WO2019196041A1 - Chiral main-chain-type azobenzene polymer aggregate and preparation method therefor - Google Patents
Chiral main-chain-type azobenzene polymer aggregate and preparation method therefor Download PDFInfo
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Definitions
- the invention relates to a method for preparing polymer aggregates in the field of polymer chemistry, in particular to a chiral main chain type azobenzene polymer aggregate and a preparation method thereof.
- the chiral solvent induction method is a common method for preparing chiral substances, although it solves the complicated synthetic steps and expensive methods that have been faced in the past by using chiral monomer polymerization and asymmetric polymerization of achiral monomers to obtain polymer chirality.
- Chiral catalysts and other problems but there are still some defects in the preparation of simple chiral aggregates.
- chiral limonene is commonly used to assemble with achiral polymers to induce chirality, but there are always limonene molecules that are difficult to remove in such aggregates, which may hinder the actual production application.
- a method for preparing chiral main chain type azobenzene polymer isomers comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added, and the mixture is allowed to stand after the inversion treatment to obtain a chiral main chain type azobenzene polymer isomerized aggregate.
- a method for preparing a chiral main chain type azobenzene polymer aggregate comprising the steps of: adding a main chain type azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially adding A good solvent and a poor solvent are allowed to stand after the inverted treatment to obtain a chiral main chain type azobenzene polymer isomer aggregate; then the chiral main chain type azobenzene polymer isomerized aggregate is treated with ultraviolet light to obtain a hand The main chain type azobenzene polymer is aggregated.
- a method for preparing a precursor system of a chiral main chain type azobenzene polymer aggregate comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added to obtain a chiral main chain type azobenzene polymer aggregate precursor system.
- the invention utilizes the aggregation induction of the chiral polysilane and the main chain azobenzene polymer in a binary solvent to obtain a heterogeneous aggregate having a chiral response, which can be rapidly selected by irradiation of ultraviolet light at 313 nm.
- the solvent in the main chain azobenzene polymer solution is chloroform
- the solvent in the chiral polysilane solution is chloroform
- the good solvent means a solvent capable of dissolving the main chain azobenzene polymer and the chiral polysilane, chloroform, tetrahydrofuran, 1,2-dichloroethane, toluene, etc., preferably chloroform;
- the poor solvent means a solvent which does not dissolve the main chain azobenzene polymer or the chiral polysilane, methanol, n-hexane, isopropanol, ethanol, cyclohexane or the like, and preferably a small molecule alcohol such as methanol.
- the concentration of the main chain azobenzene polymer solution is 1 ⁇ 10 -5 M, and the concentration of the chiral polysilane solution is 1 ⁇ 10 -5 M; the concentration is the repeating unit concentration.
- the main chain azobenzene polymer is a copolymer containing 9,9-dioctylfluorene and an azobenzene group
- the chiral polysilane is ( S )-(-)-/( R ).
- the molecular weight ( M n ) of the main chain azobenzene polymer is 23,000-24000 g/mol
- the chiral polysilane is a rod-like chiral structure
- the molecular weight ( M n ) is 20,000 to 24,000 g/mol.
- the main chain azobenzene polymer is equimolar to the chiral polysilane.
- the number of inversion treatments is 2 to 10 times, and the rest time is 1 to 5 minutes.
- the purpose of the agitation is to better interact with the chiral polysilane and the azobenzene polymer.
- the purpose of the rest is to allow the aggregate to be produced better; the preparation of the aggregate can be carried out in a normal experimental environment, without Special experimental requirements.
- the volume ratio of the total volume of the main chain azobenzene polymer solution, the chiral polysilane solution, and the good solvent to the poor solvent is (2.2:0.8) to (0.3:2.7), and the range is A chiral signal is detected, and is preferably the strongest chiral signal at 2:1; when the volume ratio of good solvent to poor solvent is out of range, aggregates will not be obtained.
- a chloroform solution of two polymers having a repeating unit concentration of 1 ⁇ 10 -5 M is prepared in advance, and one polymer contains 9,9-dioctylfluorene and azobenzene.
- the main chain copolymer F8Azo; the other is ( S )-(-)-/( R )-(+)-2-methylbutyl-n-hexylpolysilane ( S / R- PSi).
- the aggregate preparation is successful or not, one is observed by the naked eye, and the aggregate particles suspended in the solution can be seen under the light, but this method is not applicable to very minute aggregates, and the second is to use a circular dichroism spectrometer.
- the test is performed to explain to some extent the formation of aggregates.
- the chirality of chiral backbone azobenzene polymer isomers was determined by a circular dichroism spectrometer, then used 313
- the ultraviolet light at nm selectively decomposes the chiral polysilane selectively, thereby obtaining a uniform chiral F8Azo collective, that is, a chiral main chain type azobenzene polymer aggregate.
- the present invention has the following advantages over the prior art:
- the present invention utilizes a chiral polysilane which can be selectively and completely decomposed under the action of 313 nm ultraviolet light for the first time to aggregate and induce an aggregate of a main chain type azobenzene polymer having a chiral response; the hand used in the present invention
- the polysilane has a light intensity of 190.0 ⁇ W/cm2 of 313 After the ultraviolet light of nm is irradiated for 15 S, it can be selectively completely decomposed, and since the illumination promotes the ordered arrangement of the aggregates, the chirality of the induced azobenzene not only disappears but increases.
- the invention overcomes the disadvantages that the traditional chiral limonene does not completely remove the limonene molecule after the chirality is induced, and it is proved that the chiral macromolecule can also induce the chirality of the achiral polymer, and is easily exposed to ultraviolet light at 313 nm. Selectively and completely decomposed.
- Example 1 is a nuclear magnetic resonance spectrum of a copolymer F8Azo containing 9,9-dioctylfluorene and an azobenzene group in Example 1;
- Example 2 is a GPC outflow curve of a copolymer F8Azo containing 9,9-dioctylfluorene and an azobenzene group in Example 1;
- Figure 3 is a circular dichroism spectrum of chiral polysilane ( S - / R - PSi) or F8Azo aggregates in Example 1;
- Example 5 is a graph showing changes in g CD values of F8Azo- S- PSi and F8Azo- R- PSi isomeric aggregates at 475 nm in different solvent volume ratios in Example 2;
- Figure 6 is a circular dichroism spectrum of the F8Azo- S- PSi isomers in Example 3 before and after UV irradiation for 10 s;
- Figure 8 is a DLS diagram of F8Azo- S- PSi isomers in Example 3 before and after UV irradiation for 15 s.
- the chemical reagents used in this example were spectral grade pure chloroform (Dojindo) and methanol (Dojindo), and the cuvette used was an SQ grade cuvette having an outer diameter of 10 mm x 10 mm.
- GPC Gel permeation chromatography
- Circular dichroism spectrometer Japan JASCO company JASCO-725 type, measurement conditions: scanning speed 100 nm / min, wavelength range: 230 ⁇ 700 nm, wavelength accuracy: ⁇ 0.1 Nm (230 ⁇ 700 nm), bandwidth: 2 nm, response time 2 seconds, low sensitivity, room temperature test.
- Ultraviolet absorption spectra were obtained simultaneously under the above test conditions;
- a narrowly distributed UV light was obtained using a 313 nm filter (Sigma KoKi, Shanghai, China).
- the copolymer containing the 9,9-dioctylfluorene and the azobenzene group synthesized in the prior art is dissolved in chloroform and filtered under suction to remove the substance which is insoluble in the good solvent chloroform, and the concentrated solution is obtained to be coarse.
- the nuclear magnetic resonance spectrum of Fig. 1 can be clearly seen at 7.60-8.20 ppm.
- the characteristic peak corresponds to the chemical shift of hydrogen on the benzene ring in the fluorene unit and the azobenzene unit in the polymer structure, and the characteristic peak at 2.13 ppm corresponds to the nearest two of the polymer connected to the unit 9
- the chemical shift of the methylene group and the chemical shift of the methylene and methyl groups on the remaining alkyl chains occur at 0.50-1.40 ppm.
- the chirality of the azobenzene polymer can be aggregated by the non-covalent bond between the chiral polysilane and the azobenzene polymer, so that the circular dichroism spectrum can be used to detect the chirality.
- the formation of chiral aggregates can be proved to some extent.
- the obtained three (F8Azo, S-Psi, R-PSi) aggregate solutions were tested by a circular dichroism spectrometer to obtain a circular dichroism spectrum as shown in Fig. 3.
- the ultraviolet absorption region of F8Azo can be seen from the solid line in the figure. At 350 nm-550 nm, no chiral expression was observed in the corresponding region, and both polysilanes had significant chiral signals and were nearly mirror-imaged.
- the main chain type azobenzene polymer aggregate precursor system after gently inverting 8 times and then standing for 2 minutes, the isomeric aggregates of F8Azo- S- PSi or F8Azo- R- PSi were obtained; the main chain type
- the volume ratio of the total volume of the nitrogen benzene polymer solution, the chiral polysilane solution, and the good solvent to the poor solvent was 2:1.
- Figure 4 is a CD-UV spectrum of a binary dichroism spectrometer for the detection of heterogeneous aggregates. It can be seen from the figure that the chiral polysilane successfully induced the chirality of F8Azo after aggregation induction, from 350 nm to 550 nm.
- the obvious chiral signal can be known that R- PSi induces F8Azo to produce right chirality, while S- PSi induces F8Azo to produce left chirality; and after calculation, it is found that the g CD value at 475 nm is as high as 91.24 ⁇ 10 -4 ( R - PSi), -105.3 ⁇ 10 -4 ( S - PSi).
- Example 3 Decomposition of chiral polysilanes by ultraviolet light to obtain pure chiral F8Azo aggregates
- the heterogeneous aggregates of F8Azo- S- PSi or F8Azo- R- PSi were prepared according to the procedure of Example 2.
- the chirality of the aggregates was detected by a circular dichroism spectrometer, and then the UV with a wavelength of 313 nm was constructed.
- the light source of the F8Azo- S- PSi or F8Azo- R- PSi isomerized aggregates was irradiated for 10 s and then subjected to circular dichroism spectroscopy.
- the CD-UV changes of the isomers before and after UV irradiation at 313 nm were obtained (Fig. 6, Fig. 7).
- the g CD values at the 320 nm wavelength after 10 s and 15 s of UV irradiation are basically the same, indicating that the polysilane has completely decomposed after 10 s irradiation at 313 nm.
- Figure 8 is a dynamic light scattering diagram (DLS), which records the change in aggregate size before and after 313 nm irradiation for 15 s. It can be seen from the figure that the particle size of the aggregate changes after the UV light decomposes the chiral polysilane. Small, indicating that the polysilane was just decomposed, which also proved that we obtained a pure chiral azobenzene aggregate after UV irradiation.
- DLS dynamic light scattering diagram
- the above results can fully prove that the achiral main chain azobenzene polymer forms a chiral aggregate under the aggregation induction of chiral polysilane, and the fully decomposable chirality in the ultraviolet light selectivity.
- a simple chiral azobenzene aggregate was obtained after the polysilane.
- the chiral azobenzene aggregates prepared by the present invention have great potential applications in the fields of optical switches, electronic devices, storage media materials, and liquid crystal materials.
Abstract
The present invention relates to a chiral main-chain-type azobenzene polymer aggregate and a preparation method therefor, which method is specifically operated as follows: respectively taking equal amounts of 1×10-5M of a trichloromethane solution of chiral polysilane and of an azobenzene polymer using a pipette and adding same into a cuvette containing a stirrer; then adding a certain amount of a good solvent, trichloromethane, and stirring same for 2 minutes, and then moving the cuvette to a table; then adding a certain amount of a poor solvent, methanol, along a wall; and gently inverting same 8 times and then leaving same to stand for 2 minutes to obtain the chiral main-chain-type azobenzene polymer aggregate. The present invention provides a new method for preparing the chiral azobenzene polymer aggregate. After a suitable good solvent and poor solvent are found, isomeric aggregates of the main-chain-type azobenzene polymer are successfully prepared by adjusting and controlling the volume ratio of the good solvent and the poor solvent. The chiral polysilane is then selectively and completely decomposed by using ultraviolet light so as to obtain an azobenzene polymer aggregate with a single chirality.
Description
本发明涉及高分子化学领域的一种制备聚合物聚集体的方法，具体涉及手性主链型偶氮苯聚合物聚集体及其制备方法。The invention relates to a method for preparing polymer aggregates in the field of polymer chemistry, in particular to a chiral main chain type azobenzene polymer aggregate and a preparation method thereof.
在高分子研究领域中，利用分子间的作用力制备具有特殊功能的聚集体并调控其性质是一项巨大的挑战。聚集体的性能由分子在组装体中的有序度和排列状态决定，因此如何控制π-共轭分子的组装，调控响应的聚集体的结构是制备新型材料的基础。In the field of polymer research, the use of intermolecular forces to prepare aggregates with special functions and to regulate their properties is a huge challenge. The performance of the aggregate is determined by the order and arrangement of the molecules in the assembly. Therefore, how to control the assembly of the π-conjugated molecules and the structure of the aggregates that regulate the response are the basis for the preparation of new materials.
因为具有光学活性的物质在自然界和生命体中发挥着巨大的作用，所以一直是科研工作者的研究热点。手性溶剂诱导法就是制备手性物质的常用方法，虽然解决了以往利用手性单体聚合和非手性单体不对称聚合法得到聚合物手性所要面对的复杂的合成步骤和昂贵的手性催化剂等问题，但对于制备单纯的具有手性的聚集体还是存在着一定的缺陷。例如常用手性柠檬烯来与非手性的聚合物组装以诱导其手性，但是这样的聚集体中始终存在着不易除去的柠檬烯分子，对于实际的生产运用会产生一定的阻碍。Because optically active substances play a huge role in nature and living things, they have been the research hotspot of researchers. The chiral solvent induction method is a common method for preparing chiral substances, although it solves the complicated synthetic steps and expensive methods that have been faced in the past by using chiral monomer polymerization and asymmetric polymerization of achiral monomers to obtain polymer chirality. Chiral catalysts and other problems, but there are still some defects in the preparation of simple chiral aggregates. For example, chiral limonene is commonly used to assemble with achiral polymers to induce chirality, but there are always limonene molecules that are difficult to remove in such aggregates, which may hinder the actual production application.
本发明的目的在于提供一种制备偶氮苯类聚合物聚集体的新方法，也拓宽了诱导偶氮苯类聚合物手性的道路。It is an object of the present invention to provide a novel process for preparing azobenzene polymer aggregates and to broaden the path of inducing azobenzene polymer chirality.
本发明采用的具体技术方案如下：The specific technical solutions adopted by the present invention are as follows:
一种手性主链型偶氮苯聚合物异构聚集体的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，倒置处理后静置，得到手性主链型偶氮苯聚合物异构聚集体。A method for preparing chiral main chain type azobenzene polymer isomers, comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added, and the mixture is allowed to stand after the inversion treatment to obtain a chiral main chain type azobenzene polymer isomerized aggregate.
一种手性主链型偶氮苯聚合物均聚集体的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，倒置处理后静置，得到手性主链型偶氮苯聚合物异构聚集体；然后用紫外光处理手性主链型偶氮苯聚合物异构聚集体，得到手性主链型偶氮苯聚合物均聚集体。A method for preparing a chiral main chain type azobenzene polymer aggregate, comprising the steps of: adding a main chain type azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially adding A good solvent and a poor solvent are allowed to stand after the inverted treatment to obtain a chiral main chain type azobenzene polymer isomer aggregate; then the chiral main chain type azobenzene polymer isomerized aggregate is treated with ultraviolet light to obtain a hand The main chain type azobenzene polymer is aggregated.
一种手性主链型偶氮苯聚合物聚集体前驱体系的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，得到手性主链型偶氮苯聚合物聚集体前驱体系。A method for preparing a precursor system of a chiral main chain type azobenzene polymer aggregate, comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added to obtain a chiral main chain type azobenzene polymer aggregate precursor system.
本发明利用手性聚硅烷与主链型偶氮苯聚合物在二元溶剂中的聚集诱导作用得到具有手性响应的异构聚集体，经过313 nm处的紫外光的辐照可以快速选择性地完全分解掉手性聚硅烷从而得到单纯的具有单一手性的偶氮苯聚合物的聚集体，这是一个比较新颖独特的方法；其优点在于手性聚硅烷是刚性的棒状手性结构，具有很强的旋光性，能且只能被313
nm处的紫外光分解，利用本发明合适的制备条件就可以很容易的制得具有手性的偶氮苯聚合物聚集体。由于偶氮苯是对光敏感的发色团，具有偶氮苯发色团的化合物拥有丰富的光谱学和光物理的性质，因此含偶氮苯基团的聚合物的聚集体的制备技术可以应用到生产生活的方方面面，例如发光材料、电子器件等、存储介质材料等。The invention utilizes the aggregation induction of the chiral polysilane and the main chain azobenzene polymer in a binary solvent to obtain a heterogeneous aggregate having a chiral response, which can be rapidly selected by irradiation of ultraviolet light at 313 nm. Completely decomposing the chiral polysilane to obtain a simple agglomerate of a single chiral azobenzene polymer, which is a relatively novel and unique method; the advantage is that the chiral polysilane is a rigid rod-like chiral structure. Has a strong optical rotation, can only be 313
The ultraviolet light at nm is decomposed, and the chiral azobenzene polymer aggregate can be easily obtained by using the suitable preparation conditions of the present invention. Since azobenzene is a light-sensitive chromophore, and compounds having an azobenzene chromophore possess rich spectroscopic and photophysical properties, preparation techniques for aggregates of azobenzene-containing polymers can be applied. To all aspects of production and life, such as luminescent materials, electronic devices, storage media materials.
上述技术方案中，主链型偶氮苯聚合物溶液中溶剂为三氯甲烷，手性聚硅烷溶液中溶剂为三氯甲烷。In the above technical solution, the solvent in the main chain azobenzene polymer solution is chloroform, and the solvent in the chiral polysilane solution is chloroform.
上述技术方案中，良溶剂是指可以溶解主链型偶氮苯聚合物、手性聚硅烷的溶剂，三氯甲烷、四氢呋喃、1,2-二氯乙烷、甲苯等，优选三氯甲烷；不良溶剂是指不可以溶解主链型偶氮苯聚合物、手性聚硅烷的溶剂，甲醇、正己烷、异丙醇、乙醇、环己烷等，优选小分子醇，比如甲醇。In the above technical solution, the good solvent means a solvent capable of dissolving the main chain azobenzene polymer and the chiral polysilane, chloroform, tetrahydrofuran, 1,2-dichloroethane, toluene, etc., preferably chloroform; The poor solvent means a solvent which does not dissolve the main chain azobenzene polymer or the chiral polysilane, methanol, n-hexane, isopropanol, ethanol, cyclohexane or the like, and preferably a small molecule alcohol such as methanol.
上述技术方案中，主链型偶氮苯聚合物溶液的浓度为1×10
-5
M，手性聚硅烷溶液的浓度为1×10
-5
M；浓度为重复单元浓度。
In the above technical solution, the concentration of the main chain azobenzene polymer solution is 1 × 10 -5 M, and the concentration of the chiral polysilane solution is 1 × 10 -5 M; the concentration is the repeating unit concentration.
上述技术方案中，主链型偶氮苯聚合物为含有9,9-二辛基芴和偶氮苯基团的共聚物，手性聚硅烷为(
S)-(-)-/(
R)-(+)-2-甲基丁基-正己基聚硅烷；主链型偶氮苯聚合物的分子量(
M
n)为23000~24000g/mol；手性聚硅烷为棒状手性结构，分子量(
M
n)为20000~24000 g/mol。
In the above technical solution, the main chain azobenzene polymer is a copolymer containing 9,9-dioctylfluorene and an azobenzene group, and the chiral polysilane is ( S )-(-)-/( R ). -(+)-2-methylbutyl-n-hexylpolysilane; the molecular weight ( M n ) of the main chain azobenzene polymer is 23,000-24000 g/mol; the chiral polysilane is a rod-like chiral structure, and the molecular weight ( M n ) is 20,000 to 24,000 g/mol.
上述技术方案中，主链型偶氮苯聚合物与手性聚硅烷等摩尔量。In the above technical solution, the main chain azobenzene polymer is equimolar to the chiral polysilane.
上述技术方案中，倒置处理次数为2～10次；静置时间为1～5分钟。搅拌的目的是为了手性聚硅烷和偶氮苯聚合物更好地相互作用，静置的目的是为了让聚集体更好地产生；聚集体的制备在正常的实验环境中就可以进行，没有特殊的实验要求。In the above technical solution, the number of inversion treatments is 2 to 10 times, and the rest time is 1 to 5 minutes. The purpose of the agitation is to better interact with the chiral polysilane and the azobenzene polymer. The purpose of the rest is to allow the aggregate to be produced better; the preparation of the aggregate can be carried out in a normal experimental environment, without Special experimental requirements.
上述技术方案中，主链型偶氮苯聚合物溶液、手性聚硅烷溶液以及良溶剂的总体积与不良溶剂的体积比为（2.2∶0.8）～（0.3∶2.7），这个范围内都可以检测到手性信号，且优选2∶1的时候是最强的手性信号；当良溶剂和不良溶剂的体积比超出范围之后将会得不到聚集体。In the above technical solution, the volume ratio of the total volume of the main chain azobenzene polymer solution, the chiral polysilane solution, and the good solvent to the poor solvent is (2.2:0.8) to (0.3:2.7), and the range is A chiral signal is detected, and is preferably the strongest chiral signal at 2:1; when the volume ratio of good solvent to poor solvent is out of range, aggregates will not be obtained.
上述技术方案可表示如下：预先配制好重复单元浓度为1×10
-5
M的两种聚合物的三氯甲烷溶液，一种聚合物是含有9,9-二辛基芴和偶氮苯基团的主链型共聚物F8Azo；另一种是(
S)-(-)-/(
R)-(+)-2-甲基丁基-正己基聚硅烷（
S/
R-PSi）。分别吸取0.15 mL含F8Azo和
S/
R-PSi的三氯甲烷溶液于内置有搅拌磁子的3 mL的比色皿中，再加入1.7 mL的良溶剂三氯甲烷，上下倒置一次后置于磁力搅拌器上搅拌2 min。2分钟后将比色皿置于桌面上，沿比色皿的内壁加入1 mL的不良溶剂甲醇，上下轻轻倒置8次后在桌面上静置2 min从而形成稳定的手性主链型偶氮苯聚合物异构聚集体。
The above technical solution can be expressed as follows: a chloroform solution of two polymers having a repeating unit concentration of 1×10 -5 M is prepared in advance, and one polymer contains 9,9-dioctylfluorene and azobenzene. The main chain copolymer F8Azo; the other is ( S )-(-)-/( R )-(+)-2-methylbutyl-n-hexylpolysilane ( S / R- PSi). Pipette 0.15 mL of chloroform solution containing F8Azo and S / R -PSi into a 3 mL cuvette containing agitated magnetons, then add 1.7 mL of a good solvent, chloroform, and place it upside down for one time. Stir on the stirrer for 2 min. After 2 minutes, place the cuvette on the table, add 1 mL of poor solvent methanol along the inner wall of the cuvette, gently invert it up and down 8 times, and then let it stand on the table for 2 min to form a stable chiral backbone. Nitrobenzene polymer isomers.
聚集体制备成功与否，一个是通过肉眼进行观察，在灯光下可以看到悬浮在溶液里面的聚集体颗粒，但这种方法对于非常微小的聚集体就不适用，二是用圆二色光谱仪进行检测从而在一定程度上说明聚集体的形成与否。用圆二色光谱仪来检测手性主链型偶氮苯聚合物异构聚集体的手性，然后用313
nm处的紫外光选择性地完全分解手性聚硅烷，从而得到均一的具有手性的F8Azo集体，即手性主链型偶氮苯聚合物均聚集体。Whether the aggregate preparation is successful or not, one is observed by the naked eye, and the aggregate particles suspended in the solution can be seen under the light, but this method is not applicable to very minute aggregates, and the second is to use a circular dichroism spectrometer. The test is performed to explain to some extent the formation of aggregates. The chirality of chiral backbone azobenzene polymer isomers was determined by a circular dichroism spectrometer, then used 313
The ultraviolet light at nm selectively decomposes the chiral polysilane selectively, thereby obtaining a uniform chiral F8Azo collective, that is, a chiral main chain type azobenzene polymer aggregate.
由于上述技术方案的实施应用，本发明与现有的技术相比具有以下优点：Due to the implementation of the above technical solutions, the present invention has the following advantages over the prior art:
本发明首次利用在313 nm紫外光作用下可被选择性完全分解的手性聚硅烷来聚集诱导制备具有手性响应的主链型偶氮苯聚合物的聚集体；本发明中所用到的手性聚硅烷在光强为190.0
μW/cm²的 313
nm的紫外光照射15 S之后就可以被选择性地完全分解，并且由于光照促使了聚集体的有序排列，被诱导的偶氮苯的手性不但没有消失反而增强。本发明克服了传统手性柠檬烯诱导手性后不好完全除去柠檬烯分子的弊端，用事实证明手性大分子也可以诱导非手性聚合物的手性性，并且易被313 nm处的紫外光选择性地完全分解。The present invention utilizes a chiral polysilane which can be selectively and completely decomposed under the action of 313 nm ultraviolet light for the first time to aggregate and induce an aggregate of a main chain type azobenzene polymer having a chiral response; the hand used in the present invention The polysilane has a light intensity of 190.0
μW/cm2 of 313
After the ultraviolet light of nm is irradiated for 15 S, it can be selectively completely decomposed, and since the illumination promotes the ordered arrangement of the aggregates, the chirality of the induced azobenzene not only disappears but increases. The invention overcomes the disadvantages that the traditional chiral limonene does not completely remove the limonene molecule after the chirality is induced, and it is proved that the chiral macromolecule can also induce the chirality of the achiral polymer, and is easily exposed to ultraviolet light at 313 nm. Selectively and completely decomposed.
图1为实施例一中含有9,9-二辛基芴和偶氮苯基团的共聚物F8Azo的核磁共振氢谱图；1 is a nuclear magnetic resonance spectrum of a copolymer F8Azo containing 9,9-dioctylfluorene and an azobenzene group in Example 1;
图2为实施例一中含有9,9-二辛基芴和偶氮苯基团的共聚物F8Azo的GPC流出曲线图；2 is a GPC outflow curve of a copolymer F8Azo containing 9,9-dioctylfluorene and an azobenzene group in Example 1;
图3为实施例一中手性聚硅烷（
S-/
R-PSi）或者F8Azo聚集体的圆二色光谱图；
Figure 3 is a circular dichroism spectrum of chiral polysilane ( S - / R - PSi) or F8Azo aggregates in Example 1;
图4为实施例二中F8Azo-
S-PSi和F8Azo-
R-PSi异构聚集体的圆二色光谱图；
4 is a circular dichroism spectrum diagram of F8Azo- S- PSi and F8Azo- R- PSi isomers in Example 2;
图5为实施例二中不同溶剂体积比下的F8Azo-
S-PSi和F8Azo-
R-PSi异构聚集体在475
nm处的
g
CD值变化曲线图；
5 is a graph showing changes in g CD values of F8Azo- S- PSi and F8Azo- R- PSi isomeric aggregates at 475 nm in different solvent volume ratios in Example 2;
图6为施例三中F8Azo-
S-PSi异构聚集体在紫外光辐照10 s前后的圆二色光谱图；
Figure 6 is a circular dichroism spectrum of the F8Azo- S- PSi isomers in Example 3 before and after UV irradiation for 10 s;
图7为施例三中F8Azo-
R-PSi异构聚集体在紫外光辐照10 s前后的圆二色光谱图；
7 is a circular dichroism spectrum of the F8Azo- R- PSi isomeric aggregate in Example 3 before and after ultraviolet irradiation for 10 s;
图8为施例三中F8Azo-
S-PSi异构聚集体在紫外光辐照15 s前后的DLS图。
Figure 8 is a DLS diagram of F8Azo- S- PSi isomers in Example 3 before and after UV irradiation for 15 s.
本发明实施例中采用以下测试仪器及条件：The following test instruments and conditions are used in the embodiments of the present invention:
本实施例中所用的化学试剂是光谱级纯的三氯甲烷（Dojindo）和甲醇(Dojindo)，所用的比色皿是外径为10 mm×10 mm的SQ级别的比色皿。The chemical reagents used in this example were spectral grade pure chloroform (Dojindo) and methanol (Dojindo), and the cuvette used was an SQ grade cuvette having an outer diameter of 10 mm x 10 mm.
凝胶渗透色谱（GPC）：使用Waters1515凝胶色谱仪测定，使用示差折光检测器（RI2414），HR1、HR2和HR4柱子的分子量范围为100-500000 Da，以四氢呋喃（THF）为流动相，流速为1.0 mL/min，在30 ℃下进行测试，用聚苯乙烯标样或者聚丙烯酸甲酯标样对聚合物分子量进行标定；Gel permeation chromatography (GPC): determined using a Waters 1515 gel chromatograph using a refractive index detector (RI2414) with MH1, HR2 and HR4 columns with molecular weights ranging from 100 to 500,000 Da, tetrahydrofuran (THF) as mobile phase, flow rate The test was carried out at 30 °C at 1.0 mL/min, and the molecular weight of the polymer was calibrated with polystyrene standards or polymethyl acrylate standards;
核磁共振氢谱（
1H-NMR）：使用Bruker 300MHz核磁仪，以CDCl
3（氘代三氯甲烷）为溶剂，TMS（四甲基硅烷）为内标，室温下测定；
Nuclear magnetic resonance spectroscopy ( 1 H-NMR): using a Bruker 300 MHz nuclear magnetic apparatus, using CDCl 3 (deuterated chloroform) as a solvent, TMS (tetramethylsilane) as an internal standard, and measuring at room temperature;
圆二色光谱仪（CD）：日本JASCO公司JASCO-725型,测定条件：扫描速度100 nm/min，波长范围：230~700 nm，波长准确度：±0.1
nm (230~700 nm)，带宽：2 nm，响应时间2秒，低灵敏度、室温条件下测试。紫外吸收光谱在上述测试条件下同步获得；Circular dichroism spectrometer (CD): Japan JASCO company JASCO-725 type, measurement conditions: scanning speed 100 nm / min, wavelength range: 230 ~ 700 nm, wavelength accuracy: ± 0.1
Nm (230~700 nm), bandwidth: 2 nm, response time 2 seconds, low sensitivity, room temperature test. Ultraviolet absorption spectra were obtained simultaneously under the above test conditions;
光源：日本东京USHIO公司Optical ModuleX
SX-UID502HUV型的500 W的高压汞灯；Light source: USHIO Corporation Optical ModuleX, Tokyo, Japan
500W high pressure mercury lamp of the SX-UID502HUV type;
滤波片：使用313 nm的滤波片（Sigma KoKi，上海，中国）获得分布较窄的紫外光。Filter: A narrowly distributed UV light was obtained using a 313 nm filter (Sigma KoKi, Shanghai, China).
实施例一Embodiment 1
（1） 主链型偶氮苯聚合物的预处理(1) Pretreatment of main chain azobenzene polymer
将现有技术合成好的含有9,9-二辛基芴和偶氮苯基团的共聚物用三氯甲烷溶解后抽滤，除去不溶于良溶剂三氯甲烷的物质，浓缩清液得到粗产品，三氯甲烷溶解后在甲醇中沉降，静置后抽滤得到聚合物，置于30 ℃真空烘箱中干燥12 h，即得到本发明所需的主链型偶氮苯聚合物F8Azo，用于以下实验。The copolymer containing the 9,9-dioctylfluorene and the azobenzene group synthesized in the prior art is dissolved in chloroform and filtered under suction to remove the substance which is insoluble in the good solvent chloroform, and the concentrated solution is obtained to be coarse. The product, after chloroform is dissolved, precipitates in methanol, and after standing, it is filtered by suction to obtain a polymer, which is dried in a vacuum oven at 30 ° C for 12 h to obtain the main chain azobenzene polymer F8Azo required by the present invention. In the following experiment.
随后对该聚合物进行了相关的核磁共振氢谱（图1）和凝胶渗透色谱GPC（图2）测试，从图1的核磁氢谱上可以十分清晰地看出在7.60-8.20 ppm处的特征峰对应的是聚合物结构中芴单元和偶氮苯单元中苯环上的氢的化学位移，在2.13
ppm处的特征峰对应的是聚合物中与单元9位上连接的最近的两个亚甲基的化学位移，其余烷基链上的亚甲基和甲基的化学位移出现在0.50-1.40
ppm处。用凝胶渗透色谱GPC测得其数均分子量
Mn
=23900 Da，分子量分布PDI = 1.61（图2中的曲线）。
Subsequently, the polymer was subjected to the relevant nuclear magnetic resonance spectrum (Fig. 1) and gel permeation chromatography GPC (Fig. 2). The nuclear magnetic resonance spectrum of Fig. 1 can be clearly seen at 7.60-8.20 ppm. The characteristic peak corresponds to the chemical shift of hydrogen on the benzene ring in the fluorene unit and the azobenzene unit in the polymer structure, and the characteristic peak at 2.13 ppm corresponds to the nearest two of the polymer connected to the unit 9 The chemical shift of the methylene group and the chemical shift of the methylene and methyl groups on the remaining alkyl chains occur at 0.50-1.40 ppm. The number average molecular weight M n = 23900 Da and the molecular weight distribution PDI = 1.61 (curve in Fig. 2) were measured by gel permeation chromatography GPC.
（2）分别称取0.57 mg的F8Azo和0.18 mg的手性聚硅烷（(
S)-(-)-/(
R)-(+)-2-甲基丁基-正己基聚硅烷），分别加入5 mL的光谱级纯的三氯甲烷溶剂各自配成重复单元浓度为1.0×10
-5 M的溶液，加热使其完全溶解。
(2) Weigh 0.57 mg of F8Azo and 0.18 mg of chiral polysilane (( S )-(-)-/( R )-(+)-2-methylbutyl-n-hexylpolysilane), respectively 5 mL of a spectral grade pure chloroform solvent was added to prepare a solution having a repeating unit concentration of 1.0 × 10 -5 M, and heated to completely dissolve.
（3）手性聚硅烷和F8Azo均聚集体的制备(3) Preparation of chiral polysilane and F8Azo aggregates
分别吸取0.15 mL浓度为1.0×10
-5 M的F8Azo、
S-或
R-PSi的三氯甲烷溶液于内置有小搅拌子的比色皿中，再加入1.85 mL的良溶剂三氯甲烷，用磁力搅拌器搅拌2分钟后将比色皿移至桌面上，沿比色皿的内壁加入1.0
mL的不良溶剂甲醇，轻轻上下倒置8次后静置2分钟，制得了偶氮苯或是手性聚硅烷的聚集体溶液。
Pipette 0.15 mL of 1.0×10 -5 M F8Azo, S- or R- PSi in chloroform solution in a cuvette with a small stirrer, and add 1.85 mL of good solvent chloroform. After stirring for 2 minutes on the magnetic stirrer, the cuvette was transferred to the table, and 1.0 mL of a poor solvent methanol was added along the inner wall of the cuvette, and the mixture was gently inverted upside down for 8 times and allowed to stand for 2 minutes to obtain azobenzene or a hand. An aggregate solution of a polysilane.
在该体系中，通过手性聚硅烷和偶氮苯聚合物之间的非共价键作用力可以聚集诱导偶氮苯聚合物的手性，于是可以采用圆二色光谱来检测手性，也可以从一定程度上证明手性聚集体形成与否。得到的三个（F8Azo、S-Psi、R-PSi)聚集体溶液经圆二色光谱仪的测试得到如图3的圆二色光谱图，可以从图中的实线看出F8Azo的紫外吸收区域在350 nm-550 nm，并且在对应的区域没有看到手性表达，而两个聚硅烷都具有明显的手性信号，且近乎呈镜像对应关系。In this system, the chirality of the azobenzene polymer can be aggregated by the non-covalent bond between the chiral polysilane and the azobenzene polymer, so that the circular dichroism spectrum can be used to detect the chirality. The formation of chiral aggregates can be proved to some extent. The obtained three (F8Azo, S-Psi, R-PSi) aggregate solutions were tested by a circular dichroism spectrometer to obtain a circular dichroism spectrum as shown in Fig. 3. The ultraviolet absorption region of F8Azo can be seen from the solid line in the figure. At 350 nm-550 nm, no chiral expression was observed in the corresponding region, and both polysilanes had significant chiral signals and were nearly mirror-imaged.
实施例二 F8Azo-
S/
R-PSi异构聚集体的制备
Example 2 Preparation of F8Azo- S / R- PSi Isomers
（1）向内置有小搅拌子的比色皿中依次加入0.15
mL浓度为1.0×10
-5
M的F8Azo的三氯甲烷溶液和0.15
mL浓度为1.0×10
-5
M的
S-或
R-PSi的三氯甲烷溶液，再加入1.7
mL的良溶剂三氯甲烷，磁力搅拌器搅拌2分钟后将比色皿移至桌面上，沿比色皿的内壁加入1.0
mL的不良溶剂甲醇，得到手性主链型偶氮苯聚合物聚集体前驱体系；再轻轻上下倒置8次后静置2分钟，制得了F8Azo-
S-PSi或F8Azo-
R-PSi的异构聚集体；主链型偶氮苯聚合物溶液、手性聚硅烷溶液以及良溶剂的总体积与不良溶剂的体积比为2∶1。
(1) To a cuvette with a small stirrer, 0.15 mL of a 1.0 × 10 -5 M solution of F8Azo in chloroform and 0.15 mL of a 1.0 × 10 -5 M S - or R - are sequentially added. PSi chloroform solution, add 1.7 mL of good solvent chloroform, stir for 2 minutes with a magnetic stirrer, then move the cuvette to the table and add 1.0 mL of poor solvent methanol along the inner wall of the cuvette to get the hand. The main chain type azobenzene polymer aggregate precursor system; after gently inverting 8 times and then standing for 2 minutes, the isomeric aggregates of F8Azo- S- PSi or F8Azo- R- PSi were obtained; the main chain type The volume ratio of the total volume of the nitrogen benzene polymer solution, the chiral polysilane solution, and the good solvent to the poor solvent was 2:1.
图4是圆二色光谱仪对于异构聚集体检测得到的CD-UV谱图，从图中可以看出，经过聚集诱导，手性聚硅烷成功诱导了F8Azo的手性，从350 nm-550 nm处明显的手性信号可以知道
R-PSi诱导F8Azo产生右手手性，而
S-PSi诱导F8Azo产生左手手性；并且经过计算，发现475
nm处的
g
CD值高达91.24×10
-4（
R-PSi）、-105.3×10
-4（
S-PSi）。
Figure 4 is a CD-UV spectrum of a binary dichroism spectrometer for the detection of heterogeneous aggregates. It can be seen from the figure that the chiral polysilane successfully induced the chirality of F8Azo after aggregation induction, from 350 nm to 550 nm. The obvious chiral signal can be known that R- PSi induces F8Azo to produce right chirality, while S- PSi induces F8Azo to produce left chirality; and after calculation, it is found that the g CD value at 475 nm is as high as 91.24×10 -4 ( R - PSi), -105.3 × 10 -4 ( S - PSi).
（ 2 ）按照实施例二（1）中制备异构聚集体的方法，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液以及良溶剂三氯甲烷的总体积与不良溶剂甲醇按照不同的体积比（2.2∶0.8）～（0.3∶2.7）制备异构聚集体F8Azo-
S/
R-PSi，来探索良溶剂和不良溶剂不同的体积比对于聚集诱导偶氮苯手性的影响。如图5，是在不同体积比下偶氮苯所在的紫外吸收区域的475 nm处的
g
CD值的变化曲线，从曲线的变化趋势可以得出结论：优选比例为2.0:1.0，聚集诱导的效果最佳。
( 2 ) according to the method for preparing an isomeric aggregate in the second embodiment (1), the total volume of the main chain azobenzene polymer solution, the chiral polysilane solution, and the good solvent chloroform is different from the poor solvent methanol. The isomers F8Azo- S / R -PSi were prepared in a volume ratio (2.2:0.8) to (0.3:2.7) to explore the effect of different volume ratios of good solvents and poor solvents on the chirality of aggregation-induced azobenzene. Figure 5 shows the change in g CD value at 475 nm in the UV absorption region where azobenzene is present at different volume ratios. From the trend of the curve, it can be concluded that the preferred ratio is 2.0:1.0, aggregation-induced The best results.
实施例三 利用紫外光分解手性聚硅烷得到单纯的具有手性的F8Azo聚集体Example 3 Decomposition of chiral polysilanes by ultraviolet light to obtain pure chiral F8Azo aggregates
按照实施例二的步骤分别制备好F8Azo-
S-PSi或F8Azo-
R-PSi的异构聚集体，利用圆二色光谱仪来检测聚集体的手性，然后用搭建好的波长为313
nm的紫外光源对该F8Azo-
S-PSi或F8Azo-
R-PSi的异构聚集体分别辐照10 s后再次进行圆二色光谱测试。分别得到313 nm处的紫外光辐照前后异构聚集体的CD-UV变化图（图6，图7），可以看出紫外光仅辐照10 s后，300-350 nm处的手性聚硅烷的手性信号峰和紫外吸收峰近乎减弱至消失，说明手性聚硅烷基本上被分解完毕了，得到手性主链型偶氮苯聚合物均聚集体。同时，350-550
nm处的F8Azo被诱导得到的手性不但没有消失，反而手性信号明显的增强，这应该是由于光照使得聚集体排列的更加有序。
The heterogeneous aggregates of F8Azo- S- PSi or F8Azo- R- PSi were prepared according to the procedure of Example 2. The chirality of the aggregates was detected by a circular dichroism spectrometer, and then the UV with a wavelength of 313 nm was constructed. The light source of the F8Azo- S- PSi or F8Azo- R- PSi isomerized aggregates was irradiated for 10 s and then subjected to circular dichroism spectroscopy. The CD-UV changes of the isomers before and after UV irradiation at 313 nm were obtained (Fig. 6, Fig. 7). It can be seen that the chiral polymerization at 300-350 nm after only 10 s of ultraviolet light irradiation. The chiral signal peak and ultraviolet absorption peak of silane almost weakened to disappear, indicating that the chiral polysilane was basically decomposed, and the chiral main chain azobenzene polymer aggregate was obtained. At the same time, the chirality induced by F8Azo at 350-550 nm has not disappeared, but the chiral signal is obviously enhanced. This should be due to the more orderly arrangement of aggregates due to illumination.
为了证明是否得到了单纯的具有手性的F8Azo聚集体，利用313
nm处的紫外光对事先制备好的F8Azo-
S-PSi异构聚集体依次辐照5 s、10 s、15 s（对同一异构聚集体的累计辐照时间），在每次照完后利用圆二色光谱仪来检测手性和紫外的变化情况。经过计算得到表格1中的相应的
g
CD值，从表格中的数据变化可以看出，紫外光辐照5 s后
g
CD值就有很明显的变化，说明紫外光辐照5 s就可以分解大部分的手性聚硅烷。而紫外光累计辐照10 s和15 s后的320 nm波长处的
g
CD值基本一样，说明313 nm的紫外光辐照10 s后聚硅烷已经完全分解。图8为动态光散射图（DLS），记录了313 nm辐照15 s前后的聚集体粒径的变化，从图中可以看出紫外光分解完手性聚硅烷后，聚集体的粒径变小，说明聚硅烷刚好被分解掉了，这也能够证明在紫外光辐照后我们得到了单纯的具有手性性的偶氮苯聚集体。
In order to prove whether a simple chiral F8Azo aggregate was obtained, the previously prepared F8Azo- S- PSi isomers were irradiated for 5 s, 10 s, 15 s by ultraviolet light at 313 nm (for the same The cumulative irradiation time of the heterogeneous aggregates was measured by a circular dichroism spectrometer after each shot. After calculating the corresponding g CD value in Table 1, it can be seen from the data change in the table that the g CD value changes obviously after 5 s of ultraviolet light irradiation, indicating that the ultraviolet light can be decomposed after 5 s irradiation. Most of the chiral polysilanes. The g CD values at the 320 nm wavelength after 10 s and 15 s of UV irradiation are basically the same, indicating that the polysilane has completely decomposed after 10 s irradiation at 313 nm. Figure 8 is a dynamic light scattering diagram (DLS), which records the change in aggregate size before and after 313 nm irradiation for 15 s. It can be seen from the figure that the particle size of the aggregate changes after the UV light decomposes the chiral polysilane. Small, indicating that the polysilane was just decomposed, which also proved that we obtained a pure chiral azobenzene aggregate after UV irradiation.
表1 F8Azo-
S-PSi异构聚集体在紫外光依次辐照5 s、10 s、15 s后对应的
g
CD值数据表
Table 1 Corresponding g CD value data table of F8Azo- S- PSi isomers after UV irradiation for 5 s, 10 s, 15 s
上述的结果能够充分证明，非手性的主链型偶氮苯聚合物在与手性聚硅烷的聚集诱导作用下形成了具有手性的聚集体，并且在紫外光选择性的完全分解手性聚硅烷后得到了单纯的手性偶氮苯聚集体。本发明制备的手性偶氮苯聚集体在光开关、电子器件、存储介质材料以及液晶材料等领域都具有巨大的潜在用途。The above results can fully prove that the achiral main chain azobenzene polymer forms a chiral aggregate under the aggregation induction of chiral polysilane, and the fully decomposable chirality in the ultraviolet light selectivity. A simple chiral azobenzene aggregate was obtained after the polysilane. The chiral azobenzene aggregates prepared by the present invention have great potential applications in the fields of optical switches, electronic devices, storage media materials, and liquid crystal materials.
Claims (10)
- 一种手性主链型偶氮苯聚合物异构聚集体的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，倒置处理后静置，得到手性主链型偶氮苯聚合物异构聚集体。A method for preparing chiral main chain type azobenzene polymer isomers, comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added, and the mixture is allowed to stand after the inversion treatment to obtain a chiral main chain type azobenzene polymer isomerized aggregate.
- 一种手性主链型偶氮苯聚合物均聚集体的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，倒置处理后静置，得到手性主链型偶氮苯聚合物异构聚集体；然后用紫外光处理手性主链型偶氮苯聚合物异构聚集体，得到手性主链型偶氮苯聚合物均聚集体。A method for preparing a chiral main chain type azobenzene polymer aggregate, comprising the steps of: adding a main chain type azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially adding A good solvent and a poor solvent are allowed to stand after the inverted treatment to obtain a chiral main chain type azobenzene polymer isomer aggregate; then the chiral main chain type azobenzene polymer isomerized aggregate is treated with ultraviolet light to obtain a hand The main chain type azobenzene polymer is aggregated.
- 一种手性主链型偶氮苯聚合物聚集体前驱体系的制备方法，包括以下步骤，搅拌下，将主链型偶氮苯聚合物溶液、手性聚硅烷溶液加入反应器中，然后依次加入良溶剂、不良溶剂，得到手性主链型偶氮苯聚合物聚集体前驱体系。A method for preparing a precursor system of a chiral main chain type azobenzene polymer aggregate, comprising the steps of: adding a main chain azobenzene polymer solution and a chiral polysilane solution to a reactor under stirring, and then sequentially A good solvent and a poor solvent are added to obtain a chiral main chain type azobenzene polymer aggregate precursor system.
- 根据权利要求1、2或者3所述的制备方法，其特征在于，所述主链型偶氮苯聚合物溶液中溶剂为三氯甲烷，手性聚硅烷溶液中溶剂为三氯甲烷；主链型偶氮苯聚合物溶液的浓度为1×10 -5 M，手性聚硅烷溶液的浓度为1×10 -5 M；主链型偶氮苯聚合物与手性聚硅烷等摩尔量。 The preparation method according to claim 1, 2 or 3, wherein the solvent in the main chain azobenzene polymer solution is chloroform, and the solvent in the chiral polysilane solution is chloroform; the main chain The concentration of the azobenzene polymer solution is 1 × 10 -5 M, and the concentration of the chiral polysilane solution is 1 × 10 -5 M; the main chain type azobenzene polymer is equimolar to the chiral polysilane.
- 根据权利要求1、2或者3所述的制备方法，其特征在于，所述良溶剂包括三氯甲烷、四氢呋喃、1,2-二氯乙烷、甲苯；所述不良溶剂包括甲醇、正己烷、异丙醇、乙醇、环己烷；良溶剂、不良溶剂的体积比为（2.2∶0.8）～（0.3∶2.7）。The preparation method according to claim 1, 2 or 3, wherein the good solvent comprises chloroform, tetrahydrofuran, 1,2-dichloroethane, toluene; and the poor solvent includes methanol, n-hexane, The volume ratio of isopropyl alcohol, ethanol, and cyclohexane; good solvent and poor solvent is (2.2:0.8) to (0.3:2.7).
- 根据权利要求1、2或者3所述的制备方法，其特征在于，所述主链型偶氮苯聚合物为含有9,9-二辛基芴和偶氮苯基团的共聚物，手性聚硅烷为( S)-(-)-/( R)-(+)-2-甲基丁基-正己基聚硅烷；主链型偶氮苯聚合物的分子量为23000~24000g/mol；手性聚硅烷为棒状手性结构，分子量为20000~24000 g/mol。 The method according to claim 1, 2 or 3, wherein the main chain azobenzene polymer is a copolymer containing 9,9-dioctylfluorene and an azobenzene group, chirality. The polysilane is ( S )-(-)-/( R )-(+)-2-methylbutyl-n-hexylpolysilane; the molecular weight of the main chain azobenzene polymer is 23,000-24000 g/mol; The polysilane is a rod-like chiral structure with a molecular weight of 20,000 to 24,000 g/mol.
- 根据权利要求1或者2 所述的制备方法，其特征在于，倒置处理次数为2～10次；静置时间为1～5分钟。The preparation method according to claim 1 or 2, wherein the number of inversion treatments is 2 to 10 times; and the rest time is 1 to 5 minutes.
- 根据权利要求2 所述的制备方法，其特征在于，紫外光的波长为313 nm。The preparation method according to claim 2, wherein the ultraviolet light has a wavelength of 313 nm.
- 根据权利要求1、2或者3所述的制备方法制备的手性主链型偶氮苯聚合物异构聚集体、手性主链型偶氮苯聚合物均聚集体或者手性主链型偶氮苯聚合物聚集体前驱体系。A chiral main chain type azobenzene polymer isomer aggregate, a chiral main chain type azobenzene polymer aggregate or a chiral main chain type prepared by the preparation method according to claim 1, 2 or Nitrobenzene polymer aggregate precursor system.
- 权利要求9所述手性主链型偶氮苯聚合物聚集体前驱体系在制备手性主链型偶氮苯聚合物异构聚集体或者手性主链型偶氮苯聚合物均聚集体中的应用；权利要求9所述手性主链型偶氮苯聚合物异构聚集体在制备手性主链型偶氮苯聚合物均聚集体中的应用；所述主链型偶氮苯聚合物、手性聚硅烷在制备手性主链型偶氮苯聚合物异构聚集体或者手性主链型偶氮苯聚合物均聚集体中的应用。The precursor system of the chiral main chain type azobenzene polymer aggregate according to claim 9 is prepared by preparing a chiral main chain type azobenzene polymer isomer aggregate or a chiral main chain type azobenzene polymer aggregate. Application of the chiral main chain type azobenzene polymer isomeric aggregate according to claim 9 for preparing a chiral main chain type azobenzene polymer aggregate; the main chain type azobenzene polymerization And chiral polysilanes are used in the preparation of chiral main chain azobenzene polymer isomers or chiral backbone azobenzene polymer aggregates.
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