WO2019080550A1 - 一类有机聚螺格纳米聚合物材料及其制备方法 - Google Patents

一类有机聚螺格纳米聚合物材料及其制备方法

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WO2019080550A1
WO2019080550A1 PCT/CN2018/095689 CN2018095689W WO2019080550A1 WO 2019080550 A1 WO2019080550 A1 WO 2019080550A1 CN 2018095689 W CN2018095689 W CN 2018095689W WO 2019080550 A1 WO2019080550 A1 WO 2019080550A1
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organic
acid
nano
polymer material
polymer
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解令海
唐磊
魏颖
黄维
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南京邮电大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/20—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/144—Side-chains containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/45—Friedel-Crafts-type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport

Definitions

  • the invention relates to a kind of organic polyromatic nano-polymer material and a preparation method thereof, and belongs to the field of nanotechnology and organic electronics.
  • nano-scale closed-loop structure molecules such as polyrotaxane, polyporphyrin, etc., also have higher thermal stability, chemical stability and mechanical stability, which also make it suitable for organic semiconductor materials. Has great potential.
  • nanoscale closed-loop structural units To construct molecules with nanoscale closed-loop structures, the key lies in nanoscale closed-loop structural units and nano-joins. Most of the nano-scale structural units are closed-loop structures with extended sites, including rotaxane, porphyrin, cyclosiloxane, etc.
  • nano-joining the way in which nano-scale structural units are connected to each other is called nano-joining.
  • nano-joins are divided into non-covalent bond connections and covalent bond connections, and non-covalent bond connections mainly include supramolecular interactions and coordination linkages. Compared to non-covalent bond connections, covalent bond connections have better stability, a clearer spatial extension direction, and thus better designability.
  • the currently available nanoscale structure linked by covalent bonds is polyrotaxane (JJ Michels, MJO'Connell, PNTaylor, JSWilson, F. Cacialli and HL Anderson, Chem. Eur. J. 2003, 9, 6167). -6176), linear polyporphyrin (M. Hutin, JKS Prafke, B. Odell, HL Anderson, TD W Claridge, J. Am. Chem. Soc. 2013, 135, 12798-12807), banded polyporphyrin (H) .Mori, T. Tanaka, S. Lee, JMLim, D. Kim, and A. Osuka, J. Am. Chem. Soc.
  • Prof. Jie Linghai proposed a novel nano-scale three-dimensional closed-loop structure with structural rigidity—organic nano-grid (L. Wang, G.-W. Zhang, C.-J. Ou, L.-H.Xie , J.-Y. Lin, Y.-Y. Liu and W. Huang, Org. Lett., 2014, 16, 1748-1751).
  • These nano-grids have well-defined edges and vertices, active sites, and flexible one-, two-, and three-dimensional network structures that can be used to construct complex structures.
  • the nano-grid can be divided into trapezoidal, windmill-shaped, and diamond-shaped nano-grids.
  • a trapezoidal nano lattice can be constructed by a CC coupling (Suzuki or Yamamoto) reaction to construct not only a general non-conjugated nano-polyge (Q.-Y.Feng, Y.-L. Han, M.-N.Yu, B. Li, Y. Wei, L.-H Xie and W. Huang, Chin. J. Polym. Sci, 2017, 35, 87-97), it is also possible to construct a ladder-like lattice.
  • the rhombic interconnection between the diamond-shaped nano-grids can construct a diamond-shaped lattice.
  • the carbon-carbon double-bonded ladder-shaped lattice and diamond-shaped lattice have good rigidity, which can avoid the structural configuration or conformation due to the rotation of the bond. complex.
  • the rhombohedral lattices the rhomboidal unit nanocells are connected together by non-covalent bonds.
  • the use of covalent bond connections to construct diamond shaped polyge has not been reported so far.
  • spirocyclic aromatic hydrocarbons have at least four reaction sites, and their structure is a cross-type compound, this is crucial for constructing a rhombohedral nano lattice connection module.
  • the present invention realizes the effective preparation of the organic nano-diamond cell containing the spiro ring by a series of L-type synthons containing a spiro ring, which we call this
  • the organic nanodiamond cell containing a spiro ring is an organic unit lattice.
  • the Friedel-Craft reaction between different synthons containing spiro rings was developed, and the preparation of organic polyromatic nano-polymers without metal catalysis, environmental protection and atomic economy was realized.
  • Such materials can be applied to organic light-emitting devices, organic solar cells, and organic transistor memories, and have broad development prospects.
  • the present invention aims to propose a class of organic polyromatic nano-polymer materials and a preparation method thereof.
  • Fuke reaction has many advantages such as mild reaction conditions, high yield, high selectivity, simple post-treatment, green non-toxicity, etc., which overcomes the complicated synthesis steps of traditional polymer molecules, toxic after treatment, and pollution. And other issues.
  • the use of ⁇ 9-position sp3 carbon to link various organic groups can accurately synthesize polymer materials with spatially expandable complex structures, and then prepare corresponding functional organic nano-polymers.
  • An organic polyromatic nano-polymer material of the present invention comprises a structure comprising at least two kinds of terpenoid groups, wherein one type of anthracene group belongs to a 9-phenylnonanol derivative, and One type of anthracene-like group is a spiro ring structure having a geometric configuration similar to spirobifluorene, and its structural formula is as follows;
  • R 1 R 2 is the same or different and is a common alkyl chain
  • n' is a natural number of 1 to 10, and the specific structure is as follows:
  • the alkyl chain includes: 1) a linear type: a hydrogen atom, an alkane chain, an alkoxy chain, an alkyl chain in which a halogen atom such as fluorine, chlorine or bromine is introduced at a terminal; 2) a branched type: a t-butyl group and a branched alkyl chain having an oxygen atom; wherein m is a natural number from 1 to 10, and the specific structure is as follows:
  • the preparation method of the organic polyromatic nano-polymer material of the invention is: an organic nano-polymer formed by a rigid organic unit thread grid connected by a common spiral ring, the polymer comprising at least two types of terpenoid groups, one of which The hydrazine-like group belongs to the 9-phenyl sterol derivative, and the other hydrazine group is a spiro ring structure having a geometric configuration similar to spirobifluorene; the synthesis method is at room temperature, using an acid as a catalyst, and drying.
  • the A2B2 type synthon containing a spiro ring is subjected to a Friedel-Craft reaction, and the organopolyromatic nano-polymer is obtained by sharing a spiro ring, and then the final structure is obtained by Fuk end capping of the A1B1 type synthon containing a spiro ring.
  • the structural formula of the organopolyromatic nano-polymer and its reaction scheme are as follows:
  • the acid comprises a Lewis acid and a protonic acid.
  • the acid catalyst is added in an amount of 2 to 5 times the A2B2 type synthon according to the reactivity of the different substrates.
  • the reaction concentration of the A2B2 type synthon is according to the reactivity of the different substrates. Between 1-10 mmol/L.
  • the Lewis acid and protic acid are specifically: acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid or hydrofluoric acid- One type or a combination of a plurality of types of antimony pentafluoride.
  • the dried organic solvent is specifically: dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran, 1,4-dioxane Wait for one of them.
  • oligomers and polymer materials were characterized by nuclear magnetic resonance (NMR), matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS), and gel chromatography (GPC).
  • NMR nuclear magnetic resonance
  • MALDI-TOF-MS matrix-assisted laser desorption time-of-flight mass spectrometry
  • GPC gel chromatography
  • the thermal stability of the material was tested by thermogravimetric analysis and differential thermal analysis.
  • the spectral properties of this type of rhombohedral polymer were characterized by UV-fluorescence spectroscopy.
  • the material still has excellent solubility at a molecular weight of up to 1.11x10 5 ;
  • Diaryl ruthenium stacking has good photoelectric activity.
  • Figure 2b Gel chromatogram of the organopolyromatic nanopolymer 5a
  • Figure 6b CV spectrum of organic polyromatic nanopolymer 5a.
  • the invention relates to a type of organic unit screw lattice and a nano polymer material thereof, wherein the specific structural formula and reaction formula of the organic unit thread lattice are as follows:
  • R 1 is a common alkyl chain, including: 1) a linear type: a hydrogen atom, an alkane chain, an alkoxy chain, an alkyl chain having a halogen atom such as fluorine, chlorine or bromine introduced at the end; 2) branching Type: tert-butyl group and branched alkyl chain with an oxygen atom.
  • m is a natural number from 1 to 10, the specific structure is as follows:
  • n' is a natural number of 1 to 10, and the specific structure is as follows:
  • the acid comprises a Lewis acid and a protic acid, specifically acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid or hydrofluoric acid-five
  • the one or a combination of the cesium fluorides may be added in an amount of from 2 to 5 times the amount of the A1B1 type synthon depending on the reactivity of the different substrates.
  • the solvent is a dry organic solvent, specifically dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran, 1,4-dioxane, etc.
  • the reaction concentration of the A1B1 type synthon is between 1-10 mmol/L depending on the reactivity of the different substrates.
  • the specific synthesis step of the organic unit thread is: adding a quantitative acid to a round bottom flask containing a quantitative dry organic solvent, and fully dissolving the spiro ring-containing A1B1 type synthon-1 in another partially dried organic solvent.
  • the mixture was added dropwise to a round bottom flask at a dropping rate of 1 drop per second, and the reaction was stirred for 24 hours until the reaction substrate was completely reacted, and the neutralization reaction was quenched by adding water.
  • the organic layer was extracted with dichloromethane, and the organic layer was combined with methylene chloride and dried over anhydrous magnesium sulfate. The dried solvent was filtered off, and the solvent was evaporated under reduced pressure. Grid-2.
  • R 1 R 2 is the same or different and is a common alkyl chain, and includes: 1) a linear type: a hydrogen atom, an alkane chain, an alkoxy chain, an alkyl group having a halogen atom such as fluorine, chlorine or bromine at the end. Chain; 2) Branched type: tert-butyl group and branched alkyl chain with an oxygen atom.
  • m is a natural number from 1 to 10
  • the specific structure is as follows:
  • n' is a natural number of 1 to 10, and the specific structure is as follows:
  • the acid comprises a Lewis acid and a protic acid, specifically acetic acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, methanesulfonic acid, fluoromethylsulfonic acid, trifluoromethanesulfonic acid, concentrated sulfuric acid, trifluoroacetic acid or hydrofluoric acid-five
  • the one or a combination of the cesium fluorides may be added in an amount of from 2 to 5 times the amount of the A1B1 type synthon depending on the reactivity of the different substrates.
  • the solvent is a dry organic solvent, specifically dichlorobenzene, chlorobenzene, dichloromethane, chloroform, 1,2-dichloroethane, nitrobenzene, acetone, tetrahydrofuran, 1,4-dioxane, etc.
  • the reaction concentration of the A1B1 type synthon is between 1-10 mmol/L depending on the reactivity of the different substrates.
  • the specific synthesis step of the organic polyromatic nano polymer is: adding a quantitative acid to a round bottom flask containing a quantitative dry organic solvent, and fully dissolving the spiro ring-containing A2B2 type synthon-3 in another part. In an organic solvent, it is added dropwise to a round bottom flask at a drop rate of 1 drop per second, and the reaction is stirred for 1-4 h; the spiro ring-containing A1B1 type synthon-1 is sufficiently dissolved in another portion of the dried organic solvent, and added dropwise.
  • the dropping rate is 1 drop per second until the dropwise addition is completed, the reaction is stirred for 24 hours, the solvent is distilled off under reduced pressure to the remaining 5 ml of the solution, and the mixture is precipitated with methanol, extracted with acetone, and the solid portion thereof is taken and dried.
  • Example 4 Testing of the basic properties of light, electricity and heat of organic unit threaded lattice (2a), organic two-threaded (4a) and organic polyromatic nano-polymer (5a).
  • the three materials were formulated into a 10 -5 mg/mL dilute solution of chloroform.
  • the absorption spectrum and emission spectrum of the solution were measured by Shimadzu UV-3150 UV-Vis spectrometer and RF-530XPC fluorescence spectrometer.
  • the photoluminescence spectrum was measured at the maximum absorption wavelength of UV absorption.
  • the solid film was prepared by a solution spin coating film forming technique, and the spin coating solution was a 10 mg/mL solution of chloroform.
  • Thermogravimetric analysis was performed using Shimadzu DTG-60H, and Shimadzu DSC-60A was subjected to differential scanning calorimetry.
  • Electrochemical testing was performed by cyclic voltammetry (CV) testing, specifically a typical three-electrode test using a CHI660E system at room temperature using a working electrode, a platinum wire electrode, and a silver nitrate electrode. All electrochemical tests were performed.
  • the sample was dropped on a glassy carbon electrode in a nitrogen atmosphere, air-dried and then inserted into tetrabutylammonium hexafluorophosphate (0.1 mole per liter) / acetonitrile for testing at a scan rate of 0.1 V/s, measured according to CV.
  • HOMO/LUMO -(E ox /red -0.03V) - 4.8 eV, where 0.03 V is the standard potential difference of ferrocene relative to Ag/Ag + .

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Abstract

本发明涉及一类有机聚螺格纳米聚合物材料及其制备方法，属于纳米技术与有机电子领域。本发明中有机聚螺格纳米聚合物材料结构是一类由含螺环的格子组成，将其作为重复单元形成了一类特殊的纳米聚合物，该类结构共用螺环结构。其合成方法涉及含螺环的合成子，经由傅克反应，构筑了有机螺格及其纳米聚合物。通过合理的分子设计，利用傅克反应具有反应条件温和、高产率、高选择性、后处理简便、绿色无毒等诸多优点，克服了传统聚合物分子合成步骤复杂、后处理有毒、污染较大等问题。利用芴9位的sp3碳联接各类有机基团可精确合成空间可拓展的复杂结构的聚合物材料，进而制备相应的功能性有机纳米聚合物。

Description

一类有机聚螺格纳米聚合物材料及其制备方法 技术领域
本发明涉及一类有机聚螺格纳米聚合物材料及其制备方法，属于纳米技术与有机电子领域。
背景技术
目前，有机小分子、寡聚物和共轭聚合物以及堆积聚合物经历了数十年的发展，研究表明具有这些结构的分子有着良好的分子可溶性、明确的分子量、容易提纯等特点，相比于传统线性结构，具有纳米尺度的闭环结构分子如聚轮烷、聚卟啉等，还具有更高的热稳定性、化学稳定性和机械稳定性等，这也使其在有机半导体材料应用中具有巨大潜力。
构筑具有纳米尺度闭环结构的分子，关键在于纳米尺度的闭环结构单元和纳米连接。纳米尺度的结构单元大部分都是具有扩展位点的闭环结构，包括轮烷、卟啉、环硅氧烷等；另一方面，纳米尺度的结构单元间相互连接的方式则称为纳米连接，总的来说，纳米连接分为非共价键连接和共价键连接，非共价键连接主要包括超分子作用和配位连接等。相比于非共价键连接，共价键连接具有更好的稳定性、更明确的空间伸展方向，因而具有更好的可设计性。目前已有的通过共价键连接的纳米尺度结构有聚轮烷(J.J.Michels,M.J.O'Connell,P.N.Taylor,J.S.Wilson,F.Cacialli and H.L.Anderson,Chem.Eur.J.2003,9,6167-6176)、线性聚卟啉(M.Hutin,J.K.Sprafke,B.Odell,H.L.Anderson,T.D.W.Claridge，J.Am.Chem.Soc.2013,135,12798-12807)、带状聚卟啉(H.Mori,T.Tanaka,S.Lee,J.M.Lim,D.Kim,and A.Osuka，J.Am.Chem.Soc.2015,137,2097-2106)、梯状聚硅氧烷(K.W.Krantz,Journal of Organometallic c 695(2010)1363–1369)等。然而，已知的纳米尺度结构单元大多具有不规则性，单体的不规整和纳米结构的大位阻增加了纳米连接的难度，导致具有纳米尺度结构单元的聚合物聚合度不高。因此，实现规整单体的高效制备和增大纳米单体间的可连接性是合成具有大分子量的聚合物的两大至关重要的因素。
2014年，解令海教授课题组提出一种新颖的结构刚性的纳米尺度立体闭环 结构——有机纳米格(L.Wang,G.-W.Zhang,C.-J.Ou,L.-H.Xie,J.-Y.Lin,Y.-Y.Liu and W.Huang,Org.Lett.,2014,16,1748-1751)。该类纳米格具有明确的边缘和顶点、活性位点以及灵活的可用于构筑结构复杂的一维、二维和三维网状结构。依据纳米格的几何结构，纳米格可以分为梯形、风车状、和菱形纳米格。由于纳米格具有多个连接点，因此，每种纳米格都有其独特的连接方式。例如，梯形纳米格通过C-C偶联(Suzuki或者Yamamoto)反应，不仅可构筑一般的非共轭型纳米聚格(Q.-Y.Feng,Y.-L.Han,M.-N.Yu,B.Li,Y.Wei,L.-H Xie and W.Huang,Chin.J.Polym.Sci,2017,35,87-97)，还可以构筑梯状聚格。菱形纳米格之间的菱角互连，可以构筑菱形聚格。相比于碳碳单键连接的非共轭型纳米聚格，碳碳双键连接的梯状聚格和菱形聚格具有很好的刚性，可以避免由于键的旋转，导致结构构型或者构象复杂。目前关于菱形聚格的合成，都是通过非共价键将菱形单元纳米格连接在一起。然而，利用共价键连接构筑菱形聚格迄今为止没有报道过。
为了合成共价键连接的菱形聚格，我们需要设计和合成一类具有多个活性位点的潜在的菱形纳米合成子。考虑到这些要求，我们选择螺环芳烃作为中心(十字)的构建模块。由于螺环芳烃至少有四个反应位点，而且，其结构是十字交叉类化合物，这对于作为构筑菱形纳米格的连接模块是至关重要的。鉴于以上有机纳米菱形聚格的制备问题，本发明通过一系列含螺环的L型合成子，以傅克反应为基础，实现了含螺环的有机纳米菱形单元格的有效制备，我们称这种含螺环的有机纳米菱形单元格为有机单元螺格。在此基础上，发展了含螺环的不同合成子间的傅克反应，实现了无金属催化、绿色环保、原子经济的有机聚螺格纳米聚合物的制备。这类材料可应用于有机发光器件、有机太阳电池、有机晶体管存储器，具有广阔的发展前景。
发明内容
技术问题：本发明目的在于提出一类有机聚螺格纳米聚合物材料及其制备方法。通过合理的分子设计，利用傅克反应具有反应条件温和、高产率、高选择性、后处理简便、绿色无毒等诸多优点，克服了传统聚合物分子合成步骤复杂、后处理有毒、污染较大等问题。利用芴9位的sp3碳联接各类有机基团可精确合成空间可拓展的复杂结构的聚合物材料，进而制备相应的功能性有机纳米聚合物。
技术方案：本发明的一种采用有机聚螺格纳米聚合物材料，该材料的结构包含有至少两类类芴基团，其中一类类芴基团属于9-苯基芴醇衍生物，另一类类芴 基团是具有类似螺二芴的几何构型的螺环结构，其结构式如下；
Figure PCTCN2018095689-appb-000001
式中：R 1R 2相同或不同，为常见的烷基链，
Figure PCTCN2018095689-appb-000002
相同或不同，为常见的类芴螺环化合物，具体结构如下：
Figure PCTCN2018095689-appb-000003
其中氮原子上同样可以引入相关的烷基链R’，n’为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000004
Figure PCTCN2018095689-appb-000005
相同或不同，为以下结构中的一种：
Figure PCTCN2018095689-appb-000006
所述的烷基链包括：1)直链型：氢原子、烷烃链、烷氧基链、末端引入氟、氯、溴等卤素原子的烷基链；2)支化型：叔丁基和带有氧原子的支化烷基链；其中m为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000007
本发明有机聚螺格纳米聚合物材料的制备方法为：由刚性有机单元螺格通过共用螺环连接而成的有机纳米聚合物，该聚合物包含有至少两类类芴基团，其中一类类芴基团属于9-苯基芴醇衍生物，另一种类芴基团是具有类似螺二芴的几何构型的螺环结构；其合成方法为在室温下，以酸为催化剂，在干燥的有机溶剂中，利用含螺环的A2B2型合成子经傅克反应，通过共用螺环得到有机聚螺格纳米聚合物，再通过含螺环的A1B1型合成子傅克封端得到最终结构，有机聚螺格纳米聚合物结构通式及其反应路线通式如下：
Figure PCTCN2018095689-appb-000008
所述的酸包含路易斯酸和质子酸，根据不同底物的反应活性，酸催化剂加入量为A2B2型合成子的2倍至5倍；根据不同底物的反应活性，A2B2型合成子反应浓度在1-10毫摩尔/升之间。
所述的路易斯酸和质子酸具体为：醋酸、氢碘酸、氢溴酸、盐酸、甲烷磺酸、氟甲基磺酸、三氟甲磺酸、浓硫酸、三氟乙酸或氢氟酸-五氟化锑的1种或及多种的组合。
所述的干燥的有机溶剂具体为：二氯苯、氯苯、二氯甲烷、三氯甲烷、1,2- 二氯乙烷、硝基苯、丙酮、四氢呋喃、1,4-二氧六环等其中一种。
有益效果：通过核磁共振(NMR)、基质辅助激光解析时间飞行质谱(MALDI-TOF-MS)、凝胶色谱(GPC)表征了寡聚物及高聚物材料结构。通过热重分析和差热分析测试了材料的热稳定性，通过紫外-荧光光谱测试表征了这一类菱形聚合物的光谱性能。
本发明的主要优点在于：
(1)以傅克反应为基础的闭环聚合反应条件成熟、原料廉价易得、制备简单、反应条件温和、高产率、高选择性、后处理简便、绿色无毒；
(2)材料在分子量高达1.11x10 5时仍具有优良的溶解度；
(3)螺芴及二芳基芴具有高热稳定性和电化学稳定性，光谱稳定性；
(4)二芳基芴堆积作用具有良好的光电活性。
附图说明
图1a.有机二螺格4a的氢谱谱图；
图1b.有机二螺格4a的质谱谱图，
图2a.有机聚螺格纳米聚合物5a的氢谱图；
图2b.有机聚螺格纳米聚合物5a的凝胶色谱谱图，
图3.有机聚螺格纳米聚合物5a的TEM谱图，
图4a.有机二螺格4a和有机聚螺格纳米聚合物5a溶液的紫外吸收和荧光发射谱图:
图4b.有机二螺格4a和有机聚螺格纳米聚合物5a的薄膜的吸收发射光谱，
图5a.有机聚螺格纳米聚合物5a的TG谱图：
图5b.有机聚螺格纳米聚合物5a的DSC谱图,
图6a.有机二螺格4a的CV谱图；
图6b.有机聚螺格纳米聚合物5a的CV谱图。
具体实施方式
本发明的一类有机单元螺格及其纳米聚合物材料，其中有机单元螺格具体结构通式及反应路线通式如下：
Figure PCTCN2018095689-appb-000009
式中：R 1为常见的烷基链，包括：1)直链型：氢原子、烷烃链、烷氧基链、末端引入氟、氯、溴等卤素原子的烷基链；2)支化型：叔丁基和带有氧原子的支化烷基链。其中m为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000010
Figure PCTCN2018095689-appb-000011
为常见的类芴螺环化合物，具体结构如下：
Figure PCTCN2018095689-appb-000012
其中氮原子上同样可以引入相关的烷基链R’，n’为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000013
Figure PCTCN2018095689-appb-000014
为以下结构中的一种：
Figure PCTCN2018095689-appb-000015
酸包含路易斯酸和质子酸，具体为醋酸、氢碘酸、氢溴酸、盐酸、甲烷磺酸、氟甲基磺酸、三氟甲磺酸、浓硫酸、三氟乙酸或氢氟酸-五氟化锑的1种或及多种的组合，根据不同底物的反应活性，酸催化剂加入量为A1B1型合成子的2倍至5倍。
溶剂为干燥的有机溶剂，具体为二氯苯、氯苯、二氯甲烷、三氯甲烷、1,2-二氯乙烷、硝基苯、丙酮、四氢呋喃、1,4-二氧六环等其中一种，根据不同底物的反应活性，A1B1型合成子反应浓度在1-10毫摩尔/升之间。
所述的有机单元螺格的具体合成步骤是：取定量酸加入盛有定量的干燥有机溶剂的圆底烧瓶中，将含螺环的A1B1型合成子-1充分溶解在另一部分干燥的有机溶剂中，滴加到圆底烧瓶中，滴加速度1滴每秒，搅拌反应24h，至反应底物反应完全，加水淬灭中和反应。用二氯甲烷萃取，合并有机相的二氯甲烷萃取液，无水硫酸镁干燥，滤除干燥剂，减压蒸馏除去溶剂，粗产物经硅胶层析柱过柱分离得到相应目标产物有机单元螺格-2。
其有机二螺格结构通式及其反应路线通式如下：
Figure PCTCN2018095689-appb-000016
式中：R 1R 2相同或不同，为常见的烷基链，包括：1)直链型：氢原子、烷烃链、烷氧基链、末端引入氟、氯、溴等卤素原子的烷基链；2)支化型：叔丁基和带有氧原子的支化烷基链。其中m为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000017
Figure PCTCN2018095689-appb-000018
相同或不同，为常见的类芴螺环化合物，具体结构如下：
Figure PCTCN2018095689-appb-000019
其中氮原子上同样可以引入相关的烷基链R’，n’为1至10的自然数，具体结构如下：
Figure PCTCN2018095689-appb-000020
Figure PCTCN2018095689-appb-000021
相同或不同，为以下结构中的一种：
Figure PCTCN2018095689-appb-000022
酸包含路易斯酸和质子酸，具体为醋酸、氢碘酸、氢溴酸、盐酸、甲烷磺酸、氟甲基磺酸、三氟甲磺酸、浓硫酸、三氟乙酸或氢氟酸-五氟化锑的1种或及多种的组合，根据不同底物的反应活性，酸催化剂加入量为A1B1型合成子的2倍至5倍。
溶剂为干燥的有机溶剂，具体为二氯苯、氯苯、二氯甲烷、三氯甲烷、1,2-二氯乙烷、硝基苯、丙酮、四氢呋喃、1,4-二氧六环等其中一种，根据不同底物 的反应活性，A1B1型合成子反应浓度在1-10毫摩尔/升之间。
所述的有机聚螺格纳米聚合物的具体合成步骤是：取定量酸加入盛有定量的干燥有机溶剂的圆底烧瓶中，将含螺环的A2B2型合成子-3充分溶解在另一部分干燥的有机溶剂中，滴加到圆底烧瓶中，滴加速度1滴每秒，搅拌反应1-4h；将含螺环的A1B1型合成子-1充分溶解在另一部分干燥的有机溶剂中，滴加到圆底烧瓶中，滴加速度1滴每秒至滴加完成，搅拌反应24h，减压蒸馏除去溶剂至剩余5毫升溶液，用甲醇沉降，再用丙酮抽提，取其中的固体部分，烘干得到相应目标产物有机聚螺格纳米聚合物-5。
下面结合实施例来进一步描述本发明的技术方案，但这些实施例并非限制本发明的实施方式。本发明具有多种不同的实施方式，并不只限于本说明书中所述内容。本领域的技术人员在不违背本申请发明精神的情况下，所完成的方案应在本发明的范围内。
实例1：有机单元螺格-2a的制备
Figure PCTCN2018095689-appb-000023
将三氟化硼乙醚(1ml)和400ml 1,2-二氯乙烷加入到1000ml反应瓶中，搅拌均匀，在将1a(0.353g,0.5mmol,1equiv)加入盛有100ml 1,2-二氯乙烷的恒压滴液漏斗中，以每秒一滴的速度滴加到反应瓶中，滴加完后，反应5-10小时，待反应完全，加水猝灭此反应。用二氯甲烷萃取，收集有机相，无水硫酸镁干燥，滤除干燥剂，减压蒸馏除去溶剂，粗产物经硅胶层析柱进一步过柱分离提纯，得到白色固体粉末2a(0.151g,43.9％)。
1H NMR(400MHz,CDCl 3)δ7.77–7.73(t,J＝7.8Hz,4H),7.66–7.64(d,J＝7.6Hz,4H),7.57–7.52(t,J＝8.0Hz,4H),7.48–7.46(d,J＝8.0Hz,2H),7.42–7.40(d,J＝7.6Hz,2H),7.37–7.36(m,5H),7.34–7.28(m,6H),7.24–7.21(m,5H),7.14–7.10(t,J＝7.2Hz,2H),7.02–6.98(t,J＝7.4,2H),6.89–6.87(d,J＝7.6Hz,2H),6.79 –6.72(d,J＝8.8Hz,4H),6.65–6.62(d,J＝8.0Hz,4H),3.89–3.86(t,J＝6.5Hz,4H),1.80–1.73(m,4H),1.46–1.42(t,J＝6.0Hz,4H),1.30–1.27(m,16H),0.91–0.89(t,J＝4.4Hz,6H). 13C NMR(100MHz,CDCl 3)δ158.3,154.8,152.0,151.3,150.8,148.6,147.6,147.3,145.9,141.3,141.1,140.8,140.2,139.3,139.3,138.6,137.8,128.3,128.1,127.9,127.8,127.6,127.4,126.9,126.8,126.1,125.7,124.6,124.4,123.4,122.5,120.2,120.1,120.0,119.2,117.7,114.2,67.9,64.0,62.1,31.9,31.5,31.5,30.3,30.2,30.2,29.7,29.7,29.4,29.3,26.2,22.7,14.2.MALDI-TOF-MS(m/z):1377.70/1377.55[M +].
实例2：有机二螺格-4a的制备
Figure PCTCN2018095689-appb-000024
其中R＝OC 8H 17。
将三氟化硼乙醚(1ml)和400ml 1,2-二氯乙烷加入到1000ml反应瓶中，搅拌均匀，再将1a(0.353g,0.5mmol,1equiv)和3a(0.274g,0.25mmol,0.5equiv)均匀混合溶在盛有100ml 1,2-二氯乙烷的恒压滴液漏斗中，以每秒一滴的速度滴加到反应瓶中，滴加完后，反应5-10小时，待反应完全，加水猝灭此反应。用二氯甲烷萃取，收集有机相，无水硫酸镁干燥，滤除干燥剂，减压蒸馏除去溶剂，粗产物经硅胶层析柱进一步过柱分离提纯，得到微黄的固体粉末4a(0.040g,6.54％)。
1H NMR(400MHz,CDCl 3)δ7.74–7.72(d,J＝8.0Hz,2H),7.70–7.68(d,J＝7.6Hz,2H),7.67–7.64(d,J＝8.0Hz,4H),7.63–7.61(d,J＝8.0Hz,2H),7.59–7.57(m,6H),7.56-7.54(m,6H),7.54–7.51(d,J＝6.4Hz,4H),7.50–7.46(m,6H),7.42–7.40(d,J＝8.8Hz,4H),7.36–7.35(d,J＝2.8Hz,2H),7.32–7.30(d,J＝6.8Hz,4H),7.29–7.28(m,4H),7.16–7.14(d,J＝7.2Hz,2H),7.13(s,2H),7.10–7.07(d,J＝8.4,2.8Hz,4H),7.06–7.04(d,J＝8.0Hz,2H),6.97(s,2H),6.93–6.89(m,8H),6.83–6.81(d,J＝7.6Hz,4H),6.79–6.77(d,J＝9.2Hz,4H),6.59–6.57(d,J＝8.8Hz,2H),3.91–3.88(t,J＝5.8Hz,8H),2.31–2.21(m,4H),2.06–1.97(m,4H),1.79–1.70(m,8H),1.30–1.29(m,32H),0.86–0.83(m,12H).MALDI-TOF-MS(m/z): 2438.99/2439.00[M +].
实例3：有机聚螺格纳米聚合物-5a的制备
Figure PCTCN2018095689-appb-000025
其中R＝OC 8H 17。
在室温下，取3a(0.329g,0.3mmol)溶于20ml DCE中，滴加到溶有三氟化硼乙醚(0.78ml,3mmol)的40ml DCE中，滴加速度为1滴每秒，滴加完后，反应体系搅拌1-4小时；随后将溶有1a(0.021g,0.03mmol)的10ml DCE溶液滴加到反应体系中，滴加速度仍为1滴每秒，滴加完后，反应24h，待反应完成后直接旋蒸除去溶剂，直至剩下5ml反应液，然后用甲醇沉降，过滤，在索氏提取器中，对滤渣用丙酮进行抽提，得棕色产物0.304g,产率89.8％。(理论产量338.6mg)
实例4：有机单元螺格(2a)、有机二螺格(4a)和有机聚螺格纳米聚合物(5a)的光、电、热基本性质的测试。
把三种材料配成10 -5mg/mL的三氯甲烷稀溶液。采用岛津UV-3150紫外可见光谱仪和RF-530XPC荧光光谱仪进行溶液的吸收光谱和发射光谱测定，光致发光光谱是在紫外吸收的最大吸收波长下测定的。固体膜通过溶液旋涂成膜技术制备，旋涂溶液为10mg/mL的三氯甲烷溶液。采用岛津DTG-60H进行热重分析，岛津DSC-60A进行示差扫描热分析。电化学测试通过循环伏安法(CV)测试完成的，具体为在室温下通过CHI660E系统完成的，使用工作电极、铂丝电极和硝酸银电极的典型三电极测试方法，所有电化学测试均是在氮气氛围中进行的，样品滴在玻碳电极上成膜，风干后插入四丁基六氟磷酸铵(0.1摩尔每升)/乙腈中进行测试，扫描速率为0.1V/s，根据CV测量的氧化还原起始电位，材料的最高占据分子轨道(HOMO)/最低未占能量水平(LUMO)基于二茂铁的参考能级(4.8eV低于真空)估算：HOMO/LUMO＝-(E ox/red-0.03V)-4.8eV，其中0.03V是二茂铁相对于Ag/Ag +的标准电位差。

Claims (6)

  1. 一种有机聚螺格纳米聚合物材料，其特征在于该材料的结构包含有至少两类类芴基团，其中一类类芴基团属于9-苯基芴醇衍生物，另一类类芴基团是具有类似螺二芴的几何构型的螺环结构，其结构式如下；
    Figure PCTCN2018095689-appb-100001
    式中：R 1R 2相同或不同，为常见的烷基链，
    Figure PCTCN2018095689-appb-100002
    相同或不同，为常见的类芴螺环化合物，具体结构如下：
    Figure PCTCN2018095689-appb-100003
    其中氮原子上同样可以引入相关的烷基链R’，n’为1至10的自然数，具体结构 如下：
    -H -C n′H 2n′+1 -C n′H 2n′F -C n′H 2n′Cl -C n′H 2n′Br
    Figure PCTCN2018095689-appb-100004
    Figure PCTCN2018095689-appb-100005
    相同或不同，为以下结构中的一种：
    Figure PCTCN2018095689-appb-100006
  2. 根据权利要求1所述的有机聚螺格纳米聚合物材料，其特征在于，所述的烷基链包括：1)直链型：氢原子、烷烃链、烷氧基链、末端引入氟、氯、溴等卤素原子的烷基链；2)支化型：叔丁基和带有氧原子的支化烷基链；其中m为1至10的自然数，具体结构如下：
    -H -C mH 2m+1 -OC mH 2m+1 -C mH 2mF -C mH 2mCl -C mH 2mBr
    Figure PCTCN2018095689-appb-100007
  3. 一种如权利要求1所述的有机聚螺格纳米聚合物材料的制备方法，其特征在于，由刚性有机单元螺格通过共用螺环连接而成的有机纳米聚合物，该聚合物包含有至少两类类芴基团，其中一类类芴基团属于9-苯基芴醇衍生物，另一种类芴基团是具有类似螺二芴的几何构型的螺环结构；其合成方法为在室温下，以酸为催化剂，在干燥的有机溶剂中，利用含螺环的A2B2型合成子经傅克反应，通过共用螺环得到有机聚螺格纳米聚合物，再通过含螺环的A1B1型合成子傅克封端得到最终结构，有机聚螺格纳米聚合物结构通式及其反应路线通式如下：
    Figure PCTCN2018095689-appb-100008
  4. 根据权利要求3所述的有机聚螺格纳米聚合物材料的制备方法，其特征在于，所述的酸包含路易斯酸和质子酸，根据不同底物的反应活性，酸催化剂加入量为A2B2型合成子的2倍至5倍；根据不同底物的反应活性，A2B2型合成子反应浓度在1-10毫摩尔/升之间。
  5. 根据权利要求4所述的有机聚螺格纳米聚合物材料的制备方法，其特征在于，所述的路易斯酸和质子酸具体为：醋酸、氢碘酸、氢溴酸、盐酸、甲烷磺酸、氟甲基磺酸、三氟甲磺酸、浓硫酸、三氟乙酸或氢氟酸-五氟化锑的1种或及多种的组合。
  6. 根据权利要求3所述的有机聚螺格纳米聚合物材料的制备方法，其特征在于，所述的干燥的有机溶剂具体为：二氯苯、氯苯、二氯甲烷、三氯甲烷、1,2-二氯乙烷、硝基苯、丙酮、四氢呋喃、1,4-二氧六环等其中一种。
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