Fiber containing elastic wall phase change microcapsule as well as preparation method and application of fiber

Abstract

The invention relates to a fiber containing an elastic wall phase change microcapsule as well as a preparation method and application thereof, and relates to the field of composite fibers. The fiber containing the elastic wall phase change microcapsule comprises a fiber matrix and the elastic wall phase change microcapsule, the elastic wall microcapsule comprises a wall material and a core material, the wall material comprises a polyamide 66 / polyethylene glycol copolymer, and raw materials of the core material comprise polyimide aerogel and a polyethylene glycol phase change material. The fiber contains the elastic wall phase change microcapsule, and the problems that in the prior art, the microcapsule used by the phase change polyamide fiber is difficult to deform, the requirement for the particle size is strict, then a core material is prone to leakage, and the compatibility with raw materials of a fiber matrix is poor can be solved.

Description

Technical Field

[0001] The invention relates to the field of composite fibers, in particular to a fiber containing elastic wall phase change microcapsules and a preparation method and application thereof. Background Art

[0002] Polyamide fiber is widely used in textile and industrial fields due to its good wear resistance, moisture absorption and air permeability, heat resistance, dyeability, etc. It is one of the most widely used chemical fibers. With the improvement of living standards, people have a higher pursuit of comfort in daily necessities such as clothing. The development of fibers is gradually becoming intelligent, and phase change materials that can provide high resilience and adjust temperature according to the environment are also integrated into the fibers. This composite processing method combines the excellent physical properties of polyamide with the thermal regulation characteristics of phase change materials, and has many significant advantages. It can realize intelligent temperature control: phase change materials can absorb, store and release heat within a specific temperature range, thereby effectively regulating the wearer's body temperature and enhancing wearing comfort. Dynamic adaptation: phase change materials can automatically adjust according to changes in ambient temperature, and can maintain a suitable temperature whether in a cold or warm environment. The fiber body has good elasticity and wear resistance, and can maintain good elasticity and shape recovery during use. This diversified processing idea provides a variety of application possibilities and comfort, meeting the needs of the modern market for functional textiles.

[0003] The phase change polyamide fibers reported in the existing literature are mainly processed by adding phase change materials, among which the addition of microcapsules is the most convenient and reliable. In the studies of polyamide fibers containing phase change microcapsules reported in these reports, the phase change materials of the microcapsules are mainly paraffin, polyurethane-urea, eicosane (Journal of Applied Polymer Science, 2018, 136, 47408; Fiber Polymer, 2006, 7, 12-19; ​​Progress in Organic Coatings, 2021, 159, 106439.), etc., but the thermal conductivity of the above-mentioned raw material paraffin is relatively low, resulting in its efficiency in the process of heat release or absorption, and the heat conduction speed is slow. Under high temperature conditions, paraffin may volatilize, resulting in a decrease in material performance or the release of harmful gases. In addition, paraffin is a flammable material, and fire safety must be considered when using it. Polyurethane is sensitive to humidity, and moisture absorption may affect its phase change properties. Compared with other phase change materials, the hardness and flexibility of polyurethane may be limited, affecting the flexibility of application. As a phase change material with a high melting point, eicosane has a high production cost, which limits its wide application. Under high temperature or long-term use conditions, the stability of eicosane may decrease, affecting performance. In composite materials, the compatibility of eicosane is not as good as other materials, resulting in poor dispersibility or uneven performance. In addition, there are many studies that use carbon nanotubes, halloysite nanotubes, silica, lauric acid, etc. as composite materials for the preparation of phase change polyamide fibers (Composites Science and Technology, 2022, 226, 109541. Chemical Engineering Journal, 2021, 403, 126369.), but these methods cannot solve the problem of easy leakage of phase change materials. Therefore, it is particularly important to develop phase change capsule materials with better compatibility and stability for the composite preparation of polyamide fibers. Summary of the invention

[0004] In view of the above problems, the present invention provides a fiber containing elastic wall phase change microcapsules. The fiber contains elastic wall phase change microcapsules, which can overcome the problems that the microcapsules used in the phase change polyamide fiber in the prior art are difficult to deform, have strict particle size requirements, which leads to easy leakage of the core material, and have poor compatibility with the raw materials of the fiber matrix.

[0005] In order to achieve the above-mentioned purpose, the present invention provides a fiber containing elastic wall phase change microcapsules, including a fiber matrix and elastic wall phase change microcapsules. The elastic wall phase change microcapsules include wall materials and core materials. The wall material includes polyamide 66 / polyethylene glycol copolymer, and the raw materials of the core material include polyimide aerogel and polyethylene glycol phase change material.

[0006] The wall material of the elastic wall phase change microcapsule can be subjected to shear deformation but not damage during the high temperature processing of the fiber matrix raw material spinning and forming mentioned in this patent, thereby ensuring the integrity of the phase change material in the core material. Secondly, the core material is mixed with the polyimide aerogel to achieve uniform dispersion. Furthermore, the wall material of the elastic wall phase change microcapsule and the matrix polymer belong to the same polyamide class and have a certain compatibility, thereby achieving the stability of the target fiber structure and the reliability of performance.

[0007] In one embodiment, the polyamide 66 / polyethylene glycol copolymer is a block copolymer of polyamide 66 / polyethylene glycol, and the copolymerization ratio of polyamide 66 to polyethylene glycol in the polyamide 66 / polyethylene glycol copolymer is (0.5-2.5):1.

[0008] In one embodiment, the phase change enthalpy of the fiber containing the elastic wall phase change microcapsules is 10-30 J / g, and the elastic recovery rate is above 85% (@10%).

[0009] In one embodiment, the molecular weight of the polyethylene glycol phase change material is 1000-20000 g / mol.

[0010] The polyimide aerogel can be a block prepared by conventional freeze drying or supercritical drying, and can be physically crushed to a size of 2-30 microns.

[0011] In one embodiment, the wall material is coated on the surface of the core material, and the mass percentage of the core material in the elastic wall phase change microcapsule is 50-80%; the mass percentage of the polyimide aerogel in the core material is 0.05-2.0%.

[0012] In one of the embodiments, the elastic wall phase change microcapsules are distributed in the fiber matrix, and the mass ratio of the elastic wall phase change microcapsules to the fiber matrix is ​​(5-30):100.

[0013] In one of the embodiments, the raw material of the fiber matrix includes polyamide 6 / 66 copolymer and polyamide 6, and the composite ratio of the polyamide 6 / 66 copolymer and polyamide 6 is (80-50): (20-50).

[0014] In one embodiment, the copolymerization ratio of PA6 to PA66 in the polyamide 6 / 66 copolymer is (80-85): (20-15).

[0015] The sum of the weight parts of PA6 and PA66 in the above polyamide 6 / 66 copolymer is 100. When the weight part of PA6 changes from 80 to 85, the weight part of PA66 changes from 20 to 15 accordingly. Therefore, the copolymerization ratio of PA6 to PA66 in the polyamide 6 / 66 copolymer is (80-85):(20-15).

[0016] In one embodiment, the relative viscosity of the polyamide 6 / 66 copolymer is 2.4-2.8, and the relative viscosity of the polyamide 6 is 2.0-2.4.

[0017] The present invention also provides a method for preparing the fiber, comprising the following steps:

[0018] Preparation of elastic wall phase change microcapsules: mixing adipic acid and hexamethylenediamine under a protective atmosphere, heating, and cooling to obtain a polyamide 66 precursor; adding polyethylene glycol and a catalyst, heating to a polymerization temperature, and performing a polymerization reaction to obtain a wall material; mixing the raw materials of the core material under high temperature vacuum conditions to obtain a core material, dissolving the wall material in a polar solvent to obtain a wall material solution, adding the core material to the wall material solution, and drying to obtain an elastic wall phase change microcapsule;

[0019] Preparation of fibers: mixing the elastic wall phase change microcapsules and the raw materials of the fiber matrix, and spinning them to obtain fibers containing the elastic wall phase change microcapsules.

[0020] The preparation method is simple, environmentally friendly and easy to operate. The elastic wall phase change microcapsules are deformed and refined under high temperature spinning conditions through the high elastic state of the fiber matrix without breaking, and form strip distribution in the fiber in situ.

[0021] In one embodiment, the molecular weight of the polyamide 66 precursor is in the range of 1000-10000 g / mol, and the molecular weight of the polyethylene glycol is in the range of 200-800 g / mol.

[0022] In one embodiment, the relative viscosity of the wall material is 2.6-3.0, and the mass concentration of the wall material in the wall material solution is 5-20%.

[0023] In one embodiment, in the step of preparing elastic wall phase change microcapsules, the molar ratio of adipic acid to hexamethylenediamine is 1:(0.8-1.2), the heating temperature is 200-250°C, and the heating time is 2-8h; the polymerization temperature is 180-250°C, and the polymerization reaction time is 2-8h; the high temperature vacuum condition is 95-105°C, -0.15 to -0.05MPa; and the drying includes spray drying.

[0024] In one of the embodiments, in the fiber preparation step, the mixing and spinning of the elastic wall phase change microcapsules and the raw materials of the fiber matrix are achieved by blending and adding melt spinning.

[0025] In one embodiment, the blending and adding melt spinning includes the following steps: slicing elastic wall phase change microcapsules, polyamide 6 / 66 copolymer, and polyamide 6, blending one of the polyamide 6 / 66 copolymer and polyamide 6 with the elastic wall phase change microcapsules to obtain a blend, adding the blend and the remaining raw materials of the fiber matrix into two spinning screw extruders for composite spinning, respectively, for melting and homogenization, and extruding from parallel composite spinning components, cooling and solidifying, two-step drawing and heat setting processes, and oiling to obtain fibers containing elastic wall phase change microcapsules.

[0026] In one embodiment, the blending and adding melt spinning includes the following steps: slicing elastic wall phase change microcapsules, polyamide 6 / 66 copolymer, and polyamide 6, blending polyamide 6 / 66 copolymer and polyamide 6 with elastic wall phase change microcapsules respectively to obtain polyamide 6 / 66 blend and polyamide 6 blend, adding polyamide 6 / 66 blend and polyamide 6 blend into two spinning screw extruders for composite spinning respectively, melting and homogenizing, extruding from parallel composite spinning components, cooling and solidifying, two-step drawing and heat setting process, and oiling to obtain fibers containing elastic wall phase change microcapsules.

[0027] The above-mentioned blending and adding melt spinning is simple and easy to operate, and allows the elastic wall phase change microcapsules to be evenly distributed in the raw materials of the fiber matrix.

[0028] The invention also provides a fabric prepared by adopting the fiber.

[0029] The present invention also provides application of the fiber in preparing clothing, home textiles, building materials, automobile interior decoration and care products.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The present invention discloses a fiber containing an elastic wall phase change microcapsule, a preparation method thereof and an application thereof. The wall material of the elastic wall phase change microcapsule has an adaptive deformation characteristic, can be deformed at high temperature, and can maintain the deformation without damaging the wall surface after cooling, so that the phase change material in the core material can be stably present and has a high potential economic value. The fiber containing the elastic wall phase change microcapsule can overcome the problems of the microcapsules used in the phase change polyamide fiber in the prior art being difficult to deform, strict particle size requirements, and thus causing the core material to leak easily, as well as poor compatibility with the raw materials of the fiber matrix. The resilience of the fiber can reach up to 92%, and its elasticity is provided by the self-morphology of the parallel composite fiber, without the need for chemical structure design. In addition, the fiber also has the potential for phase change temperature control and can be woven and applied to clothing, medical, automotive and other industries. DETAILED DESCRIPTION

[0032] For ease of understanding of the present invention, the present invention will be described more fully below with reference to relevant embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0034] source:

[0035] Unless otherwise specified, the reagents, materials, and equipment used in this example are all commercially available; the experimental methods are all conventional experimental methods in the art unless otherwise specified.

[0036] definition:

[0037] The resilience of the polyamide fiber in the present invention is tested at room temperature using the ASTM D4964-2016 method using a WDW3020 tensile testing machine under the conditions of 10 mm / min and 50 N; the resilience of each sample is calculated using the following formula:

[0038]

[0039] L0 is the initial length, L1 is the length after stretching, and L2 is the length after recovery. Each test is repeated 5 times and the results are averaged. The length after stretching is 110% of the initial length.

[0040] Example 1

[0041] (1) Preparation of elastic wall phase change microcapsules.

[0042] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The reactor was heated to 240°C, reacted for 6 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (500 g) and polyamide 66 precursor (250 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 2:1. The reactor was heated to 230°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.8 was obtained.

[0043] The polyimide aerogel powder (average particle size 30 microns, 5 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 1 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.50%; polyamide 66 / polyethylene glycol copolymer (1.5 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of the core material in the elastic wall phase change microcapsule is 51%.

[0044] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0045] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) are composite-spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 20% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules are blended with polyamide 6 / 66, they are melt-spun with polyamide 6 through a parallel composite spinning machine.

[0046] The specific operation includes the following steps: After the elastic wall phase change microcapsules and polyamide 6 / 66 slices are fully mixed, they are added to a spinning screw extruder for composite spinning to be melted and homogenized to obtain a blend. Polyamide 6 is directly added to the second spinning screw extruder in the composite spinning machine to be melted and homogenized; the homogenized melts (i.e. the melt of the blend and the melt of polyamide 6) are extruded through the parallel composite spinning assembly, and the fiber is formed through the parallel composite spinning spinneret, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is applied to obtain fibers containing elastic wall phase change microcapsules.

[0047] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0048] The elastic polyamide fiber prepared in this embodiment has a resilience of 85% and a fiber phase change enthalpy of 14.5 J / g.

[0049] Example 2

[0050] (1) Preparation of elastic wall phase change microcapsules.

[0051] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 240°C, reacted for 8 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 7000 g / mol. PEG400 (700 g) and polyamide 66 precursor (300 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 7:3. The mixture was heated to 230°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 was obtained.

[0052] The polyimide aerogel powder (average particle size 30 microns, 1 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 2000g / mol, 0.1g) under high temperature vacuum conditions of 100°C and -0.1MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.99%; polyamide 66 / polyethylene glycol copolymer (1.5g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on polyimide aerogel powder and PEG complex (core material), and then elastic wall phase change microcapsules are obtained. The mass percentage of the core material in the elastic wall phase change microcapsules is 70%.

[0053] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0054] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) are composite spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules are mixed and spun with polyamide 6 / 66 and polyamide 6 respectively, and the process is achieved by blending and adding melt spinning.

[0055] The specific operation includes the following steps: slicing elastic wall phase change microcapsules, polyamide 6 / 66 and polyamide 6 with a total addition amount of 30%, fully mixing the elastic wall phase change microcapsules with polyamide 6 / 66 and polyamide 6, respectively, to obtain polyamide 6 / 66 blends and polyamide 6 blends, respectively adding them to two spinning screw extruders for composite spinning, melting and homogenizing to obtain melts; the melts of the polyamide 6 / 66 blends and the polyamide 6 blends are extruded from the parallel composite spinning components, and the fibers are formed through the parallel composite spinning spinnerets, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling, fibers containing elastic wall phase change microcapsules are obtained.

[0056] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0057] The elastic polyamide fiber prepared in this embodiment has a resilience of 80% and a fiber phase change enthalpy of 18 J / g.

[0058] Example 3

[0059] (1) Preparation of elastic wall phase change microcapsules.

[0060] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 230°C, reacted for 4 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 4000 g / mol. PEG800 (250 g) and polyamide 66 precursor (500 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 1:2. The mixture was heated to 240°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.7 was obtained.

[0061] The polyimide aerogel powder (average particle size 30 microns, 2 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 0.5 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.40%; polyamide 66 / polyethylene glycol copolymer (1 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of the core material in the elastic wall phase change microcapsule is 80% of the elastic wall phase change microcapsule.

[0062] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0063] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.6) and polyamide 6 (relative viscosity 2.8) are composite spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules are mixed and spun with polyamide 6 / 66 and polyamide 6 respectively, and the process is realized by blending and adding melt spinning.

[0064] The specific operation includes the following steps: slicing elastic wall phase change microcapsules, polyamide 6 / 66 and polyamide 6 with a total addition amount of 30%, fully mixing the elastic wall phase change microcapsules with polyamide 6 / 66 and polyamide 6, respectively, to obtain polyamide 6 / 66 blends and polyamide 6 blends, respectively adding them to two spinning screw extruders for composite spinning, melting and homogenizing to obtain melts; the melt of polyamide 6 / 66 blend and the melt of polyamide 6 blend are extruded from parallel composite spinning components, and the fibers are formed through parallel composite spinning spinnerets, and the spinning temperature is 250°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is performed to obtain fibers containing elastic wall phase change microcapsules. The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 250°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a circular shape to a strip-like fusiform shape under the action of shear force, and are thus distributed inside the fiber.

[0065] The elastic polyamide fiber prepared in this embodiment has a resilience of 85% and a fiber phase change enthalpy of 30 J / g.

[0066] Example 4

[0067] (1) Preparation of elastic wall phase change microcapsules.

[0068] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 240°C, reacted for 2 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 1000 g / mol. PEG200 (250 g) and polyamide 66 precursor (500 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 1:2. The mixture was heated to 230°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 was obtained.

[0069] The polyimide aerogel powder (average particle size 10 microns, 1 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 1 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.1%; polyamide 66 / polyethylene glycol copolymer (1.5 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 20%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and the PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of elastic wall phase change microcapsules in the elastic wall phase change microcapsules is 80%.

[0070] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0071] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.6) and polyamide 6 (relative viscosity 2.6) are composite-spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules are blended with the polyamide 6 / 66 fiber, they are melt-spun with the polyamide 6 through a parallel composite spinning machine.

[0072] The specific operation includes the following steps: After the elastic wall phase change microcapsules and polyamide 6 / 66 slices are fully mixed, they are added to a spinning screw extruder for composite spinning to be melted and homogenized to obtain a blend. Polyamide 6 is directly added to the second spinning screw extruder in the composite spinning machine to be melted and homogenized; the homogenized melts (i.e. the melt of the blend and the melt of polyamide 6) are extruded through the parallel composite spinning assembly, and the fiber is formed through the parallel composite spinning spinneret, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is applied to obtain fibers containing elastic wall phase change microcapsules.

[0073] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0074] The elastic polyamide fiber prepared in this embodiment has a resilience of 80% and a fiber phase change enthalpy of 25 J / g.

[0075] Example 5

[0076] (1) Preparation of elastic wall phase change microcapsules.

[0077] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 250°C, reacted for 8 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 8000 g / mol. PEG200 (500 g) and polyamide 66 precursor (250 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 2:1. The mixture was heated to 240°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 was obtained.

[0078] The polyimide aerogel powder (average particle size 30 microns, 5 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 1 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.50%; polyamide 66 / polyethylene glycol copolymer (1.5 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of the core material in the elastic wall phase change microcapsule is 60%.

[0079] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0080] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) are composite-spun in the form of a composite ratio of 50:50, wherein the added microcapsule ratio is 20% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules are blended with polyamide 6 / 66, they are melt-spun with polyamide 6 through a parallel composite spinning machine.

[0081] The specific operation includes the following steps: After the elastic wall phase change microcapsules and polyamide 6 / 66 slices are fully mixed, they are added to a spinning screw extruder for composite spinning to be melted and homogenized to obtain a blend. Polyamide 6 is directly added to the second spinning screw extruder in the composite spinning machine to be melted and homogenized; the homogenized melts (i.e. the melt of the blend and the melt of polyamide 6) are extruded through the parallel composite spinning assembly, and the fiber is formed through the parallel composite spinning spinneret, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is applied to obtain fibers containing elastic wall phase change microcapsules.

[0082] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0083] The elastic polyamide fiber prepared in this embodiment has a resilience of 87% and a fiber phase change enthalpy of 18.5 J / g.

[0084] Example 6

[0085] (1) Preparation of elastic wall phase change microcapsules.

[0086] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 240°C, reacted for 6 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (500 g) and polyamide 66 precursor (500 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 1:1. The mixture was heated to 240°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 was obtained.

[0087] The polyimide aerogel powder (average particle size 25 microns, 1 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 1 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.10%; polyamide 66 / polyethylene glycol copolymer (2.0 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of the core material in the elastic wall phase change microcapsule is 70% of the elastic wall phase change microcapsule.

[0088] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0089] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) are composite spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules are mixed and spun with polyamide 6 / 66 and polyamide 6 respectively, and the process is achieved by blending and adding melt spinning.

[0090] The specific operation includes the following steps: slicing elastic wall phase change microcapsules, polyamide 6 / 66 and polyamide 6 with a total addition amount of 30%, fully mixing the elastic wall phase change microcapsules with polyamide 6 / 66 and polyamide 6, respectively, to obtain polyamide 6 / 66 blends and polyamide 6 blends, respectively adding them to two spinning screw extruders for composite spinning, melting and homogenizing to obtain melts; the melts of the polyamide 6 / 66 blends and the polyamide 6 blends are extruded from the parallel composite spinning components, and the fibers are formed through the parallel composite spinning spinnerets, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling, fibers containing elastic wall phase change microcapsules are obtained.

[0091] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0092] The elastic polyamide fiber prepared in this embodiment has a resilience of 88% and a fiber phase change enthalpy of 20 J / g.

[0093] Example 7

[0094] (1) Preparation of elastic wall phase change microcapsules.

[0095] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 240°C, reacted for 6 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (700 g) and polyamide 66 precursor (300 g) were added to the reactor, wherein the copolymerization ratio of polyamide 66 to PEG was 7:3. The mixture was heated to 220°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 was obtained.

[0096] The polyimide aerogel powder (average particle size 10 microns, 0.5 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 1 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.05%; polyamide 66 / polyethylene glycol copolymer (2 g) is fully dissolved in hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture is spray-dried to achieve the coating of polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The core material in the elastic wall phase change microcapsule accounts for 60% of the mass percentage of the elastic wall phase change microcapsule.

[0097] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0098] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.0) are composite-spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules are blended with polyamide 6 / 66, they are melt-spun with polyamide 6 through a parallel composite spinning machine.

[0099] The specific operation includes the following steps: After the elastic wall phase change microcapsules and polyamide 6 / 66 slices are fully mixed, they are added to a spinning screw extruder for composite spinning to be melted and homogenized to obtain a blend. Polyamide 6 is directly added to the second spinning screw extruder in the composite spinning machine to be melted and homogenized; the homogenized melts (i.e. the melt of the blend and the melt of polyamide 6) are extruded through the parallel composite spinning assembly, and the fibers are formed through the parallel composite spinning spinneret, and the spinning temperature is 220°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is applied to obtain fibers containing elastic wall phase change microcapsules.

[0100] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 220°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0101] The elastic polyamide fiber prepared in this embodiment has a resilience of 88% and a fiber phase change enthalpy of 20 J / g.

[0102] Example 8

[0103] (1) Preparation of elastic wall phase change microcapsules.

[0104] Under the protection of nitrogen, adipic acid (0.1 mol, 14.61 g) and hexamethylenediamine (0.1 mol, 11.62 g) were added to the reactor. In this embodiment, the molar ratio of adipic acid to hexamethylenediamine was 1:1. The mixture was heated to 240°C, reacted for 3 hours, and then cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 1500 g / mol. PEG200 (500 g) and polyamide 66 precursor (500 g) were added to the reactor together, wherein the copolymerization ratio of polyamide 66 to PEG was 1:1. The mixture was heated to 240°C and reacted for 8 hours. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.8 was obtained.

[0105] The polyimide aerogel powder (average particle size 30 microns, 1 mg) used to prepare the core material is fully mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 0.5 g) under high temperature vacuum conditions of 100°C and -0.1 MPa to obtain polyimide aerogel powder and PEG complex (core material). In this embodiment, the mass percentage of polyimide aerogel in the core material is 0.20%; the polyamide 66 / polyethylene glycol copolymer (1 g) is fully dissolved in the hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 15%. The wall material mixture is spray-dried to achieve the coating of the polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and the PEG complex (core material), and then an elastic wall phase change microcapsule is obtained. The mass percentage of the core material in the elastic wall phase change microcapsule is 70%.

[0106] (2) Preparation of polyamide elastic fibers containing elastic wall phase change microcapsules.

[0107] The processing steps of the polyamide elastic fiber are as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) are composite-spun in the form of a composite ratio of 50:50, wherein the added elastic wall phase change microcapsules are 30% of the fiber matrix mass (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules are blended with polyamide 6 / 66, they are melt-spun with polyamide 6 through a parallel composite spinning machine.

[0108] The specific operation includes the following steps: After the elastic wall phase change microcapsules and polyamide 6 / 66 slices are fully mixed, they are added to a spinning screw extruder for composite spinning to be melted and homogenized to obtain a blend. Polyamide 6 is directly added to the second spinning screw extruder in the composite spinning machine to be melted and homogenized; the homogenized melts (i.e. the melt of the blend and the melt of polyamide 6) are extruded through the parallel composite spinning assembly, and the fiber is formed through the parallel composite spinning spinneret, and the spinning temperature is 240°C. After cooling and solidification, two-step drawing and heat setting processes, oiling is applied to obtain fibers containing elastic wall phase change microcapsules.

[0109] The elastic wall phase change microcapsules can be in a transition state between a high elastic state and a viscous flow state at 240°C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged by cracking. At this temperature, the microcapsules gradually change from a round shape to a strip-shaped shuttle shape under the action of shear force, and are distributed inside the fiber.

[0110] The elastic polyamide fiber prepared in this embodiment has a resilience of 86% and a fiber phase change enthalpy of 22 J / g.

[0111] In summary, in the past technologies for preparing polymer fibers containing phase change microcapsules, the process routes are usually complicated, and the prepared polymer fibers usually do not have good elasticity. The preparation routes of some technologies are complicated, and the adaptive deformation between the wall material and the core material of the capsule is not designed. The cooling microcapsules of some technologies contain easily volatile substances such as peppermint essential oil, which makes it difficult to ensure the long-term stability of the material.

[0112] Compared with the stability of microcapsules and the additional functions of polymer fibers in the products of the prior art, the preparation route of the present invention is simpler. The design concept of copolymerization is adopted for the design of the wall material, while the core material is regulated and designed by polyimide aerogel with strong thermal stability and common PEG phase change material. The elasticity of the fiber comes from the parallel processing means adopted in the spinning process, rather than the design concept of chemical structure elastomer. The microcapsules prepared by the present invention have similar chemical polarity between the wall material and the core material. The spraying method is adopted during compounding, and they have good compatibility and more uniform dispersion. Secondly, during high-temperature processing, the characteristics of the fluid give the microcapsules the characteristics of adaptive deformation without destroying the capsules, avoiding the risk of leakage of the phase change core material. Specifically, the microcapsules are not directly used for spinning, but added to the polymer matrix. Since the melt processing temperature of the added matrix is ​​lower than the melt flow temperature of the microcapsule wall material, it is ensured that the microcapsules only produce elastic deformation above the glass transition temperature of the material during the processing without producing melt flow, thereby achieving the purpose of the present invention.

[0113] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0114] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A fiber containing elastic wall phase change microcapsules, characterized in that: The invention comprises a fiber matrix and an elastic wall phase change microcapsule. The elastic wall phase change microcapsule comprises a wall material and a core material. The wall material comprises a polyamide 66 / polyethylene glycol copolymer. The raw material of the core material comprises a polyimide aerogel and a polyethylene glycol phase change material.

2. The fiber according to claim 1, characterized in that The polyamide 66 / polyethylene glycol copolymer is a block copolymer of polyamide 66 / polyethylene glycol, and the copolymerization ratio of polyamide 66 to polyethylene glycol in the polyamide 66 / polyethylene glycol copolymer is (0.5-2.5):

1.

3. The fiber according to claim 1, characterized in that The wall material is coated on the surface of the core material, and the mass percentage of the core material in the elastic wall phase change microcapsule is 50-80%; the mass percentage of the polyimide aerogel in the core material is 0.05-2.0%.

4. The fiber according to claim 1, characterized in that The elastic wall phase change microcapsules are distributed in the fiber matrix, and the mass ratio of the elastic wall phase change microcapsules to the fiber matrix is ​​(5-30):

100.

5. The fiber according to any one of claims 1 to 4, characterized in that The raw materials of the fiber matrix include polyamide 6 / 66 copolymer and polyamide 6, and the composite ratio of the polyamide 6 / 66 copolymer and polyamide 6 is (80-50): (20-50).

6. The fiber according to claim 5, characterized in that The copolymerization ratio of PA6 to PA66 in the polyamide 6 / 66 copolymer is (80-85): (20-15).

7. The method for preparing the fiber according to any one of claims 1 to 6, characterized in that: The following steps are involved: Preparation of elastic wall phase change microcapsules: mixing adipic acid and hexamethylenediamine under a protective atmosphere, heating, and cooling to obtain a polyamide 66 precursor; adding polyethylene glycol and a catalyst, heating to a polymerization temperature, and performing a polymerization reaction to obtain a wall material; mixing the raw materials of the core material under high temperature vacuum conditions to obtain a core material, dissolving the wall material in a polar solvent to obtain a wall material solution, adding the core material to the wall material solution, and drying to obtain an elastic wall phase change microcapsule; Preparation of fibers: mixing the elastic wall phase change microcapsules and the raw materials of the fiber matrix, and spinning them to obtain fibers containing the elastic wall phase change microcapsules.

8. The preparation method according to claim 7, characterized in that: In the step of preparing elastic wall phase change microcapsules, the molar ratio of adipic acid to hexamethylenediamine is 1:(0.8-1.2), the heating temperature is 200-250°C, and the heating time is 2-8h; the polymerization temperature is 180-250°C, and the polymerization reaction time is 2-8h; the high temperature vacuum condition is 95-105°C, -0.15 to -0.05MPa; and the drying includes spray drying.

9. A fabric, characterized in that: The fiber is prepared by using the fiber described in any one of claims 1 to 6.

10. Use of the fiber according to any one of claims 1 to 6 in the preparation of clothing, home textiles, building materials, automobile interiors, and care products.

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