TWI579307B - Preparation method and device for composite material of graphene and styrene monomer - Google Patents

Description

Composite material manufacturing method of graphene and styrene monomer and device thereof

The invention relates to a new continuous production mode of composite material manufacturing technology, in particular to a graphite ion and styrene monomer in ultrasonic operation and subsequent processes, so as to achieve specific mass production of graphene and benzene A composite suspension of ethylene monomer and a method and apparatus for producing solid particles of graphene and polystyrene composite after polymerization.

According to the styrene monomer (Styrene Monomer/SM) is a liquid organic compound which is firstly alkylated from benzene (Benzene) and ethylene (Ethylene) to form ethylbenzene (Ethylbenzene). It is formed after hydrogen reaction. Styrene monomer (SM) is an important intermediate material in the petrochemical industry and can be used to produce polystyrene plastic (PS), acrylonitrile-butadiene-styrene plastic (ABS), latex (SBL), styrene/butyl Ethylene rubber (SBR), unsaturated polyester (UPS), AS resin, SBS rubber, etc. These composite materials are widely used in the production of rubber, plastics, insulating materials, fiberglass, automobiles, hulls, food containers and carpets. Since composite materials formed by styrene monomer as a substrate have been widely developed and utilized, their material properties are mostly fixed, and styrene monomer is used in response to the development of a larger field required for the rapid development of science and technology. The continued research and development of derived composite materials is still necessary.

Furthermore, graphite is a crystalline structure composed of a plurality of graphenes, and graphene is a single-layered graphite structure in which a sp ² crystal structure is bonded to three adjacent carbon atoms. And extending into a honeycomb hexagonal two-dimensional structure, is a near-transparent nanomaterial, although it is only one atom thick, but it is 200 times stronger than steel, good conductivity, and even predict the application of graphene. It can flip the semiconductor industry dominated by 矽. At present, graphene has been widely used in the fields of semiconductors, touch panels or solar cells, and is expected to be widely used in the development of many industrial fields such as photovoltaic, green power generation, environmental biomedical sensing, and composite functional materials.

The development of composite materials derived from graphene is also the focus of research and development in various industries. If combined with styrene monomer and new composite materials, it will be able to expand the application range of styrene composite materials, and break through the progress and acceleration of new technology fields. achieve.

Therefore, the present inventors have in view of the fact that the combination of two material properties of graphene and styrene monomer which can be effectively combined into a composite material can initiate an updated application field, that is, to start research and development of a solution, and hope to develop a kind of solution. A new manufacturing method and device for graphene and styrene monomer composites and graphene and polystyrene composite particles capable of mass production, wide application of composite materials and economic benefits, to promote the industry The development of the present invention has been made by the idea of a long time.

The object of the present invention is to provide a composite material of graphene and styrene monomer and a novel manufacturing method and device thereof for graphene and polystyrene composite particles, and to combine graphene with styrene monomer and graphite. Alkene and polystyrene composites are available in a mass-produced manner and achieve excellent production economics.

A further object of the present invention is to provide a method for fabricating a composite material of graphene and styrene monomer and a device thereof, which can mix graphite fragments and styrene monomer by an effective method to produce graphene and benzene. The composite materials of ethylene monomer and polystyrene are actively expanding the application range of composite materials of styrene and its derived graphene.

In order to achieve the above object, the method comprises the steps of: mixing a plurality of graphite fragments with a liquid of a styrene monomer to form a mixture of graphite fragments and styrene monomers; and the graphite chips and the styrene single The mixture of the body is subjected to ultrasonic irradiation, so that the graphite fragments form a phase-separated layer of graphene, and the styrene monomer is embedded and intercalated to obtain a first form of graphene and styrene. Monomer composite, the first The composite material of graphene and styrene monomer in one form is an emulsion mixture, and is referred to as SMG (Styrene Monomer grapheme, SMG for short) in the first form.

The above method is carried out in a non-brightness environment, and the temperature thereof is controlled to be lower than the temperature at which the styrene monomer generates a polymerization reaction.

In the above method, ultrasonic vibration is applied to the composite material of the graphene and the styrene monomer in the first form, and the styrene monomer is stripped and delaminated to the small layer graphene, so that the small layer of graphene is sufficiently Forming a single layer of graphene, and then obtaining a composite material of graphene and styrene monomer in a second form, wherein the composite material of graphene and styrene monomer in the second form is an emulsion mixture, in the present invention It is called SMG (Styrene Monomer grapheme, SMG for short).

The method further includes continuing the atomization of the composite material of the graphene and the styrene monomer in the first form to the ultrasonic atomizer, heating to polymerize the styrene to form polystyrene, and drying the powder to form a granule. The polystyrene is coated with a small layer of graphene composite material, and the polystyrene-coated small layer graphene composite material is in the form of powder particles, and is referred to as PSG (Polystyrene grapheme, PSG for short) in the first form.

The method further includes continuing the atomization of the composite material of the graphene and the styrene monomer in the second form to the ultrasonic atomizer, heating to polymerize the styrene to form polystyrene, and drying the powder to form a granule. The polystyrene-coated single-layer graphene composite material is in the form of powder particles, and is referred to as PSG (Polystyrene grapheme, PSG for short) in the second form.

The method further includes the atomization of the composite material of the first form of graphene and styrene monomer and the polymer monomer, followed by atomization of the ultrasonic atomizer, heating to polymerize styrene and the polymer monomer to form a polymer. And granulating with dry powder to form a polymer-coated small layer graphene composite material, the polymer wrapped with a small layer of graphene composite material is in the form of powder particles, which is referred to as the first form of HPSG in the present invention. (Hybrid Polystyrene grapheme, abbreviated as HPSG), wherein the high molecular monomer comprises acrylonitrile, butadiene , or a combination thereof.

In the above method, the polymer monomer is butadiene , and the polymer forming a polymer-coated graphene-less composite material is Styrene-Butadiene Rubber (SBR).

The above method, wherein the polymer monomer is acrylonitrile and butadiene , wherein a polymer forming a polymer-coated graphene-less composite is an ABS resin ( acrylonitrile - butadiene - styrene copolymer, ABS is the acronym for Acrylonitrile Butadiene Styrene).

The method further includes the atomization of the composite material of the second form of graphene and the styrene monomer and the polymer monomer, followed by atomization of the ultrasonic atomizer, heating to polymerize the styrene and the polymer monomer to form a polymer. And granulating with dry powder to form a polymer-coated single-layer graphene composite material, the polymer-coated single-layer graphene composite material is in the form of powder particles, which is referred to as the second form of HPSG in the present invention. (Hybrid Polystyrene grapheme, abbreviated as HPSG), wherein the high molecular monomer comprises acrylonitrile, butadiene , or a combination thereof.

In the above method, the polymer monomer is butadiene , and the polymer forming a polymer-coated monolayer graphene composite is Styrene-Butadiene Rubber (SBR).

The above method, wherein the polymer monomer is acrylonitrile and butadiene , and the polymer forming a composite of a polymer-coated single-layer graphene is an ABS resin ( acrylonitrile - butadiene - styrene copolymer, ABS is the acronym for Acrylonitrile Butadiene Styrene).

The technical means of the present invention comprises: an ultrasonic oscillating device provided with an ultrasonic electric power and a frequency output member, the ultrasonic electric power and the end of the frequency output member being coupled to an ultrasonic actuator; a cooler comprising a cooling a charging slot is disposed in the cooling cylinder, and the ultrasonic actuator extends into or acts on the preparation slot, and the preparation slot is provided with at least one feeding port and a discharging port, the feeding port It is used for inputting a graphite agent and a styrene monomer suspended in an aqueous liquid and a starter, a catalyst, a suspending agent and a stabilizer required for promoting the reaction, so that the graphite chip and the styrene are formed in the preparation tank. a mixture of monomers; a storage tank connected to the discharge port by a feed pipe.

The foregoing structure further includes a motor and a supply tank, the motor is connected to the feed port by a feed pipe, and the supply tank is in communication with the feed pipe, and the supply tank is stored with a suspension The graphite chips in the aqueous liquid and the styrene monomer and the initiator, catalyst, suspending agent and stabilizer required for promoting the reaction are input into the feed port, and the supply tank is provided with a first valve to Switch whether to enter it into the feed port.

In the above configuration, the storage tank further includes a circulating pipe connected to the feeding pipe or the feeding port, and the feeding pipe is provided with a second valve.

The technical means of the present invention further includes: a storage tank in which an emulsion-like composite suspension of graphene and styrene monomer is disposed, the storage tank is provided with a product pipeline, and the product pipeline is provided a motor; a polymerization reaction cooling the tank, the polymerization reactor is provided with a connected ultrasonic atomizer at the top of the cooling tank, and the product pipeline is connected to the polymerization cooling tank through the ultrasonic atomizer. After the polymerization reaction, a row of outlets is arranged at the bottom of the cooling tank, and the discharge port is connected to a discharge pipe; an air heater is connected to the ultrasonic atomizer by a heating pipe; and a separator is connected to the discharge pipe, The separator is connected with a row of hot gas pipes connected to a motor, and the separator is provided with a bag filter; the foregoing structure, the emulsion of the emulsified composite of graphene and styrene monomer is passed through the ultrasonic atomizer After atomization to form a granule, after the polymerization, the cooling tank is heated to cause polymerization of the originally styrene monomer, and graphene is simultaneously formed. Wherein the wrap, and the dried particles, forming a second aspect of the PSG.

In the above configuration, a filter is disposed at the discharge port of the cooling cylinder after the polymerization, and a collector is provided in the subsequent portion of the separator.

The technical means of the present invention further includes: a storage tank in which a composite material of graphene, styrene monomer and polymer monomer is disposed, the storage tank is provided with a product pipeline, and the product pipeline is a motor is provided; a polymerization reaction cooling tank is provided with a liquid for adding a starter, a catalyst, a suspending agent and a stabilizer in the water to promote the reaction, and the top of the cooling tank is provided with a a connected ultrasonic atomizer, the pipeline of the product is connected to the cooling tank after the polymerization by the ultrasonic atomizer, and a row of outlets is arranged at the bottom of the cooling tank after the polymerization, and the circumference of the cooling tank is cooled after the polymerization reaction Cooling pipe is arranged around; an air heater is connected to the ultrasonic atomizer by a heating pipe; a filter separation tank, the filter separation tank is connected to the discharge port of the cooling cylinder tank by a filter inlet pipe, the filter separation tank is provided with a filter net, and the bottom of the filter separation tank is provided with a liquid discharge port; In the above configuration, the emulsified composite material of the graphene and the styrene monomer plus the polymer monomer is atomized by the ultrasonic atomizer, and then heated in the ultrasonic atomizer and the cooling tank after the polymerization reaction. The styrene monomer and the polymer monomer are polymerized to be pelletized.

In the above configuration, the polymer monomer to be separately polymerized and compounded may be acrylonitrile, butadiene or a combination thereof.

For a better understanding and understanding of the technical, methodological features and efficacies of the present invention, the preferred embodiment and the detailed description are as follows:

10‧‧‧ graphite fragments

11‧‧‧ graphite layer

12‧‧‧ Graphene

20‧‧‧styrene monomer

21‧‧‧Composite (SMG) products

30‧‧‧ preparation slot

22‧‧‧Composite (HSMG) products

40‧‧‧Ultrasonic oscillator

401‧‧‧Ultrasonic electric power and frequency output parts

41‧‧‧Ultrasonic Actuator

50‧‧‧cooler

51‧‧‧Preparation slots

511‧‧‧ Feed inlet

512‧‧‧Outlet

52‧‧‧Cooling cylinder

520‧‧‧Ultrasonic Actuator

521‧‧‧ Coolant outlet

522‧‧‧ coolant inlet

53‧‧‧Motor

531‧‧‧ Feeding tube

54‧‧‧ storage tank

541‧‧‧Transport tube

542‧‧‧Circulation tube

543‧‧‧Second valve

55‧‧‧Motor

551‧‧‧Product piping

56‧‧‧ sprayer

57‧‧‧ Supply slot

571‧‧‧First valve

60‧‧‧Polymerization Ultrasonic Spray and Powder Granulation Unit

61‧‧‧Polymerization tank

611‧‧‧ bucket

612‧‧‧Export

613‧‧‧Filter

614‧‧‧Draining tube

62‧‧‧Air heater

621‧‧‧heating line

63‧‧‧Motor

631‧‧‧Exhaust air pipe

64‧‧‧Separator

641‧‧‧ bag filter

65‧‧‧ collection trough

70‧‧‧Polymerization powder granulation device

71‧‧‧Cooling the trough after polymerization

711‧‧‧Export

72‧‧‧Filter separation tank

721‧‧‧Filter into the tube

722‧‧‧Draining port

723‧‧‧Filter

73‧‧‧ Cooling tube

731‧‧‧ Coolant inlet

Fig. 1A is a schematic view showing the mixing of graphite chips and styrene according to the present invention.

Fig. 1B is a schematic view showing the embedding of graphite fragments of the present invention.

Fig. 1C is a schematic view showing the layering of the graphite layer of the present invention.

2A-D are schematic views of the ultrasonic operation of the present invention.

Figure 3 is a schematic view of the apparatus of the present invention.

Figure 4 is a partial schematic view of the apparatus of the present invention.

Figure 5 is a schematic view of the granulation operation of the present invention.

Figure 6 is a schematic view 2 of the granulation operation of the present invention.

Figure 7 is a schematic flow chart of the process method of the present invention.

The drawings are intended to facilitate the description of the present invention, and the manufacturing method and apparatus of the present invention are only illustrated in a schematic manner, and the illustrated drawing is not limited to the shape, the aspect and the size of the actual implementation. The ratio, the shape, the aspect and the size ratio in actual implementation are a selective design.

1A to 2D are diagrams showing a basic implementation of a method for fabricating a composite material of graphene and styrene monomer and a device thereof; as shown in FIGS. 1A and 2A, the present invention is a plurality of graphite fragments 10 and benzene. The liquid phase of the ethylene monomer 20 is mixed, and the mixture of the graphite chip 10 and the styrene monomer 20 is placed in a preparation tank 30. Since the graphite chip 10 is light in weight, it floats on the styrene. Above the liquid of the monomer 20, wherein the graphite fragment 10 can be: natural graphite, synthetic graphite, graphitic carbon black, furnace black (furnace black) ), a combination of mesocarbon microbead/MCMB or highly oriented graphite sheet (HOGS) or a combination thereof. As shown in Fig. 2B, the mixture of the graphite chip 10 and the styrene monomer 20 is subjected to ultrasonic vibration/irradiation, i.e., ultrasonic vibration/irradiation operation is performed by an ultrasonic oscillating device 40, and the ultrasonic wave is irradiated/irradiated. The oscillating device 40 is extended into the mixed liquid by an ultrasonic actuator 41 (or other member having ultrasonic vibration). As the ultrasonic vibration/irradiation operation proceeds, the mixture of the graphite fragments 10 and the styrene monomer 20 will form an emulsification reaction, and the styrene monomer 20 is gradually embedded in the graphite fragments 10 and the layers and layers thereof. In the meantime, the plurality of graphite layers 11 are intercalated (see FIGS. 1B and 2C), and a small amount of single-layer graphene 12 is produced at this time, and the first form of graphene is obtained. The composite material of the styrene monomer, the composite material of the graphene and the styrene monomer of the first form is referred to as the first form of SMG (Styrene Monomer grapheme, SMG for short) in the present invention, and the first form of graphite The composite material of olefin and styrene monomer (SMG) is mainly formed by intercalation of styrene monomer 20 to graphite layer 10, including graphite layer 11 and graphene 12, but has not been completely removed. Exfoliated, as detailed later, that is, the graphite chip 10 is not completely monolayer graphene, and the first form of the graphene and styrene monomer composite (SMG) is emulsified and liquid, which has been Can be selected as a material for a specific use use.

Following the operation of ultrasonic vibration/irradiation of the composite material (SMG) of the first form of graphene and styrene monomer, as shown in the first C, 2D, the delamination and emulsification reactions are continued, and The styrene monomer 20 is subjected to an operation of removing/extracting the graphite layer 11 formed by the graphite fragments 10, at which time the graphite layer 11 of the graphite fragments 10 is subjected to an exfoliation treatment. Fully single layer graphene, and the graphene 12 will be uniformly dispersed in the benzene In the ethylene monomer 20, a composite material of the single-layer graphene and the styrene monomer of the second form is obtained, and the composite material of the graphene and the styrene monomer of the second form is referred to as the second form in the present invention. SMG (Styrene Monomer grapheme, SMG for short), and the second aspect of the composite of graphene and styrene monomer (SMG) is mainly an effluent between the graphite layers of the styrene monomer 20 and the graphite fragments 10 Formed, and the second form of the composite of graphene and styrene monomer (SMG) is also emulsified liquid, which can be used as a material for specific applications, such as products that are more prominent in graphene properties.

When the mixture of the plurality of graphite fragments 10 and the styrene monomer 20 is subjected to ultrasonic vibration/irradiation operation, the intensity and time of ultrasonic vibration/irradiation are controlled according to requirements, for example, to form the first form. The composite of graphene and styrene monomer (SMG) has weak ultrasonic vibration/irradiation and can be shorter in time; and the composite of graphene and styrene monomer (SMG) to form the second form Ultrasonic vibration/irradiation is stronger and the time can be longer. In addition, the composite of the plurality of graphite fragments 10 and the styrene monomer 20 or the composite material of the first form of graphene and styrene monomer (SMG) is subjected to ultrasonic vibration/irradiation operation without brightness ( The luminosity is carried out in an environment (e.g., a closed vessel/equipment), and the temperature thereof is controlled below the polymerization temperature of the styrene monomer 20, for example, 40 ° C or lower, in order to avoid polymerization of the styrene monomer.

Please refer to FIG. 3 and FIG. 4 together to illustrate a manufacturing apparatus for a composite material of graphene and styrene monomer according to the present invention, which comprises an ultrasonic oscillating device 40, a cooler 50, an emulsification preparation tank 51 and a storage tank 54; The ultrasonic oscillating device 40 is configured to generate ultrasonic oscillating electric power and frequency, and is provided with an ultrasonic electric power and frequency output member 401. The ultrasonic electric power and the end of the frequency output member 401 are coupled to an ultrasonic actuator 520 (transducer) And the ultrasonic actuator 520 extends into or acts on the preparation slot 51; the cooler 50 functions to provide a cooling ultrasonic actuator 520, and includes a cooling cylinder 52 for Cooling the tip of the ultrasonic actuator 520 and the preparation groove 51 for accommodating the ultrasonic wave, or the cooling cylinder 52 can form the preparation groove 51, that is, the ultrasonic emulsification preparation groove 51 is set in the cooling The cooling cylinder 52 is provided with a coolant outlet 521 and a coolant inlet 522. The coolant outlet 521 and the coolant inlet 522 are connected to the cooler 50. Further, the preparation tank 51 is provided with a inlet. Feed port 511 and discharge port 51 2, the feed port 511 is used to input an initiator, a catalyst, a suspending agent and a stabilizer required to provide graphite fragments 10 and styrene monomer 20 suspended in an aqueous liquid and to promote a reaction (stabilizing) An emulsified mixture of the graphite chips 10 and the styrene monomer 20 is formed in the preparation tank 51; and a motor 53, the motor 53 is connected to the feed port 511 by a feed pipe 531. The auxiliary force for inputting the material of the preparation tank 51 is provided; and the storage tank 54 is connected to the discharge port 512 by a delivery pipe 541. In addition, a supply tank 57 is connected to the feed pipe 531, and the supply tank 57 stores the graphite chips 10 suspended in the water liquid and the styrene monomer 20 and the initiator required for promoting the reaction ( An initiator), a catalyst, a suspending agent, and a stabilizing agent to input the feed port 511, and the supply tank 57 is provided with a first valve 571 to switch whether to input it The feed port 511.

The aforementioned initiator may be, for example, benzoyl peroxide, and the catalyst may be, for example, a peroxide, the suspending agent, for example, may be a Methyl cellulose, ethyl cellulose, the stabilizing agent, for example, may be calcium carbonate, calcium phosphates.

As described above, the mixture of the graphite chips 10 and the styrene monomer 20 is ultrasonically operated in the preparation tank 51, and the mixture of the graphite chips 10 and the styrene monomer 20 is subjected to embedding/emulsification treatment or subsequent disassembly. Layer/emulsification treatment to form a composite material (SMG) product of graphene and styrene monomer in a first form or a second form, the composite material (SMG) product being transferred to the storage tank 54 via the discharge port 512 Collect and store.

As further shown in FIG. 3, the storage tank 54 further includes a circulating pipe 542 which is connected to the feed pipe 531 (the feed port 511). When the composite material (SMG) product in the storage tank 54 is to be further detached/emulsified, the composite material (SMG) product can be re-introduced into the preparation tank 51 through the circulation pipe 542 for ultrasonic operation. In addition, the feeding tube 531 may be provided with a second valve 543 at an appropriate position for switching the material source input to the preparation groove 51.

Referring to FIG. 5, the polymerization/powder treatment of the composite material (SMG) of graphene and styrene monomer according to the first aspect or the second aspect of the present invention is illustrated, as shown in the drawing. The invention comprises a storage tank 54, a polymerization ultrasonic spray and powder granulation device 60, a spray air heater 62 and a separator 64. The liquid emulsified composite material (SMG) product is disposed in the storage tank 54. 21, that is, a composite material (SMG) product of graphene and styrene monomer in a first form or a second form after emulsification, wherein the storage tank 54 is connected to the polymerization reaction tank tank 61 by a product line 551, which is a product line A motor 55 is provided at a suitable position for providing a draw output; the polymerization ultrasonic spray and powder granulation device 60 includes a polymerization reaction tank 61, and a top end of the polymerization reaction tank 61 is provided with a An ultrasonic ultrasonic atomizer (or centrifugal water separator) 56 is connected, and the product line 551 is communicated into the polymerization reaction tank tank 61 through the ultrasonic atomizer 56, and the lower portion of the polymerization reaction tank 61 is a bucket. The groove 611 is not limited. The bottom of the bucket groove 611 is provided with a discharge port 612. The discharge port 612 is provided with a filter 613. The discharge port 612 is connected to a discharge pipe 614 to communicate with the separator 64. The air heater 62 is A heat pipe 621 is coupled to the atomizer 56 for providing hot air for granulating and drying the composite material (SMG) product 21, that is, the composite material (SMG) product 21 is atomized by the atomizer 56, after the atomizer 56 (in the polymerization reaction tank 61) is heated by the hot air to further polymerize the styrene, that is, the styrene in the composite material (SMG) product 21 is heated to generate a polymerization reaction to form graphene-coated polyphenylene. The ethylene composite particles, and at the same time, the composite material of the polystyrene is also dried by the hot air in the polymerization reaction tank 61 to be granulated (powdered). Thus, the composite material (SMG) product 21 is completely treated in the polymerization reaction tank 61 to complete the polymerization and compositing reaction of styrene, and to heat and dry to be granulated (powdered). In other words, after the granulation (powdering) treatment of the composite material (SMG) product 21 by heating and drying, the first form SMG is formed into a polystyrene-coated graphene-less composite material, the polystyrene package The composite material of the small layer graphene is in the form of powder particles, which is referred to as PSG (Polystyrene grapheme, PSG for short) in the first form, or forms a polystyrene-coated single layer graphene in the second form. The composite material, the polystyrene-coated single-layer graphene composite material is in the form of powder particles, and is referred to as PSG (Polystyrene grapheme, PSG for short) in the present invention, and the granulation (powdering) The first form of the PSG and the second form of the PSG can be selected and applied as materials for a specific use. Furthermore, the separator 64 can be a cyclone separator, and a heat exhaust pipe 631 is connected to the upper portion of the separator 64. The exhaust gas pipe 631 is connected to a motor 63 for exhausting hot air. The separator 64 is further provided with a bag filter 641 for separating the powdered PSG from the air, and then collecting it in a collecting tank 65 for industrial application.

Referring to FIG. 6, another embodiment of the powder granulation apparatus of the present invention is different from the embodiment shown in FIG. 5 in that the storage tank 54 is provided with a composite material (composite material SMG product + high). A mixture of molecular monomers, ie, a composite material (HSMG) product 22, referred to as HSMG, in English is Hybrid Styrene Monomer grapheme, wherein HSMG includes a first form of HSMG (ie, a first form of SMG + polymer monomer mixture) And the second form of HSMG (ie, a mixture of the second form of SMG + polymer monomer); the polymerized powder granulation device 70 includes a post-polymerization cooling tank 71, and the polymerization tank is provided with a cooling tank 71 A liquid in which an initiator, a catalyst, a suspending agent, and a stabilizing agent for promoting the reaction have been added to the bottom of the liquid is provided with a row of outlets 711 at the bottom, after the polymerization A cooling pipe 73 is disposed around the cooling cylinder groove 71. The cooling pipe 73 is provided with a coolant inlet 731 for entering and leaving a cooling liquid (such as water), and a coolant outlet 732. The following parts (as follows) are provided The filter separation tank 72 is connected to the discharge port 711 of the post-polymerization cooling tank 71 by a filter inlet pipe 721. The filter separation tank 72 is provided with a filter 723, and the bottom of the filter separation tank 72 is provided. A drain 722 is provided. Thus, the composite material (HSMG) product 22 is atomized by the atomizer 56, and then heated by the hot air in the atomizer 56 (the cooling tank 71 after the polymerization reaction) to generate a polymerization reaction to form a polymer and particles. And cooling by the cooling pipe 73 reduces the temperature at the discharge port 711 to about 15 ° C, and completes the treatment of styling and polymer monomer heating spray granulation polymerization, cooling and granulation. In other words, after the granulation treatment of the composite material (HSMG) product 22 by heating and drying, the first form HSMG is formed into a first form HPSG (Hybrid Polystyrene grapheme, HPSG for short), and the first form HPSG is a polymer. The composite material of the single-layer graphene is coated, or the second form HSMG forms a second form of HPSG (Hybrid Polystyrene grapheme, referred to as HPSG), and the second form of HPSG is a polymer-coated single-layer graphene composite material. At this time, the granulated first form HPSG (or the second form HPSG) is mixed with the liquid (such as water) in the polymerization cooling tank 71, and passes through the discharge port 711 and the filter inlet pipe 721 to enter the filter separation tank. Within 72, the granulated first form HPSG (or The second form HPSG) is collected by the filter 723 and collected in the filter separation tank 72, and the liquid is discharged from the liquid discharge port 722, so that the granulated HPSG is separated from the liquid, that is, the composite material is completed (HSMG). The HPSG collection operation after polymerization, cooling and granulation of the product 22, and the first form of HPSG and the second form of HPSG after granulation (powder granulation) can be selected and applied as industrial materials for specific purposes.

The above polymer monomer is acrylonitrile (Acrylonitrile), butadiene (Butadiene) or a combination thereof.

In one embodiment, the polymer monomer is butadiene , and the polymer forming a polymer-coated graphene-less composite is Styrene-Butadiene Rubber (SBR).

In one embodiment, the polymer monomer is butadiene , and the polymer forming a polymer-coated graphene-less composite is SBS rubber (Styrene-Butadiene-Styrene, SBS).

In one embodiment, the polymer monomer is acrylonitrile and butadiene , and the polymer forming a polymer-coated graphene-free composite is ABS resin ( acrylonitrile - butadiene - styrene copolymerization). ABS is the acronym for Acrylonitrile Butadiene Styrene).

In one embodiment, the polymer monomer is butadiene , and the polymer forming a polymer-coated single-layer graphene composite is Styrene-Butadiene Rubber (SBR).

In one embodiment, the polymer monomer is butadiene , and the polymer forming a polymer-coated single-layer graphene composite is SBS rubber (Styrene-Butadiene-Styrene, abbreviated: SBS).

In one embodiment, the polymer monomer is acrylonitrile and butadiene , and the polymer forming a polymer-coated single-layer graphene composite is ABS resin ( acrylonitrile - butadiene - styrene copolymerization). ABS is the acronym for Acrylonitrile Butadiene Styrene).

As shown in FIG. 7, based on the foregoing embodiment and its control conditions, the method for manufacturing a composite material of graphene and styrene monomer of the present invention and its extended application system include:

(1) A plurality of graphite fragments are mixed with a liquid of a styrene monomer to form a mixture 101S of graphite fragments and styrene monomers.

(2) applying ultrasonic vibration to the mixture of the graphite chips and the styrene monomer, and the styrene monomer is subjected to an intercalation/intercalation operation on the graphite fragments, so that the graphite fragments are phase-separated and have a plurality of graphite layers, Graphene, thereby obtaining a emulsified composite material mixture of graphene and styrene monomer in the first form; and the composite material (SMG) of the first form of graphene and styrene monomer includes a plurality of graphite layers With less layer of graphene, but the graphite layer has not been completely de-layered/Exfoliated but not sufficiently monolayered graphene 102S.

(3) applying ultrasonic vibration to the composite material (SMG) of the first form of graphene and styrene monomer, and performing the stripping/layering operation on the graphite layer by the styrene monomer to form the graphite layer a plurality of single-layer graphene, and then a second form of the emulsified composite material mixture of graphene and styrene monomer; and the second form of the single-layer graphene and styrene monomer emulsified composite material (SMG) The graphite layer has been completely delaminated/Exfoliated and fully monolayer graphitized 103S.

(4) applying a supersonic spray and heat-drying granulation or powder granulation treatment to the emulsified composite material mixture of graphene and styrene monomer suspended in the aqueous liquid in the first form or the second form, respectively A solid composite material 104S of graphene and polystyrene (PSG) in a first form or a second form is formed.

The method for manufacturing a composite material of graphene and styrene monomer and the device thereof have the advantages of the new process and mass production implementation of the combination of graphene and styrene monomer, and achieve excellent production economic benefit; It enables the mixing of graphite chips and styrene monomer by an efficient process to produce graphene and styrene monomer/polystyrene and graphene and styrene monomer + polymer monomer / polystyrene Composite materials that are actively expanding the range of applications for styrene or derived graphene composites.

In summary, the present invention is indeed a rather excellent invention, and the invention patent application is filed according to the law; however, the above description is only a preferred embodiment of the present invention, and the technical means according to the present invention are extended. Changes are intended to fall within the scope of the patent application of the present invention.

101S‧‧‧A mixture of a plurality of graphite fragments and a styrene monomer to form a mixture of graphite fragments and styrene monomer

102S‧‧‧The ultrasonic vibration is applied to the mixture of graphite fragments and styrene monomer, so that the styrene monomer is embedded/intercalated into the graphite fragments, so that the graphite fragments form phase separation and have a plurality of graphite layers Graphene, thereby obtaining a emulsified composite material mixture of graphene and styrene monomer in the first form; and the composite material (SMG) of the first form of graphene and styrene monomer includes a plurality of graphite Layer and less layer of graphene, but the graphite layer has not been completely de-layered/Exfoliated but not fully monolayer graphene

103S‧‧‧After applying the ultrasonic vibration to the composite material (SMG) of the first form of graphene and styrene monomer, the styrene monomer is subjected to peeling/layering operation on the graphite layer to make the graphite layer Forming a plurality of single-layer graphene, and then obtaining a second form of the emulsified composite material mixture of graphene and styrene monomer; and the second form of the emulsified composite material of the single-layer graphene and styrene monomer (SMG ) The graphite layer has been completely de-layered/Exfoliated and fully monolayer graphene

104S‧‧‧ applying ultrasonic wave spray and heat drying granulation or powder granulation treatment to the emulsified composite material mixture of graphene and styrene monomer in the first form or the second form suspended in the aqueous liquid Polymerization to form a solid composite of graphene and polystyrene in a first form or a second form, respectively

Claims (14)

A method for producing a composite material of graphene and styrene monomer, which is carried out in a brightness-free environment, and whose temperature is controlled below a temperature at which a styrene monomer generates a polymerization reaction, which comprises: taking a plurality of graphite fragments Mixing with a liquid of styrene monomer to form a mixture of graphite fragments and styrene monomer; applying ultrasonic wave irradiation to the mixture of the graphite fragments and the styrene monomer to form the graphite fragments into phase-separated graphite a olefin, and allowing the styrene monomer to intercalate and intercalate the graphite shard, thereby obtaining a composite material of graphene and styrene monomer in the first form, the first form of graphene and styrene monomer The composite material is an emulsified mixed liquid, and is referred to as SMG of the first form in the present invention. The method for producing a composite material of graphene and styrene monomer according to claim 1, wherein the composite material of the first form of graphene and styrene monomer is subjected to ultrasonic vibration, and the styrene is single. The layer of the graphene is stripped and delaminated, so that the small layer of graphene sufficiently forms a single layer of graphene, and then a second form of graphene and styrene monomer composite material is obtained, the second form of graphite The composite material of the olefin and the styrene monomer is an emulsified mixed liquid, and is referred to as SMG of the second form in the present invention. The method for producing a composite material of graphene and styrene monomer according to claim 1, further comprising the atomization of the composite material of the first aspect of the graphene and the styrene monomer to the ultrasonic atomizer, heating The styrene is polymerized to form polystyrene, and the dried powder is granulated to form a composite material of polystyrene-coated graphene, and the polystyrene-coated graphene-containing composite material is in the form of powder and granules. In the present invention, it is referred to as a PSG of the first form. The method for producing a composite material of graphene and styrene monomer according to claim 2, further comprising the atomization of the composite material of the second form of graphene and styrene monomer to the ultrasonic atomizer, heating The styrene is polymerized to form polystyrene, and the dried powder is granulated to form a composite material of polystyrene-coated single-layer graphene. The composite material of the polystyrene-coated single-layer graphene is in the form of powder and granules. In the present invention, it is referred to as a PSG of the second form. The manufacturer of the composite material of graphene and styrene monomer as described in claim 1 of the patent application scope The method further comprises the atomization of the composite material of the first form of graphene and styrene monomer and the polymer monomer, followed by atomization of the ultrasonic atomizer, heating to cause polymerization of styrene and the polymer monomer to form a polymer. And a dry powder granulation treatment to form a polymer-coated small layer graphene composite material, the polymer-coated small layer graphene composite material is in the form of powder particles, which is referred to as the first form of HPSG in the present invention. Wherein the high molecular monomer comprises acrylonitrile, butadiene, or a combination thereof. The method for producing a composite material of graphene and styrene monomer according to claim 5, wherein the polymer monomer is butadiene, and a polymer of a polymer-coated graphene-containing composite material is formed. It is Styrene-Butadiene Rubber (SBR). The method for producing a composite material of graphene and styrene monomer according to claim 5, wherein the polymer monomer is acrylonitrile and butadiene, wherein a polymer-coated graphene-less composite material is formed. The polymer is ABS resin (acrylonitrile-butadiene-styrene copolymer, ABS is an acronym for Acrylonitrile Butadiene Styrene). The method for producing a composite material of graphene and styrene monomer according to claim 2, further comprising the composite material of the second form of graphene and styrene monomer and the polymer monomer, which is continuously applied to the ultrasonic atomizer. The atomization and heating cause polymerization of styrene and the polymer monomer to form a polymer, and granulated with the dried powder to form a polymer-coated single-layer graphene composite material, and the polymer encapsulates the single-layer graphene. The composite material is in the form of a powder granule, which is referred to in the present invention as a second form of HPSG, wherein the high molecular monomer comprises acrylonitrile, butadiene, or a combination thereof. The method for producing a composite material of graphene and styrene monomer according to claim 8, wherein the polymer monomer is butadiene, and a polymer of a polymer-coated single-layer graphene composite material is formed. It is Styrene-Butadiene Rubber (SBR). The method for producing a composite material of graphene and styrene monomer according to claim 8 , wherein the polymer monomer is acrylonitrile and butadiene, wherein a polymer-coated single-layer graphene composite material is formed. The polymer is ABS resin (acrylonitrile-butadiene-styrene copolymer, ABS is an acronym for Acrylonitrile Butadiene Styrene). The manufacturer of the composite material of graphene and styrene monomer as described in claim 7 of the patent application scope The method further comprises a composite material manufacturing device of graphene and styrene monomer, the manufacturing device comprising: an ultrasonic oscillating device, which is provided with an ultrasonic electric power and frequency output member, the ultrasonic electric power and the end of the frequency output member Attaching an ultrasonic actuator; a cooler comprising a cooling cylinder; a preparation slot is disposed in the cooling cylinder, and the ultrasonic actuator extends into or acts on the preparation slot, the preparation slot Providing at least one inlet port and a discharge port for inputting a graphite chip and a styrene monomer suspended in the water liquid and a starter, a catalyst, a suspending agent and a stabilizer required for promoting the reaction And a mixture of the graphite chips and the styrene monomer is formed in the preparation tank; a storage tank is connected to the discharge port by a feed pipe. The method for manufacturing a composite material of graphene and styrene monomer according to claim 11, further comprising a motor and a supply tank, wherein the motor is connected to the feed port by a feed pipe, the supply tank In communication with the feed pipe, the supply tank stores graphite fragments and styrene monomer suspended in the aqueous liquid and a starter, a catalyst, a suspending agent and a stabilizer required for promoting the reaction to be input into the feed. a supply port and a first valve for switching whether to input the inlet port, wherein the storage tank further comprises a circulating pipe connected to the feed pipe or the feed pipe The inlet pipe is provided with a second valve. The method for producing a composite material of graphene and styrene monomer according to claim 12, further comprising a powder granulation manufacturing device of a composite material of graphene and styrene monomer, wherein the powder granulation manufacturing device comprises a storage tank in which an emulsion-like composite suspension of graphene and styrene monomer is disposed, the storage tank is provided with a product pipeline, and a motor is arranged on the pipeline; after a polymerization reaction Cooling the tank, after the polymerization, the top of the cooling tank is provided with a connected ultrasonic atomizer, and the product pipeline is connected through the ultrasonic atomizer into the cooling tank after the polymerization, and the bottom of the tank is cooled after the polymerization Is provided with a row of outlets, the outlet is connected to a discharge pipe; An air heater is connected to the ultrasonic atomizer by a heating pipe; a separator is connected to the discharge pipe, and the separator is connected with a row of hot gas pipes connected to a motor, and the separator is connected to a motor. a bag filter is provided; in the foregoing configuration, the emulsified composite suspension of graphene and styrene monomer is atomized by the ultrasonic atomizer to form a granule, and then heated in the cooling cylinder after the polymerization reaction to make the original The liquid styrene monomer is polymerized, and the graphene is wrapped therein, dried and granulated to form a second form of PSG, wherein a filter is arranged at the discharge port of the cooling cylinder after the polymerization reaction. The collector is provided with a collecting groove at the subsequent portion. The method for producing a composite material of graphene and styrene monomer according to claim 12, further comprising a powder granulation manufacturing device of a composite material of graphene and styrene monomer, comprising: a storage tank, The storage tank is provided with a composite material of graphene, styrene monomer and polymer monomer, the storage tank is provided with a product pipeline, the product pipeline is provided with a motor; after the polymerization reaction, the cooling cylinder tank is cooled. The liquid in the water is added with a starter, a catalyst, a suspending agent and a stabilizer which are required to promote the reaction. After the polymerization, a supersonic sprayer is connected to the top of the cooling tank, and the product is pipelined. Through the ultrasonic atomizer, the cooling tank is connected to the polymerization reactor. After the polymerization, a row of outlets is arranged at the bottom of the cooling tank, and a cooling pipe is arranged around the cooling tank after the polymerization reaction; an air heater is arranged. Connected to the ultrasonic atomizer by a heating pipe; a filter separation tank connected to the discharge port of the cooling tank after the polymerization by a filter inlet pipe, the filtration A filter screen is disposed in the groove, and a liquid discharge port is arranged at the bottom of the filter separation groove; in the foregoing configuration, the emulsified composite material of the graphene and the styrene monomer and the polymer monomer is passed through the ultrasonic atomizer sprayer. After the polymerization, the ultrasonic atomizer is heated in the cooling tank after the polymerization reaction to granulate the styrene monomer and the polymer monomer, wherein the polymer monomer is acrylonitrile (Acrylonitrile). Butadiene (Butadiene) or a combination of the above.