阅读说明：本技术 一种巯基化碳纳米管改性聚苯乙烯的制备方法和应用 (Preparation method and application of sulfhydrylation carbon nano tube modified polystyrene ) 是由 张红梅 于 2020-12-14 设计创作，主要内容包括：本发明涉及聚苯乙烯技术领域,且公开了一种巯基化碳纳米管改性聚苯乙烯,巯基化碳纳米管含有丰富的巯基基团,实现对碳纳米管的功能化表面改性,在苯乙烯乳液聚合过程中,巯基化碳纳米管的巯基与苯乙烯的烯基发生巯基-烯基点击化反应,从而将碳纳米管通过共价键与聚苯乙烯有机结合,通过化学共价键的修饰作用,明显改善了碳纳米管与聚苯乙烯的界面结合力和亲和性,避免了碳纳米管在聚苯乙烯基体中分散不均匀和发生团聚的现象,导电性和力学性能优异的碳纳米管高度分散,作为化学交联位点,显著提高了聚苯乙烯的介电性能和机械强度,拓宽了聚苯乙烯的应用范围和实际使用性能。(The invention relates to the technical field of polystyrene and discloses a mercapto-modified polystyrene with carbon nano-tubes, wherein the mercapto-modified polystyrene contains abundant mercapto groups to realize the functional surface modification of the carbon nano-tubes, in the styrene emulsion polymerization process, the sulfydryl of the sulfhydrylation carbon nano tube and the alkenyl of the styrene have sulfydryl-alkenyl click reaction, the carbon nano tube is organically combined with the polystyrene through a covalent bond, the interface bonding force and the affinity of the carbon nano tube and the polystyrene are obviously improved through the modification effect of a chemical covalent bond, the phenomena of non-uniform dispersion and agglomeration of the carbon nano tube in a polystyrene matrix are avoided, the carbon nano tube with excellent conductivity and mechanical property is highly dispersed and is used as a chemical crosslinking site, the dielectric property and the mechanical strength of the polystyrene are obviously improved, and the application range and the actual use performance of the polystyrene are widened.)

1. A sulfhydrylation carbon nano tube modified polystyrene is characterized in that: the preparation method of the sulfhydrylation carbon nano tube modified polystyrene comprises the following steps:

(1) adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid into a conical flask, adding the carbon nano tube, placing the mixture into a reflux reaction device after ultrasonic dispersion is uniform, heating the mixture to 85-95 ℃, stirring the mixture at a constant speed for reaction for 2-8 hours, adding distilled water for dilution, performing centrifugal separation, washing and drying to obtain the carboxyl carbon nano tube.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes into a conical flask, heating to 60-80 ℃, carrying out reflux reaction for 12-24h, carrying out reduced pressure distillation, washing with ethanol and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, heating to 40-60 ℃, carrying out reflux reaction for 24-36h, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding distilled water solvent, thiolated carbon nanotube, styrene, dispersant polyvinyl alcohol and initiator azobisisobutyronitrile into a conical flask, heating to 70-80 ℃, reacting for 6-12h, centrifugally separating, washing with distilled water and drying to obtain the thiolated carbon nanotube modified polystyrene, which is applied to high dielectric materials.

2. The thiolated carbon nanotube-modified polystyrene as set forth in claim 1, wherein: the reflux reaction device in the step (1) comprises a magnetic heating stirrer, the magnetic heating stirrer is arranged inside the magnetic heating stirrer, a bearing is movably connected inside the magnetic stirring stirrer, a rotating shaft is movably connected with the bearing, a rotating shaft fixedly connected with rotating pieces, magnets are fixedly connected above the rotating pieces, heating pieces are arranged on two sides inside the magnetic stirring stirrer, a conical flask is arranged above the magnetic stirring stirrer, a condensing tube is movably connected with the conical flask, and an upper water outlet and a lower water inlet are fixedly connected with the condensing tube.

3. The thiolated carbon nanotube-modified polystyrene as set forth in claim 1, wherein: the mass ratio of the thionyl chloride to the carboxyl carbon nanotube in the step (2) is 50-100: 1.

4. The thiolated carbon nanotube-modified polystyrene as set forth in claim 1, wherein: the mass ratio of the acyl chloride sulfhydrylation carbon nano tube, the triethylamine and the 2-mercaptoethanol in the step (3) is 1:50-80: 150-250.

5. The thiolated carbon nanotube-modified polystyrene as set forth in claim 1, wherein: the mass ratio of the mercapto carbon nanotube, the styrene, the polyvinyl alcohol and the azobisisobutyronitrile in the step (4) is 0.3-1:100:1.5-3.5: 5-8.

Technical Field

The invention relates to the technical field of polystyrene, in particular to a preparation method and application of mercapto carbon nanotube modified polystyrene.

Background

The dielectric material has good dielectric constant and smaller dielectric loss performance, and with the continuous development of electronic products towards miniaturization, light weight and functionalization, a high-molecular polymer-based dielectric material with excellent comprehensive performance needs to be developed.

Polystyrene has heat resistance, chemical resistance and easy processing performance, is low in cost, can be made into packaging materials, plastics, vessels and the like, and is thermoplastic plastic with wide application, but polystyrene is a typical nonpolar polymer, and has weak interface bonding force and poor affinity with polar nano fillers such as nano silicon dioxide, graphene, carbon nano tubes and the like, so that the nano fillers are easy to agglomerate in polystyrene, and the comprehensive performances of the polystyrene material, such as mechanical strength, dielectric property, flame retardance and the like, are influenced.

The carbon nano tube is a one-dimensional tubular structure formed by curling graphene sheets, has special mechanical properties, thermodynamic properties, electrical properties and the like, is an excellent nano functional filler, can improve the comprehensive properties of organic polymer materials such as epoxy resin, acrylic resin, polystyrene and the like, but has a large specific surface area and large van der Waals force among nano particles, is easy to agglomerate, and affects the properties of polymer materials such as polystyrene and the like, so that the surface modification of the carbon nano tube is improved, the interface bonding force and affinity with the polystyrene are improved, and the agglomeration is prevented from becoming a research hotspot.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a preparation method and application of sulfhydrylation carbon nano tube modified polystyrene, which improves the interface bonding force and affinity of the carbon nano tube and the polystyrene and avoids the occurrence of agglomeration.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the sulfhydrylation carbon nano tube modified polystyrene comprises the following steps:

(1) adding a mixed solution of concentrated sulfuric acid and concentrated nitric acid into a conical flask, adding the carbon nano tube, placing the mixture into a reflux reaction device after ultrasonic dispersion is uniform, heating the mixture to 85-95 ℃, stirring the mixture at a constant speed for reaction for 2-8 hours, adding distilled water for dilution, performing centrifugal separation, washing and drying to obtain the carboxyl carbon nano tube.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes into a conical flask, heating to 60-80 ℃, stirring at a constant speed, refluxing for reaction for 12-24h, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, heating to 40-60 ℃, carrying out reflux reaction for 24-36h, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding distilled water solvent, mercapto carbon nanotube, styrene, dispersant polyvinyl alcohol and initiator azobisisobutyronitrile into a conical flask, heating to 70-80 ℃, stirring at a constant speed for reaction for 6-12h, performing centrifugal separation, washing with distilled water and drying to obtain mercapto carbon nanotube modified polystyrene, wherein the mercapto carbon nanotube modified polystyrene is applied to high dielectric materials.

Preferably, the reflux reaction device in step (1) includes the magnetic heating agitator, the inside magnetic heating agitator that is provided with of magnetic heating agitator, the inside swing joint of magnetic stirring agitator has the bearing, bearing swing joint has the rotation axis, rotation axis fixedly connected with rotor, rotor top fixedly connected with magnet, the inside both sides of magnetic stirring agitator are provided with the heating plate, the magnetic stirring agitator top is a erlenmeyer flask, erlenmeyer flask swing joint has the condenser pipe, delivery port and lower water inlet on the condenser pipe fixedly connected with.

Preferably, the mass ratio of the thionyl chloride to the carboxyl carbon nanotubes in the step (2) is 50-100: 1.

Preferably, the mass ratio of the acyl chloride thiolated carbon nanotube, the triethylamine and the 2-mercaptoethanol in the step (3) is 1:50-80: 150-.

Preferably, the mass ratio of the thiolated carbon nanotubes to the styrene to the polyvinyl alcohol to the azobisisobutyronitrile in the step (4) is 0.3-1:100:1.5-3.5: 5-8.

Drawings

FIG. 1 is a schematic view of a water bath reaction apparatus;

FIG. 2 is a schematic top view of the stage;

fig. 3 is a schematic top view of the stage.

1-magnetic heating stirrer; 2-a magnetic stirrer; 3-a bearing; 4-a rotating shaft; 5-a rotating sheet; 6-a magnet; 7-heating plate; 8-conical flask; 9-a condenser pipe; 10-upper water outlet; 11-lower water inlet.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the sulfhydrylation carbon nano tube modified polystyrene is activated by mixed acid of concentrated sulfuric acid and concentrated nitric acid to obtain a carboxyl carbon nano tube, the carboxyl carbon nano tube contains rich carboxyl, the carboxyl is reacted with thionyl chloride to obtain an acyl chloride carbon nano tube, and an acyl chloride group is reacted with hydroxyl of 2-mercaptoethanol to obtain the sulfhydrylation carbon nano tube so as to realize functional surface modification of the carbon nano tube.

According to the sulfhydrylation carbon nano tube modified polystyrene, in the styrene emulsion polymerization process, sulfhydrylation of the sulfhydrylation carbon nano tube and alkenyl of styrene are subjected to sulfhydryl-alkenyl click reaction, so that the carbon nano tube is organically combined with the polystyrene through a covalent bond, the interface bonding force and affinity of the carbon nano tube and the polystyrene are obviously improved through the modification effect of a chemical covalent bond, the phenomena of non-uniform dispersion and agglomeration of the carbon nano tube in a polystyrene matrix are avoided, the carbon nano tube with excellent conductivity and mechanical property is highly dispersed and serves as a chemical crosslinking site, the dielectric property and mechanical strength of the polystyrene are obviously improved, and the practical use of the high dielectric material of the polystyrene is widened.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the sulfhydrylation carbon nano tube modified polystyrene comprises the following steps:

(1) adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding a carbon nano tube, after ultrasonic dispersion is uniform, placing the mixture into a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is arranged inside the magnetic heating stirrer, a bearing is movably connected inside the magnetic stirring stirrer, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, a magnet is fixedly connected above the rotating sheet, heating sheets are arranged on two sides inside the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condenser pipe, the condenser pipe is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 85-95 ℃, stirring reaction is carried out for 2-8h at a constant speed, adding distilled water for dilution, carrying out centrifugal separation, washing and drying.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 50-100:1 into a conical flask, heating to 60-80 ℃, stirring at a constant speed, refluxing for reaction for 12-24h, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, heating to 40-60 ℃ at the mass ratio of 1:50-80:150-250, carrying out reflux reaction for 24-36h, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding distilled water solvent, mercapto carbon nanotube, styrene, dispersant polyvinyl alcohol and initiator azobisisobutyronitrile in the mass ratio of 0.3-1:100:1.5-3.5:5-8 into a conical flask, heating to 70-80 ℃, uniformly stirring for reaction for 6-12h, centrifugally separating, washing with distilled water and drying to obtain the mercapto carbon nanotube modified polystyrene, which is applied to high dielectric materials.

Example 1

(1) Adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding carbon nano tubes, after ultrasonic dispersion is uniform, placing the mixture in a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is internally provided with the magnetic stirring, the magnetic stirring stirrer is internally and movably connected with a bearing, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, magnets are fixedly connected with the upper part of the rotating sheet, heating sheets are arranged on two sides of the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condenser pipe, the condenser pipe is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 85 ℃, stirring reaction is carried out for 2 hours at a constant speed, adding distilled water for dilution, centrifugal separation, washing.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 50:1 into a conical flask, heating to 60 ℃, stirring at a constant speed, refluxing for reaction for 12 hours, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, wherein the mass ratio of the three components is 1:50:150, heating to 40 ℃, carrying out reflux reaction for 24 hours, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding distilled water solvent, mercapto carbon nanotube, styrene, dispersant polyvinyl alcohol and initiator azobisisobutyronitrile in the mass ratio of 0.3:100:1.5:5 into a conical flask, heating to 70 ℃, stirring at a constant speed for reaction for 6 hours, performing centrifugal separation, washing with distilled water, and drying to obtain the mercapto carbon nanotube modified polystyrene 1.

Example 2

(1) Adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding carbon nano tubes, after ultrasonic dispersion is uniform, placing the mixture in a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is internally provided with the magnetic stirring, the magnetic stirring stirrer is internally and movably connected with a bearing, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, magnets are fixedly connected with the upper part of the rotating sheet, heating sheets are arranged on two sides of the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condenser pipe, the condenser pipe is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 85 ℃, stirring reaction is carried out for 4 hours at a constant speed, adding distilled water for dilution, centrifugal separation, washing.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 65:1 into a conical flask, heating to 70 ℃, stirring at a constant speed, refluxing for reaction for 18 hours, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, wherein the mass ratio of the three components is 1:60:180, heating to 50 ℃, carrying out reflux reaction for 36 hours, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding a distilled water solvent, a thiolated carbon nanotube, styrene, a dispersant polyvinyl alcohol and an initiator azobisisobutyronitrile in a mass ratio of 0.5:100:2:6 into a conical flask, heating to 75 ℃, stirring at a constant speed for reaction for 10 hours, performing centrifugal separation, washing with distilled water, and drying to obtain the thiolated carbon nanotube modified polystyrene 2.

Example 3

(1) Adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding carbon nano tubes, after ultrasonic dispersion is uniform, placing the mixture in a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is internally provided with the magnetic stirring, the magnetic stirring stirrer is internally and movably connected with a bearing, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, magnets are fixedly connected with the upper part of the rotating sheet, heating sheets are arranged on two sides of the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condensing tube, the condensing tube is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 90 ℃, stirring reaction is carried out for 4 hours at a constant speed, adding distilled water for dilution, centrifugal separation, washing.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 80:1 into a conical flask, heating to 70 ℃, stirring at a constant speed, refluxing for reaction for 18 hours, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, wherein the mass ratio of the three components is 1:70:220, heating to 50 ℃, carrying out reflux reaction for 30h, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding distilled water solvent, mercapto carbon nanotube, styrene, dispersant polyvinyl alcohol and initiator azobisisobutyronitrile in the mass ratio of 0.8:100:2.8:7 into a conical flask, heating to 75 ℃, stirring at a constant speed for reaction for 10 hours, performing centrifugal separation, washing with distilled water, and drying to obtain the mercapto carbon nanotube modified polystyrene 3.

Example 4

(1) Adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding carbon nano tubes, after ultrasonic dispersion is uniform, placing the mixture in a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is internally provided with the magnetic stirring, the magnetic stirring stirrer is internally and movably connected with a bearing, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, a magnet is fixedly connected with the upper part of the rotating sheet, heating sheets are arranged on two sides of the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condensing tube, the condensing tube is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 95 ℃, stirring reaction is carried out for 8 hours at a constant speed, adding distilled water for dilution, centrifugal separation.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 100:1 into a conical flask, heating to 80 ℃, stirring at a constant speed, refluxing for reaction for 24 hours, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, wherein the mass ratio of the three components is 1:80:250, heating to 60 ℃, carrying out reflux reaction for 36 hours, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding a distilled water solvent, a thiolated carbon nanotube, styrene, a dispersant polyvinyl alcohol and an initiator azobisisobutyronitrile in a mass ratio of 1:100:3.5:8 into a conical flask, heating to 80 ℃, stirring at a constant speed for reaction for 12 hours, performing centrifugal separation, washing with distilled water, and drying to obtain the thiolated carbon nanotube modified polystyrene 4.

Comparative example 1

(1) Adding concentrated sulfuric acid and concentrated nitric acid mixed solution into a conical flask, adding carbon nano tubes, after ultrasonic dispersion is uniform, placing the mixture in a reflux reaction device, wherein the reflux reaction device comprises a magnetic heating stirrer, the magnetic heating stirrer is internally provided with the magnetic stirring, the magnetic stirring stirrer is internally and movably connected with a bearing, the bearing is movably connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating sheet, magnets are fixedly connected with the upper part of the rotating sheet, heating sheets are arranged on two sides of the magnetic stirring device, the conical flask is arranged above the magnetic stirring device, the conical flask is movably connected with a condensing tube, the condensing tube is fixedly connected with an upper water outlet and a lower water inlet, heating is carried out to 85 ℃, stirring reaction is carried out for 8 hours at a constant speed, adding distilled water for dilution, centrifugal separation, washing.

(2) Adding thionyl chloride and carboxyl carbon nano-tubes in a mass ratio of 30:1 into a conical flask, heating to 70 ℃, stirring at a constant speed, refluxing for reaction for 18 hours, distilling under reduced pressure, washing with ethanol, and drying to obtain the acyl chloride carbon nano-tubes.

(3) Adding a dichloromethane solvent and an acyl chloride sulfhydrylation carbon nano tube into a conical flask, adding triethylamine and 2-mercaptoethanol after uniform ultrasonic dispersion, wherein the mass ratio of the three components is 1:40:120, heating to 50 ℃, carrying out reflux reaction for 36 hours, carrying out centrifugal separation to remove the solvent, washing with ethanol, and drying to obtain the sulfhydrylation carbon nano tube.

(4) Adding a distilled water solvent, a thiolated carbon nanotube, styrene, a dispersant polyvinyl alcohol and an initiator azobisisobutyronitrile in a mass ratio of 0.1:100:1:4 into a conical flask, heating to 80 ℃, stirring at a constant speed for reaction for 6 hours, performing centrifugal separation, washing with distilled water, and drying to obtain the thiolated carbon nanotube modified polystyrene comparison 1.

Dielectric property test meter for sulfhydrylation carbon nano tube modified polystyrene material

Item	Testing frequency	Dielectric constant	Dielectric loss
				Example 1	100Hz	22.6	0.168KHz
Example 2	100Hz	29.7	0.117KHz
				Example 3	100Hz	31.7	0.092KHz
Example 4	100Hz	24.0	0.157KHz
				Comparative example 1	100Hz	11.2	0.579KHz

Mechanical property test meter for sulfhydrylation carbon nano tube modified polystyrene material