CN115232322A - Preparation method and application of organic conjugated polymer - Google Patents
Preparation method and application of organic conjugated polymer Download PDFInfo
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- CN115232322A CN115232322A CN202210929610.4A CN202210929610A CN115232322A CN 115232322 A CN115232322 A CN 115232322A CN 202210929610 A CN202210929610 A CN 202210929610A CN 115232322 A CN115232322 A CN 115232322A
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Abstract
The invention discloses a preparation method of an organic conjugated polymer, which adopts solid organic matters and alkaline solids with low melting points to respectively replace a nonpolar solvent and an alkaline solvent, and the solids are heated and melted to play a role of the solvent. On one hand, naphthalene is used as a solvent, and the lamellar naphthalene can better promote the growth of the polymer, so that the polymer forms the morphological characteristics of crystals; on the other hand, the solid is not required to be dehydrated, and the reaction system is solid before being heated, so that the phenomenon of liquid gasification and escape caused by overlarge vacuum pressure is avoided, so that the reaction system can be vacuumized by adopting large vacuum pressure, air adsorbed on the surface of the solid is thoroughly pumped out, water or oxygen in the reaction system is thoroughly eliminated, the air is not required to be replaced by introducing inert gas, the operation is simple, the cost is low, and the method can be popularized and used on a large scale.
Description
Technical Field
The invention belongs to the field of synthesis and application of high polymer materials, and particularly relates to a preparation method and application of an organic conjugated polymer with simple operation, low cost and good quality.
Background
Water resources are an important material basis for economic and social sustainable development, but serious pollution is caused to fresh water resources and marine environment due to discharge of industrial organic waste liquid, leakage of crude oil and the like. For example, high-concentration organic wastewater generated in the petrochemical production process has complex components and high organic compound content, and is difficult to directly biochemically generate, so that water eutrophication and loss of animal and plant species are caused; the accident that the drilling platform is damaged or the oil tanker encounters a sea disaster to cause crude oil leakage frequently occurs, the leaked crude oil pollutes the surface plane of the sea, and a part of the leaked crude oil is intercepted by seawater with different laminar flows, and pollutants are diffused along with ocean currents to cause larger-area pollution.
The method for enriching organic compounds or crude oil leakage pollutants in water by applying adsorption technology is an economic and effective environmental protection method, and the adsorption material with excellent performance is the key of the technology. The traditional adsorbing material has the defects of low adsorption capacity, poor selectivity, poor dynamic adsorption performance, long adsorption equilibrium time and the like due to the fact that the traditional adsorbing material is made of active carbon or natural high polymer materials, and the used adsorbing material has the defects of silica gel, carbon nano tubes, organic-inorganic hybrid materials, functionalized polymers or resins and the like, but has certain defects to different degrees.
At present, organic conjugated polymers (hereinafter referred to as "CMP") have been reported as adsorbing materials. The existing CMP preparation methods basically adopt ethynylbenzene and its derivatives (such as 1,3, 5-triethylenebenzene, 1, 4-diacetylenebenzene, etc.) as a substrate A, bromophenyl benzene and its derivatives (such as 1,3, 5-tribromobenzene, 1,3, 5-tribromophenol, 1,3, 5-tribromoaniline, 1,3, 5-tribromotoluene, 1, 4-dibromobenzene, 1, 4-dibromophenol, 1, 4-dibromoaniline, 1, 4-dibromotoluene, etc.) as a substrate B, the substrate A and the substrate B are placed in a flask according to a certain proportion, then cuprous iodide and tetrakis (triphenylphosphine) palladium are added as catalysts according to a certain proportion, a nonpolar solvent and an alkaline solvent are added, and the mixture in the flask is reacted under anhydrous and oxygen-free conditions and high temperature conditions for a certain time to carry out polymerization reaction on the substrate A and the substrate B. The prepared CMP is composed of phenyl and acetylene bonds with very weak polarity, and the overall polarity of the polymer is very weak, so that the polymer has low surface free energy; the structure contains rigid and conjugated structures, and a large number of pores are generated by the accumulation of molecules to form a rough micro-nano structure. CMP has excellent hydrophobicity and stability, has small water adsorption capacity but good adsorption capacity for organic solvents, and can effectively enrich and separate organic compounds in water by utilizing the difference of the adsorption capacity of the CMP for water and other organic compounds.
However, the existing CMP preparation methods have two problems as follows:
1. when the substrate A and the substrate B are polymerized, only the morphology features of a sphere, a hollow tube and a sheet layer can be formed, and the morphology features of crystals cannot be formed.
2. The adopted nonpolar solvent and alkaline solvent are added into the flask after dehydration treatment, but a small amount of air is still mixed in the adding process. If the air is removed by vacuum pumping, the vacuum pumping pressure cannot be too high, otherwise, the liquid is gasified and escaped, and the relatively small vacuum pressure causes that the air in the reaction system cannot be completely removed. Therefore, the prior method adopts a mode of alternately vacuumizing and filling inert gas to realize the purpose of completely replacing air in a reaction system. The introduction of inert gas is mostly carried out in the following ways: firstly, directly introducing inert gas into a reaction system in a flask to displace air; secondly, filling high-purity inert gas into the glove box so as to remove oxygen and moisture in the reaction environment; thirdly, anhydrous oxygen-free inert gas is introduced into the reaction system by using a Schlenk reaction operating device. Either method has problems of complicated operation and high cost.
Disclosure of Invention
The invention provides a preparation method and application of an organic conjugated polymer, aiming at solving the technical problems in the prior art.
The invention aims to solve the technical problems in the prior art and provides a preparation method and application of an organic conjugated polymer with simple operation, low cost and good quality.
The technical solution of the invention is as follows: a preparation method of an organic conjugated polymer comprises the following steps:
a. adding a base material A and a base material B into a flask to obtain a mixture, wherein the molar ratio of the base material A to the base material B is 0.6-1.5: 1, the base A is ethynylbenzene and derivatives thereof, and the base B is bromophenyl benzene and derivatives thereof;
b. and continuously adding cuprous iodide and tetrakis (triphenylphosphine) palladium as catalysts into the flask, wherein the molar ratio of the mixture in the flask to the cuprous iodide and the tetrakis (triphenylphosphine) palladium is 1:0.02 to 0.08:0.02 to 0.1;
c. and (b) continuing adding a low-melting-point solid organic matter C and an alkaline solid D into the flask, wherein the dosage ratio of the low-melting-point organic solid C to the mixture obtained in the step a is 0.5-3g: 1mmol, wherein the molar ratio of the basic solid D to the mixture obtained in the step a is 1-10: 1;
d. vacuumizing the flask and reacting for 5 to 24h under the conditions of 90 to 250 ℃, namely, carrying out polymerization reaction on the base material A and the base material B;
e. and (3) taking out the solid in the flask, washing and drying to obtain the organic conjugated polymer.
The preferred low-melting solid organic substance C is naphthalene, a naphthalene derivative, anthracene or an anthracene derivative, and the preferred basic solid D is sodium hydroxide, potassium hydroxide or calcium oxide.
Preferably, the step d is to start a vacuum pump connected with the reaction system, preheat for 5min at 40 to 50 ℃, and then heat to 90 to 250 ℃ for reaction for 5 to 24h.
The organic conjugated polymer is applied as a catalyst, a catalyst carrier or an adsorption material.
The biggest difference between the method and the prior art is that the non-polar solvent and the alkaline solvent are respectively replaced by the solid organic matter and the alkaline solid with low melting points, and the solid plays a role of the solvent after being heated and melted. On one hand, naphthalene is used as a solvent, and the lamellar naphthalene can better promote the growth of the polymer, so that the polymer forms the morphological characteristics of crystals; on the other hand, the solid is not required to be dehydrated, and the reaction system is solid before being heated, so that the phenomenon of liquid gasification and escape caused by overlarge vacuum pressure is avoided, so that the reaction system can be vacuumized by adopting large vacuum pressure, air adsorbed on the surface of the solid is pumped out, water or oxygen in the reaction system is thoroughly eliminated, the air is not required to be replaced by introducing inert gas, the operation is simple, the cost is low, and the method can be popularized and used on a large scale.
Drawings
FIG. 1 is a schematic diagram of organic conjugated polymers prepared in examples 1 and 2 according to the present invention adsorbing an organic solvent.
FIG. 2 is an XRD picture of an organic conjugated polymer T1 prepared in an example of the present invention.
FIG. 3 is an electron microscope picture of the organic conjugated polymer T1 prepared in the example of the present invention.
Fig. 4 is an XRD picture of the organic conjugated polymer T2 prepared in the example of the present invention.
FIG. 5 is an electron microscope picture of the organic conjugated polymer T2 prepared in the example of the present invention.
Detailed Description
Example 1:
the preparation method of the organic conjugated polymer is sequentially carried out according to the following steps:
a. 6 mmol of 1,3, 5-tribromobenzene, 6 mmol of 1,3, 5-triethylynylbenzene, 300 mg of tetrakis (triphenylphosphine) palladium, 150 mg of cuprous iodide, 7 g of naphthalene, 50 mg of sodium hydroxide and a magnetic stirrer were placed in a 50mL dry round bottom flask;
b. installing an air exhaust joint with a valve on a round-bottom flask, connecting a vacuum pump and starting, opening a magnetic heating device, heating at 40 ℃ for 5min to form an anhydrous and oxygen-free environment, then heating to 120 ℃, and reacting for 10 h;
c. and taking out the product in the flask, washing with dichloromethane, acetone, deionized water and methanol respectively, and vacuumizing and drying for 3 hours at the temperature of 100 ℃ to obtain the organic conjugated polymer, namely T1.
Product evaluation of T1:
1. hydrophobicity detection of T1 materials
The contact angle of the polymer and water measured by a contact angle measuring instrument is 142 degrees, which shows that T1 has strong hydrophobic property and weak water adsorption capacity.
2. Detection of T1 capability of adsorbing organic matter
The detection method comprises the following steps: and respectively placing quantitative T1 in different solvents, standing for 5min, taking out the T1, weighing, and calculating to obtain the capacity of adsorbing the organic compound.
The results are shown in FIG. 1, with the different organic solvents shown on the ordinate and the adsorbed solvent to polymer mass ratio on the abscissa. The results show that: t1 has good adsorption capacity to organic solvents, wherein the capacity of adsorbing toluene can reach 2 times of the self weight. The difference of the adsorption capacity of T1 to water and other organic solvents can be used for desorbing organic matters in water.
3. XRD detection of T1
FIG. 2 is an XRD picture of T1, which proves that T1 has a certain ordered structure and presents the crystal characteristics.
4. Electron microscope observation of T1
The electron microscope picture of T1 is shown in figure 3, and the result shows that the method has certain orderliness.
Example 2:
the preparation method of the organic conjugated polymer is sequentially carried out according to the following steps:
a. 9 mmol of 1, 4-dibromobenzene, 6 mmol of 1,3, 5-triethylynylbenzene, 450 mg of tetrakis (triphenylphosphine) palladium, 200 mg of cuprous iodide, 7 g of naphthalene, 50 mg of potassium hydroxide and a magnetic stirrer were placed in a 50mL dry round-bottom flask;
b. installing an air exhaust joint with a valve on a round-bottom flask, connecting a vacuum pump, starting, opening a magnetic heating device, heating at 50 ℃ for 5min to form a water-free and oxygen-free environment, then heating to 150 ℃, and reacting for 10 h;
c. and taking out the product in the flask, washing the product with dichloromethane, acetone, deionized water and methanol respectively, and vacuumizing and drying the product for 3 hours at the temperature of 100 ℃ to obtain the organic conjugated polymer, namely T2.
Product evaluation of T2:
1. hydrophobicity detection of T2 materials
The contact angle of the polymer with water was 144 degrees as measured by a contact angle measuring instrument, which indicates that T2 has a very strong hydrophobic property, i.e., does not adsorb water.
2. Detection of T2 capability of adsorbing organic matter
The detection method comprises the following steps: and respectively placing the quantitative T2 in different solvents, standing for 5min, taking out the T2, weighing, and calculating to obtain the capacity of adsorbing the organic compounds.
The results are shown in FIG. 1, with the different organic solvents indicated on the ordinate and the mass ratio of adsorbed solvent to polymer on the abscissa. The results show that: t2 has good adsorption capacity to organic solvents. Due to the difference of the adsorption capacity of T2 to water and other organic solvents, the organic matters in the water are desorbed.
3. XRD detection of T2
Fig. 4 is an XRD picture of T2, and fig. 4 demonstrates that T2 has a certain ordered structure and exhibits crystal characteristics.
4. Electron microscope observation of T1
The electron microscope image of T1 is shown in figure 3, and the result shows that the crystal has certain orderliness.
Claims (4)
1. A method for preparing an organic conjugated polymer, which is characterized by comprising the following steps:
a. adding a base material A and a base material B into a flask to obtain a mixture, wherein the molar ratio of the base material A to the base material B is 0.6 to 1.5:1, the base A is ethynylbenzene and derivatives thereof, and the base B is bromophenyl benzene and derivatives thereof;
b. and continuously adding cuprous iodide and tetrakis (triphenylphosphine) palladium as catalysts into the flask, wherein the molar ratio of the mixture in the flask to the cuprous iodide and the tetrakis (triphenylphosphine) palladium is 1:0.02 to 0.08:0.02 to 0.1;
c. and (b) continuously adding a low-melting-point solid organic matter C and a basic solid D into the flask, wherein the dosage ratio of the low-melting-point organic solid C to the mixture obtained in the step a is 0.5-3g: 1mmol, wherein the molar ratio of the basic solid D to the mixture obtained in the step a is 1 to 10:1;
d. vacuumizing the flask and reacting for 5 to 24h at the temperature of 90 to 250 ℃;
e. and (3) taking out the solid in the flask, washing and drying to obtain the organic conjugated polymer.
2. The method for preparing an organic conjugated polymer according to claim 1, wherein the low-melting solid organic substance C is naphthalene, a naphthalene derivative, anthracene or an anthracene derivative, and the basic solid D is sodium hydroxide, potassium hydroxide or calcium oxide.
3. The method for producing an organic conjugated polymer according to claim 1 or 2, characterized in that: and d, starting a vacuum pump connected with the reaction system, preheating for 5min under the conditions of 40 to 50 ℃, and then heating to 90 to 250 ℃ for reaction for 5 to 24h.
4. Use of an organic conjugated polymer according to claim 1 as a catalyst, catalyst support or adsorbent material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115322337A (en) * | 2022-08-04 | 2022-11-11 | 大连理工大学 | Anhydrous and oxygen-free operation method |
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| CN112250841A (en) * | 2020-10-03 | 2021-01-22 | 大连海洋大学 | Preparation method of tubular organic conjugated polymer |
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| GB844437A (en) * | 1959-03-05 | 1960-08-10 | Petochermicals Ltd | Improvements in the production of solid polymers of unsaturated hydrocarbons |
| US3635922A (en) * | 1969-10-27 | 1972-01-18 | Firestone Tire & Rubber Co | Process for polymerizing conjugated dienes |
| US3642734A (en) * | 1969-10-27 | 1972-02-15 | Firestone Tire & Rubber Co | Polymerization process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115322337A (en) * | 2022-08-04 | 2022-11-11 | 大连理工大学 | Anhydrous and oxygen-free operation method |
| CN115322337B (en) * | 2022-08-04 | 2023-11-21 | 大连理工大学 | Anhydrous and anaerobic operation method |
| WO2024027742A1 (en) * | 2022-08-04 | 2024-02-08 | 大连理工大学 | Anhydrous anaerobic operation method |
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