该图案是通过铜板遮蔽，330-385nm范围的紫外光照射光刻而成；
图11为：(A)聚合物P1a/2a/3a粉末在浓盐酸熏陶前后的荧光光谱，激发波长为370nm；(B)涂有聚合物P1a/2a/3a的滤纸在浓盐酸熏陶前后，紫外灯下的荧光照片。
具体实施方式
以下提供的关于本发明的详细描述是为了帮助本领域的技术人员实施该发明。然而，以下的详细描述不会用于限制本发明。在不脱离本发明范围的情况下，本领域相关技术人员可以对相关的内容进行变化和修改。
本发明提供一种聚异氰的合成方法，在溶剂中，将由催化剂催化的溴代芳烃化合物、异腈化合物和炔烃化合物进行聚合反应，沉淀后得到聚异氰。所述溶剂为四氢呋喃。所述聚合反应的温度为100℃，所述聚合反应在氮气保护下进行。所述沉淀在甲醇中沉淀。
反应通式如下所示，反应的条件为a.氮气保护，聚合反应在100℃下进行18h，其中[1]＝0.1M，[2]＝0.12M，[3]＝0.1M，[Pd]＝5mol％[3]，[DPEPhos]＝10mol％[3]，Cs2CO3＝2.1equiv。b.GPC表征，THF作流动相，聚苯乙烯作参考标准：
其中，
聚合反应
为了将该反应发展成一种制备具有明确结构的聚异氰的简便工具，我们选择二溴代芳烃1a、异腈2a和二炔3a作为单体，以二甲基亚砜(DMSO)作为溶剂，进行聚合反应。反应式如下所示：
表1所示为单体投料比例对聚合反应的影响，聚合反应在催化剂Pd(OAc)2，配体DPEPhos和Cs2CO3条件下，以DMSO做溶剂，氮气保护，在100℃反应18h。其中，[3a]＝0.1M，[Pd]＝5mol％，[DPEPhos]＝10mol％，Cs2CO3＝2.1equiv。如表1所示，通过反应，可以得到70％产率的聚合物，Mw为26300(表1，编号1)。过量的异腈2a(2.4当量)可用于提高聚合反应的效率(表1，编号2)。另一方面，二溴代芳烃1a和二炔3a之间的化学计量比(1:1)非常重要，因为两者都参与到聚合物的主链构建中(表1，编号3)。
表1
考虑到钯催化剂的配体和反阴离子可能会影响到催化剂的活性，接着我们对不同类型的钯催化剂进行了筛选。表2所示为钯催化剂对聚合反应的影响。聚合反应在不同钯催化剂，配体DPEPhos和Cs2CO3条件下，以DMSO做溶剂，氮气保护，在100℃反应18h。其中，[3a]＝0.1M，[Pd]＝5mol％，[DPEPhos]＝10mol％，Cs2CO3＝2.1equiv。如表2所示，大多数的钯催化剂均显示出较差的催化活性，其中，醋酸钯Pd(OAc)2仍表现出最佳的效果(表2)。
表2
最后，我们进一步考察了溶剂的影响。表3所示为溶剂对聚合反应的影响。聚合反应在催化剂Pd(OAc)2，配体DPEPhos、Cs2CO3和指定溶剂的条件下，氮气保护，在100℃反应18h。其中，[3a]＝0.1M，[Pd]＝5mol％，[DPEPhos]＝10mol％，Cs2CO3＝2.1equiv。如表3所示，甲苯、二甲基甲酰胺(DMF)和1,4-二氧六环作为溶剂均产生相对较小分子量的聚合物，然而四氢呋喃(THF)作为溶剂可以使聚合物P1a/2a/3a的分子量进一步增加(Mw＝38200，产率＝85％；表3)。聚合后的反应液通过简单地在甲醇中沉淀，除去较小分子量的低聚物，可以很容易地获得黄色聚合物固体，并用于进一步的分析。
表3
单体范围.
通过获得优化的聚合反应条件后，我们进一步考察了单体的适用范围。表4所示为不同功能高分子聚异腈的合成。如表4所示，具有烷基、烷氧基或芳基取代的二溴代芳烃1b-d和带有不同芳环的二炔3b均可以顺利进行反应，并以较高的产率(78-93％)生成聚合物(Mw＝13200至30500)(表4，编号3-6)。值得注意的是，异腈2b也可以作为单体生成具有高分子量的聚合物(Mw＝18800)，产率为81％(表4，编号2)，进一步扩大了聚合单体的范围。
表4
结构表征
为了确定所合成聚合物的化学结构，我们通过以下反应式合成了模型化合物4。
模型反应：按照聚合物P1a/2a/3a的合成实验步骤，通过柱层析得到83％产率的黄色固体4。1H NMR(400MHz,CDCl3),δ(ppm):8.13(d,J＝8.3Hz,2H),7.63(d,J＝8.1Hz,4H),7.46(t,J＝7.6Hz,2H),7.41–7.30(m,3H),7.22–6.95(m,17H),1.55(s,9H).13C NMR(100MHz,CDCl3),δ(ppm):146.8,145.7,143.5,143.4,143.3,142.8,142.3,140.8,140.1,138.7,131.7,131.5,131.5,131.4,131.2,128.9,128.1,128.0,127.8,127.8,127.7,127.3,127.0,126.9,126.8,119.8,99.4,84.4,77.5,57.1,29.7.HRMS(MALDI-TOF):m/z[M+H+]calc’d for C45H38N,592.2999,found 592.3021.
通过对单体1a、2a、3a，模型化合物4和相应的聚合物P1a/2a/3a的红外和核磁图谱进行比较和分析，可以看到，2a在1660cm-1处的C≡N伸缩振动(图2B)以及3a在3279和2108cm-1处的≡C-H和C≡C伸缩振动(图2C)，所有这些特征峰在4和P1a/2a/3a的红外图谱中均消失了(图2D和图2E)。伴随的是，在1584和2199cm-1处分别出现了与C＝N和C≡C伸缩振动相关的两个新峰。同时，P1a/2a/3a的红外图谱几乎与模型化合物4的相同，这些进一步说明了聚合反应的发生。
在1HNMR谱中，3a的端炔氢(δ3.1ppm)几乎完全消失，进一步证实末端三键已被完全消耗(图3C)。2a在δ1.43ppm处的甲基氢位移，在反应后移至δ1.54ppm(图3B)。同时，由于亚胺基团的强吸电子性质，1a的苯基氢位移发生了较大的偏移，从δ7.54ppm移到了δ8.12ppm(图3E)。来自三种单体的氢的相应积分比(I8.12:I7.36:I1.54＝2.0:2.1:9.4)与理论值(2:2:9)一致，进一步表明发生了高效的聚合反应。13CNMR谱进一步确认了所提出的聚合物P1a/2a/3a的结构。如图4所示，P1a/2a/3a的13CNMR特征化学位移,如δ146.6ppm(C＝N)，δ99.1ppm，δ84.5ppm(炔基)和δ57.2ppm(tBu)均与模型化合物4的相同。
以下我们具体分析得到的聚异氰的性质
溶解性和热稳定性
所有得到的聚合物均可溶于常见的有机溶剂，例如THF，氯仿，DCM和DMSO等。利用热重分析(TGA)考察聚合物的热性能。通过实验可以看出，所有聚合物均具有高的热稳定性，5％的重量损失温度范围在230至300℃之间(图5)。差示扫描量热分析显示仅P1c/2a/3a具有约170℃的玻璃化转变温度(Tg)。即使加热到300℃，也没有检测到其它聚合物的玻璃化转变温度的相关信号，可能是由于这些聚合物的刚性结构所致(图6)。
光学性质
聚合物在四氢呋喃溶液(10μM)中的吸收光谱如图7所示。它们的最大吸收光谱位于320nm或350nm左右，正如预期的那样，如果聚合物具有相似的发色团，聚合物的吸收曲线亦相似。我们进一步研究了P1a/2a/3a在不同水含量(fw)的THF/水混合溶液中的荧光性质(PL)。如图8A所示，P1a/2a/3a的纯THF溶液在PL光谱中显示出几乎与横坐标平坦的线，表明聚合物在该条件下是不发光的。但加入水(聚合物的不良溶剂)后，荧光强度缓慢增加。在fw为80％时达到最高的荧光强度，此值为纯THF溶液的29倍(图8B)。这种PL行为证实了P1a/2a/3a具有AIE特性。然而，当加入超过90％的水时，荧光强度略微降低，这可能是由于在溶液中形成了较大的疏水聚合物的聚集体从而降低了AIE分子的有效浓度。
光折射：
在光学仪器中，折射率(RI)是一些关键部件(例如透镜和棱镜)非常基本和重要的参考标准。高折射率的聚合物定义为折射率大于1.50的聚合物材料。具有高折射率(n)的高分子可用作各种光学应用的候选物，例如棱镜，波导和全息图像记录系统。理论上，含有高度极化的芳环或杂原子的聚合物往往具有高的n值。通过测试可以看到，P1a/2a/3a，P1c/2a/3a和P1d/2a/3b的旋涂薄膜在632.8nm处显示出较高的n值1.6219-1.6637(图9)。据我们所知，如此高的折射率值在纯有机聚合物材料中属于最佳值的范畴。
除了折射率之外，光学色散是光学材料的另一个重要参数。材料的Abbé数值(vD)用作它的RI值随波长的变化或分散的度量，定义为(nD-1)/(nF-nC)，其中nD,nF和nC是波长分别为589.2,486.1和656.3nm的Fraunhofer D，F和C谱线的RI值。相应的D值计算为vD的倒数。因此，具有小D值的聚合物膜是工业应用所需的。如表5所示，P1/2/3的vD和D值在20-30和0.05-0.03的范围内，这在先进的聚合物材料中属于相对较小的数值。
表5
荧光图案和化学传感
由于具有AIE特征和亚胺官能团，P1a/2a/3a的聚集体或固态不仅可以用于光刻图案，如图10所示，利用紫外光照射可以刻画具有良好分辨率的二维绿色荧光图案。同时该聚合物也可以应用于化学传感器。如图11B所示，涂于滤纸上的P1a/2a/3a粉末在紫外光照射下发出强烈的荧光。当用氯化氢气体熏陶30秒后，聚合物的荧光被淬灭，如图11A中所示的PL曲线。该荧光淬灭现象可能与P1a/2a/3a的亚胺结构被质子化或水解相关。从这些实验可以看到，该类聚合物有效地结合了AIE特性与亚胺的反应多样性，这将会使它们在许多领域成为具有潜在应用价值的功能性高分子材料。
Claims (9)
1.一种聚异氰的合成方法，其特征在于，包括以下步骤：
在溶剂中，将由催化剂催化的溴代芳烃化合物、异腈化合物和炔烃化合物进行聚合反应，沉淀后得到聚异氰。
2.根据权利要求1所述的聚异氰的合成方法，其特征在于，
所述溴代芳烃化合物的结构通式如式(I)所示：Br-Ar-Br 式(I)；
所述异腈的结构通式如式(II)所示：CN-R 式(II)；
所述炔烃化合物的结构通式如式(III)所示：
所述聚异氰的结构通式如式(IV)所示：
其中，Ar选自以下结构式中的一种：
R选自以下结构式中的一种：
其中，Ar’选自以下结构式中的一种：
3.根据权利要求1所述的聚异氰的合成方法，其特征在于，所述催化剂为醋酸钯。
4.根据权利要求1所述的聚异氰的合成方法，其特征在于，所述溶剂为四氢呋喃。
5.根据权利要求1所述的聚异氰的合成方法，其特征在于，所述聚合反应的温度为100℃，所述聚合反应在氮气保护下进行。
6.根据权利要求1所述的聚异氰的合成方法，其特征在于，所述沉淀在甲醇中沉淀。
7.一种如权利要求1-6所述的合成方法制备的聚异氰。
8.一种如权利要求1-6所述的合成方法制备的聚异氰在光刻荧光图案中的应用。
9.一种如权利要求1-6所述的合成方法制备的聚异氰作为荧光化学传感器在检测氯化氢气体中的应用。
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Non-Patent Citations (1)
| Title |
|---|
| HIROTO YOSHIDA，ET AL: ""Three-Component Coupling of Arynes and Organic Bromides"", 《ANGEW. CHEM.》 * |
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