Patent
US 10,364,334Patent
Atlas literature
Patent
US 10,364,334Patent drawings and their descriptions. Click a drawing to enlarge it.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
Resistance tests on the test samples The test samples were tested after being washed for 100 times, according to the National Standard GB₁₂₀₁₄-2009 "STATIC PROTECTIVE CLOTHING ". The test results are shown in Table 1.
The continuous production equipment according to any one of claims 1 to 5, characterized in that an ultrasonic disperser is provided in the extract tank.
The continuous production equipment according to any one of claims 1 to 6, characterized in that the raw material preparation device further comprises an auxiliary material tank in which a high-shear emulsifying machine and an ultrasonic disperser are provided.
Bacteriostasis rate tests on the test samples The test samples were tested against staphylococcus aureus and candida albicans, respectively, after being washed for 5 times, according to the National Standard GB 20944.3-2008 "TEXTILES-EVALUATION FOR ANTIBACTERIAL ACTIVITY". The test results are shown in Table 1.
Far infrared radiation tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₃₀₁₂₇-2013 "TEXTILES-TESTING AND EVALUATION FOR FAR INFRARED RADIATION PROPERTIES". The test results are shown in Table 1.
Solar ultraviolet radiation protective properties tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₁₈₈₃₀-2009 "TEXTILES-EVALUATION FOR SOLAR ULTRAVIOLET RADIATION PROTECTIVE PROPERT IE S". The test results are shown in Table 1.
Burning characteristics tests on the test samples Five block samples, having a size of 8cmx lcmx0.4cm, from each test sample were tested, according to the National Standard GB₂₄₀₈-2008 "PLASTICS-DETERMINATION OF BURNING CHARACTERISTICS-HORIZONTAL AND VERTICAL TEST". The test results are shown in Table 2, wherein t i denotes the first afterf l ame time, t 2 denotes the second afterf l ame time, and t 3 denotes the third afterf l ame time. Table 1: Results of Performance Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.1.svg 4.2 6.43 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.2.svg 1.33 6.43 Black and white Table 2: Results of Burning Characteristics Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.3.svg 7.55 7.1 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.4.svg 0.91 7.1 Black and white It can be known from Table 1 that the graphene composite material according to Embodiment 2 of the present invention has a resistance up to 1.7 x106Q. It is material with good antistatic property. Meanwhile, it has excellent bacteriostasis effect against staphylococcus aureus and candida albicans, with a bacteriostasis rate greater than 99 %. This graphene composite material is also a good far infrared radiation textile, with a far infrared emissivity up to 0.92 and a far infrared radiation temperature rise of 1.6° C. In addition, this graphene composite material also has excellent solar ultraviolet radiation protective properties, with an UPF (Ultraviolet Protection Factor) greater than 50 %. In addition, it can be known from the data from Embodiments 2 to 4 that products produced by the high-shear emulsifying machine and the ultrasonic disperser during the preparation have better overall performance. It can be known from the data from Embodiments 5 to 6 that products produced by dispersing and peeling the graphene in a liquid during the preparation have better over performance than that of products produced without this operation. It can be known from Table 2 that the graphene composite material according to Embodiment 2 and Embodiment 5 can reach the intrinsic VO-level flame-retarded performance, without spread or droplets. It exhibits excellent flame-retarded performance. Example 2 By the continuous production equipment 100 for graphene composite material according to Embodiment 1, tests were conducted respectively in a case where the extraction device 130 is used (scheme 1) and in a case where the extraction device 130 is not used (scheme 2), and the utilization rate of the raw material is calculated by the following equation: utilization rate = product mass/total mass of the raw material x 100 %. In order to ensure the accuracy of test results, for each scheme, three different mass metrics are used for calculation. The results of calculation are shown in Table 3. Table 3: Test Results of Utilization Rate of the Raw Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.5.svg 2.04 5.93 Black and white It can be known from Table 3 that, by the comparison between the case where the extraction device 130 is used and the case where the extraction device 130 is not used, the whole synthesis process improves the utilization rate of the raw material by about 10 % after the extraction device 130 is used. For large-scale industrial production, the resulting cost reduction is quite considerable. In conclusion, the present invention provides continuous production equipment for graphene composite material, including a raw material preparation device and a reaction device. The raw material preparation device includes a raw material melting kettle which is provided with a high-shear emulsifying machine and an ultrasonic disperser. By the continuous production equipment, during the preparation of polyamide monomer, graphene can be better dispersed in the polyamide monomer by the combined action of high-shear stirring and ultrasonic dispersion while melting the raw material. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, the continuous production equipment further includes an extraction device by which the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The present invention further provides a preparation method for graphene composite material. The method solves the problem of low dispersibility of graphene composite material during large-scale industrial production. With the use of the continuous production equipment for graphene composite material, during the preparation, graphene can be effectively dispersed in the polyamide by the combined action of high-shear stirring and ultrasonic dispersion. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, by this preparation method, the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The foregoing descriptions are merely preferred embodiments of the present invention, and not intended to limit the present invention. For those skilled in the art, various modifications and changes may be made to the present invention. Any modifications, equivalent replacements, improvements and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Industrial applicability According to the implementations of the present invention, by the continuous production equipment and the preparation method for graphene composite material, the graphene can be effectively dispersed in the polyamide monomer and the dispersion effect is very good. The graphene can be always in the liquid-state ultrasonic peeling state. This effectively avoids the agglomeration of the graphene, so that the large-scale industrial production of the graphene composite material can be realized. The continuous production equipment can further recycle the polyamide monomer which has not been completely reacted. In this way, the industrial production cost is effectively reduced. Claims What is claimed is:
A preparation method for graphene composite material, comprising the steps of: melting polyamide monomer and graphene material in a raw material melting kettle, and peeling, dispersing and mixing under the combined action of a high-shear emulsifying machine and an ultrasonic disperser to obtain a mixture; conveying the mixture to a reaction device for polymerization reaction to obtain crude composite material; and, conveying the crude composite material to an extraction device for extraction and separation to obtain graphene composite material, and conveying polyamide monomer extract obtained by extraction back to a raw material preparation device by the liquid conveying pipe for recycle.
The preparation method for graphene composite material according to claim 8, characterized in that the graphene has a functional group which is selected from one or more of amide, amino, carboxyl, sulfonic group, epoxy group and hydroxyl, preferably amino.
The preparation method for graphene composite material according to claims 8 and 9, characterized in that the step of melting polyamide monomer and graphene material in a raw material melting kettle further comprises the steps of: peeling and dispersing the graphene material in a liquid in ultrasonic condition, then adding the obtained substance to the molten polyamide monomer, and mixing, wherein the liquid is water or a polyamide monomer solution with water as a solvent.
The preparation method for graphene composite material according to any one of claims 8 to 11, characterized in that the polymerization reaction comprises a first polymerization performed under an increased pressure and at a temperature of 240-269 °C and a second polymerization performed under a reduced pressure and at a temperature of 270-3 00°C.
The preparation method for graphene composite material according to any one of claims 8 to 12, characterized in that the temperature for melting in the raw material melting kettle is 70-100 °C.
The preparation method for graphene composite material according to any one of claims 8 to 13, characterized in that the mixture goes into a bypass pipe from a material discharge end of the melting kettle and back to the melting kettle from a material feed end of the melting kettle to realize circulation; and during the circulation, the mixture inside the bypass pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 14, characterized in that the mixture is conveyed to the reaction device by a material conveying pipe; and during the material conveying process, the mixture within the material conveying pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 15, characterized in that the preparation method further comprises the steps of: before conveying the polyamide monomer extract back to the raw material preparation device, mixing the polyamide monomer extract with graphene material, and ultrasonically peeling and dispersing by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 16, characterized in that the high-shear emulsifying machine has a stirring speed of 500-10000 r/
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material
Test samples of graphene composite material (Embodiment 2) were subjected to resistance, bacteriostasis rate, far infrared radiation, solar UV protective properties, and burning characteristics tests per Chinese national standards. Results showed resistance up to 1.7×10⁶ Ω, bacteriostasis rate >99% against staphylococcus aureus and candida albicans, far infrared emissivity of 0.92, far infrared radiation temperature rise of 1.6°C, UPF >50%, and V₀-level flame retardancy.
2 materials1 process step
Using the continuous production equipment of Embodiment 1, the utilization rate of raw material was compared between a case with extraction device (scheme 1) and without extraction device (scheme 2). Using the extraction device improved raw material utilization rate by approximately 10%.
Materials described outside the worked examples.
graphene
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Electrical resistance of graphene composite material (Embodiment 2) after 100 washes | 1700000 Ω | graphene composite material (graphene/polyamide) |
Bacteriostasis rate against staphylococcus aureus and candida albicans after 5 washes |
Patent
Atlas literature
Patent
US 10,364,334Patent drawings and their descriptions. Click a drawing to enlarge it.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
Resistance tests on the test samples The test samples were tested after being washed for 100 times, according to the National Standard GB₁₂₀₁₄-2009 "STATIC PROTECTIVE CLOTHING ". The test results are shown in Table 1.
The continuous production equipment according to any one of claims 1 to 5, characterized in that an ultrasonic disperser is provided in the extract tank.
The continuous production equipment according to any one of claims 1 to 6, characterized in that the raw material preparation device further comprises an auxiliary material tank in which a high-shear emulsifying machine and an ultrasonic disperser are provided.
Bacteriostasis rate tests on the test samples The test samples were tested against staphylococcus aureus and candida albicans, respectively, after being washed for 5 times, according to the National Standard GB 20944.3-2008 "TEXTILES-EVALUATION FOR ANTIBACTERIAL ACTIVITY". The test results are shown in Table 1.
Far infrared radiation tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₃₀₁₂₇-2013 "TEXTILES-TESTING AND EVALUATION FOR FAR INFRARED RADIATION PROPERTIES". The test results are shown in Table 1.
Solar ultraviolet radiation protective properties tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₁₈₈₃₀-2009 "TEXTILES-EVALUATION FOR SOLAR ULTRAVIOLET RADIATION PROTECTIVE PROPERT IE S". The test results are shown in Table 1.
Burning characteristics tests on the test samples Five block samples, having a size of 8cmx lcmx0.4cm, from each test sample were tested, according to the National Standard GB₂₄₀₈-2008 "PLASTICS-DETERMINATION OF BURNING CHARACTERISTICS-HORIZONTAL AND VERTICAL TEST". The test results are shown in Table 2, wherein t i denotes the first afterf l ame time, t 2 denotes the second afterf l ame time, and t 3 denotes the third afterf l ame time. Table 1: Results of Performance Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.1.svg 4.2 6.43 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.2.svg 1.33 6.43 Black and white Table 2: Results of Burning Characteristics Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.3.svg 7.55 7.1 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.4.svg 0.91 7.1 Black and white It can be known from Table 1 that the graphene composite material according to Embodiment 2 of the present invention has a resistance up to 1.7 x106Q. It is material with good antistatic property. Meanwhile, it has excellent bacteriostasis effect against staphylococcus aureus and candida albicans, with a bacteriostasis rate greater than 99 %. This graphene composite material is also a good far infrared radiation textile, with a far infrared emissivity up to 0.92 and a far infrared radiation temperature rise of 1.6° C. In addition, this graphene composite material also has excellent solar ultraviolet radiation protective properties, with an UPF (Ultraviolet Protection Factor) greater than 50 %. In addition, it can be known from the data from Embodiments 2 to 4 that products produced by the high-shear emulsifying machine and the ultrasonic disperser during the preparation have better overall performance. It can be known from the data from Embodiments 5 to 6 that products produced by dispersing and peeling the graphene in a liquid during the preparation have better over performance than that of products produced without this operation. It can be known from Table 2 that the graphene composite material according to Embodiment 2 and Embodiment 5 can reach the intrinsic VO-level flame-retarded performance, without spread or droplets. It exhibits excellent flame-retarded performance. Example 2 By the continuous production equipment 100 for graphene composite material according to Embodiment 1, tests were conducted respectively in a case where the extraction device 130 is used (scheme 1) and in a case where the extraction device 130 is not used (scheme 2), and the utilization rate of the raw material is calculated by the following equation: utilization rate = product mass/total mass of the raw material x 100 %. In order to ensure the accuracy of test results, for each scheme, three different mass metrics are used for calculation. The results of calculation are shown in Table 3. Table 3: Test Results of Utilization Rate of the Raw Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.5.svg 2.04 5.93 Black and white It can be known from Table 3 that, by the comparison between the case where the extraction device 130 is used and the case where the extraction device 130 is not used, the whole synthesis process improves the utilization rate of the raw material by about 10 % after the extraction device 130 is used. For large-scale industrial production, the resulting cost reduction is quite considerable. In conclusion, the present invention provides continuous production equipment for graphene composite material, including a raw material preparation device and a reaction device. The raw material preparation device includes a raw material melting kettle which is provided with a high-shear emulsifying machine and an ultrasonic disperser. By the continuous production equipment, during the preparation of polyamide monomer, graphene can be better dispersed in the polyamide monomer by the combined action of high-shear stirring and ultrasonic dispersion while melting the raw material. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, the continuous production equipment further includes an extraction device by which the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The present invention further provides a preparation method for graphene composite material. The method solves the problem of low dispersibility of graphene composite material during large-scale industrial production. With the use of the continuous production equipment for graphene composite material, during the preparation, graphene can be effectively dispersed in the polyamide by the combined action of high-shear stirring and ultrasonic dispersion. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, by this preparation method, the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The foregoing descriptions are merely preferred embodiments of the present invention, and not intended to limit the present invention. For those skilled in the art, various modifications and changes may be made to the present invention. Any modifications, equivalent replacements, improvements and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Industrial applicability According to the implementations of the present invention, by the continuous production equipment and the preparation method for graphene composite material, the graphene can be effectively dispersed in the polyamide monomer and the dispersion effect is very good. The graphene can be always in the liquid-state ultrasonic peeling state. This effectively avoids the agglomeration of the graphene, so that the large-scale industrial production of the graphene composite material can be realized. The continuous production equipment can further recycle the polyamide monomer which has not been completely reacted. In this way, the industrial production cost is effectively reduced. Claims What is claimed is:
A preparation method for graphene composite material, comprising the steps of: melting polyamide monomer and graphene material in a raw material melting kettle, and peeling, dispersing and mixing under the combined action of a high-shear emulsifying machine and an ultrasonic disperser to obtain a mixture; conveying the mixture to a reaction device for polymerization reaction to obtain crude composite material; and, conveying the crude composite material to an extraction device for extraction and separation to obtain graphene composite material, and conveying polyamide monomer extract obtained by extraction back to a raw material preparation device by the liquid conveying pipe for recycle.
The preparation method for graphene composite material according to claim 8, characterized in that the graphene has a functional group which is selected from one or more of amide, amino, carboxyl, sulfonic group, epoxy group and hydroxyl, preferably amino.
The preparation method for graphene composite material according to claims 8 and 9, characterized in that the step of melting polyamide monomer and graphene material in a raw material melting kettle further comprises the steps of: peeling and dispersing the graphene material in a liquid in ultrasonic condition, then adding the obtained substance to the molten polyamide monomer, and mixing, wherein the liquid is water or a polyamide monomer solution with water as a solvent.
The preparation method for graphene composite material according to any one of claims 8 to 11, characterized in that the polymerization reaction comprises a first polymerization performed under an increased pressure and at a temperature of 240-269 °C and a second polymerization performed under a reduced pressure and at a temperature of 270-3 00°C.
The preparation method for graphene composite material according to any one of claims 8 to 12, characterized in that the temperature for melting in the raw material melting kettle is 70-100 °C.
The preparation method for graphene composite material according to any one of claims 8 to 13, characterized in that the mixture goes into a bypass pipe from a material discharge end of the melting kettle and back to the melting kettle from a material feed end of the melting kettle to realize circulation; and during the circulation, the mixture inside the bypass pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 14, characterized in that the mixture is conveyed to the reaction device by a material conveying pipe; and during the material conveying process, the mixture within the material conveying pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 15, characterized in that the preparation method further comprises the steps of: before conveying the polyamide monomer extract back to the raw material preparation device, mixing the polyamide monomer extract with graphene material, and ultrasonically peeling and dispersing by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 16, characterized in that the high-shear emulsifying machine has a stirring speed of 500-10000 r/
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material
Test samples of graphene composite material (Embodiment 2) were subjected to resistance, bacteriostasis rate, far infrared radiation, solar UV protective properties, and burning characteristics tests per Chinese national standards. Results showed resistance up to 1.7×10⁶ Ω, bacteriostasis rate >99% against staphylococcus aureus and candida albicans, far infrared emissivity of 0.92, far infrared radiation temperature rise of 1.6°C, UPF >50%, and V₀-level flame retardancy.
2 materials1 process step
Using the continuous production equipment of Embodiment 1, the utilization rate of raw material was compared between a case with extraction device (scheme 1) and without extraction device (scheme 2). Using the extraction device improved raw material utilization rate by approximately 10%.
Materials described outside the worked examples.
graphene
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Electrical resistance of graphene composite material (Embodiment 2) after 100 washes | 1700000 Ω | graphene composite material (graphene/polyamide) |
Bacteriostasis rate against staphylococcus aureus and candida albicans after 5 washes |
Patent
Atlas literature
Patent
US 10,364,334Patent drawings and their descriptions. Click a drawing to enlarge it.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
Resistance tests on the test samples The test samples were tested after being washed for 100 times, according to the National Standard GB₁₂₀₁₄-2009 "STATIC PROTECTIVE CLOTHING ". The test results are shown in Table 1.
The continuous production equipment according to any one of claims 1 to 5, characterized in that an ultrasonic disperser is provided in the extract tank.
The continuous production equipment according to any one of claims 1 to 6, characterized in that the raw material preparation device further comprises an auxiliary material tank in which a high-shear emulsifying machine and an ultrasonic disperser are provided.
Bacteriostasis rate tests on the test samples The test samples were tested against staphylococcus aureus and candida albicans, respectively, after being washed for 5 times, according to the National Standard GB 20944.3-2008 "TEXTILES-EVALUATION FOR ANTIBACTERIAL ACTIVITY". The test results are shown in Table 1.
Far infrared radiation tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₃₀₁₂₇-2013 "TEXTILES-TESTING AND EVALUATION FOR FAR INFRARED RADIATION PROPERTIES". The test results are shown in Table 1.
Solar ultraviolet radiation protective properties tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₁₈₈₃₀-2009 "TEXTILES-EVALUATION FOR SOLAR ULTRAVIOLET RADIATION PROTECTIVE PROPERT IE S". The test results are shown in Table 1.
Burning characteristics tests on the test samples Five block samples, having a size of 8cmx lcmx0.4cm, from each test sample were tested, according to the National Standard GB₂₄₀₈-2008 "PLASTICS-DETERMINATION OF BURNING CHARACTERISTICS-HORIZONTAL AND VERTICAL TEST". The test results are shown in Table 2, wherein t i denotes the first afterf l ame time, t 2 denotes the second afterf l ame time, and t 3 denotes the third afterf l ame time. Table 1: Results of Performance Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.1.svg 4.2 6.43 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.2.svg 1.33 6.43 Black and white Table 2: Results of Burning Characteristics Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.3.svg 7.55 7.1 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.4.svg 0.91 7.1 Black and white It can be known from Table 1 that the graphene composite material according to Embodiment 2 of the present invention has a resistance up to 1.7 x106Q. It is material with good antistatic property. Meanwhile, it has excellent bacteriostasis effect against staphylococcus aureus and candida albicans, with a bacteriostasis rate greater than 99 %. This graphene composite material is also a good far infrared radiation textile, with a far infrared emissivity up to 0.92 and a far infrared radiation temperature rise of 1.6° C. In addition, this graphene composite material also has excellent solar ultraviolet radiation protective properties, with an UPF (Ultraviolet Protection Factor) greater than 50 %. In addition, it can be known from the data from Embodiments 2 to 4 that products produced by the high-shear emulsifying machine and the ultrasonic disperser during the preparation have better overall performance. It can be known from the data from Embodiments 5 to 6 that products produced by dispersing and peeling the graphene in a liquid during the preparation have better over performance than that of products produced without this operation. It can be known from Table 2 that the graphene composite material according to Embodiment 2 and Embodiment 5 can reach the intrinsic VO-level flame-retarded performance, without spread or droplets. It exhibits excellent flame-retarded performance. Example 2 By the continuous production equipment 100 for graphene composite material according to Embodiment 1, tests were conducted respectively in a case where the extraction device 130 is used (scheme 1) and in a case where the extraction device 130 is not used (scheme 2), and the utilization rate of the raw material is calculated by the following equation: utilization rate = product mass/total mass of the raw material x 100 %. In order to ensure the accuracy of test results, for each scheme, three different mass metrics are used for calculation. The results of calculation are shown in Table 3. Table 3: Test Results of Utilization Rate of the Raw Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.5.svg 2.04 5.93 Black and white It can be known from Table 3 that, by the comparison between the case where the extraction device 130 is used and the case where the extraction device 130 is not used, the whole synthesis process improves the utilization rate of the raw material by about 10 % after the extraction device 130 is used. For large-scale industrial production, the resulting cost reduction is quite considerable. In conclusion, the present invention provides continuous production equipment for graphene composite material, including a raw material preparation device and a reaction device. The raw material preparation device includes a raw material melting kettle which is provided with a high-shear emulsifying machine and an ultrasonic disperser. By the continuous production equipment, during the preparation of polyamide monomer, graphene can be better dispersed in the polyamide monomer by the combined action of high-shear stirring and ultrasonic dispersion while melting the raw material. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, the continuous production equipment further includes an extraction device by which the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The present invention further provides a preparation method for graphene composite material. The method solves the problem of low dispersibility of graphene composite material during large-scale industrial production. With the use of the continuous production equipment for graphene composite material, during the preparation, graphene can be effectively dispersed in the polyamide by the combined action of high-shear stirring and ultrasonic dispersion. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, by this preparation method, the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The foregoing descriptions are merely preferred embodiments of the present invention, and not intended to limit the present invention. For those skilled in the art, various modifications and changes may be made to the present invention. Any modifications, equivalent replacements, improvements and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Industrial applicability According to the implementations of the present invention, by the continuous production equipment and the preparation method for graphene composite material, the graphene can be effectively dispersed in the polyamide monomer and the dispersion effect is very good. The graphene can be always in the liquid-state ultrasonic peeling state. This effectively avoids the agglomeration of the graphene, so that the large-scale industrial production of the graphene composite material can be realized. The continuous production equipment can further recycle the polyamide monomer which has not been completely reacted. In this way, the industrial production cost is effectively reduced. Claims What is claimed is:
A preparation method for graphene composite material, comprising the steps of: melting polyamide monomer and graphene material in a raw material melting kettle, and peeling, dispersing and mixing under the combined action of a high-shear emulsifying machine and an ultrasonic disperser to obtain a mixture; conveying the mixture to a reaction device for polymerization reaction to obtain crude composite material; and, conveying the crude composite material to an extraction device for extraction and separation to obtain graphene composite material, and conveying polyamide monomer extract obtained by extraction back to a raw material preparation device by the liquid conveying pipe for recycle.
The preparation method for graphene composite material according to claim 8, characterized in that the graphene has a functional group which is selected from one or more of amide, amino, carboxyl, sulfonic group, epoxy group and hydroxyl, preferably amino.
The preparation method for graphene composite material according to claims 8 and 9, characterized in that the step of melting polyamide monomer and graphene material in a raw material melting kettle further comprises the steps of: peeling and dispersing the graphene material in a liquid in ultrasonic condition, then adding the obtained substance to the molten polyamide monomer, and mixing, wherein the liquid is water or a polyamide monomer solution with water as a solvent.
The preparation method for graphene composite material according to any one of claims 8 to 11, characterized in that the polymerization reaction comprises a first polymerization performed under an increased pressure and at a temperature of 240-269 °C and a second polymerization performed under a reduced pressure and at a temperature of 270-3 00°C.
The preparation method for graphene composite material according to any one of claims 8 to 12, characterized in that the temperature for melting in the raw material melting kettle is 70-100 °C.
The preparation method for graphene composite material according to any one of claims 8 to 13, characterized in that the mixture goes into a bypass pipe from a material discharge end of the melting kettle and back to the melting kettle from a material feed end of the melting kettle to realize circulation; and during the circulation, the mixture inside the bypass pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 14, characterized in that the mixture is conveyed to the reaction device by a material conveying pipe; and during the material conveying process, the mixture within the material conveying pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 15, characterized in that the preparation method further comprises the steps of: before conveying the polyamide monomer extract back to the raw material preparation device, mixing the polyamide monomer extract with graphene material, and ultrasonically peeling and dispersing by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 16, characterized in that the high-shear emulsifying machine has a stirring speed of 500-10000 r/
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material
Test samples of graphene composite material (Embodiment 2) were subjected to resistance, bacteriostasis rate, far infrared radiation, solar UV protective properties, and burning characteristics tests per Chinese national standards. Results showed resistance up to 1.7×10⁶ Ω, bacteriostasis rate >99% against staphylococcus aureus and candida albicans, far infrared emissivity of 0.92, far infrared radiation temperature rise of 1.6°C, UPF >50%, and V₀-level flame retardancy.
2 materials1 process step
Using the continuous production equipment of Embodiment 1, the utilization rate of raw material was compared between a case with extraction device (scheme 1) and without extraction device (scheme 2). Using the extraction device improved raw material utilization rate by approximately 10%.
Materials described outside the worked examples.
graphene
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Electrical resistance of graphene composite material (Embodiment 2) after 100 washes | 1700000 Ω | graphene composite material (graphene/polyamide) |
Bacteriostasis rate against staphylococcus aureus and candida albicans after 5 washes |
Patent
Atlas literature
Patent
US 10,364,334Patent drawings and their descriptions. Click a drawing to enlarge it.
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
Resistance tests on the test samples The test samples were tested after being washed for 100 times, according to the National Standard GB₁₂₀₁₄-2009 "STATIC PROTECTIVE CLOTHING ". The test results are shown in Table 1.
The continuous production equipment according to any one of claims 1 to 5, characterized in that an ultrasonic disperser is provided in the extract tank.
The continuous production equipment according to any one of claims 1 to 6, characterized in that the raw material preparation device further comprises an auxiliary material tank in which a high-shear emulsifying machine and an ultrasonic disperser are provided.
Bacteriostasis rate tests on the test samples The test samples were tested against staphylococcus aureus and candida albicans, respectively, after being washed for 5 times, according to the National Standard GB 20944.3-2008 "TEXTILES-EVALUATION FOR ANTIBACTERIAL ACTIVITY". The test results are shown in Table 1.
Far infrared radiation tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₃₀₁₂₇-2013 "TEXTILES-TESTING AND EVALUATION FOR FAR INFRARED RADIATION PROPERTIES". The test results are shown in Table 1.
Solar ultraviolet radiation protective properties tests on the test samples The test samples were tested after being washed for 5 times, according to the National Standard GB₁₈₈₃₀-2009 "TEXTILES-EVALUATION FOR SOLAR ULTRAVIOLET RADIATION PROTECTIVE PROPERT IE S". The test results are shown in Table 1.
Burning characteristics tests on the test samples Five block samples, having a size of 8cmx lcmx0.4cm, from each test sample were tested, according to the National Standard GB₂₄₀₈-2008 "PLASTICS-DETERMINATION OF BURNING CHARACTERISTICS-HORIZONTAL AND VERTICAL TEST". The test results are shown in Table 2, wherein t i denotes the first afterf l ame time, t 2 denotes the second afterf l ame time, and t 3 denotes the third afterf l ame time. Table 1: Results of Performance Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.1.svg 4.2 6.43 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.2.svg 1.33 6.43 Black and white Table 2: Results of Burning Characteristics Tests on the Graphene Composite Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.3.svg 7.55 7.1 Black and white SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.4.svg 0.91 7.1 Black and white It can be known from Table 1 that the graphene composite material according to Embodiment 2 of the present invention has a resistance up to 1.7 x106Q. It is material with good antistatic property. Meanwhile, it has excellent bacteriostasis effect against staphylococcus aureus and candida albicans, with a bacteriostasis rate greater than 99 %. This graphene composite material is also a good far infrared radiation textile, with a far infrared emissivity up to 0.92 and a far infrared radiation temperature rise of 1.6° C. In addition, this graphene composite material also has excellent solar ultraviolet radiation protective properties, with an UPF (Ultraviolet Protection Factor) greater than 50 %. In addition, it can be known from the data from Embodiments 2 to 4 that products produced by the high-shear emulsifying machine and the ultrasonic disperser during the preparation have better overall performance. It can be known from the data from Embodiments 5 to 6 that products produced by dispersing and peeling the graphene in a liquid during the preparation have better over performance than that of products produced without this operation. It can be known from Table 2 that the graphene composite material according to Embodiment 2 and Embodiment 5 can reach the intrinsic VO-level flame-retarded performance, without spread or droplets. It exhibits excellent flame-retarded performance. Example 2 By the continuous production equipment 100 for graphene composite material according to Embodiment 1, tests were conducted respectively in a case where the extraction device 130 is used (scheme 1) and in a case where the extraction device 130 is not used (scheme 2), and the utilization rate of the raw material is calculated by the following equation: utilization rate = product mass/total mass of the raw material x 100 %. In order to ensure the accuracy of test results, for each scheme, three different mass metrics are used for calculation. The results of calculation are shown in Table 3. Table 3: Test Results of Utilization Rate of the Raw Material SVG 15740519.12-28-2017.JBQVGO₂₈RXEAPX3.SPEC.5.svg 2.04 5.93 Black and white It can be known from Table 3 that, by the comparison between the case where the extraction device 130 is used and the case where the extraction device 130 is not used, the whole synthesis process improves the utilization rate of the raw material by about 10 % after the extraction device 130 is used. For large-scale industrial production, the resulting cost reduction is quite considerable. In conclusion, the present invention provides continuous production equipment for graphene composite material, including a raw material preparation device and a reaction device. The raw material preparation device includes a raw material melting kettle which is provided with a high-shear emulsifying machine and an ultrasonic disperser. By the continuous production equipment, during the preparation of polyamide monomer, graphene can be better dispersed in the polyamide monomer by the combined action of high-shear stirring and ultrasonic dispersion while melting the raw material. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, the continuous production equipment further includes an extraction device by which the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The present invention further provides a preparation method for graphene composite material. The method solves the problem of low dispersibility of graphene composite material during large-scale industrial production. With the use of the continuous production equipment for graphene composite material, during the preparation, graphene can be effectively dispersed in the polyamide by the combined action of high-shear stirring and ultrasonic dispersion. In this way, graphene composite material with good dispersibility and excellent properties is obtained. Meanwhile, by this preparation method, the polyamide monomer which has not been completely reacted during a reaction can be recycled. In this way, the raw material utilization rate is improved and the production cost is reduced. The foregoing descriptions are merely preferred embodiments of the present invention, and not intended to limit the present invention. For those skilled in the art, various modifications and changes may be made to the present invention. Any modifications, equivalent replacements, improvements and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention. Industrial applicability According to the implementations of the present invention, by the continuous production equipment and the preparation method for graphene composite material, the graphene can be effectively dispersed in the polyamide monomer and the dispersion effect is very good. The graphene can be always in the liquid-state ultrasonic peeling state. This effectively avoids the agglomeration of the graphene, so that the large-scale industrial production of the graphene composite material can be realized. The continuous production equipment can further recycle the polyamide monomer which has not been completely reacted. In this way, the industrial production cost is effectively reduced. Claims What is claimed is:
A preparation method for graphene composite material, comprising the steps of: melting polyamide monomer and graphene material in a raw material melting kettle, and peeling, dispersing and mixing under the combined action of a high-shear emulsifying machine and an ultrasonic disperser to obtain a mixture; conveying the mixture to a reaction device for polymerization reaction to obtain crude composite material; and, conveying the crude composite material to an extraction device for extraction and separation to obtain graphene composite material, and conveying polyamide monomer extract obtained by extraction back to a raw material preparation device by the liquid conveying pipe for recycle.
The preparation method for graphene composite material according to claim 8, characterized in that the graphene has a functional group which is selected from one or more of amide, amino, carboxyl, sulfonic group, epoxy group and hydroxyl, preferably amino.
The preparation method for graphene composite material according to claims 8 and 9, characterized in that the step of melting polyamide monomer and graphene material in a raw material melting kettle further comprises the steps of: peeling and dispersing the graphene material in a liquid in ultrasonic condition, then adding the obtained substance to the molten polyamide monomer, and mixing, wherein the liquid is water or a polyamide monomer solution with water as a solvent.
The preparation method for graphene composite material according to any one of claims 8 to 11, characterized in that the polymerization reaction comprises a first polymerization performed under an increased pressure and at a temperature of 240-269 °C and a second polymerization performed under a reduced pressure and at a temperature of 270-3 00°C.
The preparation method for graphene composite material according to any one of claims 8 to 12, characterized in that the temperature for melting in the raw material melting kettle is 70-100 °C.
The preparation method for graphene composite material according to any one of claims 8 to 13, characterized in that the mixture goes into a bypass pipe from a material discharge end of the melting kettle and back to the melting kettle from a material feed end of the melting kettle to realize circulation; and during the circulation, the mixture inside the bypass pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 14, characterized in that the mixture is conveyed to the reaction device by a material conveying pipe; and during the material conveying process, the mixture within the material conveying pipe is ultrasonically peeled and dispersed by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 15, characterized in that the preparation method further comprises the steps of: before conveying the polyamide monomer extract back to the raw material preparation device, mixing the polyamide monomer extract with graphene material, and ultrasonically peeling and dispersing by an ultrasonic disperser.
The preparation method for graphene composite material according to any one of claims 8 to 16, characterized in that the high-shear emulsifying machine has a stirring speed of 500-10000 r/
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material
Test samples of graphene composite material (Embodiment 2) were subjected to resistance, bacteriostasis rate, far infrared radiation, solar UV protective properties, and burning characteristics tests per Chinese national standards. Results showed resistance up to 1.7×10⁶ Ω, bacteriostasis rate >99% against staphylococcus aureus and candida albicans, far infrared emissivity of 0.92, far infrared radiation temperature rise of 1.6°C, UPF >50%, and V₀-level flame retardancy.
2 materials1 process step
Using the continuous production equipment of Embodiment 1, the utilization rate of raw material was compared between a case with extraction device (scheme 1) and without extraction device (scheme 2). Using the extraction device improved raw material utilization rate by approximately 10%.
Materials described outside the worked examples.
graphene
Performance values and ranges asserted in the specification or claims.
| Property | Value | Material |
|---|---|---|
Electrical resistance of graphene composite material (Embodiment 2) after 100 washes | 1700000 Ω | graphene composite material (graphene/polyamide) |
Bacteriostasis rate against staphylococcus aureus and candida albicans after 5 washes |
graphene composite material (graphene/polyamide) |
Far infrared emissivity of graphene composite material (Embodiment 2) after 5 washes | 0.92 | graphene composite material (graphene/polyamide) |
Far infrared radiation temperature rise of graphene composite material (Embodiment 2) after 5 washes | 1.6 °C | graphene composite material (graphene/polyamide) |
UPF of graphene composite material (Embodiment 2) after 5 washes | >50 % | graphene composite material (graphene/polyamide) |
Flame retardancy rating of graphene composite material (Embodiments 2 and 5) | V₀ | graphene composite material (graphene/polyamide) |
Improvement in raw material utilization rate when extraction device is used | ~10 % | polyamide monomer |
Temperature | 240–269 °C | — |
Temperature | 70–100 °C | — |
graphene composite material (graphene/polyamide) |
Far infrared emissivity of graphene composite material (Embodiment 2) after 5 washes | 0.92 | graphene composite material (graphene/polyamide) |
Far infrared radiation temperature rise of graphene composite material (Embodiment 2) after 5 washes | 1.6 °C | graphene composite material (graphene/polyamide) |
UPF of graphene composite material (Embodiment 2) after 5 washes | >50 % | graphene composite material (graphene/polyamide) |
Flame retardancy rating of graphene composite material (Embodiments 2 and 5) | V₀ | graphene composite material (graphene/polyamide) |
Improvement in raw material utilization rate when extraction device is used | ~10 % | polyamide monomer |
Temperature | 240–269 °C | — |
Temperature | 70–100 °C | — |
graphene composite material (graphene/polyamide) |
Far infrared emissivity of graphene composite material (Embodiment 2) after 5 washes | 0.92 | graphene composite material (graphene/polyamide) |
Far infrared radiation temperature rise of graphene composite material (Embodiment 2) after 5 washes | 1.6 °C | graphene composite material (graphene/polyamide) |
UPF of graphene composite material (Embodiment 2) after 5 washes | >50 % | graphene composite material (graphene/polyamide) |
Flame retardancy rating of graphene composite material (Embodiments 2 and 5) | V₀ | graphene composite material (graphene/polyamide) |
Improvement in raw material utilization rate when extraction device is used | ~10 % | polyamide monomer |
Temperature | 240–269 °C | — |
Temperature | 70–100 °C | — |
graphene composite material (graphene/polyamide) |
Far infrared emissivity of graphene composite material (Embodiment 2) after 5 washes | 0.92 | graphene composite material (graphene/polyamide) |
Far infrared radiation temperature rise of graphene composite material (Embodiment 2) after 5 washes | 1.6 °C | graphene composite material (graphene/polyamide) |
UPF of graphene composite material (Embodiment 2) after 5 washes | >50 % | graphene composite material (graphene/polyamide) |
Flame retardancy rating of graphene composite material (Embodiments 2 and 5) | V₀ | graphene composite material (graphene/polyamide) |
Improvement in raw material utilization rate when extraction device is used | ~10 % | polyamide monomer |
Temperature | 240–269 °C | — |
Temperature | 70–100 °C | — |
