Thermochromic polyamide master batch, thermochromic chinlon 6 fiber and preparation method of thermochromic polyamide master batch and thermochromic chinlon 6 fiber

Abstract

The invention discloses a thermochromic polyamide 6 master batch, a thermochromic polyamide 6 fiber and a preparation method of the thermochromic polyamide 6 fiber. The polyamide 6 master batch is prepared from the following raw materials in parts by weight: 2-5 parts of a porous nano material, 25-35 parts of dye and 60-70 parts of bright polyamide 6 slices. The porous nano material has adsorption performance, and the main component of the porous nano material is {Ag [Ag14 (iPrS) 10]} 5 < + > of a three-dimensional frame structure; the dye is Congo red, has negative charges and has a particle size of 50 nm, and 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 amino-terminated group content of 30.17 mmol / kg and a carboxyl-terminated group content of 64.81 mmol / kg. The thermochromic polyamide 6 master batch is prepared by compounding the porous nano-material with adsorption performance, the dye and the polyamide 6, and adsorption-desorption of the dye in the nano-material is controlled by changing the temperature by virtue of the property that the porosity of the porous nano-material is reduced along with temperature rise; furthermore, the thermochromism effect is achieved, and the thermochromism has reversibility.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical fibers, and particularly relates to a thermochromic polyamide 6 masterbatch, a thermochromic nylon 6 fiber and a preparation method thereof. Background Art

[0002] With the rapid development of the textile industry in recent years, consumers are paying more and more attention to the functional diversification of fibers. Functional nylon fibers prepared with polyamide 6 as the main raw material not only have the comfortable skin feel of nylon, but also provide health-related functions. Therefore, the sales volume of functional nylon fibers has increased year by year. At present, the functional nylon fiber market is dominated by health-related functional products such as moisture absorption and perspiration, cool feeling, and UV resistance. There is still a research and development gap in medical monitoring and smart wear. Considering that thermochromic textiles have demonstrated application potential in health monitoring, home decoration, smart wear and other fields, it is of great practical significance to develop a nylon fiber with thermochromic function. However, the existing thermochromic technology often seriously affects the spinning condition during the high-speed spinning of nylon, causing problems such as floating silk and broken ends, affecting product quality. Existing thermochromic related products are mainly integrated and applied to existing spinning technologies by functional devices, rather than the functionalization of the fiber itself, which limits the use of this series of fiber materials.

[0003] The Chinese patent application with application number CN201610143303.8 discloses a thermochromic polyester fiber and its preparation method. The application uses a core-skin coating to mix a masterbatch with a thermochromic function with a polyester slice as a core material, and the polyester slice is used as a skin material to prepare a thermochromic polyester fiber with a skin-core structure. Although this method achieves the thermochromic performance at the fiber level, the masterbatch will affect the spinning condition of the fiber and cannot be directly used for spinning. It can only be coated with a core-skin coating method to coat the thermochromic component with poor spinning performance in the core layer structure, which causes the color development effect to be weakened by the skin component, and the spinning condition problem of the thermochromic fiber cannot be fundamentally solved. The Chinese patent with application number CN201810478727.9 discloses a method for preparing a light / thermal dual-chromic fiber and its resulting materials and applications. The invention combines diacetylene compounds with different polymers by means of electrospinning to prepare fibers with light / thermal dual-chromic effects. However, this method is very complicated to implement, has extremely high requirements on the quality of raw materials, and is difficult to put into large-scale production. Summary of the invention

[0004] In order to solve the above problems, the present invention provides a thermochromic polyamide 6 masterbatch, a thermochromic nylon 6 fiber and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] One of the purposes of the present invention is to provide a thermochromic polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 2-5 parts of porous nanomaterials, 25-35 parts of dyes, and 60-70 parts of bright polyamide 6 slices; the porous nanomaterial has adsorption properties.

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

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

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

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

[0011] The second object of the present invention is to provide a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0012] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0013] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0014] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch.

[0015] A third object of the present invention is to provide a thermochromic nylon 6 fiber, wherein the raw material of the thermochromic nylon 6 fiber includes any one of the above-mentioned thermochromic polyamide 6 masterbatches.

[0016] Furthermore, 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.

[0017] A fourth object of the present invention is to provide a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0018] S21: drying the thermochromic polyamide 6 masterbatch and the bright polyamide 6 slice respectively, feeding the bright polyamide 6 slice from the main feeding port, throwing the thermochromic polyamide 6 masterbatch into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0019] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber;

[0020] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber.

[0021] Furthermore, in step S21, the twin-screw extruder is provided with nine temperature zones, and each temperature zone and die head temperature is 165°C-235°C.

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

[0023] 1. The present invention provides a thermochromic nylon 6 fiber, which uses a porous nanomaterial with adsorption properties. When the ambient temperature is low, the porosity of the porous nanomaterial is high, and the dye is adsorbed into the pores of the nanomaterial through electrostatic action, resulting in a lighter color; as the temperature rises, the skeleton of the porous nanomaterial shrinks, the porosity decreases, and the dye is gradually released from the pores of the porous nanomaterial, and the color is darker, thereby achieving a thermochromic effect, and its thermochromic property is reversible.

[0024] 2. In the present invention, the porous nanomaterial is a porous silver nanomaterial with a positive charge, the main component of which is a compound with a three-dimensional framework structure composed of silver ions and sulfur-containing ligands, and the molecular formula is {Ag[Ag 14 ( i PrS) 10 ]} 5+ The porous nanomaterial has a high positive charge, which leads to good dispersibility and is not easy to agglomerate in the polyamide 6 matrix. It has little effect on the spinning conditions and can be directly used for spinning.

[0025] 3. In the present invention, the dye is Congo red, which has a negative charge and has an electrostatic effect with the porous nanomaterial, which can promote the adsorption between the dye and the porous nanomaterial.

[0026] 4. The thermochromic polyamide 6 fiber provided by the present invention can be directly used for spinning by adding thermochromic polyamide 6 masterbatch. The obtained thermochromic nylon 6 fiber has good color development effect and can effectively solve the problems of poor spinning condition and poor product quality of thermochromic fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a schematic diagram of the porous nanomaterial in the present invention, in which the skeleton shrinks and the porosity decreases as the temperature rises. DETAILED DESCRIPTION

[0028] The following is a preferred embodiment and the attached Figure 1 , the present invention is further described. The endpoints and any values ​​of the ranges disclosed in the present invention 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 each range, the endpoint values ​​of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein; the materials, reagents, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels; the experimental methods in the following examples, unless otherwise specified, are all conventional methods.

[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 of porous nanomaterials, 25 parts of dyes, and 70 parts of bright polyamide 6 chips; the porous nanomaterial has adsorption properties.

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

[0032] In the porous nanomaterial, Figure 1 As shown in the figure, as the temperature rises, the metal-metal bond between Ag···Ag absorbs energy and becomes shorter, the skeleton shrinks, the porosity decreases, and the dye is gradually released from the pores of the porous silver nanomaterial, showing red; when the ambient temperature decreases, the porosity of the porous nanomaterial increases, and the dye is gradually adsorbed into the pores by the porous nanomaterial through electrostatic action, and the color becomes lighter, achieving the effect of thermochromic change, and its thermochromic change is reversible. The porous nanomaterial has good dispersibility and little effect on spinning conditions, and can be directly used for spinning.

[0033] In this embodiment, the thermochromic polyamide 6 masterbatch has a melt index of 44.34 g / 10 min, a relative viscosity of 2.4, a water content of 780 ppm, a terminal amino group content of 30.17 mmol / kg, and a terminal carboxyl group content of 64.81 mmol / kg.

[0034] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0035] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0036] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0037] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the outlet of the twin-screw extruder, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 1.

[0038] This embodiment also provides a thermochromic nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of masterbatch 1 and 90 parts of bright polyamide 6 chips.

[0039] This embodiment also provides a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0040] S21: drying the masterbatch 1 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the masterbatch 1 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, and compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0041] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0042] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 1 and has 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 intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0044] Example 2

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

[0046] The porous nanomaterial and dye of this embodiment are the same as those of embodiment 1.

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

[0048] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0049] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0050] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0051] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 2.

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

[0053] This embodiment also provides a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0054] S21: drying the masterbatch 2 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the masterbatch 2 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0055] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain 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 twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 2 and has 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 intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0058] Example 3

[0059] This embodiment provides a thermochromic polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 5 parts of porous nanomaterials, 35 parts of dyes, and 60 parts of bright polyamide 6 chips.

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

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

[0062] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0063] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0064] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0065] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 3.

[0066] This embodiment also provides a thermochromic nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of masterbatch 3 and 90 parts of bright polyamide 6 chips.

[0067] This embodiment also provides a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0068] S21: drying the masterbatch 3 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the masterbatch 3 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0069] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0070] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 3 and has a specification of 70D / 24F.

[0071] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0072] Example 4

[0073] This embodiment provides a thermochromic polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 4 parts of porous nanomaterials, 25 parts of dyes, and 71 parts of bright polyamide 6 chips.

[0074] The porous nanomaterial and dye of this embodiment are the same as those of embodiment 1.

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

[0076] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0077] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0078] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0079] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 4.

[0080] This embodiment also provides a thermochromic nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of masterbatch 4 and 90 parts of bright polyamide 6 chips.

[0081] This embodiment also provides a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0082] S21: drying the masterbatch 4 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the masterbatch 4 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0083] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0084] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 4 and has a specification of 70D / 24F.

[0085] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0086] Example 5

[0087] This embodiment provides a thermochromic polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 3 parts of porous nanomaterials, 25 parts of dyes, and 72 parts of bright polyamide 6 chips.

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

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

[0090] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0091] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0092] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0093] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 5.

[0094] This embodiment also provides a thermochromic nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of masterbatch 5 and 90 parts of bright polyamide 6 chips.

[0095] This embodiment also provides a method for preparing thermochromic nylon 6 fiber, comprising the following steps:

[0096] S21: drying the masterbatch 5 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the masterbatch 5 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0097] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0098] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 5 and has 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 intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0100] Example 6

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

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

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

[0104] This embodiment also provides a method for preparing a thermochromic polyamide 6 masterbatch, comprising the following steps:

[0105] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0106] S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt;

[0107] S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch, which is recorded as masterbatch 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 masterbatch 6 and 90 parts of bright polyamide 6 chips.

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

[0110] S21: drying the master batch 6 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the master batch 6 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, and compounding and melting it in a 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 through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0112] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber, which is recorded as fiber 6 and has a specification of 70D / 24F.

[0113] In step S12 of this embodiment, the twin-screw extruder is provided with nine temperature zones, and the temperature intervals are 225°C, 235°C, 235°C, 215°C, 205°C, 195°C, 185°C, 175°C, and 165°C, respectively, and the head temperature is: 230°C.

[0114] Comparative Example 1

[0115] The difference from Example 1 is that the comparative polyamide 6 masterbatch in this comparative example does not contain porous nanomaterials.

[0116] This comparative example provides a comparative polyamide 6 masterbatch, which is composed of the following raw materials in parts by weight: 25 parts of dye and 75 parts of bright polyamide 6 chips.

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

[0118] This comparative example also provides a method for preparing a comparative polyamide 6 masterbatch, comprising the following steps:

[0119] S11: Weigh the dye according to the set ratio, put it into the buffer bin, and put it into the hopper;

[0120] S12: feeding bright polyamide 6 chips from the main feeding port and feeding dye from the side feeding port, mixing the bright polyamide 6 chips and the dye evenly, and melt-mixing them in a twin-screw extruder to obtain a polyamide 6 masterbatch melt;

[0121] S13: extruding polyamide 6 masterbatch melt strips from the twin-screw extruder outlet, cooling the strips in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the polyamide 6 masterbatch, which is recorded as comparative masterbatch 1.

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

[0123] This comparative example also provides a method for preparing a comparative nylon 6 fiber, comprising the following steps:

[0124] S21: drying the comparative masterbatch 1 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the comparative masterbatch 1 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, and compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0125] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0126] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the comparative nylon 6 fiber, which is recorded as comparative fiber 1 and has a specification of 70D / 24F.

[0127] Comparative Example 2

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

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

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

[0131] This comparative example also provides a method for preparing a comparative polyamide 6 masterbatch, comprising the following steps:

[0132] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

[0133] S12: feeding bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a polyamide 6 masterbatch melt;

[0134] S13: extruding polyamide 6 masterbatch melt strips from the twin-screw extruder outlet, cooling the strips in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the polyamide 6 masterbatch, which is recorded as comparative masterbatch 2.

[0135] This comparative example also provides a comparative nylon 6 fiber, which is composed of the following raw materials in parts by weight: 10 parts of comparative masterbatch 2 and 90 parts of bright polyamide 6 chips.

[0136] This comparative example also provides a method for preparing a comparative nylon 6 fiber, comprising the following steps:

[0137] S21: drying the comparative masterbatch 2 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the comparative masterbatch 2 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a 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 enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0139] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the comparative nylon 6 fiber, recorded as comparative fiber 2, with a specification of 70D / 24F.

[0140] Comparative Example 3

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

[0142] This comparative example provides a comparative polyamide masterbatch 3, which is composed of the following raw materials in parts by weight: 5 parts of porous nanomaterials, 25 parts of dyes, and 70 parts of bright polyamide 6 chips.

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

[0144] This comparative example also provides a method for preparing a comparative polyamide 6 masterbatch, comprising the following steps:

[0145] S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix;

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

[0147] S13: extruding polyamide 6 masterbatch melt strips from the twin-screw extruder outlet, cooling the strips in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the comparative polyamide 6 masterbatch, which is recorded as comparative masterbatch 3.

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

[0149] This comparative example also provides a method for preparing a comparative nylon 6 fiber, comprising the following steps:

[0150] S21: drying the comparative masterbatch 3 and the bright polyamide 6 slices respectively, feeding the bright polyamide 6 slices from the main feeding port, throwing the comparative masterbatch 3 into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it in a twin-screw extruder to obtain a composite melt;

[0151] S22: the composite melt obtained in step S21 is metered by a metering pump and then enters a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber with a specification of 85D / 24F;

[0152] S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the comparative nylon 6 fiber, recorded as comparative fiber 3, with a specification of 70D / 24F.

[0153] Implementation effect evaluation:

[0154] The excellent effect of the present invention is further illustrated by conducting specific tests on the master batches 1-6, comparative master batches 1-3, fibers 1-6 and comparative fibers 1-3 obtained in Examples 1-6 and Comparative Examples 1-3. The test results are shown in the following table:

[0155] Table 1 Polyamide 6 masterbatch performance test results

[0156] Dye addition amount Porous nanomaterial addition amount Color change completion speed at 37℃(s) 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 Unable to change color Comparative Example 2 25％ 5% (no charge) Unable to change color Comparative Example 3 25% (positively charged) 5％ Unable to change color

[0157] Table 2 Statistics of nylon 6 fiber performance test results

[0158]

[0159]

[0160] It can be seen from the above table that the thermochromic polyamide 6 masterbatch provided by the present invention and the thermochromic nylon 6 fiber prepared by the present invention have good comprehensive performance, and have very good thermochromic performance and color reversibility. The present invention effectively solves the current problems of poor spinning conditions and poor product quality of thermochromic fibers.

[0161] The above is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several modifications and improvements without departing from the inventive concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A thermochromic polyamide 6 masterbatch, characterized in that: The invention is composed of the following raw materials in parts by weight: 2-5 parts of porous nanometer materials, 25-35 parts of dyes and 60-70 parts of bright polyamide 6 slices; the porous nanometer materials have adsorption properties.

2. The thermochromic polyamide 6 masterbatch according to claim 1, characterized in that: The main component of the porous nanomaterial is {Ag[Ag 14 ( i PrS) 10 ]} 5+ .

3. The thermochromic polyamide 6 masterbatch according to claim 2, characterized in that: The dye is Congo red, which has a negative charge.

4. The thermochromic polyamide 6 masterbatch according to claim 3, characterized in that: The particle size of the Congo red is 50 nm.

5. 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 / 10 min, a relative viscosity of 2.4, a water content of 780 ppm, a terminal amino group content of 30.17 mmol / kg, and a terminal carboxyl group content of 64.81 mmol / kg.

6. A method for preparing a thermochromic polyamide 6 masterbatch according to any one of claims 1 to 5, characterized in that: The following steps are involved: S11: Weigh the porous nanomaterial and the dye according to a set ratio, premix them and put them into the buffer bin, put them into the hopper and stir them with a spiral until they are evenly mixed to obtain a premix; S12: feeding the bright polyamide 6 chips from the main feeding port and feeding the premix from the side feeding port, mixing the bright polyamide 6 chips and the premix evenly, and melt-mixing them in a twin-screw extruder to obtain a thermochromic polyamide 6 masterbatch melt; S13: extruding a thermochromic polyamide 6 masterbatch melt strip from the twin-screw extruder outlet, cooling the strip in a water cooling tank, and then entering a pelletizer for pelletizing, vibration screening and blast drying to obtain the thermochromic polyamide 6 masterbatch.

7. A thermochromic nylon 6 fiber, characterized in that: The raw material of the thermochromic nylon 6 fiber includes the thermochromic polyamide 6 masterbatch described in any one of claims 1 to 5, or includes the thermochromic polyamide 6 masterbatch prepared by the preparation method described in claim 6.

8. The thermochromic nylon 6 fiber according to claim 7, characterized in that: The invention 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.

9. The method for preparing thermochromic nylon 6 fiber according to claim 8, characterized in that: The following steps are involved: S21: drying the thermochromic polyamide 6 masterbatch and the bright polyamide 6 slice respectively, feeding the bright polyamide 6 slice from the main feeding port, throwing the thermochromic polyamide 6 masterbatch into the buffer bin, lowering it into the hopper and then spirally stirring it evenly, feeding it from the side feeding port, mixing evenly, compounding and melting it 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 a spinning box, and is spun through a component to obtain a composite filament bundle, and then subjected to slow cooling, monomer suction, side-blowing cooling, bundling oiling, secondary cooling in a tunnel, stretching and shaping, and winding to obtain thermochromic POY nylon 6 fiber; S23: The thermochromic POY nylon 6 fiber obtained in step S22 is subjected to false twisting and stretching to obtain thermochromic DTY nylon 6 fiber, i.e. the thermochromic nylon 6 fiber.

10. The method for preparing thermochromic nylon 6 fiber according to claim 9, characterized in that: In step S12, the twin-screw extruder is provided with nine temperature zones, and each temperature zone and die head temperature is 165°C-235°C.

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