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 PDF

Info

Publication number
CN1101828C
CN1101828C CN98120628A CN98120628A CN1101828C CN 1101828 C CN1101828 C CN 1101828C CN 98120628 A CN98120628 A CN 98120628A CN 98120628 A CN98120628 A CN 98120628A CN 1101828 C CN1101828 C CN 1101828C
Authority
CN
China
Prior art keywords
ethylene
carbozole
poly
isotactic poly
isotactic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN98120628A
Other languages
English (en)
Other versions
CN1251844A (zh
Inventor
陈传福
粟权
陈永明
习复
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN98120628A priority Critical patent/CN1101828C/zh
Publication of CN1251844A publication Critical patent/CN1251844A/zh
Application granted granted Critical
Publication of CN1101828C publication Critical patent/CN1101828C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F26/12—N-Vinyl-carbazole

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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

一种全同立构聚N-乙烯咔唑 及其制备方法和用途
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。
Figure C9812062800051
(-)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)。
Figure C9812062800052
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
    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
a.文献参考平均值
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：
Figure C9812062800022
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：
Figure C9812062800031
(-)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。
CN98120628A 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 Expired - Fee Related CN1101828C (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
CN1251844A CN1251844A (zh) 2000-05-03
CN1101828C true CN1101828C (zh) 2003-02-19

Family

ID=5226819

Family Applications (1)

Application Number Title Priority Date Filing Date
CN98120628A Expired - Fee Related 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

Country Status (1)

Country Link
CN (1) CN1101828C (zh)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6352146A (ja) * 1986-08-22 1988-03-05 Konica Corp 正帯電用電子写真感光体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6352146A (ja) * 1986-08-22 1988-03-05 Konica Corp 正帯電用電子写真感光体

Also Published As

Publication number Publication date
CN1251844A (zh) 2000-05-03

Similar Documents

Publication Publication Date Title
Yang et al. Supramolecular polymers: historical development, preparation, characterization, and functions
Núñez et al. Icosahedral boron clusters: a perfect tool for the enhancement of polymer features
Wei et al. Chemical and electrochemical copolymerization of aniline with alkyl ring-substituted anilines
He et al. Tetraphenylethene-functionalized conjugated helical poly (phenyl isocyanide) with tunable light emission, assembly morphology, and specific applications
Jäkle Advances in the synthesis of organoborane polymers for optical, electronic, and sensory applications
Deng et al. Multicomponent click polymerization: a facile strategy toward fused heterocyclic polymers
Wang et al. Rotaxane dendrimers: alliance between giants
Leclaire et al. Octasubstituted metal-free phthalocyanine as core of phosphorus dendrimers: A probe for the properties of the internal structure
Zhang et al. Near-infrared luminescent PMMA-supported metallopolymers based on Zn–Nd schiff-base complexes
Liu et al. Helix-induced asymmetric self-assembly of π-conjugated block copolymers: from controlled syntheses to distinct properties
Su et al. Facile synthesis of poly (phenyleneethynylene)-block-polyisocyanide copolymers via two mechanistically distinct, sequential living polymerizations using a single catalyst
CN102875750B (zh) 一种聚合物-稀土离子发光胶束的制备方法
Zhang et al. Platinum acetylide complexes containing iptycene as cores: a new family of unexpected efficient organometallic gelators
Yeşilot et al. Stereochemical aspects of polyphosphazenes
CN1101828C (zh) 一种全同立构聚n－乙烯咔唑及其制备方法和用途
Hoogenboom et al. Asymmetrical supramolecular interactions as basis for complex responsive macromolecular architectures
Sheng et al. Pillar [5] arene‐Based AIE Supramolecular Polymer Networks Exhibiting Various Fluorescence to Achieve Visible Surveillance
Xu et al. Multicomponent polymerization of alkynes, sulfonyl azide, and iminophosphorane at room temperature for the synthesis of hyperbranched poly (phosphorus amidine) s
CN101392173A (zh) 电化学聚合制备共聚物发光材料的方法
Diederich Functional acetylenic molecular architecture
CN114621417B (zh) 一种光学活性螺旋聚芴嵌段聚异腈共聚物及其制备方法和用途
CN103665259B (zh) 一种耐高温且抗剪切的水溶性支化聚合物及其制备方法
Bommarito et al. Synthesis and characterization of redox polymers of [M (4-vinyl-4'-methyl-2, 2'-bipyridine) 3](PF6) 2 (M= Ru, Os)
Ren et al. Postpolymerization modification based on dynamic imine chemistry for the synthesis of functional polyacetylenes
Vokatá et al. Synthesis of biodegradable conjugated polymers with controlled backbone flexibility

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee