CN1101828C - 一种全同立构聚n－乙烯咔唑及其制备方法和用途 - Google Patents
一种全同立构聚n－乙烯咔唑及其制备方法和用途 Download PDFInfo
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Abstract
本发明一种全同立构聚N-乙烯咔唑为高全同立构的螺旋链光学活性聚合物，其全同立构摩尔分数为48.0-51.5%。本发明高全同立构聚N-乙烯咔唑是采用具有手性和立体差异性配体的有机盐为引发(催化)剂，进行立体选择性聚合制得。本发明高全同立构聚N-乙烯咔唑可作为光电材料研究中的孔洞传输层，具有低能激发特征的实际应用。
Description
本发明是关于一种全同立构聚N-乙烯咔唑及其制备方法和用途。
N-乙烯咔唑的聚合，由自由基[J.Appl.Polym.Sci.，9，3939(1965)]，普通阳离子[J.Polym.Sci.Polym.Chem.Ed.，31，319(1993)]及其电荷转移复合物[J.Macromol.Sci-Rev.Macromol.Chem.，C16(2)，129(1977-1988)]引发已经广泛地被研究并发表了很多论文。然而，这些涉及到聚N-乙烯咔唑的立体微结构(全同立构)研究并不多。早在1976年日本Okamoto等人[Macromolecules9(4)，645(1976)]采用自由基(AIBN)和阳离子(BF3OEt2)引发N-乙烯咔唑的聚合得到全同立构比例分别为20％和34％(核磁共振法测)。后来在1982年Terrell等人[Macromol.Chem.，183，363(1982)]也采用自由基(AIBN)和阳离子(BF3OEt2)，在较低温度下(-40～25℃)引发N-乙烯咔唑聚合得到全同立构的比例分别为2 -35％和38％(核磁共振法测)及44％(破化转变法测)。这些全同立构比例是检测结果的平均值。上述已有技术合成的聚N-乙烯咔唑，用于光电材料中(光、电场致发光材料)只能高能激发，所需能耗大、成本高。
本发明克服了已有合成技术中全同立构聚N-乙烯咔唑作为光电材料时高能激发、能耗大的不足，而提供一种低能激发的高全同立构的聚N-乙烯咔唑。
本发明专利是采用了新型阳离子引发(催化)剂下，N-乙烯咔唑的不对称立体选择性聚合，而得到摩尔分数为48-51.5％(核磁共振法测)、65.3-76.1％(玻璃化转变法测)的高全同立构螺旋链光学活性聚合物。其结构式如下：
本发明高全同立构聚N-乙烯咔唑的制备方法是按下列步骤进行：
1.合成具有手性和立体差异性配体(如图示一)的有机盐。
(-)鹰爪豆碱 三苯甲基左右旋异构 (+)樟脑磺酸
[(-)Sp*] [Ph3 *C] [(-)CSA*]图示一 光学活性配体的结构
2.采用上述有机盐作为引发(催化)剂，进行N-乙烯咔唑的不对称立体选择性诱导聚合，得到高全同立构的螺旋光学活性聚合物(图示二)。
图示二N-乙烯咔唑的不对称聚合
具有手性或立体差异性配体的有机盐的合成和表征：
上述图示一中配体分别以等摩尔比例同高氯酸(HClO4)或樟脑磺酸(CSA)生成相应的如下有机盐(三苯甲基以醇或氯化物形式参与反应)。(-)鹰爪豆碱高氯酸盐[(-)Sp*+ClO4 -，[α]D 25-13.2°，
(-)(Sp)2 *+(ClO4)3 -，[α]D 25-17.1°](+)樟脑磺酸三苯甲基盐[Ph3*C+(+)CSA*-，[α]D 25+45.5°](-)鹰爪豆碱(+)樟脑磺酸盐[(-)Sp*+(+)CSA*-，[α]D 25+23.4°](+)樟脑磺酸[(+)CSA*，[α]D 25+20.1°]
在以上三苯甲基盐中，三苯甲基阳离子具有左右旋异构的消旋体(图示一)，但参与引发反应时表现出较大的差异性，作为阳离子引发N-乙烯咔唑时，只有左旋或右旋异构体参与引发而进行立体选择性聚合。
在具有手性和立体差异性配体的有机盐存在下，N-乙烯咔唑的不对称立体选择性聚合。具体制备方法如下：
秤取一定量的N-乙烯咔唑单体，放入安瓿瓶中，并与真空高纯氮气管线相联，置换出空气，重复三次，用针筒注入溶剂二氯乙烷或四氢呋喃，制成浓度为0.22-0.66摩尔/升的溶液，然后将此溶液放入水浴中，恒温在温度25或40℃。(2)再将引发(催化)剂按0.5-10摩尔％(基于单体)溶于上述相应溶剂，用针筒注入单体溶液中，反应时间在0.5-140小时范围。(3)用针筒取3ml甲醇注入安培瓶中，以中止反应。然后，倒入大量的甲醇中沉淀出来，过滤，洗涤，干燥，产率15.8-100％，得到的聚N-乙烯咔唑分子量1-5万(粘度法)，旋光度[α]D 25+0.9-8.3°，全同立构分数48-51.5％(核磁共振法)或65.3-76.1％(玻璃化转变法测)。
本发明由这种新型阳离子引发(催化)剂而得到的这种高全同立构光学活性聚N-乙烯咔唑，作为光电材料(光、电场致发光材料)研究中孔洞传输层，具有低能激发，因而更具有实用意义。
本发明采用具有手性和立体差异性配体的有机盐作为引发(催化)剂，具有大侧基的烯类单体N-乙烯咔唑，进行不对称立体选择性诱导聚合，得到的聚N-乙烯咔唑的旋光度，全同立构比例与所采用的有机盐类型密切相关，从旋光度测试、核磁共振法和玻璃化转变法检测表明：这些有机盐在N-乙烯咔唑聚合过程中，引发(催化)的立体选择性诱导能力具有如下规律：
A*+B*-＞A+B*-＞A*+B-(A，B为有机盐配体缩写，*为手性特征)由此可以看出，有机盐中反离子的手性与否对诱导能力起者重大影响。
由上述有机盐引发(催化)，得到的聚N-乙烯咔唑的紫外消光系数值恰相反，而是越来越小，表明这种聚合物高分子链规整性提高，全同比例增大，所以这种新型有机盐作为引发(催化)而得到的高全同立构、低消光系数的光学活性聚N-乙烯咔唑较自由基、一般阳离子和电荷转移络合物引发而得到的低全同立构、高消光系数、无光学活性的聚N-乙烯咔唑。
上述综合结果见表I
表I.聚N-乙烯咔唑的旋光度和全同立构摩尔分数
a.文献参考平均值
| 引发(催化)剂类型 | 旋光度[α]D 25 | 全同立构分数(摩尔％) | |||
| 核磁共振法 | 玻璃化转变法 | ||||
| AIBN | 0° | 28.0 | 20.0a | 25-35.0a | - |
| H*ClO4 | 0° | 39.0 | - | - | - |
| BF3OEt2 | 0° | - | 34.0a | 38.0a | 44.0a |
| (-)Sp*+ClO4 - | +2.4° | 48.0 | - | - | 65.3 |
| (+)CSA*- | +4.2° | 50.6 | - | - | 75.0 |
| Ph3C+(+)CSA*- | +4.4° | 51.5 | - | - | 74.2 |
| (-)Sp*+(+)CSA*- | +8.3° | 51.4 | - | - | 76.1 |
实施例：例1.采用(-)Sp*+ClO4 -引发剂下，N-乙烯咔唑聚合
将1.93克N-乙烯咔唑(0.01摩尔)放入安瓿瓶中，然后与真空高纯氮气线相连，置换安瓿瓶内空气，重复三次。用针筒注入干燥重蒸的二氯甲烷80毫升，电磁搅拌使其完全溶解，再将安瓿瓶放入水浴中，维持温度40℃，0.046克(-)Sp*+ClO4 -(0.0001摩尔)溶解于1毫升二氯乙烷得到的溶液用针筒注入安瓿瓶中，反应开始，时间43小时，3毫升甲醇注入安瓿瓶中以中止反应。然后，200毫升甲醇中沉淀，过滤，洗涤，干燥，得粉末状聚合物，产率77.7％，分子量93000，旋光度[α]D 25+2.4°，全同立构比例48％。例2.采用(+)CSA*催化N-乙烯咔唑聚合
按照例1中操作进行，不同之处在于溶剂为四氢呋喃，催化剂量10％摩尔(基于单体)，反应时间48小时，产率41.8％，分子量16000，旋光度[α]D 25+4.2°，全同立构比例50.6％(核磁共振法测)，和75.0％(玻璃化转变法测)。例3.采用Ph3 *C+(+)CSA*-催化N-乙烯咔唑聚合
按照例1中操作进行。不同之处在于催化剂用量2摩尔％(基于单体)，反应温度25℃，时间28小时，产率64.8％，分子量17000，旋光度[α]D 25+4.4°，全同立构比例51.5％(核磁共振法测)和74.2％(玻璃化转变法测)。例4.采用(-)Sp*+(+)CSA*-催化N-乙烯咔唑聚合
按照例1中操作进行。不同之处在于溶剂为四氢呋喃，催化剂用量4摩尔％(基于单体)，时间118小时，产率15.8％，分子量12000，旋光度[α]D 25+8.3°，全同立构比例51.4％(核磁共振法测)和76.1％(玻璃化转变法测)。
Claims (6)
1.一种全同立构聚N-乙烯咔唑，其特征在于所述的全同立构聚N-乙烯咔唑是全同立构比例采用核磁共振谱测得为48.0-51.5％或采用测玻璃化转变法测得为65.3-76.1％的高全同立构螺旋链光学活性聚N-乙烯咔唑，其结构式
2.根据权利要求1所述的一种全同立构聚N-乙烯咔唑的制备方法，其特征在于按下列步骤进行：(1)将手性或者立体差异性配体与高氯酸(HClO4)或樟脑磺酸(CSA)按等摩尔比反应生成相应的有机盐(-)鹰爪豆碱高氯酸盐；(-)樟脑磺酸三苯甲基盐；(-)鹰爪豆碱(+)樟脑磺酸盐；(+)樟脑磺酸。(2)采用上述有机盐或酸作为引发剂，将单体N-乙烯咔唑配制成0.22-0.66摩尔/升的二氯乙烷或四氢呋喃的溶液，按单体量的0.5-10摩尔％的上述有机盐加入单体溶液中，在25-40℃下进行不对称立体选择性聚合，时间0.5-140小时，其反应方程式如下：
3.根据权利要求2所述的一种全同立构聚N-乙烯咔唑制备方法，其特征在于所述的手性或立体差异性配体的结构式如下：
(-)鹰爪豆碱 三苯甲基 左右旋异构 (+)樟脑磺酸[(-)Sp*] [Ph3 *C] [(+)CSA*]
4.根据权利要求2所述的一种全同立构聚N-乙烯咔唑制备方法，其特征在于所述有机盐合成三甲苯基以醇或氯化物形式参与反应。
5.根据权利要求3所述的一种全同立构聚N-乙烯咔唑制备方法，其特征在于所述有机盐合成三苯甲基盐中三苯甲基阳离子引发N-乙烯咔唑时，只有左或右旋异构参与引发立体选择性聚合。
6.根据权利要求1所述一种全同立构聚N-乙烯咔唑的用途，其特点在于所述的高全同光学活性聚N-乙烯咔唑作为光电材料中孔洞传输层，具有低能激发特征。
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| CN98120628A CN1101828C (zh) | 1998-10-19 | 1998-10-19 | 一种全同立构聚n－乙烯咔唑及其制备方法和用途 |
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| JPS6352146A (ja) * | 1986-08-22 | 1988-03-05 | Konica Corp | 正帯電用電子写真感光体 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6352146A (ja) * | 1986-08-22 | 1988-03-05 | Konica Corp | 正帯電用電子写真感光体 |
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