A thermochromic polyamide masterbatch, a thermochromic polyamide 6 fiber and a preparation method thereof

Abstract

The application discloses a thermochromic polyamide 6 master batch, a thermochromic polyamide 6 fiber and a preparation method thereof. The polyamide 6 master batch is composed of the following raw materials in parts by weight: porous nanomaterial 2-5 parts, dye 25-35 parts, and light polyamide 6 chip 60-70 parts. The porous nanomaterial has adsorption performance and mainly comprises a three-dimensional framework structure {Ag[Ag 14 ( i PrS) 10 ]} 5+ The dye is Congo red, has a negative charge, and has a particle size of 50 nm. The thermochromic polyamide 6 master batch has a melt index of 44.34 g / 10min, a relative viscosity of 2.4, a water content of 780 ppm, an end amino group content of 30.17 mmol / kg, and an end carboxyl group content of 64.81 mmol / kg.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical fibers, and particularly relates to a thermochromic polyamide 6 master batch, a thermochromic polyamide 6 fiber and a preparation method thereof. BACKGROUND

[0002] With the rapid development of the textile industry in recent years, consumers pay more and more attention to the functional diversification of fibers. The functional polyamide 6 fiber not only has the comfortable skin feel of polyamide 6, but also provides health-related functions, so the sales of functional polyamide 6 fibers increase year by year. At present, the functional polyamide 6 fiber market mainly focuses on moisture-wicking, cooling, anti-ultraviolet and other health function products, and there is still a research and development gap in medical monitoring and intelligent wear. Considering that thermochromic textiles have shown application potential in health monitoring, home decoration and intelligent wear, it is of great practical significance to develop a polyamide 6 fiber with thermochromic function. However, the existing thermochromic technology often seriously affects the spinning conditions during high-speed spinning of polyamide 6, causing problems such as floating and broken ends, affecting product quality. The existing thermochromic related products are mainly integrated with functional devices into the existing spinning technology, rather than functionalization of the fiber itself, which limits the use of the series of fiber materials.

[0003] A thermochromic polyester fiber and a preparation method thereof are disclosed in Chinese patent application No. CN201610143303.8. The application prepares a thermochromic polyester fiber with a skin-core structure by mixing a color master batch with thermochromic function and polyester chips as core material and using polyester chips as skin material. Although this method realizes the thermochromic performance at the fiber level, the color master batch affects the spinning conditions of the fiber, and can only be used in the form of skin-core coating, which leads to poor spinning performance of the thermochromic component in the core layer, thus weakening the color development effect and failing to fundamentally solve the spinning condition problem of the thermochromic fiber. Chinese patent application No. CN201810478727.9 discloses a preparation method of a light / heat dual-thermochromic fiber, the obtained material and application thereof. The application combines diacetylenic compounds with different high molecular polymers by electrospinning to prepare a fiber with light / heat dual-thermochromic effect. However, this method is very complicated to implement and requires high quality raw materials, making it difficult to be put into mass production. SUMMARY

[0004] To solve the above problems, the present application provides a thermochromic polyamide 6 master batch, a thermochromic polyamide 6 fiber and a preparation method thereof.

[0005] The object of the present application can be achieved by the following technical solutions:

[0006] One of the purposes of the present application is to provide a thermochromic polyamide 6 master batch, which is composed of the following raw materials in parts by weight: porous nanomaterial 2-5 parts, dye 25-35 parts, and light polyamide 6 chip 60-70 parts; the porous nanomaterial has adsorption performance.

[0007] Further, the main component of the porous nanomaterial is {Ag[Ag 14 ( i PrS) 10 ]} 5+ .

[0008] Further, the dye is Congo red, which has a negative charge.

[0009] Further, the particle size of the Congo red is 50 nm.

[0010] Further, the thermochromic polyamide 6 master batch has a melt index of 44.34 g / 10 min, a relative viscosity of 2.4, a water content of 780 ppm, an end amino group content of 30.17 mmol / kg, and an end carboxyl group content of 64.81 mmol / kg.

[0011] The second purpose of the present application is to provide a preparation method of the thermochromic polyamide 6 master batch, which comprises the following steps:

[0012] S11: The porous nanomaterial and the dye are weighed according to the set proportion, pre-mixed, and then put into the buffer bin, and then spiral stirred to mix uniformly after being put into the hopper to obtain a pre-mixed material;

[0013] S12: The light polyamide 6 chip is fed from the main feeding port, and the pre-mixed material is fed from the side feeding port, the light polyamide 6 chip and the pre-mixed material are uniformly mixed, and then melt-mixed in the double screw extruder to obtain a thermochromic polyamide 6 master batch melt;

[0014] S13: The thermochromic polyamide 6 master batch melt is extruded from the outlet of the double screw extruder, and then cooled in a water cooling tank, and then cut into particles, screened by a vibrating screen, and dried by air blowing to obtain the thermochromic polyamide 6 master batch.

[0015] The third purpose of the present application is to provide a thermochromic polyamide 6 fiber, and the raw material of the thermochromic polyamide 6 fiber comprises any one of the above thermochromic polyamide 6 master batches.

[0016] Further, the raw material is composed of the following parts by weight: thermochromic polyamide 6 master batch 10 parts, and light polyamide 6 chip 90 parts.

[0017] The fourth purpose of the present application is to provide a preparation method of the thermochromic polyamide 6 fiber, which comprises the following steps:

[0018] S21: dry the thermochromic polyamide 6 master batch and the bright polyamide 6 chips respectively, feed the bright polyamide 6 chips from the main feeding port, and feed the thermochromic polyamide 6 master batch into the buffer bin, then uniformly stir the thermochromic polyamide 6 master batch in the hopper after being lowered, and then feed the thermochromic polyamide 6 master batch from the side feeding port, and then uniformly mix the thermochromic polyamide 6 master batch, and then perform compounding and melting in the double-screw extruder to obtain a composite melt;

[0019] S22: after the composite melt obtained in step S21 is metered by a metering pump, the composite melt is introduced into a spinning box, and then a composite yarn is obtained by spinning through an assembly, and then the composite yarn is subjected to slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain a thermochromic POY polyamide 6 fiber.

[0020] S23: the thermochromic POY polyamide 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermochromic DTY polyamide 6 fiber, that is, the thermochromic polyamide 6 fiber.

[0021] Further, in step S21, the double-screw extruder is provided with nine temperature zones, and the temperature of each temperature zone and the temperature of the die head are both 165 DEG C to 235 DEG C.

[0022] Compared with the prior art, the present application has the following beneficial effects:

[0023] 1. The thermochromic polyamide 6 fiber provided by the present application adopts porous nanomaterials having adsorption performance, and when the ambient temperature is low, the porosity of the porous nanomaterials is high, and the dye is adsorbed into the pores of the nanomaterials by electrostatic action, resulting in a light color; as the temperature rises, the skeleton of the porous nanomaterials shrinks, the porosity decreases, and the dye gradually releases from the pores of the porous nanomaterials, resulting in a deep color, thereby realizing the effect of thermochromic color change, and the thermochromic color change is reversible.

[0024] 2. In the present application, the porous nanomaterials are positively charged porous silver nanomaterials, and the main component is a compound having a three-dimensional framework structure composed of silver ions and a sulfur-containing ligand, and the molecular formula is {Ag[Ag 14 ( i PrS) 10 ]} 5+ The porous nanomaterials have high positive charge, good dispersibility, and are not prone to agglomeration in the polyamide 6 matrix, have little effect on spinning, and can be directly used for spinning.

[0025] 3. In the present application, the dye is Congo red, which has a negative charge and exists in electrostatic action with the porous nanomaterials, thereby promoting the adsorption between the dye and the porous nanomaterials.

[0026] 4. The thermochromic nylon 6 fiber provided by this invention has thermochromic polyamide 6 masterbatch that can be directly used for spinning, and the resulting thermochromic nylon 6 fiber has good color development effect, which can effectively solve the problems of poor spinning condition and poor product quality of thermochromic fiber. Attached Figure Description

[0027] Figure 1 This is a schematic diagram illustrating how the porous nanomaterial shrinks in size and porosity decreases with increasing temperature in this invention. Detailed Implementation

[0028] The following describes a preferred embodiment in conjunction with the accompanying drawings. Figure 1 To further illustrate the present invention, the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values; for numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein; the materials, reagents, etc. used in the following embodiments are commercially available unless otherwise specified; the experimental methods in the following embodiments are conventional methods unless otherwise specified.

[0029] Example 1

[0030] This embodiment provides a thermochromic polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 5 parts porous nanomaterials, 25 parts dyes, and 70 parts glossy polyamide 6 chips; the porous nanomaterials have adsorption properties.

[0031] In this embodiment, the main component of the porous nanomaterial is a compound with a three-dimensional framework structure composed of silver ions and sulfur-containing ligands, with the molecular formula {Ag[Ag]}. 14 ( i PrS) 10 ]} 5+ The dye is Congo red, which carries a negative charge and has a particle size of 50 nm.

[0032] In this porous nanomaterial, such as Figure 1 As shown, with increasing temperature, the metal-metal bonds between Ag…Ag particles shorten due to energy absorption, the skeleton shrinks, and the porosity decreases. The dye is gradually released from the pores of the porous silver nanomaterial, displaying a red color. When the ambient temperature decreases, the porosity of the porous nanomaterial increases, and the dye is gradually adsorbed into the pores through electrostatic interactions, resulting in a lighter color, achieving a thermochromic effect that is reversible. This porous nanomaterial exhibits good dispersibility and minimal impact on spinning conditions, making it suitable for direct use in spinning.

[0033] In this embodiment, the thermal color-changing polyamide 6 master batch has a melt index of 44.34 g / 10 min, a relative viscosity of 2.4, a water content of 780 ppm, an end amino group content of 30.17 mmol / kg, and an end carboxyl group content of 64.81 mmol / kg.

[0034] The embodiment also provides a preparation method of the thermal color-changing polyamide 6 master batch, including the following steps:

[0035] S11: The porous nanomaterial and the dye are weighed according to a set ratio, pre-mixed, and then fed into a buffer bin. After being lowered into a hopper, the mixture is stirred by a spiral to be uniformly mixed to obtain a pre-mixed material;

[0036] S12: The light polyamide 6 chips are fed from a main feeding port, and the pre-mixed material is fed from a side feeding port. The light polyamide 6 chips and the pre-mixed material are uniformly mixed, and then melt-mixed in a double-screw extruder to obtain a thermal color-changing polyamide 6 master batch melt;

[0037] S13: The thermal color-changing polyamide 6 master batch melt is extruded from the outlet of the double-screw extruder. After being cooled by a water cooling tank, the strip is cut into particles in a granulator, screened by a vibrating screen, and air-dried to obtain the thermal color-changing polyamide 6 master batch, which is recorded as master batch 1.

[0038] The embodiment also provides a thermal color-changing polyamide 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of master batch 1 and 90 parts of light polyamide 6 chips.

[0039] The embodiment also provides a preparation method of the thermal color-changing polyamide 6 fiber, including the following steps:

[0040] S21: The master batch 1 and the light polyamide 6 chips are respectively subjected to drying treatment. The light polyamide 6 chips are fed from a main feeding port, and the master batch 1 is fed into a buffer bin. After being uniformly stirred by a spiral and lowered into a hopper, the master batch 1 is fed from a side feeding port. After being uniformly mixed, the master batch 1 and the light polyamide 6 chips are subjected to compounding and melting in a double-screw extruder to obtain a composite melt;

[0041] S22: The composite melt obtained in step S21 is metered by a metering pump and then fed into a spinning box. The composite melt is spun into a composite yarn by a component to obtain a thermal color-changing POY polyamide 6 fiber with a specification of 85D / 24F after slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding.

[0042] S23: The thermal color-changing POY polyamide 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermal color-changing DTY polyamide 6 fiber, which is the thermal color-changing polyamide 6 fiber and is recorded as fiber 1, with a specification of 70D / 24F.

[0043] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature of each zone is 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃, respectively, and the temperature of the die head is 230℃.

[0044] Embodiment 2

[0045] This embodiment provides a thermochromic polyamide 6 master batch, which is composed of the following raw materials in parts by weight: 5 parts of porous nanomaterial, 30 parts of dye, and 65 parts of bright polyamide 6 chips.

[0046] In this embodiment, the porous nanomaterial and the dye are the same as in Embodiment 1.

[0047] In this embodiment, the thermochromic polyamide 6 master batch has a melt index of 43.13 g / 10 min, a relative viscosity of 2.5, a water content of 758 ppm, an end amino group content of 30.52 mmol / kg, and an end carboxyl group content of 64.75 mmol / kg.

[0048] This embodiment also provides a preparation method of a thermochromic polyamide 6 master batch, which comprises the following steps:

[0049] S11: The porous nanomaterial and the dye are weighed according to the set proportion, pre-mixed, and then put into the buffer bin. After being lowered to the hopper, the mixture is stirred uniformly by the screw to obtain a pre-mixed material;

[0050] S12: The bright polyamide 6 chips are fed from the main feeding port, and the pre-mixed material is fed from the side feeding port. The bright polyamide 6 chips and the pre-mixed material are mixed uniformly, and then subjected to melt mixing in the twin-screw extruder to obtain a thermochromic polyamide 6 master batch melt;

[0051] S13: The thermochromic polyamide 6 master batch melt is extruded from the outlet of the twin-screw extruder. After being cooled in the water cooling tank, the strip is cut into particles in the granulator, screened by the vibrating screen, and dried by the air blowing to obtain the thermochromic polyamide 6 master batch, which is denoted as master batch 2.

[0052] This embodiment also provides a thermochromic polyamide 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of master batch 2 and 90 parts of bright polyamide 6 chips.

[0053] This embodiment also provides a preparation method of a thermochromic polyamide 6 fiber, which comprises the following steps:

[0054] S21: The master batch 2 and the bright polyamide 6 chips are subjected to drying treatment respectively. The bright polyamide 6 chips are fed from the main feeding port, and the master batch 2 is put into the buffer bin. After being lowered to the hopper, the mixture is stirred uniformly by the screw, and then fed from the side feeding port. After being mixed uniformly, the mixture is subjected to compounding and melting in the twin-screw extruder to obtain a composite melt.

[0055] S22: the composite melt obtained in step S21 is metered by a metering pump, then enters a spinning box, and is jetted by an assembly to obtain a composite yarn, and then is subjected to slow cooling, single suction, side blowing cooling, bundle oiling, secondary cooling in a duct, stretching setting, and winding to obtain a thermochromic POY nylon 6 fiber, with a specification of 85D / 24F;

[0056] S23: the thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermochromic DTY nylon 6 fiber, that is, the thermochromic nylon 6 fiber, denoted as fiber 2, with a specification of 70D / 24F.

[0057] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature ranges of the respective temperature zones are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃, and 165℃, and the die temperature is 230℃.

[0058] Example 3

[0059] This embodiment provides a thermochromic polyamide 6 master batch, which is composed of the following raw materials in parts by weight: 5 parts of porous nanomaterial, 35 parts of dye, and 60 parts of bright polyamide 6 chip.

[0060] The porous nanomaterial and the dye in this embodiment are the same as in Example 1.

[0061] In this embodiment, the thermochromic polyamide 6 master batch has a melt index of 43.55 g / 10 min, a relative viscosity of 2.5, a water content of 751 ppm, an end amino group content of 32.48 mmol / kg, and an end carboxyl group content of 66.44 mmol / kg.

[0062] This embodiment also provides a preparation method of a thermochromic polyamide 6 master batch, which comprises the following steps:

[0063] S11: the porous nanomaterial and the dye are weighed according to the set proportion, pre-mixed, and then put into a buffer bin, and then spiral stirred to be uniformly mixed after being put into a hopper to obtain a pre-mixed material;

[0064] S12: bright polyamide 6 chips are fed from a main feeding port, and the pre-mixed material is fed from a side feeding port, the bright polyamide 6 chips and the pre-mixed material are uniformly mixed, and then subjected to melt mixing in a twin-screw extruder to obtain a thermochromic polyamide 6 master batch melt;

[0065] S13: the thermochromic polyamide 6 master batch melt is extruded from the outlet of the twin-screw extruder, and then cooled by a water cooling tank, and then cut into particles, screened by a vibrating screen, and dried by air blowing to obtain the thermochromic polyamide 6 master batch, denoted as master batch 3.

[0066] The embodiment also provides a thermochromic polyamide 6 fiber, which is composed of 10 parts of the master batch 3 and 90 parts of the bright polyamide 6 chip.

[0067] The embodiment also provides a preparation method of the thermochromic polyamide 6 fiber, which comprises the following steps:

[0068] S21: The master batch 3 and the bright polyamide 6 chip are respectively subjected to drying treatment, the bright polyamide 6 chip is fed from a main feeding port, the master batch 3 is fed into a buffer bin, and then is uniformly stirred by a screw after being discharged into a hopper, and is fed from a side feeding port, and after being uniformly mixed, is subjected to compounding and melting in a double-screw extruder to obtain a composite melt;

[0069] S22: The composite melt obtained in step S21 is metered by a metering pump, and then is fed into a spinning box, and is spun by an assembly to obtain a composite yarn, and then is subjected to slow cooling, monomer suction, side air blowing cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain the thermochromic POY polyamide 6 fiber, and the specification is 85D / 24F;

[0070] S23: The thermochromic POY polyamide 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain the thermochromic DTY polyamide 6 fiber, that is, the thermochromic polyamide 6 fiber, which is recorded as fiber 3, and the specification is 70D / 24F.

[0071] In step S12 of the embodiment, the double-screw extruder is provided with nine temperature zones, and the temperature ranges of the respective temperature zones are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃ and 165℃, and the die temperature is 230℃.

[0072] Embodiment 4

[0073] The embodiment provides a thermochromic polyamide 6 master batch, which is composed of 4 parts of porous nanomaterials, 25 parts of dyes and 71 parts of bright polyamide 6 chips.

[0074] The porous nanomaterials and the dyes in the embodiment are the same as those in embodiment 1.

[0075] In the embodiment, the melt index of the thermochromic polyamide 6 master batch is 43.24 g / 10 min, the relative viscosity is 2.4, the water content is 794 ppm, the terminal amino group content is 31.54 mmol / kg, and the terminal carboxyl group content is 65.38 mmol / kg.

[0076] The embodiment also provides a preparation method of the thermochromic polyamide 6 master batch, which comprises the following steps:

[0077] S11: The porous nanomaterial and the dye were weighed according to a set ratio, mixed, and then fed into a buffer bin, and then spiral stirred to be uniformly mixed after being lowered into a hopper to obtain a premix;

[0078] S12: The light polyamide 6 chip was fed from a main feeding port, and the premix was fed from a side feeding port, the light polyamide 6 chip and the premix were uniformly mixed, and then melt-mixed in a double screw extruder to obtain a thermochromic polyamide 6 master batch melt;

[0079] S13: The thermochromic polyamide 6 master batch melt was extruded from the outlet of the double screw extruder, and then the strip was cooled in a water cooling tank, and then the strip was cut into particles in a cutting machine, vibrated and sieved, and air dried to obtain the thermochromic polyamide 6 master batch, which is denoted as master batch 4.

[0080] The embodiment also provides a thermochromic polyamide 6 fiber, which is composed of 10 parts of master batch 4 and 90 parts of light polyamide 6 chip by weight.

[0081] The embodiment also provides a preparation method of the thermochromic polyamide 6 fiber, which comprises the following steps:

[0082] S21: The master batch 4 and the light polyamide 6 chip were respectively subjected to drying treatment, the light polyamide 6 chip was fed from a main feeding port, the master batch 4 was fed into a buffer bin, and then spiral stirred to be uniformly mixed after being lowered into a hopper, and then the mixture was fed from a side feeding port, and then the mixture was subjected to compounding and melting in a double screw extruder to obtain a composite melt;

[0083] S22: The composite melt obtained in step S21 was metered by a metering pump, and then fed into a spinning box, and then a composite yarn was obtained by spinning through an assembly, and then the composite yarn was subjected to slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain a thermochromic POY polyamide 6 fiber, and the specification of the thermochromic POY polyamide 6 fiber was 85D / 24F.

[0084] S23: The thermochromic POY polyamide 6 fiber obtained in step S22 was subjected to false twist and elastic recovery to obtain a thermochromic DTY polyamide 6 fiber, which is the thermochromic polyamide 6 fiber, and is denoted as fiber 4, and the specification of the thermochromic DTY polyamide 6 fiber was 70D / 24F.

[0085] In step S12 of the embodiment, the double screw extruder is provided with nine temperature zones, and the temperature ranges of the respective temperature zones are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃ and 165℃, and the temperature of a die head is 230℃.

[0086] Example 5

[0087] The embodiment provides a thermochromic polyamide 6 master batch, which is composed of the following raw materials in parts by weight: 3 parts of porous nanomaterial, 25 parts of dye, and 72 parts of bright polyamide 6 chip.

[0088] The porous nanomaterial and the dye in the embodiment are the same as those in the embodiment 1.

[0089] In the embodiment, the thermochromic polyamide 6 master batch has a melt index of 44.64 g / 10 min, a relative viscosity of 2.4, a water content of 786 ppm, an end amino group content of 30.45 mmol / kg, and an end carboxyl group content of 65.12 mmol / kg.

[0090] The embodiment further provides a preparation method of the thermochromic polyamide 6 master batch, which comprises the following steps.

[0091] S11: The porous nanomaterial and the dye are weighed according to a set proportion, pre-mixed, and then put into a buffer bin, and then spiral stirring is performed after being lowered into a hopper until the mixture is uniform, to obtain a pre-mixed material;

[0092] S12: The bright polyamide 6 chip is fed from a main feeding port, and the pre-mixed material is fed from a side feeding port, the bright polyamide 6 chip and the pre-mixed material are uniformly mixed, and then melt mixing is performed in a double-screw extruder, to obtain a thermochromic polyamide 6 master batch melt;

[0093] S13: The thermochromic polyamide 6 master batch melt is extruded from the outlet of the double-screw extruder in the form of a strip, the strip is cooled in a water cooling tank, and then the strip is cut into particles in a granulator, vibrated and screened, and air-dried, to obtain the thermochromic polyamide 6 master batch, which is denoted as master batch 5.

[0094] The embodiment further provides a thermochromic polyamide 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of the master batch 5 and 90 parts of bright polyamide 6 chip.

[0095] The embodiment further provides a preparation method of the thermochromic polyamide 6 fiber, which comprises the following steps.

[0096] S21: The master batch 5 and the bright polyamide 6 chip are respectively subjected to drying treatment, the bright polyamide 6 chip is fed from a main feeding port, the master batch 5 is put into a buffer bin, and then spiral stirring is performed after being lowered into a hopper until the mixture is uniform, the mixture is fed from a side feeding port, and then composite melt is obtained by performing compounding and melting in a double-screw extruder;

[0097] S22: The composite melt obtained in the step S21 is metered by a metering pump and then introduced into a spinning box body, and then composite yarn is obtained by spinning through an assembly, and then the composite yarn is subjected to slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding, to obtain a thermochromic POY polyamide 6 fiber, which has a specification of 85D / 24F.

[0098] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twist texturing to obtain a thermochromic DTY nylon 6 fiber, i.e., the thermochromic nylon 6 fiber, denoted as fiber 5, with a specification of 70D / 24F.

[0099] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature of each zone is 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the die temperature is 230°C.

[0100] Embodiment 6

[0101] This embodiment provides a thermochromic polyamide 6 master batch, which is composed of the following raw materials in parts by weight: 3 parts of porous nanomaterial, 25 parts of dye, and 73 parts of bright polyamide 6 chips.

[0102] The porous nanomaterial and the dye in this embodiment are the same as in Embodiment 1.

[0103] In this embodiment, the thermochromic polyamide 6 master batch has a melt index of 45.15 g / 10 min, a relative viscosity of 2.4, a water content of 765 ppm, an end amino group content of 31.54 mmol / kg, and an end carboxyl group content of 63.45 mmol / kg.

[0104] This embodiment also provides a method for preparing a thermochromic polyamide 6 master batch, which comprises the following steps:

[0105] S11: The porous nanomaterial and the dye are weighed according to the set proportion, pre-mixed, and then put into the buffer bin. After being transferred to the hopper, the mixture is stirred by a spiral until it is uniformly mixed to obtain a pre-mixed material;

[0106] S12: The bright polyamide 6 chips are fed from the main feeding port, and the pre-mixed material is fed from the side feeding port. The bright polyamide 6 chips and the pre-mixed material are uniformly mixed, and then subjected to melt mixing in the twin-screw extruder to obtain a thermochromic polyamide 6 master batch melt;

[0107] S13: The thermochromic polyamide 6 master batch melt is extruded from the outlet of the twin-screw extruder. After being cooled in a water cooling tank, the strip is cut into particles in a granulator, screened by a vibrating screen, and dried by air blowing to obtain the thermochromic polyamide 6 master batch, denoted as master batch 6.

[0108] This embodiment also provides a thermochromic nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of master batch 6 and 90 parts of bright polyamide 6 chips.

[0109] This embodiment also provides a method for preparing a thermochromic nylon 6 fiber, which comprises the following steps:

[0110] S21: The master batch 6 and the bright polyamide 6 chip are respectively subjected to drying treatment, the bright polyamide 6 chip is fed from the main feeding port, the master batch 6 is thrown into the buffer bin, and then is uniformly stirred by the screw after being lowered into the hopper, and is fed from the side feeding port, and after being uniformly mixed, is subjected to compounding and melting in the twin-screw extruder to obtain a composite melt;

[0111] S22: The composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun by an assembly to obtain a composite yarn, and then is subjected to slow cooling, single-body suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain a thermochromic POY nylon 6 fiber, and the specification is 85D / 24F.

[0112] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermochromic DTY nylon 6 fiber, that is, the thermochromic nylon 6 fiber, which is recorded as fiber 6, and the specification is 70D / 24F.

[0113] In step S12 of the embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature ranges of the respective temperature zones are 225℃, 235℃, 235℃, 215℃, 205℃, 195℃, 185℃, 175℃ and 165℃, and the die temperature is 230℃.

[0114] Comparative Example 1

[0115] The difference between the embodiment 1 and the comparative example 1 is that the comparative polyamide 6 master batch of the comparative example does not contain porous nanomaterials.

[0116] The comparative example provides a comparative polyamide 6 master batch which is composed of the following raw materials in parts by weight: 25 parts of dye and 75 parts of bright polyamide 6 chip.

[0117] In the comparative example, the dye is Congo red.

[0118] The comparative example also provides a preparation method of the comparative polyamide 6 master batch, which comprises the following steps:

[0119] S11: The dye is weighed according to the set proportion, thrown into the buffer bin, and then lowered into the hopper;

[0120] S12: The bright polyamide 6 chip is fed from the main feeding port, and the dye is fed from the side feeding port, the bright polyamide 6 chip and the dye are uniformly mixed, and are subjected to melting and mixing in the twin-screw extruder to obtain a polyamide 6 master batch melt;

[0121] S13: The polyamide 6 master batch melt is extruded from the outlet of the twin-screw extruder, and after being cooled by a water cooling tank, is subjected to granulation, vibration screening and air blowing drying in a granulator to obtain the polyamide 6 master batch, which is recorded as comparative master batch 1.

[0122] The present comparative example also provides a comparative polyamide 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of comparative masterbatch 1, 90 parts of bright polyamide 6 chips.

[0123] The present comparative example also provides a method for preparing a comparative polyamide 6 fiber, which comprises the following steps:

[0124] S21: dry the comparative masterbatch 1 and the bright polyamide 6 chips respectively, feed the bright polyamide 6 chips from the main feeding port, and feed the comparative masterbatch 1 into the buffer bin, then spiral stir uniformly after dropping into the hopper, and feed from the side feeding port, mix uniformly, then perform compounding and melting in the twin-screw extruder to obtain a composite melt;

[0125] S22: after metering by a metering pump, the composite melt obtained in step S21 enters a spinning beam, and a component is used to spin to obtain a composite yarn, and then perform slow cooling, single-body suction, side air cooling, bundle oiling, secondary cooling in the duct, stretching and setting, and winding to obtain a thermochromic POY polyamide 6 fiber, with a specification of 85D / 24F;

[0126] S23: the thermochromic POY polyamide 6 fiber obtained in step S22 is further subjected to false twist and elastic recovery to obtain a thermochromic DTY polyamide 6 fiber, which is the comparative polyamide 6 fiber, denoted as comparative fiber 1, with a specification of 70D / 24F.

[0127] Comparative Example 2

[0128] The difference from Example 1 is that the porous nanomaterial in the present comparative example is electrically neutral, with a molecular formula of Ag[Ag 14 ( i PrS) 12 (NO3)3].

[0129] The present comparative example provides a comparative polyamide masterbatch, which is composed of the following raw materials in parts by weight: 5 parts of porous nanomaterial, 25 parts of dye, and 70 parts of bright polyamide 6 chips.

[0130] In the present comparative example, the dye is Congo red.

[0131] The present comparative example also provides a method for preparing a comparative polyamide 6 masterbatch, which comprises the following steps:

[0132] S11: weigh the porous nanomaterial and the dye according to the set ratio, mix in advance, and then feed into the buffer bin, spiral stir uniformly after dropping into the hopper to obtain a premix;

[0133] S12: feed the bright polyamide 6 chips from the main feeding port, and feed the premix from the side feeding port, mix the bright polyamide 6 chips and the premix uniformly, and perform melt mixing in the twin-screw extruder to obtain a polyamide 6 masterbatch melt.

[0134] S13: The polyamide 6 master batch melt strip is extruded from the twin-screw extruder outlet, the strip is cooled in a water cooling tank, and then is cut into particles, screened and air-dried in a cutting machine to obtain the polyamide 6 master batch, which is denoted as comparative master batch 2.

[0135] The present comparative example also provides a comparative polyamide 6 master batch, which is composed of the following raw materials in parts by weight: 5 parts of the porous nanomaterial, 25 parts of the dye, and 70 parts of the bright polyamide 6 chip.

[0136] The present comparative example also provides a preparation method of the comparative polyamide 6 master batch, which comprises the following steps:

[0137] S21: The comparative master batch 2 and the bright polyamide 6 chip are respectively subjected to drying treatment, the bright polyamide 6 chip is fed from the main feeding port, the comparative master batch 2 is put into the buffer bin, and then is uniformly stirred by the screw after being lowered into the hopper, and is fed from the side feeding port, and after being uniformly mixed, is subjected to compounding and melting in the twin-screw extruder to obtain a composite melt;

[0138] S22: The composite melt obtained in step S21 is metered by a metering pump, and then is introduced into a spinning beam, and is spun into a composite yarn by an assembly to obtain a composite yarn, and then is subjected to slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain a thermochromic POY polyamide 6 fiber, and the specification is 85D / 24F;

[0139] S23: The thermochromic POY polyamide 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermochromic DTY polyamide 6 fiber, which is the comparative polyamide 6 fiber, and is denoted as comparative fiber 2, and the specification is 70D / 24F.

[0140] Comparative Example 3

[0141] The difference from Example 1 is that the dye in the present comparative example has a positive charge.

[0142] The present comparative example provides a comparative polyamide master batch 3, which is composed of the following raw materials in parts by weight: 5 parts of the porous nanomaterial, 25 parts of the dye, and 70 parts of the bright polyamide 6 chip.

[0143] In the present comparative example, the dye is rhodamine B, has a positive charge, and has a particle size of 50 nm.

[0144] The present comparative example also provides a preparation method of the comparative polyamide 6 master batch, which comprises the following steps:

[0145] S11: The porous nanomaterial and the dye are weighed according to the set proportion, are put into the buffer bin after being premixed, are uniformly stirred by the screw after being lowered into the hopper, and a premixed material is obtained;

[0146] S12: feeding the bright polyamide 6 chips from the main feeding port, feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix uniformly, and performing melt mixing in the twin-screw extruder to obtain a polyamide 6 master batch melt;

[0147] S13: extruding the polyamide 6 master batch melt strip from the outlet of the twin-screw extruder, after the strip is cooled in the water cooling tank, the strip is cut into particles in a granulator, screened in a vibrating screen, and air-dried to obtain the comparative polyamide 6 master batch, denoted as comparative master batch 3.

[0148] The present comparative example also provides a comparative polyamide 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of the comparative master batch 3 and 90 parts of bright polyamide 6 chips.

[0149] The present comparative example also provides a method for preparing a comparative polyamide 6 fiber, which comprises the following steps:

[0150] S21: drying the comparative master batch 3 and the bright polyamide 6 chips respectively, feeding the bright polyamide 6 chips from the main feeding port, feeding the comparative master batch 3 into the buffer bin, uniformly stirring by the screw after being lowered into the hopper, feeding from the side feeding port, uniformly mixing, and performing compounding and melting in the twin-screw extruder to obtain a composite melt;

[0151] S22: after the composite melt obtained in step S21 is metered by a metering pump, the composite melt is introduced into a spinning box body and is spun into a composite yarn by an assembly, and then the composite yarn is subjected to slow cooling, monomer suction, side air cooling, bundle oiling, secondary cooling in a duct, stretching and setting, and winding to obtain a thermochromic POY polyamide 6 fiber, and the specification is 85D / 24F;

[0152] S23: the thermochromic POY polyamide 6 fiber obtained in step S22 is subjected to false twist and elastic recovery to obtain a thermochromic DTY polyamide 6 fiber, that is, the comparative polyamide 6 fiber, denoted as comparative fiber 3, and the specification is 70D / 24F.

[0153] Evaluation of implementation effects:

[0154] The following specific tests on the master batches 1-6, the comparative master batches 1-3, the fibers 1-6 and the comparative fibers 1-3 prepared in Examples 1-6 and Comparative Examples 1-3 further illustrate the excellent effects achieved by the present application, and the test results are shown in the following table:

[0155] Table 1: Test results of polyamide 6 master batch performance

[0156] Dye addition amount Porous nanomaterial addition amount Color change completion speed (s) at 37°C Example 1 25％ 5％ 1 Example 2 30％ 5％ 1.5 Example 3 35％ 5％ 2.1 Example 4 25％ 4％ 3.3 Example 5 25％ 3％ 6.2 Example 6 25％ 2％ 11.9 Comparative Example 1 25％ 0 No color change Comparative Example 2 25％ 5% (uncharged) No color change Comparative Example 3 25% (positively charged) 5％ No color change

[0157] Table 2: Statistical table of polyamide 6 fiber performance test results

[0158]

[0159]

[0160] As can be seen from the above table, the thermochromic polyamide 6 master batch provided by the application and the thermochromic polyamide 6 fiber prepared by the application have good comprehensive performance, and have good thermochromic performance and color change reversibility, and effectively solve the problems of poor spinning condition and poor product quality of the current thermochromic fiber.

[0161] The above only describes the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the protection scope of the present application.

Claims

1. A thermochromic polyamide 6 masterbatch, characterized in that, It is composed of the following raw materials in parts by weight: 2-5 parts porous nanomaterials, 25-35 parts dye, and 60-70 parts of glossy polyamide 6 chips; the porous nanomaterials have adsorption properties; The main component of the porous nanomaterial is {Ag[Ag]} which has a three-dimensional framework structure. 14 ( i PrS) 10 ]} 5+ ; The dye is Congo Red, which carries a negative charge.

2. The thermochromic polyamide 6 masterbatch according to claim 1, characterized in that, The Congo red has a particle size of 50 nm.

3. The thermochromic polyamide 6 masterbatch according to claim 1, characterized in that, The thermochromic polyamide 6 masterbatch has a melt index of 44.34 g / 10min, a relative viscosity of 2.4, a water content of 780 ppm, a terminal amino content of 30.17 mmol / kg, and a terminal carboxyl content of 64.81 mmol / kg.

4. A method for preparing a thermochromic polyamide 6 masterbatch according to any one of claims 1-3, characterized in that, Includes the following steps: S11: Weigh the porous nanomaterials and dyes according to the set ratio, premix them and put them into the buffer bin. After being placed into the hopper, stir them with a spiral until they are evenly mixed to obtain the premixed material. S12: Feed bright polyamide 6 chips from the main feed port and premix from the side feed port. Mix the bright polyamide 6 chips and premix evenly and then melt-mix in a twin-screw extruder to obtain thermochromic polyamide 6 masterbatch melt. S13: Thermochromic polyamide 6 masterbatch melt strip is extruded from the outlet of the twin-screw extruder. After being cooled by a water cooling tank, the strip enters a pelletizer for pelletizing, vibration screening and blower drying to obtain the thermochromic polyamide 6 masterbatch.

5. A thermochromic nylon 6 fiber, characterized in that, The raw materials for the thermochromic nylon 6 fiber include the thermochromic polyamide 6 masterbatch as described in any one of claims 1-3 or the thermochromic polyamide 6 masterbatch prepared by the preparation method described in claim 4.

6. The thermochromic nylon 6 fiber according to claim 5, characterized in that, It is composed of the following raw materials in parts by weight: 10 parts of thermochromic polyamide 6 masterbatch and 90 parts of glossy polyamide 6 chips.

7. The method for preparing thermochromic nylon 6 fiber according to claim 6, characterized in that, Includes the following steps: S21: The thermochromic polyamide 6 masterbatch and glossy polyamide 6 chips are dried separately. The glossy polyamide 6 chips are fed into the main feed port. The thermochromic polyamide 6 masterbatch is put into the buffer bin, lowered into the hopper and stirred evenly by a spiral. It is then fed into the side feed port. After being mixed evenly, it is compounded and melted in a twin-screw extruder to obtain a composite melt. S22: The composite melt obtained in step S21 is metered by a metering pump and then enters the spinning box. The composite filament is obtained by spinning through the component. Then, it is subjected to slow cooling, monomer suction, side blowing cooling, bundle oiling, secondary cooling in the channel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber. S23: The thermochromic POY nylon 6 fiber obtained in step S22 is then subjected to false twisting and texturing to obtain thermochromic DTY nylon 6 fiber, which is the thermochromic nylon 6 fiber.

8. The method for preparing thermochromic nylon 6 fiber according to claim 7, characterized in that, In step S21, the twin-screw extruder has nine temperature zones, and the temperature of each temperature zone and the die head is 165℃-235℃.

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