阅读说明：本技术 一类具有周期结构的侧链型聚集诱导发光液晶高分子及其制备方法 (Side chain type aggregation-induced emission liquid crystal polymer with periodic structure and preparation method thereof ) 是由 韩丽 李旭文 李杨 马红卫 冷雪菲 王艳色 张瑞雪 于 2021-08-12 设计创作，主要内容包括：一类具有周期结构的侧链型聚集诱导发光液晶高分子及其制备方法,属于高分子材料技术领域。该液晶高分子由烷基锂引发的Si-H官能化DPE与异戊二烯/苯乙烯的活性阴离子共聚合制备的周期共聚物主链与乙烯基末端的氰基二苯乙烯基液晶在催化剂作用下通过硅氢加成方法制备而成。本发明制备的液晶单体及液晶功能化聚合物呈现可调的液晶性和聚集诱导发光AIE特性；该类材料集AIE发光特性和液晶性于一身,具有较好的稳定性,并且显著调控液晶的光学特性和热性能；周期功能单元序列可控聚合物具有独特的密度分布和分子作用力；利用构建一种独特的分子作用力模型实现发光液晶高分子稳定的AIE效应和明显的液晶性能,对新型发光液晶功能材料的发展具有重要意义。(A side chain type aggregation-induced emission liquid crystal polymer with a periodic structure and a preparation method thereof belong to the technical field of polymer materials. The liquid crystal polymer is prepared by a hydrosilylation method under the action of a catalyst, wherein the hydrosilylation method comprises a periodic copolymer main chain prepared by the copolymerization of Si-H functionalized DPE initiated by alkyl lithium and active anion of isoprene/styrene, and a cyano distyryl liquid crystal at the tail end of a vinyl group. The liquid crystal monomer and the liquid crystal functional polymer prepared by the invention have adjustable liquid crystal property and aggregation-induced emission AIE (induced emission) characteristics; the material integrates AIE luminescence property and liquid crystal property, has better stability, and obviously regulates and controls optical property and thermal property of liquid crystal; the polymer with the controllable periodic functional unit sequence has unique density distribution and molecular acting force; the stable AIE effect and obvious liquid crystal performance of the luminous liquid crystal polymer are realized by constructing a unique molecular acting force model, and the method has important significance for the development of novel luminous liquid crystal functional materials.)

1. A side chain type aggregation-induced emission liquid crystal polymer with a periodic structure is characterized in that the side chain type aggregation-induced emission liquid crystal polymer takes hydrosilylation-functionalized DPE and isoprene or styrene as alternating units to obtain a Si-H functionalized periodic copolymer main chain, and two cyano distyryl liquid crystal monomers M with vinyl ends are grafted to the periodic copolymer through a hydrosilylation methodObtaining a functional liquid crystal polymer with an alternate structure main chain on the main chain; its number average molecular weight M_nIn the range of 10-100 kg-mol-¹The molecular weight distribution index PDI ranges from 1.08 to 1.39.

2. The side chain type aggregation-induced emission liquid crystal polymer having a periodic structure of claim 1, wherein the hydrosilylation catalyst is Pt (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane or chloroplatinic acid H₂PtCl₆·6H₂And O is one of the compounds.

3. The side-chain aggregation-induced emission liquid crystal polymer having a periodic structure of claim 1, wherein the alkyl lithium is selected from monofunctional alkyl lithium initiators.

4. The side-chain aggregation-induced emission liquid crystalline polymer having a periodic structure of claim 1, wherein the Si-H functionalized periodic copolymer backbone is prepared by a living anionic polymerization method using alkyl lithium-initiated bis-Si-H functionalized DPE and Ip, and has a structural form of P-P (D-2 SiH/Ip); the structure form of the prepared luminescent liquid crystal polymer (SC-AIE-LLCP) with the side chain containing cyano distyryl based on the main chain of the periodic copolymer is P-P (D-2SiH/Ip) -M; wherein Ip represents isoprene, D-2SiH represents 1, 1-Diphenylethylene (DPE) derivative containing double Si-H functional groups, p represents a periodic sequence structure, and M represents cyano distyryl liquid crystal monomer.

5. The side chain type aggregation-induced emission liquid crystal polymer with periodic structure as claimed in claim 1, wherein the Si-H functionalized periodic copolymer main chain is prepared by a living anion polymerization method from bis-Si-H functionalized DPE and St initiated by alkyl lithium, and the structure form of the DPE is P-P (D-2SiH/St), and the prepared side chain stilbene-containing emission liquid crystal polymer (SC-AIE-LLCP) based on the periodic copolymer main chain has the structure form of P-P (D-2SiH/St) -M; wherein St represents styrene, D-2SiH represents 1, 1-Diphenylethylene (DPE) derivative containing double Si-H functional groups, p represents a periodic sequence structure, and M represents cyano distyryl liquid crystal monomer.

6. The side-chain aggregation-induced emission liquid crystal polymer having a periodic structure of claim 1, wherein the Si-H functionalized periodic copolymer backbone is prepared by a living anion polymerization method by using Si-H functionalized DPE and Ip initiated by alkyl lithium, and the structure form of the Si-H functionalized DPE and Ip is P-P (D-SiH/Ip), and the structure form of the prepared side-chain stilbene-containing emission liquid crystal polymer (SC-AIE-LLCP) based on the periodic copolymer backbone is P-P (D-SiH/Ip) -M; wherein Ip represents isoprene, D-SiH represents a 1, 1-Diphenylethylene (DPE) derivative containing a single Si-H functional group, p represents a periodic sequence structure, and M represents a cyano distyryl liquid crystal monomer.

7. The side chain type aggregation-induced emission liquid crystal polymer having a periodic structure as claimed in claim 1, wherein the Si-H functionalized periodic copolymer main chain is prepared by a living anion polymerization method from Si-H functionalized DPE and St initiated by alkyl lithium, and the structure form of the prepared Si-H functionalized DPE and St is P-P (D-SiH/St), and the structure form of the prepared side chain stilbene-containing emission liquid crystal polymer (SC-AIE-LLCP) based on the periodic copolymer main chain is P-P (D-SiH/St) -M; wherein St represents styrene, D-SiH represents 1, 1-Diphenylethylene (DPE) derivative containing single Si-H functional group, p represents periodic sequence structure, and p represents periodic sequence structure.

8. A preparation method of the side chain type aggregation-induced emission liquid crystal polymer with the periodic structure as claimed in any one of claims 1 to 7, characterized by comprising the following steps:

s1 preparation of Cyanodistyryl liquid Crystal monomer

S1-1: synthesis of intermediate 1-1

Under the protection of argon, adding 1-bromooctadecane, 4-hydroxybenzaldehyde, anhydrous potassium carbonate and N, N-dimethylformamide DMF into a flask, reacting at 70-140 ℃ for 10-48h, pouring a reaction system into a sodium hydroxide solution, stirring at room temperature for 6-24h, filtering after the reaction is finished to obtain a crude product, and carrying out aftertreatment on the crude product to obtain an intermediate 1-1; the mol ratio of the 1-bromooctadecane, the 4-hydroxybenzaldehyde and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6;

s1-2: synthesis of intermediates 1-2

Under the protection of argon, adding the intermediates 1-1, 4-hydroxybenzyl acetonitrile, sodium hydroxide and absolute ethyl alcohol into a flask, reacting at 50-80 ℃ for 3-10h, acidifying the system for 6-48h, filtering after the reaction to obtain a crude product, and performing aftertreatment on the crude product to obtain an intermediate 1-2; the molar ratio of the intermediate 1-1, the 4-hydroxybenzeneacetonitrile to the sodium hydroxide is 1 (1.1-1.5) to 2-6;

s1-3: synthesis of intermediates 1 to 3

Under the protection of argon, adding the intermediate 1-2, 6-chloro-1-hexanol, anhydrous potassium carbonate and DMF into a flask, reacting at 70-140 ℃ for 10-48h, filtering to obtain a crude product after the reaction is finished, and performing post-treatment on the crude product to obtain an intermediate 1-3; the mol ratio of the intermediate 1-2, the 6-chlorine-1-hexanol and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6;

s1-4: synthesis of liquid Crystal monomer Vinyl-phenyl-Cyano (M)₁)

Adding 4- (allyloxy) benzoic acid and thionyl chloride into a flask, reacting for 6-12h at 50-70 ℃, and then removing the solvent by reduced pressure rotary evaporation to obtain oily liquid; adding the oily liquid, the intermediate 1-3, pyridine and chloroform into a flask, and reacting at 50-70 ℃ for 6-48 h; after the reaction is finished, removing the solvent by reduced pressure rotary evaporation, carrying out acidification treatment for 6-48h, and purifying to obtain a liquid crystal monomer Vinyl-phenyl-Cyano (M)₁) (ii) a The molar ratio of the 4- (allyloxy) benzoic acid to the thionyl chloride to the intermediate 1-3 is (1.1-1.5) to (4-8) to 1;

s1-5: synthesis of intermediate 2-1

Under the protection of argon, p-hydroxybenzeneboronic acid, p-bromophenylacetonitrile and tetrakis (triphenylphosphine) palladium Pd (PPh)₃)₄Adding sodium carbonate, THF and deionized water into a flask, reacting at 60-90 deg.C for 10-48h, acidifying the system for 6-48h, and addingExtracting and recrystallizing to obtain an intermediate 2-1; the p-hydroxyphenylboronic acid, the p-bromophenylacetonitrile and the Pd (PPh)₃)₄The molar ratio of (1), (1.1-1.3) to (0.005);

s1-6: synthesis of intermediate 2-2

Under the protection of argon, adding the intermediate 1-1, the intermediate 2-1, sodium hydroxide and absolute ethyl alcohol into a flask, reacting for 3-10h at 50-80 ℃, acidifying the system for 6-48h after the reaction is finished, performing suction filtration to obtain a crude product, and performing post-treatment on the crude product to obtain an intermediate 2-2; the molar ratio of the intermediate 1-1 to the intermediate 2-1 to the sodium hydroxide is 1 (1.1-1.5) to 2-6;

s1-7: synthesis of intermediates 2 to 3

Under the protection of argon, adding the intermediate 2-2, 6-chloro-1-hexanol, anhydrous potassium carbonate and DMF into a flask, reacting at 70-140 ℃ for 12-48h, performing suction filtration after the reaction to obtain a crude product, and performing post-treatment on the crude product to obtain an intermediate 2-3; the mol ratio of the intermediate 2-2, the 6-chlorine-1-hexanol and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6;

s1-8: synthesis of liquid Crystal monomer Vinyl-biphenyl-Cyano (M)₂)

Adding 4- (allyloxy) benzoic acid and thionyl chloride into a flask, reacting for 6-12h at 50-70 ℃, and removing a solvent to obtain oily liquid after the reaction is finished; adding the oily liquid, the intermediate 2-3, pyridine and chloroform into a flask, reacting at 50-70 ℃ for 6-24h, removing the solvent, acidifying for 6-48h, filtering to obtain a crude product, and purifying the crude product to obtain a liquid crystal monomer Vinyl-biphenyl-cyanol (M)₂) (ii) a The molar ratio of the 4- (allyloxy) benzoic acid to the thionyl chloride to the intermediate 2-3 is (1.1-1.5) to (4-8) to 1;

s2 preparation of Si-H functionalized DPE and Ip/St periodic copolymer backbone P-P (D-2SiH/Ip), P-P (D-2SiH/St), P-P (D-SiH/Ip), P-P (D-SiH/St)

S2-1: synthesis of the polymeric monomer DPE-SiH

Under the protection of anhydrous and oxygen-free argon, adding methyl triphenyl phosphonium bromide, potassium tert-butoxide and THF into a flask, and stirring at-10-0 ℃ for 60-90min until the system becomes bright yellow; dripping THF solution of 4-bromophenyl-4' -phenyl ketone BP-Br into the reaction system, stirring for 30-60min, heating to 50-60 deg.C, and reacting for 12-14 h; after the reaction is finished, stopping the reaction by using deionized water, and extracting ethyl acetate and saturated salt water; purifying the crude product to obtain colorless viscous liquid DPE-Br; the mol ratio of BP-Br, potassium tert-butoxide and methyl triphenyl phosphonium bromide is 1 (1.5-3) to 2-4;

uniformly stirring DPE-Br in THF, slowly dropwise adding into magnesium chips, adding iodine particles to initiate Grignard reaction, adding dimethylchlorosilane solution into the magnesium chips, and reacting for 16-25h at 20-50 ℃; extracting with ethyl acetate and saturated brine; purifying the crude product to obtain colorless viscous liquid DPE-SiH; the mol ratio of DPE-Br to magnesium chips to dimethylchlorosilane is 1 (4-6) to 2.5-4;

s2-2: synthesis of the polymeric monomer DPE-2SiH

Under the protection of anhydrous and oxygen-free argon, methyl triphenyl phosphonium bromide, potassium tert-butoxide and THF are stirred for 60-90min at-10-0 ℃, and the system becomes bright yellow; dripping THF solution of 4, 4-dibromo benzophenone BP-2Br into a reaction system, and stirring at-10-0 ℃ for 10-12 h; after the reaction is finished, stopping the reaction by using deionized water, and extracting ethyl acetate and saturated salt water; purifying the crude product to obtain white solid DPE-2 Br; the mol ratio of BP-2Br, potassium tert-butoxide and methyl triphenyl phosphonium bromide is 1 (1.5-3) to 2-4;

adding magnesium chips into a flask, dissolving dimethylchlorosilane into THF, dropwise adding into the flask, and stirring for reaction for 1-2 h; adding a THF solution dissolved with DPE-2Br into the system dropwise, and reacting at 55-65 ℃ for 12-14 h; pouring the reaction product into n-hexane for sedimentation, and purifying the crude product to obtain a flaky crystal DPE-2 SiH; the mol ratio of the DPE-2Br to the magnesium chips to the dimethylchlorosilane is 1 (4-6) to 2.5-4;

s3 synthesizing cycle sequence controllable silicon-hydrogen functionalized polymer main chain

S3-1: synthesis of periodic copolymer P-P (D-2SiH/Ip)

Under the anhydrous and anaerobic conditions, adding DPE-2SiH and benzene into a polymerization bottle, uniformly mixing, injecting an initiator by using a sealed injector, initiating for 30 minutes, and adding Ip and a regulator Tetramethylethylenediamine (TMEDA); after reacting for 7d at room temperature, adding isopropanol to terminate the reaction; precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain periodic copolymer main chain P-P (D-2 SiH/Ip); the mol ratio of DPE-2SiH to Ip is 1: 1-1: 4, the mol ratio of an initiator to a regulator is 1 (1-1.5), and the mol ratio of the initiator to DPE-SiH is 1 (5-20);

s3-2: synthesis of periodic copolymer P-P (D-2SiH/St)

Under the anhydrous and anaerobic conditions, adding DPE-2SiH and benzene into a polymerization bottle, uniformly mixing, injecting an initiator by using a sealed injector, initiating for 30 minutes, and adding St; after reacting for 3d at room temperature, adding isopropanol to terminate the reaction; precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain periodic copolymer main chain P-P (D-2 SiH/St); the mol ratio of DPE-2SiH to St is 1: 1-1: 4, and the mol ratio of an initiator to DPE-2SiH is 1 (5-20);

s3-3: synthesis of periodic copolymer P-P (D-SiH/Ip)

Under the anhydrous and anaerobic condition, adding DPE-SiH and benzene into a polymerization bottle, uniformly mixing, and injecting an initiator by using a sealed injector; after 30 minutes of initiation, Ip and TMEDA were added; after reacting for 7d at room temperature, adding isopropanol to terminate the reaction; precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain periodic copolymer main chain P-P (D-SiH/Ip); the mol ratio of DPE-SiH to Ip is 1: 1-1: 4, the mol ratio of an initiator to a regulator is 1 (1-1.5), and the mol ratio of the initiator to DPE-SiH is 1 (5-20);

s3-4: synthesis of periodic copolymer P-P (D-SiH/St)

Adding DPE-SiH and benzene into a polymerization bottle under the anhydrous and anaerobic conditions, uniformly mixing, and injecting an initiator by using a sealed injector; after 30 minutes of initiation, St is added; after reacting for 3d at room temperature, adding isopropanol to terminate the reaction; precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain periodic copolymer main chain P-P (D-SiH/St); the mol ratio of DPE-SiH to St is 1: 1-1: 4, and the mol ratio of an initiator to DPE-SiH is 1 (5-20);

s4 preparation of side chain type aggregation-induced emission liquid crystal polymer SC-AIE-LLCP with periodic structure

In an inert gas protection system, putting a periodic copolymer main chain and a liquid crystal monomer of cyano-stilbene at a vinyl terminal into an ampoule bottle according to a molar ratio of 1: 1-1: 2, adding toluene after anhydrous and oxygen-free treatment, adding 10-50ml of toluene into every 100mg of the polymer main chain correspondingly, stirring uniformly, dropwise adding a catalyst for hydrosilylation reaction, sealing the ampoule bottle, and reacting at 40-80 ℃ for 24-72 hours; after the reaction is finished, removing the toluene solvent, using THF and absolute ethyl alcohol/absolute ethyl ether for multiple times of sedimentation, and drying the product to constant weight to obtain the SC-AIE-LLCP with the periodic structure.

Technical Field

The invention belongs to the technical field of functional polymer materials, and relates to a side chain type aggregation-induced emission liquid crystal polymer with a periodic structure and a preparation method thereof.

Background

Luminescent Liquid Crystal Polymers (LLCP) have both luminescent properties and ordered arrangement of liquid crystals, have excellent processability, good thermal stability and the like, and are favored in the fields of display and anti-counterfeiting materials, information storage and encryption, sensors and the like. Currently, the thermal performance, liquid crystal texture, and light-emitting characteristics of LLCP can be controlled by adjusting the structure of the luminescent mesogen, such as spacer length, end group length, electron supply, electron-withdrawing group, steric effect, etc., or changing the position of the luminescent mesogen in the polymer chain, such as chain end, in-chain, and side chain. The side chain type luminescent liquid crystal polymer (SC-LLCP) refers to the LLCP with luminescent liquid crystal elements positioned at the side chain, and the polymer has the advantages of simple synthesis, various structures, designability and adjustable performance, and is widely used for developing multifunctional polymer materials.

Studies have shown that luminescent materials can be classified into luminescence quenching type (ACQ) and aggregation-induced emission type (AIE) according to the difference in luminescent properties of luminescent groups. The traditional organic luminescent material is aggregated to cause the phenomenon of luminescence quenching (ACQ): luminescence can be stabilized in a dilute solution, and in a high-concentration solution or an aggregate state (molten or solid state), loss of non-radiative energy is increased due to intermolecular interaction, and the luminescence efficiency is remarkably reduced or even does not emit (quench). However, the application of organic light emitting materials in dilute solution is very limited, and how to achieve aggregation-induced emission (AIE) in a high concentration solution or in an aggregated state (molten or solid state) is crucial. In the literature, "aggregation-induced emission of 1-methyl-1,2,3,4, 5-pentaphenylsilole", Tang Ben fai et al report that a class of molecules with a strong conjugated structure, 1-methyl-1,2,3,4,5-pentaphenylsilole, exhibits the AIE phenomenon: no luminescence occurs in the dilute solution state, but luminescence increases in the aggregate state. With the rapid development of the synthesis and application of AIE materials, the regulation and development of AIE becomes an important research topic in the field of polymer science. Apparently, the AIE properties are related to the molecular interactions of the luminophoric elements, and the most important to achieve the regulation of AIE is to achieve the control of molecular forces.

As is well known, the liquid crystal optical properties and thermal properties of side chain type liquid crystal polymers (SCLCPs) are closely related to the molecular interaction of mesogens, and the subject group is dedicated to the regulation and control research of the molecular interaction of mesogens, including the important control of the molecular acting force of mesogens such as the topological structure (the doctor thesis of korea "design synthesis and performance regulation and control research of side chain liquid crystal polymers"), the block structure (the doctor thesis of rallan "controllable synthesis and performance research of azobenzene liquid crystal polymer network") and the microstructure (the doctor thesis of huangshui "synthesis of multifunctional liquid crystal polymers based on polybutadiene regulation and control"). Research shows that the synthesis of liquid crystal macromolecules has been developed from past non-quantitative research into the current controllable functionality and grafting density, and the main driving effects of molecular acting force and functional group density are revealed to a certain extent. However, the research of "functional density" based on random polymer is still limited to the quantitative concept of "concentration and dilution", and because of the problems of lack of regulation and control means of liquid crystal polymer structure, the problem of not being able to realize the accurate "positioning" of liquid crystal functional group still exists.

With the intensive research of polymer science on functional polymers, the sequence-controllable functional polymer has specific functional group positions, namely 'positioning', reveals specific intermolecular and intramolecular interactions, displays a 'quantitative' concept different from that of controllable functional density, and realizes the functional polymer materialThe material is developed from 'quantitative' to 'fixed'. The master academic thesis of Zhu Ci, the "synthesis and performance research of a sequence-controllable functional polymer" reports a liquid crystal polymer and a fluorescent polymer with controllable liquid crystal and fluorescent group sequences and preparation thereof, and confirms that the sequence distribution of mesogens and fluorescent elements in side chains plays an important role in regulating and controlling the liquid crystal performance and the fine-tuning effect on the fluorescence quantum yield, and can be defined as a "spacer effect": continuous structures (Uni-), of Si-H functionalized polystyrene (PS-SiH), of styrene (St) with dimethylamino/Si-H or methoxy/Si-H functionalized 1, 1-diphenylethylene derivatives (NMe)₂-alternating structures (Alt-), graded structures (Gra-), and statistical four-interval structures (Int-), prepared by copolymerization of DPE-SiH or MeO-DPE-SiH. The result shows that for SCLCPs, as Uni-has higher molecular acting force, Uni-shows better liquid crystal texture and wider liquid crystal interval, however, for coumarin-based fluorescent polymers, the Uni-coumarin-based fluorescent polymers show obvious ACQ phenomenon, and compared with Gra-and Int-, as Alt-has higher molecular acting force, Alt-has higher fluorescence quantum yield. Obviously, for SCLCPs, high molecular acting force is beneficial to stabilizing liquid crystal phase, and as the side chain molecular spacing distance is increased, the "spacing effect" is more remarkable, the liquid crystal performance is obviously reduced or even disappears; for ACQ-type fluorescent polymers, high molecular forces lead to fluorescence quenching, while too low molecular forces are disadvantageous for increasing fluorescence quantum yield. In conclusion, the "spacer effect" is worth further study on the synchronous control of the light emitting characteristics and liquid crystal properties of LLCP.

The polymer with controllable Periodic (Periodic, Peri-) functional unit sequence has strict ABAB (alternating structure) or ABBABB type repeating Periodic rule, has unique density distribution and molecular acting force, has the performance completely different from the properties of corresponding block or random copolymers, and is a very important research model for liquid crystal macromolecules and fluorescent macromolecules which are remarkably controlled by the molecular acting force. The development of a novel periodic structure AIE side chain type luminescent liquid crystal polymer (SC-LLCP) and the establishment of a unique molecular acting force model to realize stable AIE effect and obvious liquid crystal performance of the luminescent liquid crystal polymer have important research significance and potential application prospect, which are also the technical problems to be solved urgently in the application.

The cyano stilbene and the derivative thereof are typical luminescent materials, not only have liquid crystal properties, but also present AIE properties, have high fluorescence quantum yield, and can realize reversible switching of liquid crystal and aggregation-induced emission properties under light stimulation. The present invention employs a living anionic polymerization process to prepare a periodic copolymer backbone of Si-H functionalized DPE with isoprene (Ip) or St. By a hydrosilylation method, the cyano stilbene derivative at the vinyl terminal is efficiently grafted to the main chain of the copolymer with a periodic structure, so that a side chain type aggregation-induced emission liquid crystal polymer (AIE-SC-LLCP) with the periodic structure can be obtained, and the structural-effect relation of the structure and the performance is disclosed.

Disclosure of Invention

The invention provides a side chain type aggregation-induced emission liquid crystal polymer (Peri-SC-AIE-LLCP) with a periodic structure, which integrates AIE light-emitting characteristics and liquid crystallinity, has better stability, and obviously regulates and controls optical characteristics and thermal properties of liquid crystal.

In order to achieve the purpose, the invention adopts the following technical scheme:

a side chain type aggregation-induced emission liquid crystal polymer (SC-AIE-LLCP) with a periodic structure is prepared from a Si-H functionalized periodic copolymer main chain and a vinyl-terminated cyano distyryl liquid crystal through a hydrosilylation method under the action of a catalyst. The liquid crystal polymer takes hydrosilation functionalized DPE and isoprene or styrene as alternating units, and two cyano distyryl liquid crystal monomers M at the tail ends of vinyl groups are grafted to a main chain by a hydrosilation addition method to obtain the functionalized liquid crystal polymer with the main chain with an alternating structure. Number average molecular weight (M) of the SC-AIE-LLCP_n) In the range of 10-100 kg. mol^-1Molecular weight distribution index (PDI) ranging from 1.08 to 1.39;

further, the catalyst of the hydrosilylation method is Pt (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane (Ka)rstedt catalyst) or chloroplatinic acid (H)₂PtCl₆·6H₂O).

Further, the alkyl lithium is selected from monofunctional alkyl lithium initiators, including but not limited to n-butyl lithium (n-BuLi), sec-butyl lithium (sec-BuLi).

Further, the Si-H functionalized periodic copolymer backbone is an alkyl lithium initiated bis Si-H functionalized DPE prepared by a living anionic polymerization process with Ip in the structural form of P-P (D-2SiH/Ip), wherein Ip represents isoprene, D-2SiH represents a 1, 1-Diphenylethylene (DPE) derivative containing a bis Si-H functional group, and P represents a periodic sequence structure. The structure form of the prepared luminescent liquid crystal polymer (SC-AIE-LLCP) with the side chain containing the cyano distyryl group based on the main chain of the periodic copolymer is P-P (D-2SiH/Ip) -M, wherein D-2SiH is a 1, 1-distyryl ethylene (DPE) derivative containing a bis-Si-H functional group, Ip represents isoprene, M represents a cyano distyryl liquid crystal monomer, and P represents a periodic sequence structure.

Further, the Si-H functionalized periodic copolymer backbone is an alkyllithium initiated bis-Si-H functionalized DPE prepared by a living anionic polymerization process with St in the structural form P-P (D-2SiH/St), wherein St represents styrene, D-2SiH represents a bis-Si-H functional group containing 1, 1-Diphenylethylene (DPE) derivative, and P represents a periodic sequence structure. The structure form of the prepared luminescent liquid crystal polymer (SC-AIE-LLCP) containing cyano distyryl in the side chain based on the main chain of the periodic copolymer is P-P (D-2SiH/St) -M, wherein D-2SiH is a 1, 1-Distyryl (DPE) derivative containing a bis-Si-H functional group, St represents styrene, M represents a cyano distyryl liquid crystal monomer, and P represents a periodic sequence structure.

Further, the Si-H functionalized periodic copolymer backbone is prepared by a living anionic polymerization method by using alkyl lithium initiated Si-H functionalized DPE and Ip, wherein the structure is P-P (D-SiH/Ip), wherein Ip represents isoprene, D-SiH represents 1, 1-Diphenylethylene (DPE) derivative containing single Si-H functional group, and P represents periodic sequence structure. The structure form of the prepared luminescent liquid crystal polymer (SC-AIE-LLCP) containing cyano distyryl in the side chain based on the main chain of the periodic copolymer is P-P (D-SiH/Ip) -M, wherein D-SiH is a 1, 1-Diphenylethylene (DPE) derivative containing a single Si-H functional group, Ip represents isoprene, M represents a cyano distyryl liquid crystal monomer, and P represents a periodic sequence structure.

Further, the Si-H functionalized periodic copolymer backbone is an alkyllithium initiated Si-H functionalized DPE prepared by a living anionic polymerization process with St in the structural form P-P (D-SiH/St), wherein St represents styrene, D-SiH represents a 1, 1-Diphenylethylene (DPE) derivative containing a single Si-H functional group, and P represents a periodic sequence structure. The structure form of the prepared luminescent liquid crystal polymer (SC-AIE-LLCP) containing cyano distyryl in the side chain based on the main chain of the periodic copolymer is P-P (D-SiH/St) -M, wherein D-SiH is a 1, 1-Diphenylethylene (DPE) derivative containing a single Si-H functional group, St represents styrene, M represents a cyano distyryl liquid crystal monomer, and P represents a periodic sequence structure.

A preparation method of side chain type aggregation-induced emission liquid crystal macromolecules with periodic structures comprises the following steps:

s1 preparation of Cyanodistyryl liquid Crystal monomer

S1-1: synthesis of intermediate 1-1

Under the protection of argon, adding 1-bromooctadecane, 4-hydroxybenzaldehyde, anhydrous potassium carbonate and N, N-Dimethylformamide (DMF) into a flask, and reacting at 70-140 ℃ for 10-48 h. And after the reaction is finished, pouring the reaction system into a large amount of sodium hydroxide solution, stirring at room temperature for 6-24h, filtering after the reaction is finished to obtain a crude product, recrystallizing the crude product by using hot ethanol, putting the precipitated solid in a vacuum oven, and drying to constant weight to obtain an intermediate 1-1. Wherein the mol ratio of the 1-bromooctadecane, the 4-hydroxybenzaldehyde and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6.

S1-2: synthesis of intermediates 1-2

Under the protection of argon, adding the intermediate 1-1, 4-hydroxybenzyl acetonitrile, sodium hydroxide and absolute ethyl alcohol into a flask, and reacting for 3-10h at 50-80 ℃. And after the reaction is finished, acidifying the system for 6-48h, filtering to obtain a crude product after the reaction is finished, and recrystallizing with ethyl acetate. And (3) putting the precipitated solid in a vacuum oven, and drying to constant weight to obtain an intermediate 1-2. Wherein the molar ratio of the intermediate 1-1, the 4-hydroxybenzeneacetonitrile and the sodium hydroxide is 1 (1.1-1.5) to 2-6.

S1-3: synthesis of intermediates 1 to 3

Under the protection of argon, adding the intermediate 1-2, 6-chloro-1-hexanol, anhydrous potassium carbonate and DMF into a flask, reacting at 70-140 ℃ for 10-48h, filtering after the reaction is finished to obtain a crude product, firstly extracting with dichloromethane, and then recrystallizing with acetone. And (4) putting the precipitated solid in a vacuum oven, and drying to constant weight to obtain an intermediate 1-3. Wherein the mol ratio of the intermediate 1-2, the 6-chlorine-1-hexanol and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6.

S1-4: synthesis of liquid Crystal monomer Vinyl-phenyl-Cyano (M)₁)

4- (allyloxy) benzoic acid and thionyl chloride were added to the flask and reacted at 50-70 ℃ for 6-12 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. Adding the oily liquid, the intermediate 1-3, pyridine and chloroform into a flask, and reacting at 50-70 ℃ for 6-48 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the mixture is placed in a large amount of dilute hydrochloric acid for acidification for 6 to 48 hours. Purifying liquid crystal monomer Vinyl-phenyl-Cyano (M) by column chromatography (eluent is ethyl acetate and n-hexane)₁). Wherein the mol ratio of the 4- (allyloxy) benzoic acid to the thionyl chloride to the intermediate 1-3 is (1.1-1.5) to (4-8) to 1.

S1-5: synthesis of intermediate 2-1

Under the protection of argon, p-hydroxybenzeneboronic acid, p-bromophenylacetonitrile and tetrakis (triphenylphosphine) palladium (Pd (PPh)₃)₄) Adding sodium carbonate, THF and deionized water into a flask, reacting at 60-90 deg.C for 10-48h, acidifying the system for 6-48h after reaction, extracting with saturated saline water and ethyl acetate, and recrystallizing with hot ethanol to obtain intermediate 2-1. Wherein, the p-hydroxybenzeneboronic acid, the p-bromophenylacetonitrile and the Pd (PPh)₃)₄The molar ratio of (1), (1.1-1.3) to (0.005).

S1-6: synthesis of intermediate 2-2

Under the protection of argon, adding the intermediate 1-1, the intermediate 2-1, sodium hydroxide and absolute ethyl alcohol into a flask, reacting for 3-10h at 50-80 ℃, acidifying the system for 6-48h after the reaction is finished, performing suction filtration to obtain a crude product, recrystallizing with ethyl acetate, placing the separated solid in a vacuum oven, and drying to constant weight to obtain the intermediate 2-2. Wherein the molar ratio of the intermediate 1-1 to the intermediate 2-1 to the sodium hydroxide is 1 (1.1-1.5) to 2-6.

S1-7: synthesis of intermediates 2 to 3

Under the protection of argon, adding the intermediate 2-2, 6-chloro-1-hexanol, anhydrous potassium carbonate and DMF into a flask, reacting at 70-140 ℃ for 12-48h, performing suction filtration after the reaction is finished to obtain a crude product, extracting with dichloromethane, recrystallizing with toluene, placing the separated solid in a vacuum oven, and drying to constant weight to obtain an intermediate 2-3. Wherein the mol ratio of the intermediate 2-2, the 6-chlorine-1-hexanol and the anhydrous potassium carbonate is 1 (1.1-1.5) to 2-6.

S1-8: synthesis of liquid Crystal monomer Vinyl-biphenyl-Cyano (M)₂)

Adding 4- (allyloxy) benzoic acid and thionyl chloride into a flask, reacting for 6-12h at 50-70 ℃, decompressing and rotary-distilling to remove an oily liquid obtained by a solvent after the reaction is finished, adding the oily liquid, an intermediate 2-3, pyridine and chloroform into the flask, reacting for 6-24h at 50-70 ℃, removing the solvent after the reaction is finished, putting the system into a large amount of diluted hydrochloric acid for acidification for 6-48h, filtering to obtain a crude product, and purifying a liquid crystal monomer Vinyl-biphenol-cyanoo (M) by using a column chromatography (eluent is ethyl acetate and n-hexane)₂). Wherein the mol ratio of the 4- (allyloxy) benzoic acid to the thionyl chloride to the intermediate 2-3 is (1.1-1.5) to (4-8) to 1.

S2 preparation of Si-H functionalized DPE and Ip/St periodic copolymer backbone P-P (D-2SiH/Ip), P-P (D-2SiH/St), P-P (D-SiH/Ip), P-P (D-SiH/St)

S2-1: synthesis of the polymeric monomer DPE-SiH

Under the protection of anhydrous and oxygen-free argon, methyl triphenyl phosphonium bromide, potassium tert-butoxide and THF are added into a flask and stirred for 60-90min at-10-0 ℃, and the system becomes bright yellow. And (2) dripping a THF solution of 4-bromophenyl-4' -phenyl ketone (BP-Br) into the reaction system, stirring for 30-60min, heating to 50-60 ℃, and reacting for 12-14 h. After the reaction, the reaction solution is quenched by 5-10mL of deionized water, and extracted by ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-Br as a colorless viscous liquid. The mol ratio of BP-Br, potassium tert-butoxide and methyl triphenyl phosphonium bromide is 1 (1.5-3) to 2-4.

And (2) uniformly stirring DPE-Br in THF, slowly dropwise adding into magnesium chips, adding iodine particles to initiate a Grignard reaction, adding a dimethylchlorosilane solution into the magnesium chips, and reacting for 16-25h at 20-50 ℃. Extracted with ethyl acetate and brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-SiH as a colorless viscous liquid. The mol ratio of DPE-Br, magnesium chips and dimethylchlorosilane is 1 (4-6) to 2.5-4.

S2-2: synthesis of the polymeric monomer DPE-2SiH

Under the protection of anhydrous and oxygen-free argon, methyl triphenyl phosphonium bromide, potassium tert-butoxide and THF are stirred for 60-90min at-10-0 ℃, and the system becomes bright yellow. And (3) dripping a THF solution of 4, 4-dibromobenzophenone (BP-2Br) into the reaction system, and stirring at-10-0 ℃ for 10-12 h. After the reaction, the reaction solution is quenched by 5-10mL of deionized water, and extracted by ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-2Br as a white solid. The mol ratio of BP-2Br, potassium tert-butoxide and methyl triphenyl phosphonium bromide is 1 (1.5-3) to 2-4.

Adding magnesium chips into a flask, dissolving dimethylchlorosilane into THF, dropwise adding into the flask, and stirring for reaction for 1-2 h; and (3) adding a THF solution dissolved with DPE-2Br into the system dropwise, and reacting at 55-65 ℃ for 12-14 h. And pouring the reaction product into n-hexane for sedimentation, and purifying the crude product by using a column chromatography (eluent is ethyl acetate and n-hexane) to obtain sheet crystal DPE-2 SiH. The mol ratio of DPE-2Br, magnesium chips and dimethylchlorosilane is 1 (4-6) to 2.5-4.

S3 synthesizing cycle sequence controllable silicon-hydrogen functionalized polymer main chain

S3-1: synthesis of periodic copolymer P-P (D-2SiH/Ip)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-2SiH and benzene are added into a polymerization bottle, the mixture is uniformly mixed, and an initiator is injected by a sealed injector. After 30 minutes of initiation, Ip and the regulator Tetramethylethylenediamine (TMEDA) were added. The mol ratio of DPE-2SiH to Ip is 1: 1-1: 4, the mol ratio of the initiator to the regulator is 1 (1-1.5), and the mol ratio of the initiator to DPE-SiH is 1 (5-20). After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/Ip).

S3-2: synthesis of periodic copolymer P-P (D-2SiH/St)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-2SiH and benzene are added into a polymerization bottle, the mixture is uniformly mixed, and an initiator is injected by a sealed injector. After 30 minutes of initiation, St is added. The mol ratio of DPE-2SiH to St is 1: 1-1: 4, and the mol ratio of the initiator to DPE-2SiH is 1 (5-20). After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, carrying out suction filtration, and then putting the obtained solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/St).

S3-3: synthesis of periodic copolymer P-P (D-SiH/Ip)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-SiH and benzene are added into a polymerization bottle and mixed evenly, and an initiator is injected by a sealed syringe. After 30 minutes of initiation, Ip and TMEDA were added. The mol ratio of DPE-SiH to Ip is 1: 1-1: 4, the mol ratio of the initiator to the regulator is 1 (1-1.5), and the mol ratio of the initiator to DPE-SiH is 1 (5-20). After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/Ip).

S3-4: synthesis of periodic copolymer P-P (D-SiH/St)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-SiH and benzene are added into a polymerization bottle and mixed evenly, and an initiator is injected by a sealed syringe. After 30 minutes of initiation, St is added. The mol ratio of DPE-SiH to St is 1: 1-1: 4, and the mol ratio of the initiator to DPE-SiH is 1 (5-20). After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/St).

S4 preparation of side chain type aggregation induced emission liquid crystal polymer (SC-AIE-LLCP) having periodic structure

In an inert gas protection system, putting a periodic copolymer main chain and a liquid crystal monomer of the cyano-stilbene at the vinyl terminal into an ampoule bottle according to a molar ratio of 1: 1-1: 2, adding toluene after anhydrous and oxygen-free treatment, uniformly stirring, dropwise adding a catalyst for hydrosilylation reaction, correspondingly adding 10-50ml of toluene into every 100mg of the polymer main chain, sealing the ampoule bottle, and reacting at 40-80 ℃ for 24-72 hours;

after the reaction is finished, the toluene solvent is removed firstly, then THF and absolute ethyl alcohol/absolute ethyl ether are used for multiple times of sedimentation, excessive monomers are removed, the product is placed in an oven and dried to constant weight, and SC-AIE-LLCP with a periodic structure is obtained.

The invention has the beneficial effects that:

the liquid crystal monomer and the liquid crystal functional polymer prepared by the invention have adjustable liquid crystal property and aggregation-induced emission AIE (induced emission) characteristics; the material integrates AIE luminescence property and liquid crystal property, has better stability, and obviously regulates and controls optical property and thermal property of liquid crystal; the polymer with the controllable periodic functional unit sequence has unique density distribution and molecular acting force; the stable AIE effect and obvious liquid crystal performance of the luminous liquid crystal polymer are realized by constructing a unique molecular acting force model, and the method has important significance for the development of novel luminous liquid crystal functional materials.

Detailed Description

The following examples are presented as further illustrations and are not intended to limit the scope of the claims.

Example 1:

first step synthesizing liquid crystal monomers of Vinyl-phenyl-Cyano and Vinyl-biphenyl-Cyano

1.1) Synthesis of intermediate 1-1:

1-bromooctadecane (7.00g, 21.1mmol), 4-hydroxybenzaldehyde (2.83g, 23.2mmol) and anhydrous potassium carbonate (5.81g, 42.1mmol) and 300mL of DMF were charged under argon protection into a 500mL three-necked flask and reacted at 70 ℃ for 48 h. After the reaction was completed, the system was poured into 300mL of 5% wt sodium hydroxide solution and stirred at room temperature for 24 h. And (4) carrying out suction filtration and then recrystallizing by using hot ethanol. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-1.

1.2) Synthesis of intermediates 1-2:

intermediate 1-1(7.00g,18.7mmol), 4-hydroxybenzeneacetonitrile (2.74g,20.6mmol), sodium hydroxide (1.50g, 37.4mmol) and 250mL of anhydrous ethanol were added to a 500mL three-necked flask under argon. The reaction was carried out at 80 ℃ for 10 h. After the reaction was complete, the system was acidified for 48 h. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-2.

1.3) Synthesis of intermediates 1-3:

intermediate 1-2(7.00g,14.3mmol), 6 chloro-1-hexanol (1.92g,15.7mmol) and anhydrous potassium carbonate (3.94g,28.6mmol) and 200mL of DMF were charged under argon protection into a 500mL three-necked flask and reacted at 70 ℃ for 48 h. And after the reaction is finished, carrying out suction filtration. After extraction with dichloromethane, it is recrystallized from acetone. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-3.

1.4) Synthesis of liquid Crystal monomer Vinyl-phenyl-Cyano:

4- (allyloxy) benzoic acid (1.66g,9.3mmol) and thionyl chloride (2.47mL,34.0mmol) were added to a 250mL flask and reacted at 50 ℃ for 12 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid, intermediates 1 to 3(5.00g,8.5mmol), 9mL of pyridine and 35mL of chloroform were added to the flask and reacted at 50 ℃ for 48 hours. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 48 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-phenyl-Cyano (M)₁)。

1.5) Synthesis of intermediate 2-1

P-hydroxyphenylboronic acid (5.00g,36.2mmol), p-bromophenylacetonitrile (7.77g,39.8mmol) and Pd (PPh) under the protection of argon₃)₄(0.23g, 0.18mmol) in 120mL of THF was added to 500mL of THFIn a flask, 2M 120mL sodium carbonate (12.80g, 120.0mmol) solution was added and reacted at 60 ℃ for 48 h. After the reaction was completed, the system was acidified for 24 hours and extracted with saturated brine and ethyl acetate. The solid was recrystallized from hot ethanol to give intermediate 2-1.

1.6) Synthesis of intermediate 2-2

Intermediate 2-1(3.07g,14.7mmol) was reacted with product 1-1(5.00g,13.3mmol) and sodium hydroxide (1.07g, 26.7mmol) and 120mL of absolute ethanol under argon protection in a 250mL flask at 50 ℃ for 10 h. After the reaction is finished, the system is acidified for 48 hours. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-2.

1.7) Synthesis of intermediates 2 to 3

The product, 2-2(5g,8.8mmol), potassium carbonate (2.44g,17.6mmol), 6-chloro-1-hexanol (1.19g,9.7mmol) and 120mL of DMF were added under argon protection to a 250mL flask and reacted at 70 ℃ for 48 h. And after the reaction is finished, carrying out suction filtration. The mixture was extracted with dichloromethane and recrystallized from toluene. And (3) putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-3.

1.8) Synthesis of liquid Crystal monomer Vinyl-biphenyl-Cyano (M)₂)

4- (allyloxy) benzoic acid (1.66g,9.3mmol) and thionyl chloride (2.47mL,34.0mmol) were added to a 250mL flask and reacted at 50 ℃ for 12 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid and intermediate 2-3(5.66g,8.5mmol) were dissolved in a mixture of 5mL pyridine and 20mL chloroform and reacted at 50 ℃ for 48 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 48 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-biphenyl-Cyano (M)₂)。

Secondly, synthesizing DPE-SiH and DPE-2SiH monomers

2-1: synthesis of the polymeric monomer DPE-SiH

Methyltriphenylphosphine bromide (41.33g,115.4mmol), potassium tert-butoxide (9.71g,86.5mmol) and 100mL THF were added to a 500mL flask under anhydrous and oxygen-free argon and stirred at-10 deg.C for 90min until the system became bright yellow. 100mL of THF solution containing BP-Br (15g,57.7mmol) was added dropwise to the reaction system, stirred for 60min, then heated to 60 ℃ and reacted for 14 h. After the reaction was completed, the reaction mixture was quenched with 10mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-Br as a colorless viscous liquid.

DPE-Br (10.00g,38.8mmol) was stirred well in 300mL THF, slowly added dropwise to magnesium turnings (3.72g,155.0mmol), added with iodine particles to initiate Grignard reaction, added with dimethylchlorosilane (9.07g,96.9mmol) solution, and reacted at 50 ℃ for 16 h. Extracted with ethyl acetate and brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-SiH as a colorless viscous liquid.

2-2: synthesis of the polymeric monomer DPE-2SiH

Methyltriphenylphosphine bromide (31.81g,88.8mmol), potassium tert-butoxide (7.47g,66.6mmol) and 270mL of THF were stirred at-10 deg.C for 90min under anhydrous and oxygen-free argon shield, and the system turned bright yellow. A solution of 200mL BP-2Br (15.00g,44.4mmol) in THF was added dropwise to the reaction and stirred at-10 ℃ for 12 h. After the reaction was completed, the reaction mixture was quenched with 10mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-2Br as a white solid.

Magnesium chips (2.86g,119.1mmol) are added into a 500mL flask, dimethylchlorosilane (6.97g,74.4mmol) is dissolved in 120mL THF, and then the solution is added into the flask dropwise and stirred for reaction for 2 hours; 100mL of a THF solution containing DPE-2Br (10g,29.8mmol) was added dropwise to the above system and reacted at 55 ℃ for 12 hours. And pouring the reaction product into n-hexane for sedimentation, and purifying the crude product by using a column chromatography (eluent is ethyl acetate and n-hexane) to obtain sheet crystal DPE-2 SiH.

Thirdly, synthesizing the silicon-hydrogen functionalized polymer main chain with controllable periodic sequence

3.1) Synthesis of periodic copolymer P-P (D-2SiH/Ip)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-2SiH (0.59g,2mmol) and 6mL of benzene are added into a polymerization bottle, mixed uniformly, and an initiator sec-Bu is injected by a sealed syringeLi (756. mu.L, 0.34 mmol). After 30 minutes of reaction, Ip (0.14g,2mmol) and TMEDA (0.06g,0.34mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/Ip). Finally, the periodic copolymer main chain P-P (D-2SiH/Ip) is obtained, and the number average molecular weight of the polymer is 2.4kg & mol^-1The molecular weight distribution index was 1.19.

3.2) Synthesis of periodic copolymer P-P (D-2SiH/St)

The reaction was carried out in a dry, oxygen-free glove box, DPE-2SiH (0.59g,2mmol), 6mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (756. mu.L, 0.34mmol) was injected using a sealed syringe. After 30 min of reaction St (0.21g,2mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, carrying out suction filtration, and then putting the obtained solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/St). Finally, the periodic copolymer main chain P-P (D-2SiH/St) is obtained, and the number average molecular weight of the polymer is 3.3kg & mol^-1The molecular weight distribution index was 1.20.

3.3) Synthesis of periodic copolymer P-P (D-SiH/Ip)

The reaction was carried out in a dry, oxygen-free glove box, DPE-SiH (0.48g,2mmol), 6mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (756. mu.L, 0.34mmol) was injected using a sealed syringe. After 30 minutes of initiation, Ip (0.14g,2mmol) and TMEDA (0.06g,0.34mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/Ip). Finally, the periodic copolymer main chain P-P (D-SiH/Ip) is obtained, and the number average molecular weight of the polymer is 3.7kg & mol^-1The molecular weight distribution index was 1.23.

3.4) Synthesis of periodic copolymer P-P (D-SiH/St)

The reaction is carried out in a water-free and oxygen-free glove box, DPE-SiH (0.48g,2mmol) and 6mL benzene are added into a polymerization bottle, mixed uniformly and injected by a sealed syringeInitiator sec-BuLi (756. mu.L, 0.34 mmol). After 30 min of initiation, St (0.21,2mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/St). Finally, the periodic copolymer main chain P-P (D-SiH/St) is obtained, and the number average molecular weight of the polymer is 4.9kg & mol^-1The molecular weight distribution index was 1.30.

Fourthly, synthesizing the side chain type liquid crystal polymer with controllable period sequence

4.1) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.82g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₁The number average molecular weight of the cyanobenzene-containing stilbene-based polymer was 15.5 kg. mol^-1The molecular weight distribution index was 1.17.

4.2) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.90g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of toluene after anhydrous and anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 50 ℃ for 96 h. After the reaction was completed, the solvent was removed. 15mL of THF was added to dissolve the dried solid, and the solution was added35mL of anhydrous ether was added, and centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₂The number average molecular weight of the cyanobenzene-containing stilbene based polymer was 17.2 kg. mol^-1The molecular weight distribution index was 1.17.

4.3) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-2SiH/St) prepared in the third step and 0.72g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/St) -M with aggregation-induced emission₁The number average molecular weight of the cyanobenzene-containing stilbene-based polymer was 20.2 kg. mol^-1The molecular weight distribution index was 1.20.

4.4) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-2SiH/St) prepared in the third step and 0.79g of liquid crystal monomer Vinyl-biphenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is uniformly stirred, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer with aggregation-induced emissionp-P(D-2SiH/St)-M₂The number average molecular weight of the cyanobenzene-containing stilbene based polymer was 23.1 kg. mol^-1The molecular weight distribution index was 1.20.

4.5) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.49g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₁The number average molecular weight of the cyanobenzene-containing stilbene based polymer was 14.4 kg. mol^-1The molecular weight distribution index was 1.21.

4.6) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.54g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of toluene after anhydrous and anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₂The number average molecular weight of the cyanobenzene-containing stilbene-based polymer was 15.2 kg. mol^-1The molecular weight distribution index was 1.19.

4.7) Synthesis sideChain liquid crystalline polymers P-P (D-SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.43g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₁The number average molecular weight of the cyanobenzene-containing stilbene based polymer was 19.8 kg. mol^-1The molecular weight distribution index was 1.15.

4.8) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.2g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.48g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₂The number average molecular weight of the cyanobenzene-containing stilbene based polymer was 21.1 kg. mol^-1The molecular weight distribution index was 1.15.

Example 2:

first step synthesizing liquid crystal monomers of Vinyl-phenyl-Cyano and Vinyl-biphenyl-Cyano

1.1) Synthesis of intermediate 1-1:

1-bromooctadecane (5.00g, 15.1mmol), 4-hydroxybenzaldehyde (2.20g, 18.1mmol) and anhydrous potassium carbonate (8.34g, 60.4mmol) and 200mL of DMF were added under argon protection to a 500mL three-necked flask and reacted at 105 ℃ for 24 h. After the reaction was completed, the system was poured into 300mL of 5% wt sodium hydroxide solution and stirred at room temperature for 24 h. And (4) carrying out suction filtration and then recrystallizing by using hot ethanol. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-1.

1.2) Synthesis of intermediates 1-2:

intermediate 1-1(5.00g,13.4mmol), 4-hydroxybenzeneacetonitrile (2.13g,16.0mmol), sodium hydroxide (2.82g, 53.6mmol) and 200mL of absolute ethanol were added to a 500mL three-necked flask under argon. The reaction was carried out at 65 ℃ for 7 h. After the reaction was complete, the system was acidified for 24 h. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-2.

1.3) Synthesis of intermediates 1-3:

intermediate 1-2(5.00g,10.2mmol), 6 chloro-1-hexanol (1.50g,12.3mmol), anhydrous potassium carbonate (5.632g,40.8mmol) and 150mL DMF were charged under argon protection into a 500mL three-necked flask and reacted at 105 ℃ for 24 h. And after the reaction is finished, carrying out suction filtration. After extraction with dichloromethane, it is recrystallized from acetone. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-3.

1.4) Synthesis of liquid Crystal monomer Vinyl-phenyl-Cyano:

4- (allyloxy) benzoic acid (1.10g,6.1mmol) and thionyl chloride (2.22mL,30.6mmol) were added to a 250mL flask and reacted at 60 ℃ for 10 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid, intermediates 1 to 3(3.00g,5.1mmol), 5mL of pyridine and 20mL of chloroform were added to the flask and reacted at 60 ℃ for 24 hours. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 12 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-phenyl-Cyano (M)₁)。

1.5) Synthesis of intermediate 2-1

Under the protection of argon, the catalyst is prepared byHydroxyphenylboronic acid (3.00g,21.7mmol), p-bromophenylacetonitrile (5.1g,26.1mmol) and Pd (PPh)₃)₄(0.1g, 0.08mmol) was dissolved in 60mL of THF and charged into a 250mL flask, and 2M 30mL of a solution of sodium carbonate (6.4g, 60mmol) was added and reacted at 75 ℃ for 24 h. After the reaction was completed, the system was acidified for 24 hours and extracted with saturated brine and ethyl acetate. The solid was recrystallized from hot ethanol to give intermediate 2-1.

1.6) Synthesis of intermediate 2-2

Intermediate 2-1(0.86g,4.1mmol) was reacted with product 1-1(3.00g,4.9mmol) and sodium hydroxide (0.80g, 20.0mmol) and 90mL of absolute ethanol under argon protection in a 250mL flask at 65 ℃ for 7 h. After the reaction is finished, the system is acidified for 24 hours. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-2.

1.7) Synthesis of intermediates 2 to 3

The product 2-2(3.00g,5.3mmol), potassium carbonate (1.83g,13.3mmol), 6-chloro-1-hexanol (0.78g,6.4mmol) and 120mL of DMMF were added to a 250mL flask under argon protection and reacted at 105 ℃ for 24 h. And after the reaction is finished, carrying out suction filtration. The mixture was extracted with dichloromethane and recrystallized from toluene. And (3) putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-3.

1.8) Synthesis of liquid Crystal monomer Vinyl-biphenyl-Cyano (M)₂)

4- (allyloxy) benzoic acid (0.80g,4.5mmol) and thionyl chloride (1.31mL,18.0mmol) were added to a 250mL flask and reacted at 60 ℃ for 10 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid and intermediate 1-3(2.5g,3.7mmol) were dissolved in a mixture of 5mL pyridine and 20mL chloroform and reacted at 60 ℃ for 24 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 24 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-biphenyl-Cyano (M)₂)。

Secondly, synthesizing DPE-SiH and DPE-2SiH monomers

2-1: synthesis of the polymeric monomer DPE-SiH

Methyltriphenylphosphine bromide (41.34g,115.4mmol), potassium tert-butoxide (8.63g,76.9mmol) and 200mL THF were added to a 1000mL flask under anhydrous and oxygen-free argon and stirred at-5 ℃ for 75min, whereupon the system turned bright yellow. 100mL of BP-Br (10.00g,38.5mmol) in THF was added dropwise to the reaction system, stirred for 45min, then heated to 55 ℃ and reacted for 13 h. After the reaction was completed, the reaction mixture was quenched with 8mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-Br as a colorless viscous liquid.

DPE-Br (5.00g,19.4mmol) was stirred in 100mL THF, slowly added dropwise to magnesium turnings (2.33g,96.9mmol), added with iodine particles to initiate Grignard reaction, added with dimethylchlorosilane (5.44g,58.1mmol) solution, and reacted at 50 ℃ for 16 h. Extracted with ethyl acetate and brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-SiH as a colorless viscous liquid.

2-2: synthesis of the polymeric monomer DPE-2SiH

Methyltriphenylphosphine bromide (31.80g,88.8mmol), potassium tert-butoxide (6.64g,59.2mmol) and 360mL THF were stirred at-10 deg.C for 75min under anhydrous and oxygen-free argon shield and the system turned bright yellow. 200mL of BP-2Br (10g,29.6mmol) in THF was added dropwise to the reaction and stirred at-5 ℃ for 12 h. After the reaction was completed, the reaction mixture was quenched with 10mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-2Br as a white solid.

Magnesium chips (1.79g,74.4mmol) are added into a 500mL flask, dimethylchlorosilane (4.18g,44.6mmol) is dissolved in 120mL of THF, and then the solution is dropwise added into the flask to be stirred and reacted for 2 hours; 100mL of a THF solution containing DPE-2Br (5g,14.9mmol) was added dropwise to the above system and reacted at 60 ℃ for 12 hours. And pouring the reaction product into n-hexane for sedimentation, and purifying the crude product by using a column chromatography (eluent is ethyl acetate and n-hexane) to obtain sheet crystal DPE-2 SiH.

Thirdly, synthesizing the silicon-hydrogen functionalized polymer main chain with controllable periodic sequence

3.1) Synthesis of periodic copolymer P-P (D-2SiH/Ip)

The reaction was carried out in a dry, oxygen-free glove box, DPE-2SiH (0.44g,1.5mmol), 6mL benzene were added to the polymerization flask, mixed well, and initiator n-BuLi (378. mu.L, 0.17mmol) was injected using a sealed syringe. After 30 minutes of reaction, Ip (0.2g,3mmol) and TMEDA (0.04g,0.22mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/Ip).

3.2) Synthesis of periodic copolymer P-P (D-2SiH/St)

The reaction was carried out in a dry, oxygen-free glove box, DPE-2SiH (0.44g,1.5mmol), 6mL benzene were added to the polymerization flask, mixed well, and initiator n-BuLi (756. mu.L, 0.34mmol) was injected using a sealed syringe. After 30 min of reaction St (0.31g,3mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, carrying out suction filtration, and then putting the obtained solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/St).

3.3) Synthesis of periodic copolymer P-P (D-SiH/Ip)

The reaction was carried out in a dry and oxygen-free glove box, DPE-SiH (0.3g,1.5mmol), 6mL benzene were added to the polymerization flask, mixed well, and initiator n-BuLi (378. mu.L, 0.17mmol) was injected using a sealed syringe. After 30 minutes of initiation, Ip (0.2,3mmol) and TMEDA (0.04g,0.22mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/Ip).

3.4) Synthesis of periodic copolymer P-P (D-SiH/St)

The reaction was carried out in a dry and oxygen-free glove box, DPE-SiH (0.3g,1.5mmol), 6mL benzene were added to the polymerization flask, mixed well, and initiator n-BuLi (378. mu.L, 0.17mmol) was injected using a sealed syringe. After 30 min of initiation, St (0.31g,3mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/St).

Fourthly, synthesizing the side chain type liquid crystal polymer with controllable period sequence

4.1) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.92g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous anaerobic treatment is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₁。

4.2) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 1.02g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous and anaerobic treatment is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₂。

4.3) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-2SiH/St) prepared in the third step and 0.72g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 40 ℃ for 72 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/St) -M with aggregation-induced emission₁。

4.4) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.89g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous and anaerobic treatment is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/St) -M with aggregation-induced emission₂。

4.5) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.55g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Placing the residual solid inDrying in a vacuum oven to constant weight to obtain periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₁。

4.6) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.61g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous anaerobic treatment is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₂。

4.7) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.49g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₁。

4.8) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.15g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.54g of liquid crystal monomer Vinyl-biphenyl-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is uniformly stirred, 3 drops of chloroplatinic acid catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 60 ℃ for 48 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 15mL of THF, 35mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₂。

Example 3

First step synthesizing liquid crystal monomers of Vinyl-phenyl-Cyano and Vinyl-biphenyl-Cyano

1.1) Synthesis of intermediate 1-1:

1-bromooctadecane (3.00g, 9.0mmol), 4-hydroxybenzaldehyde (1.43g, 11.7mmol) and anhydrous potassium carbonate (3.74g, 27.1mmol) and 200mL of DMF were charged under argon protection into a 500mL three-necked flask and reacted at 140 ℃ for 10 h. After the reaction was completed, the system was poured into 300mL of 5% wt sodium hydroxide solution and stirred at room temperature for 6 h. And (4) carrying out suction filtration and then recrystallizing by using hot ethanol. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-1.

1.2) Synthesis of intermediates 1-2:

intermediate 1-1(3.00g,8.0mmol), 4-hydroxybenzeneacetonitrile (1.39g,10.4mmol), sodium hydroxide (0.96g, 24.0mmol) and 200mL of absolute ethanol were added to a 500mL three-necked flask under argon. The reaction was carried out at 80 ℃ for 3 h. After the reaction was complete, the system was acidified for 6 h. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-2.

1.3) Synthesis of intermediates 1-3:

intermediate 1-2(3.00g,6.1mmol), 6 chloro-1-hexanol (0.97g,8.0mmol) and anhydrous potassium carbonate (2.54g,18.4mmol) and 150mL of DMF were added under argon protection to a 250mL three-necked flask and reacted at 140 ℃ for 10 h. And after the reaction is finished, carrying out suction filtration. After extraction with dichloromethane, it is recrystallized from acetone. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 1-3.

1.4) Synthesis of liquid Crystal monomer Vinyl-phenyl-Cyano:

4- (allyloxy) benzoic acid (0.39g,2.2mmol) and thionyl chloride (0.80mL,11.0mmol) were added to a 250mL flask and reacted at 70 ℃ for 6 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid, intermediates 1 to 3(1.00g,1.7mmol), 5mL of pyridine and 20mL of chloroform were added to the flask and reacted at 70 ℃ for 6 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 6 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-phenyl-Cyano (M)₁)。

1.5) Synthesis of intermediate 2-1

Under the protection of argon, p-hydroxybenzeneboronic acid (2.00g,14.4mmol), p-bromophenylacetonitrile (3.67g,18.8mmol) and Pd (PPh)₃)₄(0.1g, 0.08mmol) was dissolved in 60mL of THF and charged into a 250mL flask, and 2M 30mL of a solution of sodium carbonate (6.4g, 60mmol) was added and reacted at 90 ℃ for 10 h. After the reaction was completed, the system was acidified for 6 hours and extracted with saturated brine and ethyl acetate. The solid was recrystallized from hot ethanol to give intermediate 2-1.

1.6) Synthesis of intermediate 2-2

Intermediate 2-1(1.45g,6.9mmol) was reacted with product 1-1(2.00g,5.3mmol) and sodium hydroxide (0.64g, 16.0mmol) and 90mL of absolute ethanol under argon protection in a 250mL flask at 80 ℃ for 3 h. After the reaction is finished, the system is acidified for 6 hours. And (4) carrying out suction filtration and then recrystallizing by using ethyl acetate. And putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-2.

1.7) Synthesis of intermediates 2 to 3

The product, 2-22.00g,3.5mmol, potassium carbonate (1.46g,1.1mmol), 6-chloro-1-hexanol (0.56g,4.6mmol) and 80mL of DMF were added under argon protection to a 250mL flask and reacted at 140 ℃ for 10 h. And after the reaction is finished, carrying out suction filtration. The mixture was extracted with dichloromethane and recrystallized from toluene. And (3) putting the obtained solid into a vacuum oven to be dried to constant weight to obtain an intermediate 2-3.

1.8) Synthesis of liquid Crystal monomer Vinyl-biphenyl-Cyano (M)₂)

4- (allyloxy) benzoic acid (0.52g,4.5mmol) and thionyl chloride (1.10mL,18.0mmol) were added to a 250mL flask and reacted at 70 ℃ for 6 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation to obtain oily liquid. The oily liquid and intermediate 1-3(2.5g,3.7mmol) were dissolved in a mixture of 5mL pyridine and 20mL chloroform and reacted at 70 ℃ for 6 h. After the reaction is finished, the solvent is removed by reduced pressure rotary evaporation, and the system is put into a large amount of dilute hydrochloric acid for acidification for 6 hours. Purifying the crude product by column chromatography (eluent is ethyl acetate and n-hexane) to obtain liquid crystal monomer Vinyl-biphenyl-Cyano (M)₂)。

Secondly, synthesizing DPE-SiH and DPE-2SiH monomers

2-1: synthesis of the polymeric monomer DPE-SiH

Methyltriphenylphosphine bromide (27.56g,76.9mmol), potassium tert-butoxide (6.47g,57.7mmol) and 200mL THF were added to a 1000mL flask under anhydrous and oxygen-free argon and stirred at 0 deg.C for 90min until the system became bright yellow. 100mL of BP-Br (5.00g,19.2mmol) in THF solution was added dropwise to the reaction system, stirred for 60min, then heated to 60 ℃ and reacted for 12 h. After the reaction was completed, the reaction mixture was quenched with 10mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-Br as a colorless viscous liquid.

DPE-Br (3.00g,11.6mmol) was stirred well in 100mL THF, slowly added dropwise to magnesium turnings (1.67g,69.8mmol), added with iodine particles to initiate Grignard reaction, added with dimethylchlorosilane (4.35g,46.5mmol) solution, and reacted at 20 ℃ for 25 h. Extracted with ethyl acetate and brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-SiH as a colorless viscous liquid.

2-2: synthesis of the polymeric monomer DPE-2SiH

Methyltriphenylphosphine bromide (21.2g,59.2mmol), potassium tert-butoxide (4.98g,44.4mmol) and 360mL of THF were stirred at 0 deg.C for 90min under anhydrous and oxygen-free argon atmosphere to turn the system to bright yellow. A solution of 200mL BP-2Br (5.00g,14.8mmol) in THF was added dropwise to the reaction and stirred at 0 deg.C for 12 h. After the reaction was completed, the reaction mixture was quenched with 10mL of deionized water and extracted with ethyl acetate and saturated brine. The crude product was purified by column chromatography (eluent n-hexane) to give DPE-2Br as a white solid.

Magnesium chips (1.29g,53.6mmol) are added into a 500mL flask, dimethylchlorosilane (3.34,35.7mmol) is dissolved in 120mL of THF, and then the solution is dropwise added into the flask to be stirred and reacted for 2 hours; 100mL of a THF solution containing DPE-2Br (3.00g,8.9mmol) was added dropwise to the above system and reacted at 65 ℃ for 12 hours. And pouring the reaction product into n-hexane for sedimentation, and purifying the crude product by using a column chromatography (eluent is ethyl acetate and n-hexane) to obtain sheet crystal DPE-2 SiH.

Thirdly, synthesizing the silicon-hydrogen functionalized polymer main chain with controllable periodic sequence

3.1) Synthesis of periodic copolymer P-P (D-2SiH/Ip)

The reaction was carried out in a dry, oxygen-free glove box, DPE-2SiH (0.59g,2mmol), 8mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (236. mu.L, 0.1mmol) was injected using a sealed syringe. After 30 min of reaction, Ip (0.56,8mmol) and TMEDA (0.03g,0.15mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/Ip).

3.2) Synthesis of periodic copolymer P-P (D-2SiH/St)

The reaction was carried out in a dry, oxygen-free glove box, DPE-2SiH (0.59g,2mmol), 8mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (236. mu.L, 0.1mmol) was injected using a sealed syringe. After 30 min of reaction St (0.84g,8mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, carrying out suction filtration, and then putting the obtained solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer main chain P-P (D-2 SiH/St).

3.3) Synthesis of periodic copolymer P-P (D-SiH/Ip)

The reaction was carried out in a dry, oxygen-free glove box, DPE-SiH (0.48g,2mmol), 8mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (236. mu.L, 0.1mmol) was injected using a sealed syringe. After 30 minutes of initiation, Ip (0.54g,8mmol) and TMEDA (0.03g,0.15mmol) were added. After 7 days at room temperature, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/Ip).

3.4) Synthesis of periodic copolymer P-P (D-SiH/St)

The reaction was carried out in a dry, oxygen-free glove box, DPE-SiH (0.48g,2mmol), 8mL benzene were added to the polymerization flask, mixed well, and the initiator sec-BuLi (236. mu.L, 0.1mmol) was injected using a sealed syringe. After 30 min of initiation, St (0.84g,8mmol) was added. After reacting at room temperature for 3d, the reaction was terminated by adding isopropanol. And (3) precipitating the reaction solution in a large amount of methanol, filtering, and drying the obtained solid in a vacuum oven to constant weight to obtain the periodic copolymer main chain P-P (D-SiH/St).

Fourthly, synthesizing the side chain type liquid crystal polymer with controllable period sequence

4.1) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.82g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 50mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is uniformly stirred, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₁。

4.2) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.91g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 50mL of toluene after anhydrous and anaerobic treatment is added, and after uniform stirring, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/Ip) -M with aggregation-induced emission₂。

4.3) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-2SiH/St) prepared in the third step and 0.72g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 20mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2SiH/St) -M with aggregation-induced emission₁。

4.4) Synthesis of side-chain liquid crystalline Polymer P-P (D-2SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-2SiH/Ip) prepared in the third step and 0.79g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous and anaerobic treatment is added, and after uniform stirring, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-2S) with aggregation-induced emissioniH/St)-M₂。

4.5) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₁

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.49g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 50mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of absolute ethanol was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-phenyl-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₁。

4.6) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/Ip) -M₂

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-SiH/Ip) prepared in the third step and 0.54g of liquid crystal monomer Vinyl-biphenol-Cyano prepared in the first step are placed in an ampoule bottle, 50mL of toluene after anhydrous and anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/Ip) -M with aggregation-induced emission₂。

4.7) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/St) -M₁

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.43g of liquid crystal monomer Vinyl-phenyl-Cyano prepared in the first step are placed in an ampoule bottle, 40mL of toluene after anhydrous anaerobic treatment is added, and after the mixture is stirred uniformly, 3 drops of Karstedt catalyst are added dropwise.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₁。

4.8) Synthesis of side-chain liquid crystalline Polymer P-P (D-SiH/St) -M₂

In a closed glove box for removing water and oxygen, 0.1g of periodic copolymer main chain P-P (D-SiH/St) prepared in the third step and 0.48g of liquid crystal monomer Vinyl-biphenyl-Cyano prepared in the first step are placed in an ampoule bottle, 50mL of anhydrous and anaerobic treated toluene is added, and after uniform stirring, 3 drops of Karstedt catalyst are added.

After the ampoule was sealed, it was taken out of the glove box. The reaction was carried out at 80 ℃ for 24 h. After the reaction was completed, the solvent was removed. The dried solid was dissolved by adding 8mL of THF, 30mL of dehydrated ether was added to the solution, and the solution was centrifuged five times to remove excess liquid crystal monomer Vinyl-biphenol-Cyano. Putting the residual solid into a vacuum oven to be dried to constant weight to obtain the periodic copolymer P-P (D-SiH/St) -M with aggregation-induced luminescence₂。

The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.