Hyperbranched conductive dispersant, conductive master batch and preparation method and application thereof

Abstract

The invention discloses a hyperbranched conductive dispersant, a conductive master batch and a preparation method and application thereof, and belongs to the technical field of conductive master batches. The molecular formula of the hyperbranched conductive dispersant is as follows: # imgabs0 # n is 55-60. The preparation method of the hyperbranched conductive dispersant comprises the following steps: adding hyperbranched polysiloxane and hydrochloric acid into a polyaniline solution for reaction in a protective atmosphere at room temperature; the mass ratio of the hyperbranched polysiloxane to the hydrochloric acid to polyaniline in the polyaniline solution is (5-15): (0.4-0.6): (48-52); the reaction time is 72 to 80 hours. The preparation method of the hyperbranched conductive dispersant is simple and easy to operate. The obtained hyperbranched conductive dispersant can be used for preparing conductive master batches containing carbon black and chinlon 6, the spinning period of the conductive master batches can be prolonged, the phenomena of filament breaking, frequent net changing and the like of the conductive master batches during long-period spinning production are avoided, and in addition, the conductivity of the conductive master batches can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of conductive masterbatch, and in particular to a hyperbranched conductive dispersant, a conductive masterbatch, and a preparation method and application thereof. Background Art

[0002] Nylon 6 fiber has excellent physical properties, such as high strength, good moisture absorption, and bright dyeing, making it a key raw material for clothing textiles. Conductive nylon 6 fabrics can be used in antistatic textiles, electromagnetic radiation shielding textiles, smart textiles, and military textiles.

[0003] Conductive nylon 6 fabric is typically produced by adding conductive fillers to a nylon 6 matrix and spinning it. Carbon black, the most widely used and cost-effective conductive filler, can be added to nylon 6 at high loadings. However, when used in long spinning cycles, the resulting conductive masterbatch is prone to problems such as yarn breakage and frequent screen changes. Adding additives to address these issues can reduce the conductivity of the masterbatch.

[0004] Therefore, how to avoid the phenomenon of broken wires and frequent screen changes during long-cycle spinning production of the conductive masterbatch without reducing the conductivity of the above-mentioned conductive masterbatch 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 the present invention is to provide a hyperbranched conductive dispersant, a conductive masterbatch and a preparation method and application thereof, so as to solve or improve the above technical problems.

[0007] The present invention can be implemented like this:

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

[0009] Among them, the value of n is 55 to 60.

[0010] In a second aspect, the present invention provides a method for preparing a hyperbranched conductive dispersant according to the aforementioned embodiment, comprising the following steps: adding hyperbranched polysiloxane and hydrochloric acid to a polyaniline solution under a protective atmosphere and room temperature to react;

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

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

[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° C. to 120° C., and then heating to 160° C. to 180° C. at a heating rate of 8° C. / h to 12° C. / h.

[0015] In a third aspect, the present invention provides an application of the hyperbranched conductive dispersant according to the aforementioned embodiment, wherein the application includes at least one of the following aspects:

[0016] Application 1: Hyperbranched conductive dispersants are used to extend the spinning cycle of conductive masterbatches 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] In a fourth aspect, the present invention provides a conductive masterbatch, wherein every 100 parts of raw materials for preparing the conductive masterbatch include, by weight, 30 to 40 parts of carbon black, 54 to 68 parts of nylon 6, and 1 to 4 parts of a hyperbranched conductive dispersant as described in the aforementioned embodiment.

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

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

[0021] In an optional embodiment, carbon black is mixed with a hyperbranched conductive dispersant and an additive 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 rate of 5Hz to 8Hz; the twin-screw extruder is divided into first to fifth temperature zones, and the temperatures of the first to fifth temperature zones are 210℃ to 230℃, 230℃ to 250℃, 230℃ to 250℃, 230℃ to 245℃ and 230℃ to 245℃ respectively; the main engine speed is 180r / min to 250r / min.

[0023] In an optional embodiment, 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 according to the aforementioned embodiment, for example, using the conductive masterbatch in the preparation of textiles.

[0025] The beneficial effects of the present invention include:

[0026] The present invention uses a polyaniline solution, a hyperbranched polysiloxane, and hydrochloric acid to prepare a hyperbranched conductive dispersant. The combination of the spatial spherical structure of the hyperbranched polysiloxane and the conjugated rigid structure of the polyaniline enables the prepared hyperbranched conductive dispersant to achieve good dispersion of carbon black even with a relatively low addition amount. Furthermore, polyaniline not only has good compatibility with carbon black but also forms a conductive network with carbon black through π bonds. This conductive network structure can significantly improve the conductivity of the composite material. Furthermore, the molecular structure of the hyperbranched conductive dispersant provided by the present invention contains a large number of ether bonds and hydroxyl groups, which facilitates 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, thereby promoting dispersion and compatibility. Therefore, the hyperbranched polysiloxane provided by the present invention can not only improve the dispersion of carbon black in nylon 6, but also improve the conductive properties of the composite material.

[0027] The hyperbranched conductive dispersant provided by the present invention is simple and easy to prepare. The resulting hyperbranched conductive dispersant can be used to prepare conductive masterbatches containing nylon 6 and a high loading of carbon black. This method not only extends the spinning cycle of the conductive masterbatch, avoiding problems such as yarn breakage and frequent screen changes during long-cycle spinning production, but also improves the conductivity of the conductive masterbatch. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

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

[0030] Figure 2 This is the SEM image of the conductive masterbatch prepared in Comparative Example 1. DETAILED DESCRIPTION

[0031] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0032] The hyperbranched conductive dispersant, conductive masterbatch, preparation method and application thereof provided by the present invention are described in detail below.

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

[0034] The value of n is 55 to 60 (e.g., 55, 56, 57, 58, 59, or 60). The hyperbranched conductive dispersant has good compatibility with both carbon black and nylon 6, and is inherently conductive, achieving both dispersing and conductive effects. When combined with nylon 6 and a high loading of carbon black to prepare a conductive masterbatch, the conductive masterbatch can maintain its conductivity while avoiding problems such as yarn breakage and frequent screen changes that can occur during long-cycle spinning of the conductive masterbatch.

[0035] Correspondingly, the present invention also provides a method for preparing the hyperbranched conductive dispersant, which comprises the following steps: adding hyperbranched polysiloxane and hydrochloric acid to a polyaniline solution under a protective atmosphere and room temperature to carry out a reaction.

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

[0037] In some optional embodiments, the polyaniline solution can be obtained by dissolving polyaniline in dimethyl sulfoxide. For example, the polyaniline and dimethyl sulfoxide can be mixed at 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 optional embodiments, the reaction time of the polyaniline solution, hyperbranched polysiloxane and hydrochloric acid can be 72 h to 80 h, such as 72 h, 74 h, 76 h, 78 h or 80 h, or other values within the range of 72 h to 80 h.

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

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

[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 (such as 105°C, 110°C, 115°C, 118°C or 120°C, etc.), followed by heating at a rate of 8°C / h to 12°C / h (such as 8°C / h, 9°C / h, 10°C / h, 11°C / h or 12°C / h, etc.) to 160°C to 180°C (such as 160°C, 165°C, 170°C, 175°C or 180°C, etc.).

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

[0045] As mentioned above, the present invention uses a polyaniline solution, a hyperbranched polysiloxane, and hydrochloric acid to prepare a hyperbranched conductive dispersant. The spatial three-dimensional spherical structure of the hyperbranched polysiloxane and the conjugated rigid structure of the polyaniline are combined, so that the prepared hyperbranched conductive dispersant can achieve good dispersion of carbon black with a relatively small addition amount. Moreover, 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 greatly improve the conductivity of the composite material. In addition, the molecular structure of the hyperbranched conductive dispersant provided by the present invention contains a large number of ether bonds and hydroxyl groups, which is conducive to the formation of dynamic non-covalent hydrogen bonds. This characteristic may help the hyperbranched conductive dispersant to form good compatibility with carbon black and nylon 6, which can promote dispersion and compatibility. Therefore, the hyperbranched polysiloxane provided by the present invention can not only improve the dispersion effect of carbon black in nylon 6, but also improve the conductive properties of the composite material.

[0046] Accordingly, the present invention provides applications of the above-mentioned hyperbranched conductive dispersant, for example, it can be used to extend the spinning cycle of a conductive masterbatch containing carbon black and nylon 6; and / or, to improve the conductivity of the conductive masterbatch containing carbon black and nylon 6.

[0047] In addition, the present invention also provides a conductive masterbatch. Calculated by weight, every 100 parts of raw materials for preparing 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 above-mentioned hyperbranched conductive dispersant.

[0048] The amount of carbon black 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 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 the 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 part to 4 parts. In some preferred embodiments, the amount of the hyperbranched conductive dispersant does not exceed 3 parts, such as 1 part to 3 parts.

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

[0052] Furthermore, the raw materials for preparation may further include an auxiliary agent. The amount of the auxiliary agent used 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 auxiliary agent may exemplarily include at least one of a lubricant and an antioxidant. The lubricant may exemplarily include at least one of EAA wax and EVA wax, preferably EAA wax. The antioxidant may exemplarily include at least one of antioxidant 1098 and antioxidant 1010.

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

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

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

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

[0058] In some optional embodiments, the extrusion conditions include: a feeding rate of 5Hz to 8Hz (such as 5Hz, 5.5Hz, 6Hz, 6.5Hz, 7Hz, 7.5Hz or 8Hz, etc.); the twin-screw extruder is divided into a first temperature zone to a fifth temperature zone, and the temperatures of the first temperature zone to the fifth temperature zone are 210℃ to 230℃ (such as 210℃, 215℃, 220℃, 225℃ or 230℃, etc.), 230℃ to 250℃ (such as 230℃, 235℃, 240℃, 245℃ or 250℃, etc.), 230℃ to 250℃ (such as 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.); 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, low shear force, and it will be unfavorable for the mixing and dispersion of the materials; if the feeding speed is too fast, it will be unfavorable for the plasticization of the resin.

[0060] If the temperature in the first temperature zone is too low, it will be detrimental to the plasticization of the resin in the later stage; if the temperature in the first temperature zone is too high, it will lead to poor material feeding and easy bridging.

[0061] In some optional embodiments, the pelletizing conditions include: a pelletizing rate of 5 Hz to 15 Hz (such as 5 Hz, 6 Hz, 7 Hz, 8 Hz, 9 Hz, 10 Hz, 11 Hz, 12 Hz, 13 Hz, 14 Hz or 15 Hz, etc.).

[0062] Furthermore, the present invention also provides applications of the conductive masterbatch, such as using it to prepare textiles, including but not limited to antistatic textiles, anti-electromagnetic radiation textiles, smart textiles and military textiles.

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

[0064] Example 1

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

[0066] Among them, n is 55 to 60.

[0067] The preparation method of the hyperbranched conductive dispersant comprises:

[0068] S1: Preparation of hyperbranched polysiloxane.

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

[0070] S2: Preparation of hyperbranched conductive dispersant.

[0071] 50 g of polyaniline was added to 500 g of dimethyl sulfoxide, and the mixture was mechanically stirred at 20° C. for 30 min under nitrogen protection to fully dissolve the polyaniline, thereby obtaining a polyaniline solution.

[0072] 10 g of the hyperbranched polysiloxane from S1 and 0.5 g of hydrochloric acid were added dropwise to the polyaniline solution, and stirring was continued for 72 hours. After the reaction, the reaction product was washed with excess methanol and then filtered. This washing and filtration cycle was repeated three times. The solid was then vacuum-dried at 50°C for 24 hours to obtain a 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] 50 g of polyaniline was added to 500 g of dimethyl sulfoxide, and the mixture was mechanically stirred at 20° C. for 30 min under nitrogen protection to fully dissolve the polyaniline, thereby obtaining a polyaniline solution.

[0078] 5 g of the hyperbranched polysiloxane from S1 and 0.4 g of hydrochloric acid were added dropwise to the polyaniline solution, and stirring was continued for 76 hours. After the reaction, the reaction product was washed with excess methanol and then filtered. This washing and filtration cycle was repeated three times. The solid was then vacuum-dried at 45°C for 28 hours to obtain a 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] 50 g of polyaniline was added to 500 g of dimethyl sulfoxide, and the mixture was mechanically stirred at 20° C. for 30 min under nitrogen protection to fully dissolve the polyaniline, thereby obtaining a polyaniline solution.

[0084] 15 g of the hyperbranched polysiloxane from S1 and 0.6 g of hydrochloric acid were added dropwise to the polyaniline solution, and stirring was continued for 80 hours. After the reaction, the reaction product was washed with excess methanol and then filtered. This washing and filtration cycle was repeated three times. The solid was then vacuum-dried at 55°C for 20 hours to obtain a hyperbranched conductive dispersant.

[0085] Example 4

[0086] This embodiment provides a conductive masterbatch, the raw materials for preparing the conductive masterbatch are composed 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 the conductive masterbatch comprises:

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

[0089] S2: Add the dried carbon black, EAA wax, hyperbranched conductive dispersant, and antioxidant into a high-pressure mixer in proportion, and stir at 80°C and 500 rpm for 10 minutes to obtain a mixture;

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

[0091] S4: The mixed materials in steps S2 and S3 are transported to the feed hopper of the twin-screw extruder by means of an elevator and fed at a feeding rate of 6 Hz; the temperatures of the five temperature zones of the twin-screw extruder are set to 215°C, 240°C, 245°C, 245°C, and 240°C, respectively, and the main engine speed is 200 r / min. The extruded materials are pelletized in a water tank at a rate of 6 Hz to obtain conductive masterbatch (such as Figure 1 shown).

[0092] Example 5

[0093] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0094] Example 6

[0095] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0096] Example 7

[0097] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0098] Example 8

[0099] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0100] Example 9

[0101] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0102] Example 10

[0103] The difference between this embodiment and embodiment 4 is that the raw materials for preparing the conductive masterbatch are composed 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 embodiment 1, and 0.5 parts of antioxidant 1098.

[0104] Example 11

[0105] This embodiment provides a conductive masterbatch, the raw materials for preparing the conductive masterbatch are composed 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, the raw materials for preparing the conductive masterbatch are composed 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 S1 of the hyperbranched conductive dispersant, KH-560 coupling agent and diethylene glycol at a molar ratio of 1:2 are placed in a 250 mL three-necked flask equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen, the initial reaction temperature is 105°C, then raised to 160°C at a rate of 8°C / h and allowed to react for 4 hours. Small molecules with a molecular weight below 1000 are then removed by dialysis.

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

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

[0113] Example 14

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

[0115] In the preparation method for a hyperbranched conductive dispersant, step S1 is as follows: KH-560 coupling agent and diethylene glycol at a molar ratio of 1:3 are placed in a 250 mL three-necked flask equipped with a stirrer, thermometer, and reflux condenser. Under nitrogen, the reaction temperature is initially set at 120°C, then raised to 180°C at a rate of 12°C / h and allowed to react for 4 hours. Small molecules with a molecular weight below 1000 are then removed by dialysis.

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

[0117] Comparative Example 1

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

[0119] The SEM image of the conductive masterbatch prepared in this comparative example is as follows Figure 2 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 by S1 in 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 are composed 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] That is, 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 are composed 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 increases and the amount of hyperbranched conductive dispersant used decreases.

[0128] Comparative Example 5

[0129] The difference between this comparative example and Example 4 is that the raw materials for preparing the conductive masterbatch are composed 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, and the amount of hyperbranched conductive dispersant used 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 are composed 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 increased and the amount of carbon black 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 are 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 and the amount of carbon black used is increased.

[0137] Test example

[0138] The conductivity and material properties of the conductive masterbatches prepared in Examples 4 to 14 and Comparative Examples 1 to 7 during the preparation process were compared. In addition, the longest spinning time achievable 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 (unit: Ω) of the conductive masterbatch was measured using a surface resistance tester. Specifically, the conductive masterbatch was dried and then directly measured.

[0140] B. Material dispersibility: melt index was measured using ASTM D1238 at 260°C and 2.16 kg. The unit of melt index is g / 10 min.

[0141] C. Preliminary determination of spinning time: In order to preliminarily determine the length of the conductive masterbatch spinning time in a relatively short period of time, the time corresponding to the screen change is characterized when the melt pressure of the spinning melt flowing through the single screw is greater than 8MPa. The test conditions are: the temperatures of the five temperature zones of the single-screw spinning machine are 260℃, 285℃, 285℃, 285℃ and 285℃, and the filter mesh size is 400 mesh. The unit is min.

[0142] Table 1 Test results

[0143] Surface resistance Melt index Spinning time 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 embodiment of the present invention is used together with nylon 6 and a relatively high amount of carbon black to prepare a conductive masterbatch. This can prevent the conductive masterbatch from breaking and frequent screen changes that are prone to occur during long-cycle spinning production without reducing its conductivity.

[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 the conductive masterbatch containing carbon black and nylon 6, but also improve the conductivity of the conductive masterbatch containing carbon black and nylon 6.

[0146] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall 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: Among them, the value of n is 55 to 60.

2. A method for preparing a hyperbranched conductive dispersant according to claim 1, characterized in that: The following steps are involved: Under protective atmosphere and room temperature, hyperbranched polysiloxane and hydrochloric acid are added to the polyaniline solution to react; 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); and the reaction time is 72h-80h.

3. The preparation method according to claim 2, characterized in that The preparation of the hyperbranched polysiloxane comprises: mixing a KH-560 coupling agent and diethylene glycol under protective atmosphere conditions and reacting the mixture; Wherein, 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° C. to 120° C., and then heating to 160° C. to 180° C. at a heating rate of 8° C. / h to 12° C. / h.

4. A use of the hyperbranched conductive dispersant according to 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 a conductive masterbatch containing carbon black and nylon 6.

5. A conductive masterbatch, characterized in that: In parts by weight, every 100 parts of raw materials for preparing 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 according to claim 1.

6. The conductive masterbatch according to claim 5, characterized in that The preparation raw materials further include 1 to 2 parts of auxiliary agents; the auxiliary agents include at least one of a lubricant and an antioxidant.

7. A method for preparing a conductive masterbatch according to claim 5 or 6, characterized in that: The method comprises the following steps: mixing the prepared raw materials according to a proportion, then performing twin-screw extrusion, and pelletizing.

8. The preparation method according to claim 7, characterized in that The carbon black is mixed with a hyperbranched conductive dispersant and an auxiliary agent 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 Extrusion conditions include: a feed rate of 5 Hz to 8 Hz; the twin-screw extruder is divided into first to fifth temperature zones, with temperatures of the first to fifth temperature zones being 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.; and a main engine speed of 180 r / min to 250 r / min. And / or, the pelletizing conditions include: a pelletizing rate of 5 Hz to 15 Hz.

10. Use of the conductive masterbatch according to claim 5 or 6 in the preparation of textiles.

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