CN114479390B - Preparation method of graphene oxide/phenol red type polyarylester composite material - Google Patents
Preparation method of graphene oxide/phenol red type polyarylester composite material Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention provides a preparation method of a graphene oxide/phenol red polyarylate composite material, which comprises the following steps: adding graphene oxide into an aqueous solution, preparing graphene oxide suspension, adding ethylenediamine, cleaning, and drying to prepare aminated graphene oxide; adding NaOH into deionized water, stirring and dissolving, weighing phenol red and BTEAC, adding into NaOH solution, and stirring until the phenol red and BTEAC are completely dissolved to obtain a mixed solution; weighing aminated graphene oxide, adding the aminated graphene oxide into the mixed solution, and stirring to obtain a black-red solution; preparing graphene oxide/phenol red polyarylate products through a series of steps of mixing and stirring, precipitating, filtering, washing and drying; the method has the characteristics of high polymerization rate, short polymerization time, low polymerization temperature, high polymer yield and large molecular weight, the obtained copoly-aromatic ester has a large hanging side group, the method has a wider and adjustable performance range compared with the traditional polyarylester, and the addition of the graphene oxide also improves the processability of the polyarylester material, so that the application range of the traditional polyarylester is widened.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a graphene oxide/phenol red type polyarylate composite material.
Background
Graphene oxide has potential applications in various fields and has attracted considerable attention in the industry. Many companies worldwide have been devoted to industrial applications of graphene oxide-based materials such as thermal management, multifunctional composites, anticorrosive coatings, lubricants, energy storage, environmental protection, and biomedical. Graphene Oxide (GO) is structurally similar to graphene, but has abundant oxygen-containing groups on the carbon skeleton, and in the last decade we have witnessed intensive research hotspots worldwide. Moreover, graphene oxide is considered as one of the materials with the greatest application prospects in the production of industrial-grade graphene materials and other composite materials for various reasons.
Polyarylates (PAR), also known as aromatic polyesters, are a series of thermoplastic specialty engineering materials that contain aromatic ring structures in their molecular backbones and are linked by ester linkages. Polyarylate material is one of LCP, which has very good resistance (cold, heat and hydrolysis corrosion resistance), dimensional and performance stability, low hygroscopicity, good flame retardant properties and very good electromagnetic properties, particularly in military materials applications, specialty materials applications, cable materials. The various properties of the polyarylate material (abrasion resistance, chemical resistance, photo-aging resistance, low moisture absorption, etc.) are significantly higher than those of poly (paraphenylene terephthalamide) (PPTA) fibers, so that the LCP polyarylate fibers can be better adapted to severe environments such as extreme cold and extreme heat. Although the polyarylate is excellent in heat stability, there are some disadvantages in that the polyarylate has high melt viscosity, poor fluidity, poor solubility and processability due to its relatively high rigidity, and particularly, thin-wall and large-sized products are difficult to manufacture. Therefore, it is necessary to provide a preparation process of the graphene oxide/phenol red type polyarylate composite material.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide/phenol red type polyarylate composite material to overcome the problems.
The technical scheme of the invention is as follows:
the preparation method of the graphene oxide/phenol red polyarylate composite material comprises the following steps:
(1) Sequentially adding phenol red and BTEAC into a sodium hydroxide solution, stirring and mixing, and taking out after fully mixing to obtain a mixed solution;
(2) Mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
(3) Adding the acyl chloride solution into dichloromethane, stirring and mixing, and taking out after the acyl chloride solution is fully dissolved, so as to obtain an acyl chloride solution dissolved in the dichloromethane;
(4) Adding graphene oxide into water, and performing ultrasonic treatment to obtain graphene oxide suspension;
(5) Adding ethylenediamine into the graphene oxide suspension, and performing stirring treatment, washing treatment and drying treatment to obtain aminated graphene oxide;
(6) Adding the aminated graphene oxide into the mixed solution for ultrasonic treatment to obtain a black-red solution;
(7) Dropwise adding the acyl chloride solution dissolved in dichloromethane into the black-red solution, and stirring to obtain a reaction solution;
(8) Adding the reaction solution into methanol for precipitation, filtering and washing treatment to obtain polyester;
(9) Adding the polyester into acetone, stirring, dissolving and filtering to obtain a polyester solution;
(10) And adding the polyester solution into methanol, and performing precipitation, filtration, washing and drying treatment to obtain the graphene oxide/phenol red polyarylate product.
Further, the ratio of the amounts of the substances of phenol red, BTEAC and sodium hydroxide in step (1) is (30-100): (5-15): (100-150).
Further, the concentration of sodium hydroxide in the step (1) is 1mol/L.
Further, in the step (4), the graphene oxide is 0% -0.36% of phenol red content, and the concentration of the graphene oxide suspension is 1g/L.
Further, the time of the ultrasonic treatment in the step (4) is 0.5 to 1.5 hours.
Further, the temperature of the stirring treatment in the step (5) is 50 ℃, and the stirring time is 24 hours.
Further, the time of the ultrasonic treatment in the step (6) is 1 hour.
Further, the temperature of the stirring treatment in the step (7) is 0-10 ℃, and the stirring time is 4 hours.
Further, the washing agent in the step (8) is deionized water.
Further, the washing agent in the step (10) is methanol, and the drying treatment is performed for 24 hours.
The invention provides a preparation method of a graphene oxide/phenol red type polyarylate composite material, which has the characteristics of high polymerization rate, short polymerization time, low polymerization temperature, high polymer yield and large molecular weight, and the obtained copolyarylate has a hanging large side group, so that the preparation method has a wider and adjustable performance range compared with the traditional polyarylate, and the addition of the graphene oxide also improves the processability of the polyarylate material, and expands the application range of the traditional polyarylate.
Drawings
FIG. 1 is an infrared spectrum of a graphene oxide/phenol red type polyarylate composite material prepared in examples 1-4 in a preparation method of the graphene oxide/phenol red type polyarylate composite material;
FIG. 2 is a graph of the data of X-ray diffraction analysis of the graphene oxide/phenol red type polyarylate composite material prepared in examples 1-4 in the preparation method of the graphene oxide/phenol red type polyarylate composite material;
fig. 3 is a process flow diagram of a method for preparing a graphene oxide/phenol red type polyarylate composite material according to the present invention.
Wherein G1 is the phenol red type polyarylate composite material prepared in example 1; g2 is the graphene oxide/phenol red type polyarylate composite material prepared in the embodiment 2; g3 is the graphene oxide/phenol red type polyarylate composite material prepared in the embodiment 3; g4 is the graphene oxide/phenol red type polyarylate composite material prepared in example 4.
Detailed Description
The preparation method of the graphene oxide/phenol red polyarylate composite material comprises the following steps of including a three-neck flask, a controllable adjusting condenser tube, a collecting bottle, a magnetic stirrer, an ultrasonic cleaner and the like; the three-neck flask is connected with a controllable adjusting condensing pipe, the controllable adjusting condensing pipe is connected with a collecting bottle through a bent pipe, the collecting bottle is connected with the condensing pipe through a conduit, and the condensing pipe is connected with the Monte washing bottle through a rubber pipe.
The preparation raw materials are as follows: sodium hydroxide, phenol red, BTEAC, methylene chloride, terephthaloyl chloride, isophthaloyl chloride, graphene oxide, ethylenediamine, methanol, acetone, and deionized water.
The preparation method comprises the following steps:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 100-150ml of deionized water is measured and poured into the three-neck flask, 100-150ml of 1mol/L NaOH is measured and poured into a beaker, 30-100mmol of phenol red is dissolved in NaOH solution, stirring is carried out to fully dissolve the phenol red, then 5-15mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: taking 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50-150mmol of acyl chloride into dichloromethane, stirring to fully dissolve the acyl chloride, and obtaining acyl chloride solution dissolved in the dichloromethane;
step four: adding graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Wherein the ratio of the amounts of phenol red, BTEAC and sodium hydroxide in step (1) is (30-100): (5-15): (100-150); in the step (4), the graphene oxide has phenol red content of 0% -0.36%.
In order to make the above objects, features and advantages of the present invention more comprehensible, the following embodiments accompanied with examples are further described. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath, an ice-water mixture is put into the water bath, 100ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 30mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, then 5mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 50mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: dropwise adding an acyl chloride solution dissolved in dichloromethane into the mixed solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step six: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step seven: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain a phenol red polyarylate product.
Example 2
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath, an ice-water mixture is put into the water bath, 100ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 30mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, then 5mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 50mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.036mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 3
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath, an ice-water mixture is put into the water bath, 100ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 30mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, then 5mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: taking 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50-150mmol of acyl chloride into dichloromethane, stirring to fully dissolve the acyl chloride, and obtaining acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.072mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 4
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath, an ice-water mixture is put into the water bath, 100ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 30mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, then 5mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 50mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.108mmol of graphene oxide into the aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L graphene oxide suspension;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 5
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 150ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 100mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 15mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 150mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: dropwise adding an acyl chloride solution dissolved in dichloromethane into the mixed solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step six: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step seven: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain a phenol red polyarylate product.
Example 6
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 150ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 100mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 15mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 150mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.12mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 7
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 150ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 100mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 15mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 150mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.24mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 8
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 150ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 100mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 15mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 150mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.36mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 9
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 125ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 70mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 10mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 100mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: dropwise adding an acyl chloride solution dissolved in dichloromethane into the mixed solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step six: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step seven: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain a phenol red polyarylate product.
Example 10
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 125ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 70mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 10mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 100mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.084mmol of graphene oxide into an aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 11
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 125ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 70mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 10mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 100mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.168mmol of graphene oxide into the aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Example 12
The preparation method of the graphene oxide/phenol red type polyarylate composite material is shown as follows:
step one: a three-neck round bottom flask is provided with a magnetic stirrer and a constant-temperature water bath kettle, an ice-water mixture is put into the water bath kettle, 125ml of deionized water is measured and poured into the three-neck flask, 150ml of 1mol/L NaOH is measured and poured into the beaker, 70mmol of phenol red is dissolved in the NaOH solution, stirring is carried out to fully dissolve the phenol red, 10mmol of BTEAC is added, stirring is carried out to fully dissolve the phenol red, and a mixed solution is obtained;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
step three: 150ml of dichloromethane solution is measured by a measuring cylinder, poured into a beaker, 100mmol of acyl chloride is added into dichloromethane, and the mixture is stirred to be fully dissolved, so as to obtain acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.252mmol of graphene oxide into the aqueous solution, and performing ultrasonic treatment for 0.5-1.5 hours to prepare a graphene oxide suspension with the concentration of 1 g/L;
step five: adding 20ml of ethylenediamine into graphene oxide suspension, and performing mechanical stirring treatment for 24 hours at 50 ℃, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding the aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersing instrument for ultrasonic treatment for 1 hour to disperse the beaker into a black-red solution;
step seven: dropwise adding an acyl chloride solution dissolved in dichloromethane into a black-red solution at the temperature of 0-10 ℃, and strongly stirring at a high speed for 4 hours at a low temperature by using a magnetic stirrer to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing the precipitate with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to fully dissolve the polyester, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the polyester solution, filtering out insoluble solid impurities, precipitating the polyester solution in methanol, filtering out a polymer, washing the polymer twice to three times with methanol, and carrying out vacuum drying at a high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
The graphene oxide/bisphenol-a type polyarylate products prepared in examples 1 to 4 were tested.
Test 1: infrared spectroscopic analysis
According to GB/T6040-2019, samples are mixed with potassium bromide according to a ratio of 1:100 in mass ratio, grinding and mixing uniformly in agate grinding body, loading into a die, pressing into tablets by using a YP-2 tablet press, and testing by using an infrared spectrometer.
Test 2: x-ray diffraction analysis
According to GB/T37983-2019, a computer is started, a tested sample is placed on a test frame, the set angle range is 5-50 degrees, and the X-ray diffraction analysis is carried out on the graphene oxide/phenol red polyarylate under the test condition of 5 degrees/min.
From the test results, the following conclusions were drawn:
referring to fig. 1, fig. 1 is an infrared spectrogram of a graphene oxide/phenol red type polyarylate composite material prepared in examples 1-4 in the preparation method of the graphene oxide/phenol red type polyarylate composite material; as shown in fig. 1. Wherein 1007cm -1 Is C-a stretching vibration peak of O-C. 3474cm -1 Is a-OH hydroxyl telescopic vibration peak of 2972cm -1 Is C-H telescopic vibration peak 1741cm -1 Is characterized by an absorption peak of the ester compound, 1504cm -1 、1632cm -1 Is the backbone vibration peak of benzene ring, and 725-825cm -1 The vibration peak of (2) is the result of the bending vibration of paraphthaloyl chloride C-H.
Referring to fig. 2, fig. 2 is an X-ray diffraction analysis data diagram of the graphene oxide/phenol red type polyarylate composite material prepared in examples 1 to 4 in the preparation method of the graphene oxide/phenol red type polyarylate composite material according to the present invention; as shown in fig. 2, the peak of the phenol red type polyarylate to which graphene oxide was added was relatively close to that of the pure graphene oxide type polyarylate, both of which were relatively sharp, and no remaining peaks appeared, indicating that the addition of graphene oxide did not damage the liquid crystal structure of the phenol red type polyarylate, and the crystallinity was high. The graphene oxide is well dispersed in the matrix of the phenol red polyester to improve the flexibility of the phenol red polyester, and the molecular chains of the phenol red polyarylate are orderly arranged among different sheets of the graphene oxide due to the doping of the graphene oxide, so that stacking and overlapping of the molecular chains of the polyarylate are avoided, and the molecular chain movement of the polyarylate is accelerated. The introduction of new synthetic monomers can destroy the regularity of the molecular chain of the polyarylester, prevent the molecular chain segments from being closely packed, promote the diffusion of solvent molecules and further improve the processability of the polyarylester. Improving its solubility and processability, and improving its thermal stability.
In summary, the preparation method of the graphene oxide/phenol red polyarylate composite material comprises a series of steps of mixing, stirring, precipitating, filtering, washing and drying, and the graphene oxide/phenol red polyarylate composite material is prepared by infrared spectrum analysis and X-ray diffraction analysis, and according to analysis results, the chain structure of the graphene oxide/phenol red polyarylate composite material contains a graphene oxide/phenol red structural unit, a terephthaloyl structural unit and an isophthaloyl structural unit, and the interface polycondensation reaction is carried out at the temperature of 0-10 ℃ by taking quaternary ammonium salt as a phase transfer catalyst. The method has the characteristics of high polymerization rate, short polymerization time, low polymerization temperature, high polymer yield and large molecular weight, the obtained copoly-aromatic ester has a large hanging side group, the method has a wider and adjustable performance range compared with the traditional polyarylester, and the addition of the graphene oxide also improves the processability of the polyarylester material, so that the application range of the traditional polyarylester is widened.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The preparation method of the graphene oxide/phenol red type polyarylate composite material is characterized by comprising the following steps of:
(1) Sequentially adding phenol red and BTEAC into a sodium hydroxide solution, stirring and mixing, and taking out after fully mixing to obtain a mixed solution;
(2) Mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out to obtain an acyl chloride solution after the isophthaloyl dichloride and terephthaloyl dichloride are fully mixed;
(3) Adding the acyl chloride solution into dichloromethane, stirring and mixing, and taking out after the acyl chloride solution is fully dissolved, so as to obtain an acyl chloride solution dissolved in the dichloromethane;
(4) Adding graphene oxide into water, and performing ultrasonic treatment to obtain graphene oxide suspension;
(5) Adding ethylenediamine into the graphene oxide suspension, and performing stirring treatment, washing treatment and drying treatment to obtain aminated graphene oxide;
(6) Adding the aminated graphene oxide into the mixed solution for ultrasonic treatment to obtain a black-red solution;
(7) Dropwise adding the acyl chloride solution dissolved in dichloromethane into the black-red solution, and stirring to obtain a reaction solution;
(8) Adding the reaction solution into methanol for precipitation, filtering and washing treatment to obtain polyester;
(9) Adding the polyester into acetone, stirring, dissolving and filtering to obtain a polyester solution;
(10) And adding the polyester solution into methanol, and performing precipitation, filtration, washing and drying treatment to obtain the graphene oxide/phenol red polyarylate product.
2. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the ratio of the amounts of the substances of phenol red, BTEAC and sodium hydroxide in step (1) is (30-100): (5-15): (100-150).
3. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the concentration of the sodium hydroxide in the step (1) is 1mol/L.
4. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: in the step (4), the graphene oxide is 0-0.36% of phenol red content, the content of the graphene oxide is not zero, and the concentration of the graphene oxide suspension is 1g/L.
5. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the time of the ultrasonic treatment in the step (4) is 0.5-1.5 hours.
6. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the temperature of the stirring treatment in the step (5) is 50 ℃, and the stirring time is 24 hours.
7. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the time of the ultrasonic treatment in the step (6) was 1 hour.
8. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the temperature of the stirring treatment in the step (7) is 0-10 ℃, and the stirring time is 4 hours.
9. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the washing agent in the step (8) is deionized water.
10. The method for preparing the graphene oxide/phenol red type polyarylate composite material according to claim 1, which is characterized in that: the washing agent in the washing treatment in the step (10) is methanol, and the drying treatment is carried out for 24 hours.
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