CN114479390A - 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 type polyarylate composite material, which comprises the following steps: adding graphene oxide into an aqueous solution to prepare a 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 the NaOH solution, and stirring until the phenol red and the 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 a graphene oxide/phenol red polyarylate product through a series of steps of mixing, 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 polyarylester has suspended large side groups, and has a wider and adjustable performance range compared with the traditional polyarylester, and the addition of the graphene oxide also improves the processing performance of the polyarylester material and enlarges the application range of the traditional polyarylester.
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 polyarylate composite material.
Background
Graphene oxide has potential applications in various fields and has attracted wide attention in the industry. Many companies around the world have been working on industrial applications of graphene oxide-based materials, such as thermal management, multifunctional composites, anti-corrosive coatings, lubricants, energy storage, environmental protection, and biomedicine. Graphene Oxide (GO), which is structurally similar to graphene but has abundant oxygen-containing groups on the carbon skeleton, has witnessed a worldwide intense research hot trend in the last decade. And for various reasons, graphene oxide is considered to be the material with the greatest application prospect in the production of industrial-grade graphene materials and other composite materials.
Polyarylates (PAR), also known as aromatic polyesters, are a series of thermoplastic specialty engineering materials containing aromatic ring structures in the main molecular chain and linked by ester bonds. Polyarylate material is one of the LCPs, which has very good resistance (cold, heat and hydrolytic corrosion resistance), dimensional and performance stability, low hygroscopicity, good flame retardant properties and very good electromagnetic properties, especially in military material applications, specialty material applications, cable materials. The various properties (abrasion resistance, chemical corrosion resistance, light aging resistance, low moisture absorption rate and the like) of the polyarylate material are obviously higher than those of poly-p-phenylene terephthamide (PPTA) fibers, so that the LCP polyarylate fibers can better adapt to severe environments such as extreme cold, extreme heat and the like. Although polyarylate is excellent in thermal stability, there are some disadvantages in that it has high melt viscosity, poor fluidity, poor dissolution property, and processability due to its relatively high rigidity, and in particular, it is difficult to prepare thin-walled and large-sized products. Therefore, it is necessary to provide a preparation process of the graphene oxide/phenol red 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:
a preparation method of a 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 after fully mixing to obtain an acyl chloride solution;
(3) adding the acyl chloride solution into dichloromethane, stirring and mixing, and taking out after full dissolution to obtain an acyl chloride solution dissolved in dichloromethane;
(4) adding graphene oxide into water, and performing ultrasonic treatment to obtain a 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, filtration and washing to obtain polyester;
(9) adding the polyester into acetone, stirring for dissolving, and filtering to obtain a polyester solution;
(10) and adding the polyester solution into methanol, and performing precipitation, filtration, washing and drying to obtain a graphene oxide/phenol red polyarylate product.
Further, the ratio of the amounts of the phenol red, the BTEAC and the sodium hydroxide in the step (1) is (30-100): (5-15): (100-150).
Further, the concentration of the sodium hydroxide in the step (1) is 1 mol/L.
Further, in the step (4), the content of the graphene oxide is 0% -0.36% of the content of the phenol red, and the concentration of the graphene oxide suspension is 1 g/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 stirring treatment in the step (7) is carried out at a temperature of 0-10 ℃ for 4 hours.
Further, the detergent for the washing treatment in the step (8) is deionized water.
Further, the detergent of the washing treatment in the step (10) is methanol, and the time of the drying treatment is 24 hours.
The invention provides a preparation method of a graphene oxide/phenol red polyarylate composite material, which has the characteristics of high polymerization rate, short polymerization time, low polymerization temperature, high polymer yield and large molecular weight, the obtained polyarylester has suspended large side groups, and has a wider and adjustable performance range compared with the traditional polyarylester, and the addition of graphene oxide also improves the processing performance of the polyarylate material and enlarges the application range of the traditional polyarylate.
Drawings
Fig. 1 is an infrared spectrum of graphene oxide/phenol red polyarylate composite materials prepared in examples 1 to 4 in the preparation method of the graphene oxide/phenol red polyarylate composite material of the present invention;
fig. 2 is a data diagram of X-ray diffraction analysis of graphene oxide/phenol red polyarylate composites prepared in examples 1 to 4 in the preparation method of the graphene oxide/phenol red polyarylate composites of the present invention.
Wherein G1 is the phenol red polyarylate composite prepared in example 1; g2 is the graphene oxide/phenol red polyarylate composite prepared in example 2; g3 is the graphene oxide/phenol red polyarylate composite prepared in example 3; g4 is 0. graphene oxide/phenol red polyarylate composite prepared in example 4.
Fig. 3 is a flowchart of a preparation method of the graphene oxide/phenol red polyarylate composite material of the present invention.
Detailed Description
A preparation method of a graphene oxide/phenol red polyarylate composite material comprises the following steps that instrument equipment of the preparation method comprises a three-neck flask, a controllable adjusting condenser pipe, a collecting bottle, a magnetic stirrer, an ultrasonic cleaner and the like; the controllable condenser pipe of adjusting is connected to the three-necked flask, and controllable condenser pipe of adjusting passes through the return bend and connects the receiving flask, and the receiving flask passes through pipe connection condenser pipe, and the condenser pipe passes through the rubber tube and connects the Meng wash-bottle.
The preparation raw materials are as follows: sodium hydroxide, phenol red, BTEAC, dichloromethane, terephthaloyl chloride, isophthaloyl chloride, graphene oxide, ethylenediamine, methanol, acetone and deionized water.
The preparation method comprises the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 100 plus 150ml of deionized water, pouring the deionized water into the three-neck flask, measuring 100 plus 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 30-100mmol of phenol red in a NaOH solution, stirring to fully dissolve the phenol red, adding 5-15mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: weighing 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50-150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in the dichloromethane;
step four: adding graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
Wherein, the mass ratio of phenol red, BTEAC and sodium hydroxide in the step (1) is (30-100): (5-15): (100- > 150); in the step (4), the content of the graphene oxide is 0-0.36% of phenol red.
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying the present invention are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 100ml of deionized water, pouring into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring into a beaker, dissolving 30mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 5mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in 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 for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying under vacuum at high temperature for 24 hours to obtain the phenol red polyarylate product.
Example 2
The preparation method of the graphene oxide/phenol red polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 100ml of deionized water, pouring into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring into a beaker, dissolving 30mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 5mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.036mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 100ml of deionized water, pouring into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring into a beaker, dissolving 30mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 5mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: weighing 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50-150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in the dichloromethane;
step four: adding 0.072mmol of graphene oxide into an aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 100ml of deionized water, pouring into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring into the beaker, dissolving 30mmol of phenol red in a NaOH solution, stirring to fully dissolve the phenol red, adding 5mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 50mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.108mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 150ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 100mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 15mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in 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 for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying under vacuum at high temperature for 24 hours to obtain the phenol red polyarylate product.
Example 6
The preparation method of the graphene oxide/phenol red polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 150ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 100mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 15mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.12mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 150ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 100mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 15mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.24mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 150ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 100mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 15mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 150mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.36mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing with deionized water for several times to obtain polyester;
step nine: adding polyester into dichloromethane, stirring to dissolve the polyester fully, and filtering out insoluble solid impurities to obtain a polyester solution;
step ten: dissolving the polyester solution in acetone, stirring to fully dissolve the solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 125ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 70mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 10mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 100mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in 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 for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step five: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying under vacuum at high temperature for 24 hours to obtain the phenol red polyarylate product.
Example 10
The preparation method of the graphene oxide/phenol red polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 125ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 70mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 10mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 100mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.084mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 125ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 70mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 10mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 100mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.168mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, mechanically stirring at 50 ℃ for 24 hours, washing, and drying to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at 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 polyarylate composite material is shown in the embodiment by the following steps:
the method comprises the following steps: preparing a three-neck round-bottom flask with a magnetic stirrer and a constant-temperature water bath, putting an ice-water mixture into the water bath, measuring 125ml of deionized water, pouring the deionized water into the three-neck flask, measuring 150ml of 1mol/L NaOH by using a measuring cylinder, pouring the NaOH into the beaker, dissolving 70mmol of phenol red in the NaOH solution, stirring to fully dissolve the phenol red, adding 10mmol of BTEAC, and stirring to fully dissolve the phenol red to obtain a mixed solution;
step two: mixing and stirring isophthaloyl dichloride and terephthaloyl dichloride, and taking out after fully mixing to obtain an acyl chloride solution;
step three: measuring 150ml of dichloromethane solution by using a measuring cylinder, pouring the dichloromethane solution into a beaker, adding 100mmol of acyl chloride into dichloromethane, and stirring to fully dissolve the acyl chloride to obtain an acyl chloride solution dissolved in dichloromethane;
step four: adding 0.252mmol of graphene oxide into the aqueous solution, and carrying out ultrasonic treatment for 0.5-1.5 hours to prepare 1g/L of graphene oxide suspension;
step five: adding 20ml of ethylenediamine into the graphene oxide suspension, and performing mechanical stirring treatment at 50 ℃ for 24 hours, washing treatment and drying treatment to prepare aminated graphene oxide;
step six: adding aminated graphene oxide into the mixed solution, properly shaking the beaker, and then putting the beaker into an ultrasonic dispersion 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 the black red solution at the temperature of 0-10 ℃, and strongly stirring for 4 hours at a high speed by using a magnetic stirrer at a low temperature to obtain a reaction mixture;
step eight: pouring the reaction mixture into methanol, filtering the precipitate, and washing 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 solution, filtering out insoluble solid impurities, then precipitating the polyester solution in methanol, filtering out a polymer, washing with methanol for two to three times, and drying in vacuum at high temperature for 24 hours to obtain the graphene oxide/phenol red polyarylate product.
The graphene oxide/bisphenol-A polyarylate products prepared in examples 1-4 were tested.
Test 1: infrared spectroscopic analysis
According to GB/T6040-2019, mixing the sample and potassium bromide according to the ratio of 1: 100, grinding and mixing evenly in an agate grinding body, filling the mixture into a die, pressing the mixture into tablets by using an YP-2 tablet press, and testing by using an infrared spectrometer.
And (3) testing 2: x-ray diffraction analysis
According to GB/T37983-.
According to the test results, the following conclusions are reached:
referring to fig. 1, fig. 1 is an infrared spectrum of a graphene oxide/phenol red polyarylate composite prepared in examples 1 to 4 in the preparation method of the graphene oxide/phenol red polyarylate composite according to the present invention; as shown in fig. 1. Wherein 1007cm-1Is the stretching vibration peak of C-O-C. 3474cm-1is-OH hydroxyl stretching vibration peak, 2972cm-1Is C-H stretching vibration peak, 1741cm-1Is a characteristic absorption peak of the ester compound, 1504cm-1、1632cm-1Is the vibration peak of the skeleton of the benzene ring, and 725-825cm-1The vibration peak of (A) is the result of the C-H bending vibration of the p-phthaloyl chloride and the m-phthaloyl chloride.
Referring to fig. 2, fig. 2 is a data diagram of X-ray diffraction analysis of graphene oxide/phenol red polyarylate composite materials prepared in examples 1 to 4 in the preparation method of the graphene oxide/phenol red polyarylate composite material according to the present invention; as shown in fig. 2, the peak of the phenol red polyarylate to which the graphene oxide was added was relatively close to the peak of the pure graphene oxide polyarylate, both of which were relatively sharp, and no remaining peak was present, indicating that the addition of the graphene oxide did not destroy the liquid crystal structure of the phenol red polyarylate and that the crystallinity was high. The graphene oxide is well dispersed in the matrix of the phenol red type polyester, so that the flexibility of the phenol red type polyester is improved, and the molecular chains of the phenol red type polyarylate are orderly arranged among different layers of the graphene oxide by doping of the graphene oxide, so that the stacking and overlapping of the molecular chains of the polyarylate are avoided, and the movement of the molecular chains is accelerated. The introduction of new synthetic monomers can destroy the regularity of a polyarylate molecular chain, prevent the tight packing of molecular chain segments, promote the diffusion of solvent molecules and further improve the processability of the polyarylate molecular chain. Improve the solubility and processability and improve the thermal stability.
In summary, according to the preparation method of the graphene oxide/phenol red polyarylate composite material, the graphene oxide/phenol red polyarylate composite material is prepared through a series of steps of mixing, stirring, precipitating, filtering, washing and drying, and the analysis result shows that 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 performed at 0-10 ℃ by using a quaternary ammonium salt as a phase transfer catalyst, so as to prepare the graphene oxide/phenol red polyarylate. The method has the characteristics of high polymerization rate, short polymerization time, low polymerization temperature, high polymer yield and large molecular weight, the obtained polyarylester has suspended large side groups, and has a wider and adjustable performance range compared with the traditional polyarylester, and the addition of the graphene oxide also improves the processing performance of the polyarylester material and enlarges the application range of the traditional polyarylester.
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 attributes 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 description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a graphene oxide/phenol red polyarylate composite material is characterized by comprising 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 after fully mixing to obtain an acyl chloride solution;
(3) adding the acyl chloride solution into dichloromethane, stirring and mixing, and taking out after full dissolution to obtain an acyl chloride solution dissolved in dichloromethane;
(4) adding graphene oxide into water, and performing ultrasonic treatment to obtain a 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, filtration and washing to obtain polyester;
(9) adding the polyester into acetone, stirring for dissolving, and filtering to obtain a polyester solution;
(10) and adding the polyester solution into methanol, and performing precipitation, filtration, washing and drying to obtain a graphene oxide/phenol red polyarylate product.
2. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: in the step (1), the mass ratio of the phenol red, the BTEAC and the sodium hydroxide is (30-100): (5-15): (100-150).
3. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the concentration of the sodium hydroxide in the step (1) is 1 mol/L.
4. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: in the step (4), the content of the graphene oxide is 0% -0.36% of that of the phenol red, and the concentration of the graphene oxide suspension is 1 g/L.
5. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the time of the ultrasonic treatment in the step (4) is 0.5 to 1.5 hours.
6. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the temperature of the stirring treatment in the step (5) is 50 ℃, and the stirring time is 24 hours.
7. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the time of the ultrasonic treatment in the step (6) is 1 hour.
8. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the stirring treatment in the step (7) is carried out at the temperature of 0-10 ℃ for 4 hours.
9. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: and (4) the detergent for washing treatment in the step (8) is deionized water.
10. The preparation method of the graphene oxide/phenol red polyarylate composite material according to claim 1, wherein: the washing agent of the washing treatment in the step (10) is methanol, and the drying treatment time is 24 hours.
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