Graphene polyester fiber and manufacturing method thereof

Abstract

The invention discloses a graphene polyester fiber and a manufacturing method thereof. The manufacturing method of the graphene polyester fiber comprises the following steps: performing a modification procedure to form a modified layer on the surface of graphene powder so as to obtain modified graphene powder; the modified layer is formed by attaching a modifier to the surface of the graphene powder, and the modifier is silane or titanate. Mixing the modified graphene powder and first polyester, and performing a granulation procedure to obtain the graphene master batch. And mixing the graphene master batch and second polyester, and carrying out a spinning procedure to prepare the graphene polyester fiber.

Description

Technical Field

[0001] The present application relates to a graphene polyester fiber and a method for manufacturing the same, and in particular to a graphene polyester fiber with good temperature retention effect and a method for manufacturing the same. Background Art

[0002] Existing graphene polyester fibers are produced by adding graphene slurry during the polyester synthesis process or by melt spinning.

[0003] However, graphene is an inorganic material and polyester is an organic material. The poor dispersion of graphene in polyester can easily lead to too fast a pressure rise rate during the spinning process and negatively affect the quality of the yarn. For example, poor dispersion of graphene in polyester can lead to reduced yarn strength and poor yarn heat retention.

[0004] Therefore, how to improve the quality of graphene polyester fiber by improving the composition and preparation method and overcome the defects in the manufacturing method of graphene polyester fiber has become one of the important issues that this business wants to solve. Summary of the invention

[0005] The technical problem to be solved by the present application is to provide a graphene polyester fiber and a method for manufacturing the same in view of the deficiencies in the prior art.

[0006] In order to solve the above technical problems, one of the technical solutions adopted in this application is to provide a method for manufacturing graphene polyester fiber. The method for manufacturing graphene polyester fiber includes the following steps: performing a modification procedure to form a modified layer on the surface of the graphene powder to obtain modified graphene powder. The modified layer is formed by attaching a modifier to the surface of the graphene powder, and the modifier is silane or titanate. The modified graphene powder is mixed with a first polyester and a granulation procedure is performed to obtain a graphene masterbatch. The graphene masterbatch is mixed with a second polyester and a spinning procedure is performed to obtain graphene polyester fiber.

[0007] Furthermore, in the modification process, a modification solution is sprayed on the surface of the graphene powder to obtain the modified graphene powder, and the modification solution includes a modifier.

[0008] Furthermore, the modified solution is sprayed on the surface of the graphene powder and then dried to obtain the modified graphene powder, wherein the content of the modifier in the modified graphene powder is 1 weight percent to 5 weight percent.

[0009] Furthermore, the intrinsic viscosity of the first polyester is greater than the intrinsic viscosity of the second polyester.

[0010] Furthermore, the intrinsic viscosity of the first polyester is 0.8 to 1.0, and the intrinsic viscosity of the second polyester is 0.6 to 0.7.

[0011] Furthermore, the material of the first polyester is polybutylene terephthalate.

[0012] Furthermore, the material of the second polyester is polyethylene terephthalate.

[0013] Furthermore, in the granulation process, the content of modified graphene powder in the graphene masterbatch is 3 to 8 weight percent.

[0014] In order to solve the above technical problems, another technical solution adopted by the present application is to provide a graphene polyester fiber. The graphene polyester fiber includes a polyester resin and a modified graphene powder, wherein the modified graphene powder is dispersed in the polyester resin, and the modified graphene powder includes a graphene powder and a modified layer, wherein the modified layer is formed by attaching a modifier to the surface of the graphene powder, and the modifier is silane or titanate.

[0015] Furthermore, the polyester resin includes polybutylene terephthalate and polyethylene terephthalate.

[0016] One of the beneficial effects of the present application is that the graphene polyester fiber and the manufacturing method thereof provided in the present application can improve the dispersibility of the graphene powder in the graphene polyester fiber through the technical solutions of "the modifier is silane or titanate", "mixing the modified graphene powder with the first polyester and performing a granulation process" and "mixing the graphene masterbatch with the second polyester and performing a spinning process".

[0017] In order to further understand the features and technical contents of the present application, please refer to the following detailed description and drawings of the present application. However, the drawings provided are only for reference and illustration and are not intended to limit the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a flow chart of the steps of the method for manufacturing graphene polyester fiber of the present application. DETAILED DESCRIPTION

[0019] The following is an explanation of the implementation methods of the "graphene polyester fiber and its manufacturing method" disclosed in the present application through specific examples. Those skilled in the art can understand the advantages and effects of the present application from the contents disclosed in this specification. The present application can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present application. In addition, the drawings of the present application are only simple schematic illustrations and are not depicted in actual size. It is stated in advance. The following implementation methods will further explain the relevant technical content of the present application in detail, but the disclosed content is not intended to limit the scope of protection of the present application. In addition, the term "or" used in this article may include any one or more combinations of the associated listed items depending on the actual situation.

[0020] The present application provides a graphene polyester fiber and a method for manufacturing the same. Graphene powder can be evenly dispersed in the polyester fiber, so that the graphene polyester fiber has good quality. In addition, in the process of manufacturing the graphene polyester fiber, the pressure rise rate of the spinning equipment is slow, so a higher yield can be achieved.

[0021] See also Figure 1 As shown, the method for manufacturing the graphene polyester fiber of the present application includes steps S1 to S3. In summary, the method for manufacturing the graphene polyester fiber of the present application can be divided into: a modification process, a granulation process and a spinning process.

[0022] In the modification procedure (corresponding to step S1), the graphene powder is modified to form a modified layer on the surface of the graphene powder to obtain modified graphene powder.

[0023] The modified layer has good compatibility with polyester, so the dispersibility of graphene powder in polyester can be improved. When the dispersibility of graphene powder in polyester is improved, the pressure rise rate in the spinning process can be further reduced.

[0024] In an exemplary embodiment, the modified layer is formed by attaching a modifying agent to the surface of the graphene powder. For example, the modifying agent can be prepared into a modifying solution, and then the modifying agent can be attached to the surface of the graphene powder by spraying.

[0025] Forming the modified layer by spraying can save the amount of modifier and reduce the residual amount of solvent, so that it is suitable for clothing and textiles. In addition, the time required to dry the graphene powder can be shortened by spraying. Compared with the method of forming the modified layer by immersion, the method of forming the modified layer by spraying can use the least amount of modifier and form an extremely thin modified layer while having a modified effect.

[0026] In order to ensure that the modified layer has the effect of improving the dispersibility of graphene powder in polyester, a modified solution is prepared by mixing a modifier and a solvent in a volume ratio of 1:4 to 1:8. Preferably, the volume ratio of the modifier to the solvent is 1:5 to 1:7. In addition, during the spraying of the modified solution, stirring is performed to help form a uniform modified layer on the graphene powder.

[0027] Specifically, in the modification process, the graphene powder is stirred at a stirring rate of 250 rpm to 1000 rpm, and the prepared modification solution is sprayed onto the graphene powder at a rate of 0.5 ml / min to 1.5 ml / min. Then, the graphene powder is dried at a temperature of 100°C to 140°C for 2 hours, and the modified graphene powder can be obtained after the solvent evaporates.

[0028] In the present application, the modifier is silane or titanate. Moreover, after experimental testing, it is found that titanate is preferably used to form the modified layer, which can further improve the dispersibility of graphene powder in polyester. The specific experimental data will be described later.

[0029] Specifically, when the modifier is silane, the modifier may be 3-acryloxypropyltrimethylsilane or triethoxyvinylsilane. When the modifier is titanate, the modifier may be oleyl titanate, pyrophosphate titanate, isostearyl titanate or stearyl titanate. The solvent in the modified solution may be isopropanol, but the present application is not limited thereto.

[0030] In order to quantify the content of the modifier on the modified graphene powder, the weight of the graphene powder and the modified graphene powder are weighed respectively, and the content of the modifier in the modified graphene powder can be calculated. From the results, it can be seen that if the total weight of the modified graphene powder is 100 weight percent, the content of the modifier in the modified graphene powder is 1 weight percent to 5 weight percent, and preferably, the content of the modifier in the modified graphene powder is 1 weight percent to 3 weight percent.

[0031] In addition, a multi-layered graphene powder can be selected. Preferably, the graphene powder has a structure of less than ten layers. Preferably, the average particle size of the graphene powder can be less than 1 micron.

[0032] In the granulation process (corresponding to step S2), the modified graphene powder is mixed with the first polyester to form a first polyester mixture, and then the first polyester mixture is used to prepare a graphene masterbatch. The preparation of the graphene masterbatch can help disperse the modified graphene powder, so as to facilitate the production of high-quality graphene fibers in the subsequent spinning process.

[0033] In an exemplary embodiment, the modified graphene powder is added to polybutylene terephthalate (PBT) powder and stirred at a speed of 1500 rpm to 2000 rpm to form a first polyester mixture. In other words, the first polyester can be polybutylene terephthalate (PBT), and the intrinsic viscosity (IV) of the polybutylene terephthalate particles is 0.8 to 1.0.

[0034] Next, the first polyester mixture is sent to a screw extruder via a lower hopper. The rubber strip extruded by the screw extruder is cooled in a cooling water tank, dried by an air knife, and then pelletized to obtain graphene masterbatch.

[0035] It is particularly noted that polybutylene terephthalate has higher crystallinity than polyethylene terephthalate and slightly better heat resistance, and can be directly used to make masterbatch. Therefore, in order to avoid the crystallization process, it is better to use polybutylene terephthalate powder to make graphene masterbatch in the granulation process.

[0036] Generally speaking, in order to achieve better mixing and dispersion effects, a twin screw extruder with a higher aspect ratio (L / D) is used. Since the modified graphene powder in this application has a modified layer, and the graphene masterbatch will be subjected to a spinning process later. Therefore, in the granulation process, a twin screw extruder with a higher aspect ratio (L / D) can be used. Specifically, the aspect ratio (L / D) of the twin screw extruder is 50 to 60, and preferably, the aspect ratio (L / D) can be 52 to 56.

[0037] In addition, the temperature of the extruder is set to 250° C. to 260° C., and the rotation speed of the extruder can be set to 230 rpm to 270 rpm, so that the modified graphene powder and the polybutylene terephthalate powder can be uniformly mixed.

[0038] In order to optimize the dispersion effect of modified graphene powder in polyester, the weight ratio of modified graphene powder to polybutylene terephthalate powder can be adjusted to obtain a graphene masterbatch with an effective concentration of 2 weight percent to 10 weight percent. In the specification, the effective concentration of the graphene masterbatch refers to the weight percentage concentration of the modified graphene powder in the graphene masterbatch. Preferably, the effective concentration of the graphene masterbatch is 3 weight percent to 8 weight percent.

[0039] In the spinning process (corresponding to step S3), the graphene masterbatch is mixed with the second polyester to form a second polyester mixture, and then the second polyester mixture is used to prepare the graphene polyester fiber.

[0040] The graphene powder in the graphene polyester fiber will reduce the friction coefficient of the fiber. Therefore, during the winding process of the graphene polyester fiber, as the yarn cake is wound larger, it is easy for the yarn cake to collapse directly due to incomplete winding of the yarn.

[0041] In order to overcome this problem, polyethylene terephthalate (PET) particles can be used as the second polyester to increase the friction coefficient of the fiber. Preferably, full dull polyethylene terephthalate particles can be used as the second polyester, and the intrinsic viscosity of the polyethylene terephthalate particles is 0.6 to 0.7.

[0042] In addition, in order to avoid powder agglomeration, which negatively affects the quality of graphene polyester fiber, the polyethylene terephthalate pellets can be pre-treated at a temperature of 65°C to 75°C. In the pre-treatment process, in addition to drying the polyethylene terephthalate pellets, the crystallinity of the polyethylene terephthalate pellets can also be improved. The high crystallinity can prevent the polyester pellets from agglomerating due to moisture, and can also facilitate the subsequent drying step.

[0043] Similarly, the graphene masterbatch may also undergo another pre-treatment procedure, wherein the graphene masterbatch is placed at a temperature of 130° C. to 150° C. for 4 to 6 hours to remove moisture from the graphene masterbatch.

[0044] In an exemplary embodiment, the second polyester mixture is sent to a spinning machine through a lower hopper, and the melting temperature of the spinning machine can be set to 230°C to 280°C. After the heated and molten second polyester mixture flows through the spinning manifold, it first passes through a non-woven filter and metal sand to ensure that there is no incompletely melted second polyester mixture in the melt. Finally, after the melt flows out through the spinneret, graphene polyester fiber can be obtained. After the graphene polyester fiber is air-cooled, it is oiled by an oil nozzle and wound at a speed of 3000 m / min to 3500 m / min.

[0045] In addition, the graphene polyester fiber can be processed by false twisting to form a draw texturing yarn (DTY) from a partially oriented yarn (POY).

[0046] Finally, the effective concentration of the graphene polyester fiber is 0.01 weight percent to 0.15 weight percent. In the specification, the effective concentration of the graphene polyester fiber refers to the weight percentage concentration of the modified graphene powder in the graphene polyester fiber. Preferably, the effective concentration of the graphene polyester fiber is 0.02 weight percent to 0.1 weight percent.

[0047] It is particularly noted that polybutylene terephthalate powder is added in the granulation process to produce graphene masterbatch, and polyethylene terephthalate particles are added in the spinning process to produce graphene polyester fiber. If the order of adding the above polyester materials is reversed, the strength of the graphene polyester fiber will be poor.

[0048] According to the above content, in terms of improving the dispersibility of graphene powder, the modification process, granulation process, and spinning process can all improve the dispersibility of graphene powder in polyester fiber. In detail, the modification process is an improvement in the composition of graphene powder, while the granulation process and spinning process are improvements in the process.

[0049] During the modification process, a modified layer is formed on the surface of the graphene powder, so the dispersibility of the graphene powder in polyester can be improved by improving the composition.

[0050] In the granulation process, the modified graphene powder is dispersed in the first polyester, which can be regarded as the first dispersion. In the spinning process, the graphene masterbatch is dispersed in the second polyester, which can be regarded as the second dispersion. Through two dispersion steps (granulation process and spinning process), the graphene powder can be evenly dispersed in the polyester.

[0051] If the modified graphene powder is directly added to the polyester and then the spinning process is carried out (i.e. the granulation process is omitted), it will take more time to disperse the modified graphene powder due to the difference in material between the modified graphene powder and the polyester.

[0052] Therefore, the present application combines the improvement in materials and the improvement in process to achieve the effect of improving the dispersibility of graphene powder in polyester.

[0053] In addition, the improvement of graphene powder in dispersion can be reflected in the pressure rise value in the spinning process. In the same time, if the graphene powder has better dispersion in polyester, the pressure rise value in the spinning equipment is lower, and if the graphene powder has poor dispersion in polyester, the pressure rise value in the spinning equipment is higher. The specific experimental data will be described later.

[0054] It should be noted that in the granulation process and the spinning process, the polyester material will undergo a heating and melting step respectively. That is, the first polyester will undergo two heating and melting processes, and the second polyester will undergo one heating and melting process. However, each time the polyester material undergoes a heating and melting step, part of the polymer will be thermally cracked, causing the mechanical strength and tensile strength of the polyester material to slightly decrease.

[0055] Therefore, in order to make the graphene polyester fiber have uniform physical properties, the intrinsic viscosity of the first polyester can be controlled to be greater than the intrinsic viscosity of the second polyester, and the intrinsic viscosity of the first polyester and the intrinsic viscosity of the second polyester must both be less than or equal to 1.0.

[0056] In an exemplary embodiment, the difference between the intrinsic viscosity of the first polyester and the intrinsic viscosity of the second polyester is 0.1 to 0.2. In this way, even if the first polyester undergoes two heating and melting processes, it can still have similar physical properties to the second polyester that has undergone one heating and melting process.

[0057] After comprehensively evaluating the process convenience, manufacturing time, and properties of the graphene polyester fiber, in a preferred embodiment, the intrinsic viscosity of the first polyester is 0.8 to 1.0, and the intrinsic viscosity of the second polyester is 0.6 to 0.7.

[0058] [Experimental data]

[0059] In order to conveniently illustrate the efficacy of the present application, according to the above step S1, the modified graphene powders of samples 1 to 5 are prepared. According to the above step S2, the modified graphene powders or unmodified graphene powders of samples 1 to 5 are used to manufacture the graphene masterbatches of samples 6 to 11. According to the above step S3, the graphene masterbatches of samples 6 to 11 are used to prepare the graphene polyester fibers of Examples 1 to 5 and Comparative Example 1.

[0060] [Modified graphene powders of samples 1 to 5]

[0061] The difference between samples 1 to 5 is that different modifiers are used. The specific modifiers are listed in Table 1.

[0062] The modifier and isopropanol (solvent) are mixed in a mass ratio of 1:6 to prepare a modified solution, and the modified solution is sprayed on the graphene powder at a rate of 1 ml per minute with a blade stirring rate of 250 rpm, and then the blade stirring rate is adjusted to 1000 rpm. After the modified solution is sprayed, the modified graphene powder can be obtained.

[0063] By weighing the graphene powder and the modified graphene powder respectively, the amount of the modifier attached to the graphene powder can be calculated, and the results are listed in Table 1.

[0064] Table 1

[0065]

[0066] [Graphene masterbatch of samples 6 to 11]

[0067] The graphene masterbatches of samples 6 to 10 are made from the modified graphene powders of samples 1 to 5 in sequence, for example, sample 6 is made from sample 1, sample 7 is made from sample 2, and so on. The graphene masterbatch of sample 11 is made from unmodified graphene powder.

[0068] The modified graphene powder (or unmodified graphene powder) and polybutylene terephthalate powder (first polyester, intrinsic viscosity of 0.8) are mixed at a weight ratio of 5:95, and stirred and mixed at a speed of 1800 rpm to form a first polyester mixture. The first polyester mixture is sent to a screw extruder with a length-to-diameter ratio (L / D) of 54, and the screw temperature is set to 250° C. to 260° C. and the speed is 250 rpm to obtain a graphene masterbatch.

[0069] That is to say, the effective concentration of the modified graphene powder in the graphene masterbatch of samples 6 to 10 is 3 weight percent, and the effective concentration of the graphene powder in the graphene masterbatch of sample 11 is 3 weight percent.

[0070] [Graphene polyester fibers of Examples 1 to 5 and Comparative Example 1]

[0071] The graphene polyester fibers of Examples 1 to 5 are made from the graphene masterbatches of Samples 6 to 10 in sequence, for example, Example 1 is made from Sample 6, Example 2 is made from Sample 7, and so on. The graphene polyester fiber of Comparative Example 1 is made from the graphene masterbatch of Sample 11.

[0072] According to the contents in Table 2, graphene masterbatch, polyethylene terephthalate pellets (PET pellets) (second polyester, intrinsic viscosity of 0.7) and antioxidants are mixed to form a second polyester mixture. Then, the second polyester mixture is sent to a spinning machine, and the temperature of the spinning machine is set to 230° C. to 280° C. to produce graphene polyester fibers. The antioxidant in Table 2 is bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (model: RC PEP36).

[0073] In the process of manufacturing graphene polyester fibers, the filtration pressure difference before and after the spinneret is measured per unit time (8 hours) to evaluate the dispersibility of graphene powder in polyester, and the results are listed in Table 2.

[0074] After the graphene polyester fiber was prepared, the graphene polyester fiber was woven into a garter sample. According to the far infrared textile verification specification (FTTS-FA-010 2007), the garter sample was placed under a halogen lamp, 100 cm apart, and irradiated with a power of 500 watts for 10 minutes, and the temperature of the garter sample before and after irradiation was measured to evaluate the temperature retention effect of the garter sample. The temperature measurement results of the garter sample are listed in Table 3.

[0075] Table 2

[0076]

[0077]

[0078] Table 3

[0079] (℃) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Temperature before irradiation 20.3 20.5 20.2 20.8 20.6 20.1 Temperature after irradiation 31.0 32.4 32.6 34.7 32.8 23.7 Temperature difference 10.7 11.9 12.3 13.9 12.1 3.6

[0080] From the results in Table 2, it can be seen that the graphene powder can be evenly dispersed in the graphene polyester fiber through the modification process, the granulation process and the spinning process. Therefore, in the spinning process, the spinning equipment can have a lower pressure rise value, which is conducive to long-term manufacturing and can have a higher yield. Specifically, after 8 hours of continuous spinning, the pressure rise value of the spinning equipment can be less than 2.5 bar / g, and preferably, the pressure rise value of the spinning equipment can be 0.2 bar / g to 1.5 bar / g.

[0081] From the results in Table 3, it can be seen that the graphene polyester fiber of the present application can have a higher temperature after being irradiated by a far-infrared lamp. Therefore, the graphene polyester fiber has a good temperature retention effect and can be applied to warm textiles. Specifically, after irradiation with a 500-watt halogen lamp at a distance of 100 cm for 10 minutes, the temperature of the graphene polyester fiber can rise by more than 5°C, preferably, the temperature of the graphene polyester fiber can rise by 8°C to 15°C.

[0082] [Beneficial Effects of Embodiments]

[0083] One of the beneficial effects of the present application is that the graphene polyester fiber and the manufacturing method thereof provided in the present application can improve the dispersibility of the graphene powder in the graphene polyester fiber through the technical solutions of "the modifier is silane or titanate", "mixing the modified graphene powder with the first polyester and performing a granulation process" and "mixing the graphene masterbatch with the second polyester and performing a spinning process".

[0084] Furthermore, a minimum amount of modified solution can be used by spraying to form a modified layer on the surface of the graphene powder to improve the dispersibility of the graphene powder in the polyester material.

[0085] In addition, by using polybutylene terephthalate as the first polyester and polyethylene terephthalate as the second polyester, the graphene polyester fiber can have appropriate friction to prevent the yarn cake from collapsing directly when winding. Moreover, by adding the first polyester and the second polyester, the graphene powder can go through two dispersion steps (granulation process and spinning process) to help evenly disperse the graphene powder in the polyester.

[0086] The contents disclosed above are only preferred feasible embodiments of the present application, and are not intended to limit the protection scope of the claims of the present application. Therefore, all equivalent technical changes made using the contents of the present application specification and drawings are included in the protection scope of the claims of the present application.

Claims

1. A method for producing graphene polyester fiber, characterized in that: The method for manufacturing the graphene polyester fiber comprises: Performing a modification procedure to form a modified layer on the surface of the graphene powder to obtain modified graphene powder; wherein the modified layer is formed by attaching a modifier to the surface of the graphene powder, and the modifier is silane or titanate; Mixing the modified graphene powder with the first polyester and performing a granulation process to obtain a graphene masterbatch; and The graphene masterbatch is mixed with a second polyester and subjected to a spinning process to obtain graphene polyester fibers.

2. The manufacturing method according to claim 1, characterized in that: In the modification procedure, a modification solution is sprayed on the surface of the graphene powder to obtain modified graphene powder, and the modification solution includes the modifier.

3. The manufacturing method according to claim 2, characterized in that: The modified solution is sprayed on the surface of the graphene powder and then dried to obtain the modified graphene powder; wherein the content of the modifier in the modified graphene powder is 1 weight percent to 5 weight percent.

4. The manufacturing method according to claim 1, characterized in that: The intrinsic viscosity of the first polyester is greater than the intrinsic viscosity of the second polyester.

5. The manufacturing method according to claim 4, characterized in that: The intrinsic viscosity of the first polyester is 0.8 to 1.0, and the intrinsic viscosity of the second polyester is 0.6 to 0.

7.

6. The manufacturing method according to claim 1, characterized in that: The material of the first polyester is polybutylene terephthalate.

7. The manufacturing method according to claim 1, characterized in that: The material of the second polyester is polyethylene terephthalate.

8. The manufacturing method according to claim 1, characterized in that: In the granulation process, the content of the modified graphene powder in the graphene masterbatch is 3 to 8 weight percent.

9. A graphene polyester fiber, characterized in that: The graphene polyester fiber comprises: Polyester resin; and Modified graphene powder is dispersed in the polyester resin; wherein the modified graphene powder comprises graphene powder and a modified layer, the modified layer is formed by a modifier attached to the surface of the graphene powder, and the modifier is silane or titanate.

10. The graphene polyester fiber according to claim 9, characterized in that: The polyester resin includes polybutylene terephthalate and polyethylene terephthalate.

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