CN111287003B - Water-based graphene PTC conductive dye, preparation method thereof and conductive fiber treated by dye - Google Patents

Water-based graphene PTC conductive dye, preparation method thereof and conductive fiber treated by dye Download PDF

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CN111287003B
CN111287003B CN202010237706.5A CN202010237706A CN111287003B CN 111287003 B CN111287003 B CN 111287003B CN 202010237706 A CN202010237706 A CN 202010237706A CN 111287003 B CN111287003 B CN 111287003B
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conductive
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ptc
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dye
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CN111287003A (en
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张�林
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Material And Industrial Technology Research Institute Beijing
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Abstract

The invention provides a water-based graphene PTC conductive dye which comprises the following components in parts by weight: 15-40 parts of PTC functional components, 10-20 parts of adhesive, 5-20 parts of conductive filler, 20-60 parts of deionized water, 5-10 parts of emulsifier and 1-5 parts of other auxiliary agents. The invention also provides a preparation method of the water-based graphene PTC conductive dye and a graphene PTC conductive fiber obtained by processing the water-based graphene PTC conductive dye. By using the conductive filler and the PTC functional components in the water-based graphene PTC conductive dye, the conductive fiber with the self-temperature-limiting function can be prepared, and meanwhile, the flexible, comfortable and safe use performance of the fiber is considered.

Description

Water-based graphene PTC conductive dye, preparation method thereof and conductive fiber treated by dye
Technical Field
The invention relates to the technical field of fiber manufacturing, in particular to a water-based graphene PTC conductive dye, a preparation method of the dye and graphene PTC conductive fibers obtained by processing the water-based graphene PTC conductive dye.
Background
The conductive fibers applied to the traditional electric heating fabrics are mainly metal or metal-plated fibers, carbon fibers and the like, and the defects of hard fibers, poor comfort, poor kneading resistance and the like generally exist. Meanwhile, the traditional electric heating fabric does not have self-temperature control (PTC) performance, the heating power temperature needs to be adjusted through external control, and the danger of overheating caused by faults or extreme use conditions exists. Therefore, it is desirable to provide a conductive fiber with a temperature self-control function, while simultaneously achieving flexibility, comfort and safety of the fiber.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a water-based graphene PTC conductive dye.
The second purpose of the invention is to provide a preparation method of the water-based graphene PTC conductive dye.
The third purpose of the invention is to provide the graphene PTC conductive fiber obtained by processing the aqueous graphene PTC conductive dye.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a water-based PTC graphene conductive dye which comprises the following components in parts by weight: 15-40 parts of PTC functional components, 10-20 parts of adhesive, 5-20 parts of conductive filler, 20-60 parts of deionized water, 5-10 parts of emulsifier and 1-5 parts of other auxiliary agents.
Preferably, the PTC functional component is selected from at least one of paraffin, stearic acid, polycaprolactone, polyethylene glycol.
Preferably, the emulsifier is a nonionic surfactant or an anionic surfactant, and the HLB value is 14-16.
Preferably, the adhesive is selected from at least one of aqueous polyurethane resin, epoxy resin modified polyurethane resin and organic silicon modified polyurethane resin.
Preferably, the conductive filler is at least one of graphene and carbon nanotubes.
Preferably, the other auxiliary agent is selected from at least one of a defoaming agent, a dispersing agent and an adhesion promoter.
Preferably, the defoaming agent is selected from at least one of TEGO901W, BYK019 and BYK 025; the dispersant is selected from at least one of TEGO760W, AFCONO5065 and BYK 9076; the adhesion promoter is selected from at least one of hydroxymethyl cellulose, polyethylene oxide and polyacrylamide.
The invention also relates to a preparation method of the water-based PTC graphene conductive dye, which comprises the following steps:
1) dissolving the emulsifier in the deionized water to obtain a uniform solution;
2) slowly adding the PTC functional component into the uniform solution, and emulsifying to obtain a first emulsion;
3) adding the adhesive and other additives into the first emulsion, uniformly mixing, adding a conductive filler, and uniformly mixing to obtain a second emulsion;
4) and grinding the second emulsion to enable the average particle size of the filler to be less than or equal to 2 microns, thereby obtaining the water-based PTC graphene conductive dye.
The invention also relates to a conductive fiber obtained by processing the water-based PTC graphene conductive dye.
Preferably, the conductive fiber is prepared by the following method:
4) desizing: desizing the base material fiber;
preferably, the desizing treatment is carried out by treating the base material fiber in a sodium carbonate solution with the mass concentration of 0.2-0.5% for 50-120 min at the temperature of 90-100 ℃.
Preferably, the base material fiber is selected from at least one of viscose, terylene, chinlon, aramid fiber and acrylic fiber.
5) Surface grafting modification: adopting a silane coupling agent to carry out surface grafting modification on the desized base material fiber:
preferably, silane coupling agent hydrolysate is adopted to perform soaking modification on the desized fiber, and the modification time is 3-5 h;
preferably, the silane coupling agent is selected from at least one of KH550 and KH 570.
6) Dyeing: placing the surface grafting modified substrate fiber into the graphene PTC conductive dye for dyeing;
preferably, the dyeing temperature is 70-90 ℃ and the dyeing time is 0.5-2 h.
4) And (3) upper protective layer: dissolving an adhesive in water to prepare a sizing solution, taking the dyed fiber out, drying, sizing, drying and forming to obtain the graphene PTC conductive fiber.
Preferably, the mass concentration of the adhesive in the sizing liquid is 4-8%.
The invention has the beneficial effects that:
the invention provides a water-based graphene PTC conductive dye, a preparation method of the water-based graphene PTC conductive dye, and graphene PTC conductive fibers obtained by processing the water-based graphene PTC conductive dye. According to the invention, the conductive filler and the PTC functional component are used in the water-based graphene PTC conductive dye, so that the conductive fiber with the self-temperature-limiting function can be prepared, and meanwhile, the flexible, comfortable and safe use performance of the fiber is considered.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a water-based PTC graphene conductive dye which comprises the following components in parts by weight: 15-40 parts of PTC functional components, 10-20 parts of adhesive, 5-20 parts of conductive filler, 20-60 parts of deionized water, 5-10 parts of emulsifier and 1-5 parts of other auxiliary agents.
In one embodiment of the present invention, the PTC functional component is selected from at least one of paraffin, stearic acid, polycaprolactone, polyethylene glycol. The phase-change heat storage material comprises an organic phase-change material and an inorganic phase-change material. The present invention limits the PTC functional component to an organic phase change material because it can be emulsified by an emulsifier to obtain a uniform emulsion, whereas an inorganic phase change material (such as calcium chloride hexahydrate) cannot be dispersed in an aqueous solution to obtain an emulsion.
The PTC functional components are crystalline polymer phase-change heat storage materials, and when the materials are added into conductive fibers, the temperature is increased when current passes through the fibers. When the temperature reaches the phase transition temperature of the PTC functional component, the material is changed from a crystalline state to a molten state, and a conductive path is cut off. At this time, the resistance of the component increases and the current passing through the conductive fiber is reduced to prevent the temperature from continuing to rise, so that both the PTC functional component and the conductive fiber containing the above component have a self-temperature-controlling function. In order to realize phase change, the molecular weight of the paraffin is preferably 350-500, the molecular weight of the polyethylene glycol is preferably 3500-4000, and the stearic acid and the polycaprolactone are fixed molecular weights.
Since the above PTC functional components are insoluble in water, an emulsifier needs to be added to uniformly disperse them in water to obtain a stable emulsion. The emulsifier is a surfactant, and the molecule contains hydrophilic groups and lipophilic groups. To indicate the hydrophilicity or lipophilicity of an emulsifier, the hydrophilic-lipophilic balance (HLB) value is generally used. The lower the HLB value, the more lipophilic it is; conversely, the higher the HLB value, the more hydrophilic it is. The HLB value of each emulsifier varies and a suitable emulsifier must be selected in order to obtain a stable emulsion.
In one embodiment of the invention, the emulsifier is a nonionic surfactant or an anionic surfactant, and the HLB value is 14-16, which is the optimal HLB value for emulsifying the melted PTC functional component. Useful emulsifiers include APG1214 (dodecyl glucoside), sodium dodecyl sulfate, Tween-80, fatty alcohol-polyoxyethylene ether, and the like. The fatty alcohol-polyoxyethylene ether comprises peregal O, SA20, A20, O20, O25 and OS 15.
In one embodiment of the present invention, the adhesive is selected from at least one of an aqueous polyurethane resin, an epoxy resin-modified polyurethane resin, and a silicone-modified polyurethane resin. The function is to enhance the adhesion of the PTC functional components and the conductive filler on the surface of the fiber.
In one embodiment of the present invention, in order to make the dye conductive, a conductive filler needs to be added. The conductive filler is at least one of graphene and carbon nanotubes.
In one embodiment of the invention, the further auxiliary agent is selected from at least one of a defoamer, a dispersant, an adhesion promoter. Further, the defoaming agent is selected from at least one of TEGO901W, BYK019 and BYK 025; the dispersant is selected from at least one of TEGO760W, AFCONO5065 and BYK 9076; the adhesion promoter is at least one selected from hydroxymethyl cellulose, polyethylene oxide and polyacrylamide.
The embodiment of the invention also relates to a preparation method of the water-based PTC graphene conductive dye, which comprises the following steps:
1) dissolving an emulsifier in deionized water to obtain a uniform solution;
2) slowly adding the PTC functional component into the uniform solution, and emulsifying to obtain a first emulsion;
3) adding the adhesive and other additives into the first emulsion, uniformly mixing, adding the conductive filler, and uniformly mixing to obtain a second emulsion;
4) and grinding the second emulsion by a horizontal grinder to ensure that the average particle size of the filler is less than or equal to 2 mu m to obtain the water-based PTC graphene conductive dye.
The invention also relates to a conductive fiber obtained by treating the water-based PTC graphene conductive dye, which is prepared by the following method:
1) desizing: desizing the base material fiber to remove the sizing agent on the surface of the fiber, so as to facilitate subsequent surface grafting modification and dyeing;
in one embodiment of the invention, the desizing treatment is carried out by treating the base material fiber in a sodium carbonate solution with the mass concentration of 0.2-0.5% for 50-120 min at 90-100 ℃.
In one embodiment of the present invention, the substrate fiber is at least one selected from the group consisting of viscose, polyester, nylon, aramid, and acrylic.
2) Surface grafting modification: adopting a silane coupling agent to carry out surface grafting modification on the desized base material fiber so as to improve the color fastness, crease resistance and shape retention property and the like:
in one embodiment of the invention, silane coupling agent hydrolysate is adopted to perform soaking modification on the desized fiber, and the modification time is 3-5 h.
In one embodiment of the invention, the silane coupling agent hydrolysate is prepared by mixing silane, deionized water, ethanol and acetic acid in a ratio of 10: 80: 10: mixing at the normal temperature according to the volume ratio of 1-5, and stirring for 4-5 h.
In one embodiment of the present invention, the silane coupling agent is selected from at least one of KH550 and KH 570.
3) Dyeing: placing the surface grafting modified base material fiber in graphene PTC conductive dye for dyeing;
in one embodiment of the invention, the dyeing temperature is 70-90 ℃ and the dyeing time is 0.5-2 h.
4) And (3) upper protective layer: dissolving the adhesive in water to prepare sizing liquid, taking the dyed fiber out, drying, sizing, drying and forming to obtain the graphene PTC conductive fiber.
In one embodiment of the invention, the mass concentration of the sizing agent in the sizing solution is 4% to 8%.
According to the invention, the coating with PTC electric conduction and protection functions is constructed on the surface of the base material fiber to obtain the conductive fiber, so that the conductive fiber has the hand feeling of the base material fiber (such as terylene), and meanwhile, the PTC component in the conductive layer also has the function of self temperature limitation of the conductive fiber, and has intelligence and safety performance.
Example 1
(1) Preparation of aqueous PTC graphene conductive dye
Based on the total weight of the dye, the dye comprises the following components in parts by weight: 15-40 parts of PTC functional components, 10-20 parts of adhesive, 5-20 parts of conductive filler, 20-60 parts of deionized water, 5-10 parts of emulsifier and 1-5 parts of other auxiliary agents. The specific materials and proportions of the components are changed, and the details are shown in Table 1.
TABLE 1
Figure BDA0002431558730000061
Figure BDA0002431558730000071
The preparation method of the water-based PTC graphene conductive dye comprises the following steps:
1) dissolving an emulsifier in deionized water to obtain a uniform solution;
2) slowly adding the PTC functional components into the uniform solution, and emulsifying by using an emulsifying machine to obtain a first emulsion;
3) adding the adhesive and other additives into the first emulsion, mixing for 15min, adding the conductive filler, and mixing for 30min to obtain a second emulsion;
4) and grinding the second emulsion to ensure that the average particle size of the filler is less than or equal to 2 mu m, thereby obtaining the water-based PTC graphene conductive dye.
(2) Preparation of conductive fibers
1) Desizing: desizing polyester fibers in a sodium carbonate solution with the mass concentration of 0.3% for 60min at the temperature of 90-100 ℃.
2) Surface grafting modification: adopting silane coupling agent hydrolysate to perform soaking modification on the desized fiber for 4 hours; the silane coupling agent hydrolysate is prepared by mixing KH550, deionized water, ethanol and acetic acid according to the weight ratio of 10: 80: 10: 3, mixing at normal temperature, and stirring for 4-5 h.
3) Dyeing: and (3) placing the surface grafting modified fiber into the graphene PTC conductive dye obtained in the examples and the comparative examples for dyeing, wherein the dyeing temperature is 80 ℃, and the dyeing time is 1 h.
4) And (3) upper protective layer: dissolving the adhesive in water to obtain sizing liquid with the mass concentration of 5%, taking out the dyed fibers, drying, sizing by a sizing machine, drying and forming to obtain the graphene PTC conductive fibers.
The graphene PTC conductive fibers obtained in the examples and the comparative examples are subjected to conductivity and self-temperature control tests according to GB/T29470-2012, and the test results are shown in Table 2.
TABLE 2
Examples/comparative examples Line resistance (omega/cm) PTC strength
Example 1 300 4
Example 2 310 3
Example 3 350 3
Example 4 300 3.5
Example 5 280 3
Comparative example 1 260 1
Comparative example 2 320 2
Comparative example 3 / 0
The data in table 2 show that the graphene PTC conductive fiber obtained by treating the aqueous graphene PTC conductive dye provided by the invention has excellent conductivity and self-temperature control capability. If the HLB value of the inorganic phase-change material or the emulsifier is not within the range defined in the present invention, the above properties are reduced.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (7)

1. The water-based PTC graphene conductive dye is characterized by comprising the following components in parts by weight: 15-40 parts of PTC functional components, 10-20 parts of adhesive, 5-20 parts of conductive filler, 20-60 parts of deionized water, 5-10 parts of emulsifier and 1-5 parts of other auxiliary agents;
the PTC functional component is selected from at least one of paraffin, stearic acid, polycaprolactone and polyethylene glycol;
the emulsifier is a nonionic surfactant or an anionic surfactant, and the HLB value is 14-16;
the conductive filler is at least one of graphene and carbon nano tube,
the molecular weight of the paraffin is 350-500, and the molecular weight of the polyethylene glycol is 3500-4000;
the emulsifier comprises dodecyl glucoside APG1214, sodium dodecyl sulfate, Tween-80 or fatty alcohol polyoxyethylene ether.
2. The aqueous PTC graphene conductive dye according to claim 1, wherein the adhesive is at least one selected from the group consisting of aqueous polyurethane resin, epoxy resin modified polyurethane resin, and silicone modified polyurethane resin.
3. The aqueous PTC graphene conductive dye according to claim 1, wherein the other auxiliary agents are selected from at least one of a defoamer, a dispersant, an adhesion promoter;
the defoaming agent is selected from at least one of TEGO901W, BYK019 and BYK 025; the dispersant is selected from at least one of TEGO760W, AFCONO5065 and BYK 9076; the adhesion promoter is selected from at least one of hydroxymethyl cellulose, polyethylene oxide and polyacrylamide.
4. The method for preparing the aqueous PTC graphene conductive dye according to any one of claims 1 to 3, comprising the steps of:
1) dissolving the emulsifier in the deionized water to obtain a uniform solution;
2) adding the PTC functional component into the uniform solution, and emulsifying to obtain a first emulsion;
3) adding the adhesive and other additives into the first emulsion, uniformly mixing, adding a conductive filler, and uniformly mixing to obtain a second emulsion;
4) and grinding the second emulsion to enable the average particle size of the filler to be less than or equal to 2 microns, thereby obtaining the water-based PTC graphene conductive dye.
5. An electrically conductive fiber treated with the aqueous PTC graphene conductive dye according to any one of claims 1 to 3.
6. The conductive fiber according to claim 5, which is prepared by:
1) desizing: desizing the base material fiber;
2) surface grafting modification: adopting a silane coupling agent to carry out surface grafting modification on the desized base material fiber:
3) dyeing: placing the surface grafting modified substrate fiber into the water-based PTC graphene conductive dye for dyeing;
4) and (3) upper protective layer: dissolving an adhesive in water to prepare a sizing solution, taking the dyed fiber out, drying, sizing, drying and forming to obtain the graphene PTC conductive fiber.
7. The conductive fiber according to claim 6, wherein in the step 1), the base material fiber is treated in a sodium carbonate solution with a mass concentration of 0.2-0.5% for 50-120 min at 90-100 ℃;
and/or the base material fiber is selected from at least one of viscose, terylene, chinlon, aramid fiber and acrylic fiber;
and/or, in the step 3), soaking and modifying the desized fiber by adopting silane coupling agent hydrolysate;
and/or in the step 4), the mass concentration of the adhesive in the sizing liquid is 4-8%.
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