阅读说明：本技术 基于动态亚胺大环的超分子聚合物及其制备方法 (Dynamic imine macrocycle-based supramolecular polymer and preparation method thereof ) 是由 何振峰 王超 王艳红 霍育锋 程原 张磊 王鸣丽 于 2019-11-12 设计创作，主要内容包括：本发明公开了一种基于动态亚胺大环的超分子聚合物,是以结构式(III)所示的桥连双萘衍生物D1与结构式(IV)所示的桥连双萘衍生物D2为原料,由D1中的醛基与D2中的氨基连接形成动态亚胺键,静置自组装得到以桥连双萘为骨架,三乙烯基二胺阳离子为客体模板,利用非共价作用诱导和动态亚胺键连接构建动态亚胺大环形成的超分子聚合物。本发明的超分子聚合物结构中含有可逆非共价作用和动态共价键,赋予了超分子聚合物以刺激响应性、降解回收可循环利用的特性。<Image he="254" wi="174" file="DEST_PATH_IMAGE001.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="123" wi="158" file="197271DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a supramolecular polymer based on a dynamic imine macrocycle, which is prepared by taking a bridging dinaphthalene derivative D1 shown in a structural formula (III) and a bridging dinaphthalene derivative D2 shown in a structural formula (IV) as raw materials, connecting an aldehyde group in D1 with an amino group in D2 to form a dynamic imine bond, standing for self-assembly to obtain the supramolecular polymer formed by taking bridging dinaphthalene as a framework, taking trivinyldiamine cations as an object template, and utilizing non-covalent effect to induce and connect with the dynamic imine bond to construct the dynamic imine macrocycle. The structure of the supermolecule polymer contains reversible noncovalent action and dynamic covalent bonds, and the supermolecule polymer is endowed with the characteristics of stimulation responsiveness, degradation and recycling.)

1. A supramolecular polymer based on a dynamic imine macrocycle is prepared from a bridged bis-naphthalene derivative D1 shown in a structural formula (III) and a bridged bis-naphthalene derivative D2 shown in a structural formula (IV):

aldehyde group in D1 and amino group in D2 are connected to form a dynamic imine bond, standing and self-assembling are carried out to obtain the supermolecular polymer of the dynamic imine macrocycle, wherein bridging dinaphthalene is used as a framework, trivinyldiamine cation is used as an object template, and non-covalent effect is utilized to induce and connect with the dynamic imine bond.

2. The supramolecular polymer as claimed in claim 1, having the structure shown in the following structural formula (V):

3. the process for preparing supramolecular polymer based on dynamic imine macrocycles as claimed in claim 1, wherein said supramolecular polymer is prepared by dissolving equimolar amount of bridged bis-naphthalene derivative D1 shown in formula (III) and bridged bis-naphthalene derivative D2 shown in formula (IV) in mixed solution of chloroform and acetonitrile, standing at room temperature, removing solvent after completing self-assembly reaction, and drying.

4. The process according to claim 3, wherein the mixed solution of chloroform and acetonitrile is a mixed solution obtained by mixing chloroform and acetonitrile at a volume ratio of 1: 1.

5. The method according to claim 3, wherein the standing time at room temperature is not less than 12 hours.

6. The method according to claim 3, wherein the bridged bis-naphthalene derivatives D1 and D2 are dissolved in a mixed solution, and then subjected to the self-assembly reaction after the ultrasonication and the standing.

7. The method according to claim 6, wherein the sonication time is 0.5 h.

8. The process according to claim 3, wherein the bridged bis-naphthalene derivative D1 represented by the formula (III) is a bridged bis-naphthalene compound represented by the formula (I) M1 and 1, 1-dichloromethyl ether as starting materials:

in a dichloromethane solvent system at 0 ℃, under the existence of a catalyst titanium tetrachloride, carrying out an hydroformylation reaction to prepare a bridged dinaphthalene compound M2 shown in a structural formula (II);

in an acetonitrile solvent system, a bridged dinaphthalene compound M2 shown in a structural formula (II) and triethylene diamine are used as raw materials and react at the temperature of 80-85 ℃ to prepare the bridged dinaphthalene derivative D1 shown in the structural formula (III).

Technical Field

The invention relates to a supermolecule polymer, in particular to a dynamic imine macrocyclic supermolecule polymer which is constructed by using bridged dinaphthalene as a framework and utilizing non-covalent action and dynamic covalent bonds, and a preparation method of the supermolecule polymer.

Background

Supramolecular polymers have the dual properties of macromolecules and supramolecular assemblies. The high molecular characteristics give it material properties, exhibiting mechanical strength and viscoelasticity similar to those of conventional polymers. And the characteristics of self-repairing, low-temperature processing, stimulus responsiveness and the like are endowed by the chemical characteristics of the supermolecule.

After more than 20 years of development, the aspects of the design of building elements of the supermolecular polymer, the structure of the supermolecular polymer and the like are greatly enriched. The building elements are gradually transited to metal coordination, host-guest action, pi-pi accumulation, electrostatic action, charge transfer and the like from the original multiple hydrogen bonds. Supramolecular polymers have also evolved gradually from investigating structural to functional properties. The supermolecule polymer has wide application prospect in the fields of intelligent materials, tissue engineering, drug carriers and the like due to good physical and chemical properties.

However, the present characterization of supramolecular polymers presents certain difficulties, especially the characterization of molecular weight.

Among the numerous building blocks, macrocyclic host and guest blocks are often used to build supramolecular polymers. This is probably due to the many host-guest motifs of macrocycles currently available, the generally strong bonding forces, the easy control of the bonding orientation, and the switching characteristics of the stimulus response.

However, although macrocyclic hosts have many advantages in building supramolecular polymers, the synthesis of most macrocyclic hosts is difficult, mainly with low yields of ring closure.

The dynamic covalent macrocyclic ring can make up the defect of low yield of the macrocyclic closed ring of the main body. Dynamic covalent bonds have properties similar to non-covalent interactions, and thus, dynamic covalent macrocycles are generally thermodynamic products, the formation of which has the property of supramolecular self-assembly and the properties of "self-proofreading" and "self-error correction" during self-assembly into rings. The presence of guest template molecules can alter the product distribution, facilitate the formation of dynamic covalent macrocycles and even achieve quantitative yields.

Meanwhile, the dynamic covalent macrocycle can respond when the external environment changes (such as temperature, concentration, acid and alkali, addition of an object and the like), so that the structure changes, and the dynamic covalent macrocycle has wider stimulus responsiveness. Thus, dynamic covalent macrocycles have different properties than traditional macrocycle hosts. Whereas supramolecular polymers based on dynamic covalent macrocycles will also have unique properties or functions.

Disclosure of Invention

The invention aims to provide a supramolecular polymer based on a dynamic imine macrocyclic ring and a preparation method of the supramolecular polymer.

The supermolecule polymer based on the dynamic imine macrocycle is prepared by taking a bridging dinaphthalene derivative D1 shown in a structural formula (III) and a bridging dinaphthalene derivative D2 shown in a structural formula (IV) as raw materials, connecting aldehyde groups in D1 and amino groups in D2 to form dynamic imine bonds, standing for self-assembly to obtain the supermolecule polymer based on the dynamic imine macrocycle, wherein the bridging dinaphthalene is used as a framework, trivinyldiamine cations are used as an object template, and non-covalent effect is used for inducing and the dynamic imine bonds are connected to construct the supermolecule polymer based on the dynamic imine macrocycle.

The nuclear magnetic resonance spectrum and the high-resolution mass spectrum are used for representing, and the structure of the supermolecule polymer obtained by the invention is shown as the following structural formula (V).

The invention utilizes the non-covalent action of host and guest supermolecules, dynamic imine bond connection self-assembly forms a supermolecule polymer based on dynamic imine macrocycle, and the reversible host and guest non-covalent action and dynamic covalent bond endow the supermolecule polymer with stimulation responsiveness, thereby realizing the degradation, recycling and cyclic utilization of the supermolecule polymer material.

According to the invention, equimolar amounts of bridged bis-naphthalene derivatives D1 and D2 are dissolved in a mixed solution of chloroform and acetonitrile for self-assembly reaction, aldehyde groups and amino groups undergo Schiff base reaction to form dynamic imine bonds, and a 1+1 dynamic imine macrocyclic supramolecular polymer is formed under the induction of a trivinyldiamine ion guest in a D1 structure.

According to the structural formula (V) of the supramolecular polymer, in a reaction system, a trivinyldiamine ion in a molecular structure of one bridged dinaphthalene derivative D1 is taken as a guest fragment, a dinaphthalene framework motif formed by bridging another molecule of the bridged dinaphthalene derivative D1 and a molecule of the bridged dinaphthalene derivative D2 is induced to form a dynamic imine macrocyclic structure through non-covalent interaction, bridged dinaphthalene in the former molecule is induced to form a ring by the trivinyldiamine ion guest fragment in other molecular structures of D1 in the system, and the structural unit alternately and repeatedly forms a linear supramolecular polymer long chain. The structure of the supermolecule polymer is formed by the dynamic imine macrocycle and non-covalent interaction, so that the supermolecule polymer has dynamic equilibrium reversibility and is in a dynamic system, and the molecular weight of the supermolecule polymer is difficult to characterize. But the dynamic equilibrium reversibility is sensitive to external environmental conditions, and the stimulation responsiveness, degradable recycling and self-repairing characteristics of the supramolecular polymer are endowed.

The preparation method of the supramolecular polymer based on the dynamic imine macrocycle comprises the following steps: dissolving equimolar amounts of a bridged bis-naphthalene derivative D1 shown in structural formula (III) and a bridged bis-naphthalene derivative D2 shown in structural formula (IV) in a mixed solution of chloroform and acetonitrile, standing at room temperature, removing the solvent after completing the self-assembly reaction, and drying to prepare the supramolecular polymer.

In the above production method, the mixed solution of chloroform and acetonitrile is preferably a mixed solution obtained by mixing chloroform and acetonitrile at a volume ratio of 1: 1.

Further, the standing time at room temperature should be not less than 12 h.

More specifically, in the preparation method of the present invention, it is preferable that the bridged bis-naphthalene derivatives D1 and D2 are dissolved in a mixed solution, and then subjected to ultrasonic treatment and then allowed to stand for self-assembly reaction.

The time of the ultrasonic treatment is preferably 0.5 h.

The inventors of the present invention have specifically provided a process for the synthesis of the bridged binaphthyl derivative D2 of formula (IV) from 2, 6-dihydroxynaphthalene as a starting material in the literature Zhenfeng He, Gang Ye, Wei Jiang, Imineovercycles with Deep Capacity, Guest-Selected Format of Syn/anti configuration and Guest-Controlled reconfiguration, chem.

Similarly, the bridged binaphthyl derivative D1 represented by the structural formula (III) of the present invention is also prepared from the bridged binaphthyl compound M1 represented by the following structural formula (I).

The preparation of a specific bridged bis-naphthalene derivative D1 is given below: in a dichloromethane solvent system at 0 ℃, taking a bridged bis-naphthalene compound M1 shown in a structural formula (I) and 1, 1-dichloromethyl ether as raw materials, and reacting in the presence of a catalyst titanium tetrachloride to prepare a bridged bis-naphthalene compound M2 shown in a structural formula (II); in an acetonitrile solvent system, a bridged dinaphthalene compound M2 shown in a structural formula (II) and triethylene diamine are used as raw materials and react at the temperature of 80-85 ℃ to prepare the bridged dinaphthalene derivative D1 shown in the structural formula (III).

The invention successfully synthesizes the supramolecular polymer based on the dynamic imine macrocycle, and has the innovation that the supramolecular polymer simultaneously has reversible non-covalent action of a subject and an object and a dynamic covalent bond, so that the supramolecular polymer is endowed with stimulus responsiveness. And importantly, the nuclear magnetic resonance spectrogram of the product shows that the product after reaction has no characteristic peaks of raw materials, and the raw material bridged bis-naphthalene derivatives D1 and D2 have no residue and are almost completely self-assembled into a supramolecular polymer, which shows that the invention can prepare the supramolecular polymer material with high yield.

The structure of the supramolecular polymer contains dynamic covalent bonds and non-covalent interactions, the dynamic covalent bonds and the non-covalent interactions have dynamic balance reversible property, and reversible reaction of bond breaking of-C = N-and reversible conversion of dissociation and assembly of non-covalent interactions (hydrogen bonds) can be realized when external conditions (such as temperature and pH value) are changed, so that the supramolecular polymer material is endowed with the characteristics of degradation, recycling, cyclic utilization, self-repair and the like. The composite coating formed by adding the supramolecular polymer disclosed by the invention into paint can realize self-repairing of a scraped coating.

Drawings

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a bridged binaphthyl compound M1.

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a bridged binaphthyl derivative D2.

FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the bridged binaphthyl compound M2.

FIG. 4 is a NMR spectrum of a bridged binaphthyl derivative D1.

FIG. 5 shows the NMR spectrum of the supramolecular polymer shown in structural formula (V).

FIG. 6 is a high resolution mass spectrum of a supramolecular polymer represented by structural formula (V).

Detailed Description

The following examples are only preferred embodiments of the present invention and are not intended to limit the present invention in any way. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

The bridged bis-naphthalene compound M1 represented by the structural formula (I) and the bridged bis-naphthalene derivative D2 represented by the structural formula (IV) were synthesized according to the methods reported in the literature, Zhenfeng He, Gang Ye, Wei Jiang, Imine Macrocycle with deep Capacity, Guest-Selected Format of Syn/Anti Configuration and Guest-Controlled reconfiguration, chem.

The nmr hydrogen spectra of M1 and D2 are given in fig. 1 and 2, respectively.

Compound M1(280mg, 0.6mmol) was dissolved in 6mL of anhydrous dichloromethane with stirring at 0 ℃ and 1, 1-dichloromethyl ether (0.22mL, 2.4mmol) was added. Removing TiCl with a syringe₄(460mg, 2.4mmol) was slowly added to the above mixed solution, and the reaction was continued with stirring for 1 h. The reaction was allowed to return to room temperature and stirred for a further 2.5 h.

The reaction solution was poured into a saturated aqueous sodium bicarbonate solution, and extracted with dichloromethane (40mL × 3). The organic phase was washed with saturated aqueous sodium bicarbonate (100mL) and deionized water (100mL) in that order 3 times and dried over anhydrous sodium sulfate. Filtering, collecting filtrate, and distilling under reduced pressure to obtain a crude product. The crude product was applied to a silica gel column, and separation and purification were carried out using cyclohexane: dichloromethane = 1: 1 as an eluent, to obtain 270mg of a yellow solid of the bridged binaphthyl compound M2 represented by the structural formula (II), with a yield of 86%. The NMR spectrum is shown in FIG. 3.

Compound M2(270mg, 458mmol) was dissolved in 4ml of acetonitrile solvent with stirring, and 40ml of a solution of trivinyldiamine (7.8g, 70.0mmol) in acetonitrile with stirring was slowly added dropwise at 80 ℃ and the reaction was continued with stirring for 12 hours after completion of the dropwise addition.

The reaction solution was cooled to room temperature, 40mL of diethyl ether was added, and filtration and collection of a filter cake were carried out to dry the product to obtain 172mg of a bridged binaphthyl derivative D1 represented by the structural formula (III) as a white solid with a yield of 40%. The NMR spectrum of the prepared D1 is shown in FIG. 4.

The bridged dinaphthalene derivatives D1(26.2mg, 0.05mmol) and D2(41.40mg, 0.05mmol) are dissolved in 4mL of a mixed solution of chloroform: acetonitrile = 1: 1 (V: V), the mixed solution is treated by ultrasonic treatment for 0.5h and is kept still at room temperature for 12h, after almost all aldehyde groups and amino groups are converted into imine bonds, the solvent is removed and vacuum drying is carried out, and the supramolecular polymer based on the dynamic imine macrocycle is prepared.

Figure 5 shows the nmr hydrogen spectra of the supramolecular polymers prepared and compared to the spectra of the starting bridged bis-naphthalene derivatives D1(III) and D2 (IV). As can be seen from the figure, the aldehyde group (10.8ppm) in the structure III disappeared after the reaction, a characteristic new peak (-CH = N-) of the imine bond (-CH = N-) was generated in the spectrum III + IV (9.1ppm), and methylene (-CH) adjacent to the amino group in IV₂-) after the reaction, shifted from 4.1ppm to 5.7ppm and 4.6ppm, indicating the formation of a dynamic imine macrocycle of trans structure. Furthermore, the methylene (-CH) group of the triethylenediamine ion guest in the III structure₂The characteristic peak of about-N-) 3.0ppm is divided into two groups of peaks and shifts due to the non-covalent action and the influence of asymmetric space structure after the reaction, and methylene adjacent to an ionic group generates high field shift, further, the dynamic imine macrocycle is formed by taking trivinyldiamine ions as an object template and inducing III and IV bridged dinaphthalene framework units through the non-covalent action.

Figure 6 shows the high resolution mass spectrum of the supramolecular polymer produced. The mass spectrum ion peak 1237.6985 in the figure, which corresponds to the molecular weight 1237.6988 of the supramolecular polymer repeat unit, indicates that the bridged bis-naphthalene derivatives D1 and D2 self-assemble to form supramolecular polymers.