CN103242526A - Preparation method of photoresponse type hyperbranched zinc phthalocyanine polymer - Google Patents

Abstract

The invention discloses a method for preparing a light-responsive hyperbranched zinc phthalocyanine polymer, which comprises the following steps: monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy base)-azobenzene and zinc acetate, the polymerization system was dissolved in N,N -dimethylcaproamide inert solvent, under the protection of argon, under the condition of 150-180 ^o C, the reaction was carried out for 1 day After 7 days (the present invention takes one day of reaction as an example), a hyperbranched zinc phthalocyanine polymer containing an azophenyl group is prepared. By adopting the technical scheme of the present invention, the flexible chain-containing azophenyl group is introduced into the phthalocyanine hyperbranched polymer system for the first time, which improves its solubility and processing performance in organic solvents, and at the same time obtains a series of new rare reported The photoresponsive hyperbranched zinc phthalocyanine polymer; and the synthesis method using biphenyl dicyanonitrile derivatives as raw materials can reduce reaction steps, reduce the waste rate of raw materials, and realize the rational utilization of resources.

Description

A kind of preparation method of photoresponsive hyperbranched zinc phthalocyanine polymer

technical field

The invention relates to a synthesis method of a hyperbranched zinc phthalocyanine polymer containing an azophenyl group, in particular to a preparation method of a photoresponsive hyperbranched zinc phthalocyanine polymer.

Background technique

In the family of π-π conjugated macrocyclic structures, phthalocyanines and porphyrins with two-dimensional 18π-electron conjugated structures have been one of the research hotspots of optoelectronic materials. The cyclic structure of phthalocyanine is more rigid than that of porphyrin, and the π-π interaction between its metal complexes is stronger, and it is easy to form a supramolecular structure. And the phthalocyanine compound has good stability to heat, light and environment. At the same time, about 70 kinds of metal atoms can coordinate well with the phthalocyanine ring, which greatly increases the selectivity of the central metal atom.

Phthalocyanine compounds are one of the important photoelectric functional materials due to their advantages of low price, low toxicity, good thermal stability, etc., and wide spectral response range, and have been applied in many fields, such as sensitization in photodynamic therapy Agents, desulfurization catalysts in petroleum processing, electrocatalysts in redox reactions in fuel cells, and materials such as fluorescent probes, electroluminescence, and information storage. However, most phthalocyanine compounds have disadvantages such as insoluble and infusible, which limit their wide application in the above-mentioned aspects. In order to overcome the shortcomings of the above-mentioned phthalocyanine compounds and effectively utilize various functionalities of phthalocyanine compounds, introducing special functional functional groups into phthalocyanine compounds or introducing phthalocyanine compounds into polymer chains is to enhance its An effective way to improve its solubility and processing properties.

At present, the different characteristics of azobenzene cis-trans isomers and various photoresponse phenomena induced by cis-trans isomerization have attracted extensive attention of researchers. Photoresponsive materials containing azophenyl elements exhibit many unique properties, such as photodynamic nano-micro-machines, light-driven molecular switches, information storage, surface relief gratings and command surfaces, nonlinear optical materials and photonic materials, etc. Therefore, the design of introducing azophenyl group into the phthalocyanine material system can endow the phthalocyanine material with more optical properties.

Due to the dual properties of phthalocyanine and polymer, polymer metal phthalocyanine is expected to be greatly improved in processability and solubility compared with small molecule phthalocyanine derivatives, and it can endow materials with special properties. become a research hotspot. Similar to polymer porphyrin metal complexes, polymer metal phthalocyanine compounds are mainly divided into two categories according to the polymerization method: one is polymetal phthalocyanine, which uses metal phthalocyanine as the basic unit for covalent bond condensation or coordination polymerization. Polymetallophthalocyanines can be divided into two types according to their different combinations, namely planar polymerized metallophthalocyanines (A) and axially polymerized metallophthalocyanines (B). The other is polymer-supported metallophthalocyanines, which can be combined with polymer carriers in three ways: covalent bonding (CI), coordination bonding (CZa), and physical adsorption (CZb). In the molecular structure of phthalocyanine, there are four benzene rings with the same positions and activities. Therefore, the phthalocyanine ring is connected with another phthalocyanine through the cyclized benzene ring to form A-type polymer metal phthalocyanine. The ligands of this type of polymer metal phthalocyanine are part of the polymer chain, usually have poor solubility, but have good thermal stability and catalytic and electrochemical properties.

The hyperbranched phthalocyanines currently synthesized and reported are basically synthesized using biphthalonitrile as raw materials. However, in the method for preparing hyperbranched phthalocyanine polymers, most systems have disadvantages such as relatively simple monomer structure, poor solubility and processability, and single functionality. However, there is no corresponding technical report on the system of introducing photoresponsive azophenyl groups into hyperbranched zinc phthalocyanine polymers.

Contents of the invention

The purpose of the present invention is to overcome the above problems existing in the prior art, and to provide a method for preparing a photoresponsive hyperbranched zinc phthalocyanine polymer.

In order to achieve the above-mentioned technical purpose and achieve the above-mentioned technical effect, the present invention is realized through the following technical solutions:

A preparation method of photoresponsive hyperbranched zinc phthalocyanine polymer, comprising the following steps:

A polymerization system composed of monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene and zinc acetate, the polymerization system is dissolved in N, N -di Methylhexanamide inert solvent, under the protection of argon, under the condition of 150-180 ^o C, the reaction is carried out for 1 to 7 days respectively (this patent takes the reaction of one day as an example), and the azophenyl group is prepared Hyperbranched zinc phthalocyanine polymers. The obtained hyperbranched zinc phthalocyanine polymer has good solubility in organic solvents.

Further, the molar ratio of the monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene to zinc acetate is 3:1; the monomer The volume ratio of 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene to the N, N -dimethylcaproamide inert solvent is 1: 6~12.

The beneficial effects of the present invention are:

By adopting the technical scheme of the present invention, for the first time, the flexible chain-containing azophenyl group is introduced into the phthalocyanine hyperbranched polymer system, while enhancing its solubility and processing performance, a series of new rare reported hyperbranched zinc is also obtained Phthalocyanine polymers; and the adopted biphenyl dicyanonitrile synthesis method directly synthesizes hyperbranched zinc phthalocyanine polymers from monomers and zinc salts in one step, which can reduce reaction steps, reduce the waste rate of raw materials, and realize the rationalization of resources use.

The above description is only an overview of the technical solutions of the present invention. In order to understand the technical means of the present invention more clearly and implement them according to the contents of the description, the preferred embodiments of the present invention and accompanying drawings are described in detail below. The specific embodiment of the present invention is given in detail by the following examples and accompanying drawings.

Description of drawings

The accompanying drawings described here are used to provide a further understanding of the present invention and constitute a part of the application. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations to the present invention. In the attached picture:

Figure 1 is the general structural formula of a hyperbranched zinc phthalocyanine polymer containing an azophenyl group (n>1 in the formula);

Fig. 2 is the schematic flow sheet that prepares the hyperbranched zinc phthalocyanine polymer containing azophenyl group in embodiment one;

Fig. 3 is the NMR figure of the monomer obtained in Example 1;

Fig. 4 is the NMR figure of the polymer obtained in Example 1;

Fig. 5 is the ultraviolet-visible spectrogram of the polymer obtained in embodiment one;

Fig. 6 is the photoisomerization cycle diagram of the polymer obtained in embodiment one;

Fig. 7 is the thermogravimetric analysis (TGA) spectrogram of the polymer obtained in embodiment one;

Figure 8 is the infrared absorption spectrum of the polymer obtained in Example 1.

Detailed ways

The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments.

A preparation method of photoresponsive hyperbranched zinc phthalocyanine polymer, comprising the following steps:

A polymerization system composed of monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene and zinc acetate, the polymerization system is dissolved in N, N -di Methylhexanamide inert solvent, under the protection of argon, under the condition of 150-180 ^o C, the reaction is carried out for 1 to 7 days respectively (this patent takes the reaction of one day as an example), and the azophenyl group is prepared Hyperbranched zinc phthalocyanine polymers. The obtained hyperbranched zinc phthalocyanine polymer has good solubility in organic solvents.

Further, the molar ratio of the monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene to zinc acetate is 3:1; the monomer The volume ratio of 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene to the N, N -dimethylcaproamide inert solvent is 1: 6~12.

Embodiments of the invention:

Chemical reagents used: 3,4-dicyanophenol, 99%, Acros; 1,6-dibromohexane, 98%, Acros; p-nitrophenol, 98%, Aladdin; p-nitrophenol, 98% , China National Pharmaceutical (Group) Shanghai Chemical Reagent Company; Dimethylsulfoxide, 99%, China National Pharmaceutical (Group) Shanghai Chemical Reagent Company; N, N -dimethylformamide, 99%, China National Pharmaceutical (Group) Shanghai Chemical Reagent Company Company; N, N -dimethylacetamide, 97%, China National Pharmaceutical (Group) Shanghai Chemical Reagent Company; neutral alumina 100-200 mesh, FCP for column chromatography, China National Pharmaceutical (Group) Shanghai Chemical Reagent Company; Potassium hydroxide, anhydrous magnesium sulfate, anhydrous potassium carbonate and potassium iodide, analytically pure, China Pharmaceutical (Group) Shanghai Chemical Reagent Company; chloroform, methanol, ethyl acetate and petroleum ether, analytically pure, Changshu Yangyuan Chemical Reagents Ltd.

Test equipment and conditions:

Gel permeation chromatography: GPC 1515 from Waters, USA; measurement conditions: three columns HR1, HR3 and HR4 used in series, differential detector, mobile phase tetrahydrofuran (1 mL/min), column temperature 30 ^o C, Calibration with polystyrene standards.

Nuclear Magnetic Resonance: 400 MHz; Determination Conditions: DMSO-d6 (monomer) or CDCl ₃ (polymer) as solvent, tetramethylsilane as internal standard, test temperature 25 ^o C.

Ultraviolet absorption spectrum: measured by UV-3150 ultraviolet-visible spectrometer of Shimadzu Corporation.

Infrared absorption spectrum: measured by Mangna-550 Nicocet infrared spectrometer, KBr tablet method.

The thermogravimetric analysis (TGA) of the polymer was measured by a SDT-2960TG/DTA thermogravimetric instrument under nitrogen protection (100 mL/min), and the heating rate was 10 ^o C/min.

Embodiment one: preparation contains the hyperbranched zinc phthalocyanine polymer of azophenyl group

(1) Preparation of monomers: Add 2.88 g of 3,4-dicyanophenol and 12.20 g of 1,6-dibromohexane to 60 mL of N, N -dimethylformamide in sequence , stirred at room temperature for 1 hour under the protection of argon, and then added 12.35 g of potassium carbonate to the above solution in batches, and added a small amount of potassium iodide, and continued to stir and react at room temperature for 24 hours. The reaction solution was extracted with chloroform, washed with saturated brine and deionized water three times successively, the organic layer was collected and dried overnight by adding anhydrous magnesium sulfate, filtered and concentrated to obtain a crude product, which was washed with petroleum ether/acetic acid The eluent of ethyl ester was separated by column chromatography to obtain a pure intermediate. Dissolve 2.30 g of the intermediate and 4.14 g of potassium carbonate in 40 mL of N, N -dimethylformamide, react at 80 ^o C, heat and stir for 5 hours, then add 0.64 g of 4,4- Dihydroxyazobenzene and a small amount of potassium iodide continued to react for 12 hours. Extract with chloroform, and wash with saturated brine and deionized water three times successively, collect the organic layer and add anhydrous magnesium sulfate to dry overnight, filter, and obtain the crude product after rotary evaporation, and reconstitute the crude product with dimethyl sulfoxide Crystallization to obtain pure monomer.

(2) Preparation of hyperbranched zinc phthalocyanine polymers containing azophenyl groups: In a clean 5 mL ampoule, add the monomer and zinc acetate in sequence at a ratio of 3:1, and add an appropriate amount of solvent ( N, N -di methylacetamide) dissolved. The ampoule was sealed with argon gas for 10 minutes for deoxygenation, and the sealed ampoule was placed in a reactor at 150–180 ^o C for the reaction at the scheduled time. Take out the ampoule bottle at the predetermined time point, open the seal, pour the polymer into methanol for sedimentation, and extract with methanol after suction filtration until the supernatant is colorless, then reverse phase extraction with tetrahydrofuran, and then concentrate by rotary evaporation to obtain a polymer. The polymer was dried in a vacuum drying oven at room temperature to a constant weight, weighed, and the monomer conversion rate was calculated. The obtained hyperbranched zinc phthalocyanine polymer has good solubility in organic solvents.

It can be seen from Figure 2 that the corresponding hydrogen chemical shifts (a, b, c, d, e, f, g, h) can be found in one-to-one correspondence on the NMR map, and the integral ratio between them (a :b:c:d:e:f:g = 8:8:8:4:2:6:2 ) and theoretical value (a:b:c:d:e:f:g= 8:8:8 :4:2:6:2) are very consistent, confirming that the obtained product is the target compound we need.

It can be seen from Figure 3 that the corresponding hydrogen chemical shifts (a, b, c) can be found in one-to-one correspondence on the NMR map, and the integral ratio between them (a:b:c = 21:8:17 ) and the theoretical value (a:b:c = 20:8:16) are relatively consistent, because there is a small amount of water and solvent peaks (CDCl ₃ ) in the system, which makes the number of hydrogen (a,c) more than the theoretical value , confirming that the obtained product is the target compound we need.

Table 1: Molecular weight and molecular weight distribution data of polymers

The polymer is a hyperbranched polymer, and since there are structures with different degrees of branching in the system, its molecular weight and molecular weight distribution data are M _{n (GPC)} = 14820 g/mol, M _w / M _n = 1.10; M _{n ( GPC) =} 8490 g/mol, Mw _/ Mn = 1.10 and Mn _{(GPC) =} 4820 g/mol, Mw _/ Mn = 1.10.

Table 2: Elemental analysis results of monomers and polymers (values in brackets are theoretical values)

The content of carbon, hydrogen and nitrogen in the monomer is almost the same as the theoretical value; the carbon content of the polymer is lower than that of the monomer, and this is due to the polymerization to form phthalocyanine rings.

As shown in Figure 4, the maximum absorption of the polymer Q band is around 680 nm, which is exactly the characteristic of the absorption spectrum of a typical phthalocyanine metal complex. The intensity of the B band absorption (355 nm) of the polymer is obviously stronger than that of the Q band (678 nm). nm), which is caused by the overlapping of the absorption band of the azophenyl group (360 nm, π-π*, trans structure) and the band of phthalocyanine B.

As shown in Figure 5, hyperbranched zinc phthalocyanine also has cis-trans isomerism because it contains an azophenyl group, that is, under the action of ultraviolet light, the azo molecule of the trans structure can become unstable after absorbing photons The cis structure can be changed back to the trans structure through thermal relaxation, and after several cycles, it shows better photoresponsiveness.

As shown in Figure 6, the initial decomposition temperature of the polymer is 330 ^o C, and the residual rate of the polymer reaches 42% at 800 ^o C, indicating that the hyperbranched zinc phthalocyanine polymer has good thermal properties and thermo-oxidative stability.

As shown in Figure 7, there is a weak cyano peak at 2290 cm ^-1 , and there are obvious characteristic absorption peaks of phthalocyanine ring at 1010 cm ^-1 , which means that 4,4′-(6-(3, 4-dicyanophenoxy)-hexyloxy)-azobenzene reacted to produce hyperbranched zinc phthalocyanine polymer.

The following conclusions can be drawn from the above data:

(1) The introduction of azophenyl group increases the processability of hyperbranched zinc phthalocyanine, showing good photoresponsiveness.

(2) The cyclization rate of hyperbranched zinc phthalocyanine can be adjusted by changing the reaction time and the ratio of monomer and zinc salt.

(3) The whole reaction is simple and easy to operate, which fundamentally overcomes the shortcomings of complex synthesis steps and harsh conditions in the traditional method.

The above descriptions are only preferred embodiments of the invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (2)

1. A preparation method for photoresponsive hyperbranched zinc phthalocyanine polymer, comprising the following steps: Step 1) Polymerization system composed of monomer 4,4′-(6-(3,4-dicyanophenoxy)-hexyloxy)-azobenzene and zinc acetate, dissolve the polymerization system in N, N -dimethylcaproamide inert solvent, under the protection of argon, under the condition of 150-180 ^o C, the reaction was carried out for 1 to 7 days respectively (this patent takes the reaction of one day as an example), and the preparation containing azophenyl group of hyperbranched zinc phthalocyanine polymers. 2. the preparation method of photoresponsive type hyperbranched zinc phthalocyanine polymer according to claim 1, is characterized in that, described monomer 4,4 '-(6-(3,4-dicyanophenoxy )-hexyloxy)-azobenzene and zinc acetate in a mol ratio of 3:1; the monomer 4,4'-(6-(3,4-dicyanophenoxy)-hexyloxy) - The volume ratio of azobenzene to the N, N -dimethylcaproamide inert solvent is 1:6-12, and the obtained hyperbranched zinc phthalocyanine polymer has better solubility in organic solvents.

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