A hyperbranched conductive dispersant, conductive master batch and preparation method and application thereof

Abstract

The application discloses a kind of hyperbranched conductive dispersant, conductive master batch and its preparation method and application, belong to conductive master batch technical field.The molecular formula of the hyperbranched conductive dispersant is as follows: the value of n is 55~60.The preparation method of the hyperbranched conductive dispersant includes: in the condition of protective atmosphere and room temperature, hyperbranched polysiloxane and hydrochloric acid are added in polyaniline solution to carry out reaction;The mass ratio of hyperbranched polysiloxane, hydrochloric acid and polyaniline in polyaniline solution is (5~15):(0.4~0.6):(48~52);Reaction time is 72h~80h.The preparation method of the hyperbranched conductive dispersant is simple, easy to operate.The hyperbranched conductive dispersant thus obtained can be used to prepare conductive master batch containing carbon black and nylon 6, can extend the spinning cycle of conductive master batch, avoid the phenomenon such as broken yarn and frequent screen change of conductive master batch in long-period spinning production, in addition, it can also improve the conductivity of conductive master batch.

Description

Technical Field

[0001] This invention relates to the field of conductive masterbatch technology, and more specifically, to a hyperbranched conductive dispersant, conductive masterbatch, its preparation method and application. Background Technology

[0002] Nylon 6 fiber possesses excellent physical properties, such as high strength, good moisture absorption, and vibrant color, making it one of the main raw materials for apparel textiles. Conductive nylon 6 fabrics can be used in antistatic textiles, electromagnetic radiation shielding textiles, smart textiles, and military textiles.

[0003] Conductive nylon 6 fabrics are typically produced by adding conductive fillers to a nylon 6 matrix and then spinning. Carbon black, as the most widely used and cost-effective conductive filler, can cause problems such as yarn breakage and frequent screen changes when added to nylon 6 at high concentrations. Adding auxiliaries to improve these issues can reduce the conductivity of the conductive masterbatch.

[0004] Therefore, how to avoid the problems such as filament breakage and frequent screen replacement that are prone to occur during long-cycle spinning production of conductive masterbatches without reducing their conductivity has become an urgent problem to be solved in this field.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a hyperbranched conductive dispersant, conductive masterbatch, and their preparation method and application, so as to solve or improve the above-mentioned technical problems.

[0007] This invention can be implemented as follows:

[0008] In a first aspect, the present invention provides a hyperbranched conductive dispersant, the molecular formula of which is as follows:

[0009] Where n takes values ​​from 55 to 60.

[0010] In a second aspect, the present invention provides a method for preparing a hyperbranched conductive dispersant as described in the foregoing embodiments, comprising the following steps: under a protective atmosphere and at room temperature, adding hyperbranched polysiloxane and hydrochloric acid to a polyaniline solution to carry out a reaction;

[0011] The mass ratio of hyperbranched polysiloxane, hydrochloric acid, and polyaniline in the polyaniline solution is (5-15):(0.4-0.6):(48-52); the reaction time is 72-80 h.

[0012] In an optional embodiment, the preparation of hyperbranched polysiloxane includes: reacting a mixture of KH-560 coupling agent and diethylene glycol under a protective atmosphere.

[0013] The molar ratio of KH-560 coupling agent to diethylene glycol is 1:2 to 1:3.

[0014] The reaction conditions include: an initial reaction temperature of 105℃~120℃, followed by a heating rate of 8℃ / h~12℃ / h to 160℃~180℃.

[0015] Thirdly, the present invention provides an application of the hyperbranched conductive dispersant as described in the foregoing embodiments, the application comprising at least one of the following aspects:

[0016] Application 1: Hyperbranched conductive dispersant is used to extend the spinning cycle of conductive masterbatch containing carbon black and nylon 6.

[0017] Application 2: Hyperbranched conductive dispersants are used to improve the conductivity of conductive masterbatches containing carbon black and nylon 6.

[0018] Fourthly, the present invention provides a conductive masterbatch, wherein, by weight, every 100 parts of the raw materials for preparing the conductive masterbatch comprises 30 to 40 parts of carbon black, 54 to 68 parts of nylon 6, and 1 to 4 parts of the hyperbranched conductive dispersant as described in the foregoing embodiments.

[0019] In an optional embodiment, the raw materials also include 1 to 2 parts of an auxiliary agent; the auxiliary agent includes at least one of a lubricant and an antioxidant.

[0020] Fifthly, the present invention provides a method for preparing conductive masterbatch as described in the foregoing embodiments, comprising the following steps: mixing the raw materials according to the specified ratio, followed by twin-screw extrusion and pelletizing.

[0021] In an optional embodiment, carbon black is mixed with a hyperbranched conductive dispersant and additives to obtain a composite raw material; the composite raw material and nylon 6 are extruded in a twin-screw extruder and then pelletized.

[0022] In an optional embodiment, the extrusion conditions include: a feeding speed of 5 Hz to 8 Hz; the twin-screw extruder is divided into five temperature zones, with temperatures of 210°C to 230°C, 230°C to 250°C, 230°C to 250°C, 230°C to 245°C, and 230°C to 245°C, respectively; and the main extruder speed is 180 r / min to 250 r / min.

[0023] In an optional implementation, the pelletizing conditions include a pelletizing rate of 5 Hz to 15 Hz.

[0024] In a sixth aspect, the present invention provides an application of the conductive masterbatch as described in the foregoing embodiments, for example, in the preparation of textiles.

[0025] The beneficial effects of this invention include:

[0026] This invention utilizes a polyaniline solution, hyperbranched polysiloxane, and hydrochloric acid to prepare a hyperbranched conductive dispersant. The combination of the three-dimensional spherical structure of the hyperbranched polysiloxane and the conjugated rigid structure of polyaniline allows the prepared hyperbranched conductive dispersant to achieve good dispersion of carbon black with a relatively small amount. Furthermore, polyaniline not only exhibits good compatibility with carbon black but can also form a conductive network with carbon black through π bonds. This conductive network structure can significantly improve the conductivity of the composite material. In addition, the molecular structure of the hyperbranched conductive dispersant provided by this invention contains a large number of ether bonds and hydroxyl groups, which is beneficial for the formation of dynamic non-covalent hydrogen bonds. This characteristic may contribute to the good compatibility of the hyperbranched conductive dispersant with carbon black and nylon 6, promoting both dispersion and compatibility. Therefore, the hyperbranched polysiloxane provided by this invention not only improves the dispersion effect of carbon black in nylon 6 but also enhances the conductivity of the composite material.

[0027] The preparation method of the hyperbranched conductive dispersant provided by this invention is simple and easy to operate. The hyperbranched conductive dispersant obtained thereby can be used to prepare conductive masterbatches containing nylon 6 and a high amount of carbon black. It can not only extend the spinning cycle of the conductive masterbatch and avoid phenomena such as yarn breakage and frequent screen changes during long-cycle spinning production, but also improve the conductivity of the conductive masterbatch. Attached Figure Description

[0028] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 SEM image of the conductive masterbatch prepared in Example 4;

[0030] Figure 2 The image shows a SEM image of the conductive masterbatch prepared in Comparative Example 1. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0032] The hyperbranched conductive dispersant, conductive masterbatch, their preparation method, and applications provided by this invention will be described in detail below.

[0033] This invention provides a hyperbranched conductive dispersant, the molecular formula of which is as follows:

[0034] Where n takes the value of 55 to 60 (e.g., 55, 56, 57, 58, 59, or 60). This hyperbranched conductive dispersant has good compatibility with both carbon black and nylon 6, and it itself has conductive properties, thus possessing both dispersing and conductive effects. When it is used together with nylon 6 and carbon black with a high filler content to prepare conductive masterbatch, it can avoid the problems of yarn breakage and frequent screen changes that are prone to occur during long-cycle spinning production of conductive masterbatch without reducing the conductivity of the conductive masterbatch.

[0035] Accordingly, the present invention also provides a method for preparing the above-mentioned hyperbranched conductive dispersant, the method comprising the following steps: under a protective atmosphere and at room temperature, adding hyperbranched polysiloxane and hydrochloric acid to a polyaniline solution for reaction.

[0036] The protective atmosphere can be an argon atmosphere and / or a nitrogen atmosphere. The room temperature can be, for example, 15°C to 30°C.

[0037] In some alternative embodiments, the polyaniline solution can be obtained by dissolving polyaniline in dimethyl sulfoxide, exemplary of which it can be obtained by mixing polyaniline and dimethyl sulfoxide in a mass ratio of 1:8 to 1:12. In some more typical embodiments, the mass ratio of polyaniline to dimethyl sulfoxide can be 1:10.

[0038] In some optional embodiments, the mass ratio of hyperbranched polysiloxane, hydrochloric acid, and polyaniline in the polyaniline solution can be (5-15):(0.4-0.6):(48-52). In some more typical embodiments, the mass ratio of hyperbranched polysiloxane, hydrochloric acid, and polyaniline in the polyaniline solution is 10:0.5:50.

[0039] In some alternative embodiments, the reaction time of the polyaniline solution, hyperbranched polysiloxane, and hydrochloric acid can be 72h to 80h, such as 72h, 74h, 76h, 78h, or 80h, or other values ​​within the range of 72h to 80h.

[0040] After the reaction of polyaniline solution, hyperbranched polysiloxane and hydrochloric acid is completed, the resulting reaction product is washed with excess methanol, then filtered, and the process is repeated several times (the specific settings can be adjusted according to actual conditions). The solid is then vacuum dried at 45℃~55℃ for 20h~28h.

[0041] In some alternative embodiments, the preparation of the above-mentioned hyperbranched polysiloxane may include: reacting a mixture of KH-560 coupling agent and diethylene glycol under a protective atmosphere.

[0042] The molar ratio of KH-560 coupling agent to diethylene glycol can be 1:2 to 1:3, such as 1:2, 1:2.2, 1:2.5, 1:2.8 or 1:3, or other values ​​within the range of 1:2 to 1:3.

[0043] In some optional embodiments, the reaction conditions include: an initial reaction temperature of 105°C to 120°C (e.g., 105°C, 110°C, 115°C, 118°C, or 120°C), followed by a heating rate of 8°C / h to 12°C / h (e.g., 8°C / h, 9°C / h, 10°C / h, 11°C / h, or 12°C / h) to 160°C to 180°C (e.g., 160°C, 165°C, 170°C, 175°C, or 180°C).

[0044] After the reaction between KH-560 coupling agent and diethylene glycol is completed, small molecules with a molecular weight of less than 1000 are removed by dialysis.

[0045] Continuing from the above, this invention uses a polyaniline solution, hyperbranched polysiloxane, and hydrochloric acid to prepare a hyperbranched conductive dispersant. The combination of the three-dimensional spherical structure of the hyperbranched polysiloxane and the conjugated rigid structure of polyaniline allows the prepared hyperbranched conductive dispersant to achieve good dispersion of carbon black with a relatively small amount. Furthermore, polyaniline not only has good compatibility with carbon black but can also form a conductive network with carbon black through π bonds. This conductive network structure can significantly improve the conductivity of the composite material. In addition, the molecular structure of the hyperbranched conductive dispersant provided by this invention contains a large number of ether bonds and hydroxyl groups, which is beneficial for the formation of dynamic non-covalent hydrogen bonds. This characteristic may help the hyperbranched conductive dispersant form good compatibility with carbon black and nylon 6, promoting dispersion and compatibility. Therefore, the hyperbranched polysiloxane provided by this invention not only improves the dispersion effect of carbon black in nylon 6 but also enhances the conductivity of the composite material.

[0046] Accordingly, the present invention provides applications of the above-mentioned hyperbranched conductive dispersant, for example, for extending the spinning cycle of conductive masterbatch containing carbon black and nylon 6; and / or for improving the conductivity of conductive masterbatch containing carbon black and nylon 6.

[0047] In addition, the present invention also provides a conductive masterbatch, wherein, by weight, every 100 parts of the raw materials for preparing the conductive masterbatch includes 30 to 40 parts of carbon black, 54 to 68 parts of nylon 6, and 1 to 4 parts of the above-mentioned hyperbranched conductive dispersant.

[0048] The amount of carbon black used can be 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, or 40 parts, or other values ​​within the range of 30 to 40 parts. In some preferred embodiments, the amount of carbon black used does not exceed 35 parts, such as 30 to 35 parts.

[0049] The amount of nylon 6 can be 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, or 68 parts, or other values ​​within the range of 54 to 68 parts. In some preferred embodiments, the amount of nylon 6 is not less than 60 parts, such as 60 to 67 parts.

[0050] The amount of hyperbranched conductive dispersant can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 4 parts, or other values ​​within the range of 1 to 4 parts. In some preferred embodiments, the amount of hyperbranched conductive dispersant does not exceed 3 parts, such as 1 to 3 parts.

[0051] If the amount of hyperbranched conductive dispersant is too high, it can easily lead to a decrease in screw shear force and affect dispersion.

[0052] Furthermore, the above-mentioned raw materials may also include auxiliary agents. The amount of auxiliary agents may be 1 to 2 parts, such as 1 part, 1.5 parts or 2 parts, or other values ​​within the range of 1 to 2 parts.

[0053] The additives may, by way of example, include at least one of a lubricant and an antioxidant. The lubricant may, by way of example, include at least one of EAA wax and EVA wax, preferably EAA wax. The antioxidant may, by way of example, include at least one of antioxidant 1098 and antioxidant 1010.

[0054] In some alternative embodiments, the surface resistivity of the conductive masterbatch does not exceed 1.8 × 10⁻⁶. 3 Ω; In some optional embodiments, the melt index of the conductive masterbatch is not less than 5 g / 10 min, such as 5.1 g / 10 min to 9.0 g / 10 min; In some optional embodiments, the spinning time corresponding to the conductive masterbatch is not less than 20 min, such as 20 min to 26 min.

[0055] In some preferred embodiments, the surface resistivity of the conductive masterbatch does not exceed 1.8 × 10⁻⁶. 3 The melt index of the conductive masterbatch is not less than 5 g / 10 min and the corresponding spinning time is not less than 20 min.

[0056] Accordingly, the present invention also provides a method for preparing the above-mentioned conductive masterbatch, comprising the following steps: mixing the raw materials according to the ratio, followed by twin-screw extrusion and pelletizing.

[0057] In some optional embodiments, when the raw materials for preparing the conductive masterbatch simultaneously include a hyperbranched conductive dispersant, nylon 6, carbon black, and additives, the method for preparing the conductive masterbatch includes: mixing carbon black with the hyperbranched conductive dispersant and additives to obtain a composite raw material; extruding the composite raw material and nylon 6 in a twin-screw extruder, followed by pelletizing.

[0058] In some optional embodiments, the extrusion conditions include: a feed rate of 5Hz to 8Hz (e.g., 5Hz, 5.5Hz, 6Hz, 6.5Hz, 7Hz, 7.5Hz, or 8Hz); the twin-screw extruder is divided into five temperature zones, with temperatures of 210℃ to 230℃ (e.g., 210℃, 215℃, 220℃, 225℃, or 230℃), 230℃ to 250℃ (e.g., 230℃, 235℃, 240℃, 245℃, or 250℃), and 230℃ to 250℃ (e.g., 2...). 30℃, 235℃, 240℃, 245℃ or 250℃, etc.), 230℃~245℃ (such as 230℃, 235℃, 240℃ or 245℃, etc.) and 230℃~245℃ (such as 230℃, 235℃, 240℃ or 245℃, etc.); the main engine speed is 180r / min~250r / min (such as 180r / min, 190r / min, 200r / min, 210r / min, 220r / min, 230r / min, 240r / min or 250r / min, etc.).

[0059] If the feeding speed is too slow, there will be insufficient material in the screw barrel, resulting in low shear force, which is not conducive to the mixing and dispersion of the material; if the feeding speed is too fast, it is not conducive to resin plasticization.

[0060] If the temperature of the first temperature zone is too low, it will not be conducive to the later plasticization of the resin; if the temperature of the first temperature zone is too high, it will lead to poor material feeding and easy bridging.

[0061] In some optional implementations, the pelletizing conditions include a pelletizing rate of 5 Hz to 15 Hz (e.g., 5 Hz, 6 Hz, 7 Hz, 8 Hz, 9 Hz, 10 Hz, 11 Hz, 12 Hz, 13 Hz, 14 Hz or 15 Hz).

[0062] Furthermore, the present invention also provides applications of the above-mentioned conductive masterbatch, such as its use in the preparation of textiles, including but not limited to antistatic textiles, electromagnetic radiation shielding textiles, smart textiles, and military textiles.

[0063] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0064] Example 1

[0065] This embodiment provides a hyperbranched conductive dispersant, the molecular formula of which is as follows:

[0066] Where n is 55 to 60.

[0067] The preparation method of this hyperbranched conductive dispersant includes:

[0068] S1: Preparation of hyperbranched polysiloxanes.

[0069] 40g of KH-560 coupling agent and 45g of diethylene glycol were added to a 250mL three-necked flask equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen protection, the initial reaction temperature was 110℃, and then the temperature was increased to 170℃ at a rate of 10℃ / h. Small molecules with a molecular weight below 1000 were then removed by dialysis.

[0070] S2: Preparation of hyperbranched conductive dispersant.

[0071] Add 50g of polyaniline to 500g of dimethyl sulfoxide, and under nitrogen protection, mechanically stir at 20°C for 30min to fully dissolve the polyaniline, thus obtaining a polyaniline solution.

[0072] Take 10g of the hyperbranched polysiloxane from S1 and 0.5g of hydrochloric acid, and add them dropwise to the above polyaniline solution, and continue stirring for 72h. After the reaction is complete, add excess methanol to wash the reaction product, then filter it. Repeat the washing and filtration process three times. Then, dry the solid under vacuum at 50℃ for 24h to obtain the hyperbranched conductive dispersant.

[0073] Example 2

[0074] The difference between this embodiment and Embodiment 1 is that the preparation method of the hyperbranched conductive dispersant provided in this embodiment includes:

[0075] S1: Same as Example 1.

[0076] S2: Preparation of hyperbranched conductive dispersant.

[0077] Add 50g of polyaniline to 500g of dimethyl sulfoxide, and under nitrogen protection, mechanically stir at 20°C for 30min to fully dissolve the polyaniline, thus obtaining a polyaniline solution.

[0078] Take 5g of hyperbranched polysiloxane from S1 and 0.4g of hydrochloric acid, and add them dropwise to the above polyaniline solution, stirring for 76h. After the reaction is complete, wash the reaction product with excess methanol, then filter it. Repeat the washing and filtration process three times. Finally, dry the solid under vacuum at 45℃ for 28h to obtain the hyperbranched conductive dispersant.

[0079] Example 3

[0080] The difference between this embodiment and Embodiment 1 is that the preparation method of the hyperbranched conductive dispersant provided in this embodiment includes:

[0081] S1: Same as Example 1.

[0082] S2: Preparation of hyperbranched conductive dispersant.

[0083] Add 50g of polyaniline to 500g of dimethyl sulfoxide, and under nitrogen protection, mechanically stir at 20°C for 30min to fully dissolve the polyaniline, thus obtaining a polyaniline solution.

[0084] Take 15g of hyperbranched polysiloxane from S1 and 0.6g of hydrochloric acid, and add them dropwise to the above polyaniline solution, and continue stirring for 80h. After the reaction is complete, add excess methanol to wash the reaction product, then filter it. Repeat the washing and filtration process three times. Then, dry the solid under vacuum at 55℃ for 20h to obtain the hyperbranched conductive dispersant.

[0085] Example 4

[0086] This embodiment provides a conductive masterbatch, which is prepared from raw materials consisting of 63.5 parts of nylon 6, 33 parts of carbon black, 1.5 parts of EAA wax, 1.5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0087] The preparation method of this conductive masterbatch includes:

[0088] S1: Dry nylon 6 and carbon black separately;

[0089] S2: The dried carbon black, EAA wax, hyperbranched conductive dispersant and antioxidant are added into a high-speed mixer in proportion and stirred for 10 minutes at 80℃ and 500r / min to obtain a mixture;

[0090] S3: Add the dried nylon 6 to the high-speed mixer in proportion and stir for 5 minutes at 100 r / min;

[0091] S4: The material mixed in steps S2 and S3 is conveyed to the feed hopper of the twin-screw extruder using an elevator, and fed at a rate of 6 Hz. The temperatures of the five temperature zones of the twin-screw extruder are set to 215℃, 240℃, 245℃, 245℃, and 240℃ respectively, and the main extruder speed is 200 r / min. The extruded material is pelletized in a water tank at a rate of 6 Hz to obtain conductive masterbatch (e.g., Figure 1 (As shown).

[0092] Example 5

[0093] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 63 parts of nylon 6, 32.5 parts of carbon black, 1.5 parts of EAA wax, 2.5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0094] Example 6

[0095] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 64 parts of nylon 6, 33 parts of carbon black, 1.5 parts of EAA wax, 1 part of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0096] Example 7

[0097] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 67 parts of nylon 6, 30 parts of carbon black, 1.5 parts of EAA wax, 1 part of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0098] Example 8

[0099] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 61 parts of nylon 6, 35 parts of carbon black, 1.5 parts of EAA wax, 2 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0100] Example 9

[0101] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 60 parts of nylon 6, 35 parts of carbon black, 1.5 parts of EAA wax, 3 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0102] Example 10

[0103] The difference between this embodiment and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 54 parts of nylon 6, 40 parts of carbon black, 1.5 parts of EAA wax, 4 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0104] Example 11

[0105] This embodiment provides a conductive masterbatch, which is prepared from raw materials consisting of 63.5 parts of nylon 6, 33 parts of carbon black, 1.5 parts of EAA wax, 1.5 parts of the hyperbranched conductive dispersant provided in Example 2, and 0.5 parts of antioxidant 1098.

[0106] Example 12

[0107] This embodiment provides a conductive masterbatch, which is prepared from raw materials consisting of 63.5 parts of nylon 6, 33 parts of carbon black, 1.5 parts of EAA wax, 1.5 parts of the hyperbranched conductive dispersant provided in Example 3, and 0.5 parts of antioxidant 1098.

[0108] Example 13

[0109] The difference between this embodiment and embodiment 4 is that:

[0110] In the preparation method of the hyperbranched conductive dispersant, S1 is as follows: KH-560 coupling agent and diethylene glycol are added to a 250 mL three-necked flask at a molar ratio of 1:2. The three-necked flask is equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen protection, the initial reaction temperature is 105℃, and then the temperature is increased to 160℃ at a rate of 8℃ / h, and the reaction is carried out for 4 hours. Then, small molecules with a molecular weight below 1000 are removed by dialysis.

[0111] The lubricant in the conductive masterbatch is EVA wax, and the antioxidant is 1010.

[0112] During the preparation of conductive masterbatch, the extrusion conditions include: a feeding speed of 5 Hz; temperatures of the first to fifth temperature zones of the twin-screw extruder of 210℃, 230℃, 240℃, 235℃ and 230℃, respectively; a main extruder speed of 180 r / min; and a pelletizing rate of 5 Hz.

[0113] Example 14

[0114] The difference between this embodiment and embodiment 4 is that:

[0115] In the preparation method of the hyperbranched conductive dispersant, S1 is as follows: KH-560 coupling agent and diethylene glycol are added to a 250 mL three-necked flask at a molar ratio of 1:3. The three-necked flask is equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen protection, the initial reaction temperature is 120℃, and then the temperature is increased to 180℃ at a rate of 12℃ / h, and the reaction is carried out for 4 hours. Then, small molecules with a molecular weight below 1000 are removed by dialysis.

[0116] During the preparation of conductive masterbatch, the extrusion conditions include: a feeding speed of 8 Hz; temperatures of the first to fifth temperature zones of the twin-screw extruder of 230℃, 250℃, 250℃, 245℃ and 240℃, respectively; a main extruder speed of 250 r / min; and a pelletizing rate of 15 Hz.

[0117] Comparative Example 1

[0118] The difference between this comparative example and Example 4 is that the hyperbranched polysiloxane prepared in S1 of Example 1 is used in an equal amount to replace the hyperbranched conductive dispersant.

[0119] The SEM image of the conductive masterbatch prepared in this comparative example is shown below. Figure 2 As shown.

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 5 is that the hyperbranched conductive dispersant is replaced by an equal amount of the hyperbranched polysiloxane prepared in S1 of Example 1.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 64 parts of nylon 6, 34 parts of carbon black, 1.5 parts of EAA wax, and 0.5 parts of antioxidant 1098.

[0124] In other words, in this comparative example, the raw materials for preparing the conductive composite material do not contain any dispersant.

[0125] Comparative Example 4

[0126] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 63.5 parts of nylon 6, 34 parts of carbon black, 1.5 parts of EAA wax, 0.5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0127] That is, the amount of nylon 6 used increased, while the amount of hyperbranched conductive dispersant used decreased.

[0128] Comparative Example 5

[0129] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 60 parts of nylon 6, 33 parts of carbon black, 1.5 parts of EAA wax, 5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0130] That is, the amount of nylon 6 used is reduced, while the amount of hyperbranched conductive dispersant is increased.

[0131] Comparative Example 6

[0132] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 69.5 parts of nylon 6, 27 parts of carbon black, 1.5 parts of EAA wax, 1.5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0133] That is, the amount of nylon 6 used increased, while the amount of carbon black used decreased.

[0134] Comparative Example 7

[0135] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch consist of 54.5 parts of nylon 6, 42 parts of carbon black, 1.5 parts of EAA wax, 1.5 parts of the hyperbranched conductive dispersant provided in Example 1, and 0.5 parts of antioxidant 1098.

[0136] That is, the amount of nylon 6 used is reduced, while the amount of carbon black used is increased.

[0137] Test case

[0138] The conductivity and material properties of the conductive masterbatches prepared in Examples 4-14 and Comparative Examples 1-7 were compared. Furthermore, the longest achievable spinning time for each conductive masterbatch was compared. The results are shown in Table 1. The test items and methods are as follows:

[0139] A. Conductivity: The surface resistance (in Ω) of the conductive masterbatch is characterized by testing it using a surface resistance meter. Specifically, each conductive masterbatch is measured directly after drying.

[0140] B. Material dispersibility: The melt flow index was characterized using ASTM D1238, with test conditions of 260℃ and 2.16 kg. The unit of melt flow index is g / 10min.

[0141] C. Preliminary determination of spinning time: In order to preliminarily determine the length of the spinning time of the conductive masterbatch in a short period of time, the time required for screen replacement when the melt pressure of the spinning melt flowing through the single screw is greater than 8MPa is used as the characterization. The test conditions are: the temperature of the five temperature zones of the single screw spinning machine is 260℃, 285℃, 285℃, 285℃ and 285℃, the screen mesh is 400 mesh, and the unit is min.

[0142] Table 1 Test Results

[0143] Example 4 <![CDATA[0.9×10 3 ]]> 7.5 35 Example 5 <![CDATA[0.7×10 3 ]]> 8.5 36 Example 6 <![CDATA[1.1×10 3 ]]> 5.9 25 Example 7 <![CDATA[1.5×10 3 ]]> 6.5 26 Example 8 <![CDATA[0.5×10 3 ]]> 8.0 32 Example 9 <![CDATA[0.3×10 3 ]]> 9.0 29 Example 10 <![CDATA[<0.2×10 3 ]]> 5.1 20 Example 11 <![CDATA[1.8×10 3 ]]> 7.9 33 Example 12 <![CDATA[0.6×10 3 ]]> 7.2 31 Example 13 <![CDATA[1.0×10 3 ]]> 7.3 27 Example 14 <![CDATA[1.1×10 3 ]]> 7.4 35 Comparative Example 1 <![CDATA[3.0×10 3 ]]> 7.6 33 Comparative Example 2 <![CDATA[2.0×10 3 ]]> 7.7 33 Comparative Example 3 Unable to granulate 0 0 Comparative Example 4 <![CDATA[0.9×10 3 ]]> 0.3 0 Comparative Example 5 <![CDATA[0.8×10 3 ]]> 9.2 10 Comparative Example 6 <![CDATA[1.0×10 4 ]]> 8.3 38 Comparative Example 7 <![CDATA[<0.2×10 3 ]]> 0 0

[0144] As can be seen from Table 1, the hyperbranched conductive dispersant provided in the embodiments of the present invention, together with nylon 6 and carbon black with a high filler content, can prepare conductive masterbatch without reducing the conductivity of conductive masterbatch, and can also avoid phenomena such as yarn breakage and frequent screen replacement that are easy to occur during long-cycle spinning production of conductive masterbatch.

[0145] In summary, the hyperbranched conductive dispersant with a specific molecular formula provided by the present invention can not only extend the spinning cycle of conductive masterbatch containing carbon black and nylon 6, but also improve the conductivity of conductive masterbatch containing carbon black and nylon 6.

[0146] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A hyperbranched conductive dispersant, characterized in that, The molecular formula of the hyperbranched conductive dispersant is as follows: Where n takes values ​​from 55 to 60.

2. A method for preparing the hyperbranched conductive dispersant as described in claim 1, characterized in that, Includes the following steps: Under a protective atmosphere and at room temperature, hyperbranched polysiloxane and hydrochloric acid were added to a polyaniline solution to carry out a reaction. The mass ratio of the hyperbranched polysiloxane, the hydrochloric acid, and the polyaniline in the polyaniline solution is (5-15):(0.4-0.6):(48-52); the reaction time is 72-80 h.

3. The preparation method according to claim 2, characterized in that, The preparation of the hyperbranched polysiloxane includes: reacting a mixture of KH-560 coupling agent and diethylene glycol under a protective atmosphere. The molar ratio of the KH-560 coupling agent to the diethylene glycol is 1:2 to 1:

3. The reaction conditions include: an initial reaction temperature of 105℃~120℃, followed by a heating rate of 8℃ / h~12℃ / h to 160℃~180℃.

4. An application of the hyperbranched conductive dispersant as described in claim 1, characterized in that, The application includes at least one of the following aspects: Application 1: The hyperbranched conductive dispersant is used to extend the spinning cycle of conductive masterbatch containing carbon black and nylon 6. Application 2: The hyperbranched conductive dispersant is used to improve the conductivity of conductive masterbatch containing carbon black and nylon 6.

5. A conductive masterbatch, characterized in that, By weight, every 100 parts of the raw materials used to prepare the conductive masterbatch include 30 to 40 parts of carbon black, 54 to 68 parts of nylon 6, and 1 to 4 parts of the hyperbranched conductive dispersant as described in claim 1.

6. The conductive masterbatch according to claim 5, characterized in that, The raw materials for preparation also include 1 to 2 parts of additives; the additives include at least one of lubricant and antioxidant.

7. A method for preparing the conductive masterbatch as described in claim 5 or 6, characterized in that, The process includes the following steps: mixing the raw materials according to the specified ratio, followed by twin-screw extrusion and pelletizing.

8. The preparation method according to claim 7, characterized in that, Carbon black is mixed with hyperbranched conductive dispersant and additives to obtain a composite raw material; the composite raw material and nylon 6 are extruded in a twin-screw extruder and then pelletized.

9. The preparation method according to claim 8, characterized in that, The extrusion conditions include: a feed rate of 5Hz to 8Hz; the twin-screw extruder is divided into five temperature zones, with temperatures of 210℃ to 230℃, 230℃ to 250℃, 230℃ to 250℃, 230℃ to 245℃, and 230℃ to 245℃, respectively; and the main extruder speed is 180r / min to 250r / min. And / or, pelletizing conditions include: pelletizing rate of 5Hz to 15Hz.

10. The use of a conductive masterbatch as described in claim 5 or 6 in the preparation of textiles.

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