Fiber containing phase change microcapsules with elastic walls, and methods of making and using the same

Abstract

The present application relates to a kind of elastic wall phase change microcapsule-containing fiber and its preparation method and application, it relates to composite fiber field.Elastic wall phase change microcapsule-containing fiber includes fiber matrix, elastic wall phase change microcapsule, elastic wall microcapsule includes wall material, core material, wall material includes polyamide 66 / polyethylene glycol copolymer, the raw material of core material includes polyimide aerogel, polyethylene glycol phase change material.Elastic wall phase change microcapsule is contained in the fiber, can overcome the microcapsule used in the prior art phase change polyamide fiber difficult to deform, particle size size requirement is strict, in turn lead to core material is easily leaked, and the compatibility of the raw material of fiber matrix is poor.

Description

TECHNICAL FIELD

[0001] The present application 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

[0002] Polyamide fibers are widely used in the textile and industrial fields due to their good wear resistance, moisture absorption and air permeability, heat resistance, dyeability, etc., and are one of the most widely used chemical fibers. With the improvement of living standards, people have higher pursuit of comfort of life goods such as clothing. The development of fibers gradually tends to be intelligent, and phase change materials that can provide high elasticity and adjust temperature according to the environment are also integrated into fibers. This composite processing method combines the excellent physical properties of polyamide and the heat regulating characteristics of phase change materials, has many significant advantages, and can realize intelligent temperature control: phase change materials can absorb, store and release heat in a specific temperature range, thereby effectively adjusting the body temperature of the wearer and enhancing the wearing comfort. Dynamic adaptation: phase change materials can automatically adjust according to changes in environmental temperature, and can maintain an appropriate temperature in both cold and warm environments. The fiber body has good elasticity and wear resistance, and can maintain good elasticity and shape recovery ability during use. This diversified processing idea provides multiple application possibilities and comfort, meeting the demand of modern market for functional textiles.

[0003] The phase change polyamide fibers reported in the existing literature are mainly prepared by adding phase change materials for composite processing, among which the addition of microcapsules is the most convenient and reliable. In these reported studies of polyamide fibers containing phase change microcapsules, 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.) and the like. However, the thermal conductivity of the above-mentioned raw material paraffin is relatively low, which leads to a decrease in efficiency and a slow heat conduction speed in the process of heat release or absorption. 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 needs to be considered when using it. Polyurethane is sensitive to humidity, and after absorbing moisture, its phase change performance may be affected. Compared with other phase change materials, the hardness and flexibility of polyurethane may be limited, affecting the flexibility of application. As a high-melting-point phase change material, 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 the performance. In composite materials, the compatibility of eicosane is not as good as that of other materials, resulting in poor dispersibility or uneven performance. In addition, there are many studies on the use of composite materials such as carbon nanotubes, halloysite nanotubes, silicon dioxide and lauric acid (Composites Science and Technology, 2022, 226, 109541. Chemical Engineering Journal, 2021, 403, 126369.) for the preparation of phase change polyamide fibers. However, these methods cannot solve the problem of easy leakage of phase change materials. Therefore, it is particularly important to develop a phase change capsule material with better compatibility and stability for the composite preparation of polyamide fibers. SUMMARY

[0004] In view of the above problems, the present application provides a fiber containing elastic wall phase change microcapsules, which contains elastic wall phase change microcapsules in the fiber, which can overcome the problems of difficult deformation of microcapsules used in the prior art phase change polyamide fibers, strict particle size requirements, and easy leakage of core materials, and poor compatibility with the raw materials of the fiber matrix.

[0005] In order to achieve the above purpose, the present application provides a fiber containing elastic wall phase change microcapsules, which comprises a fiber matrix and elastic wall phase change microcapsules, the elastic wall phase change microcapsules comprise a wall material and a core material, the wall material comprises a polyamide 66 / polyethylene glycol copolymer, and the raw material of the core material comprises a polyimide aerogel and a polyethylene glycol phase change material.

[0006] The elastic wall phase change microcapsule wall material can withstand shearing deformation without being damaged during high temperature processing of the fiber substrate raw material spinning forming mentioned in the patent, thereby ensuring the integrity of the phase change material in the core material. Secondly, the core material is uniformly dispersed by mixing with the polyimide aerogel. In addition, the wall material of the elastic wall phase change microcapsule and the base polymer belong to the same polyamide class and have certain compatibility, realizing the stability of the obtained target fiber structure and the reliability of the 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 value of the elastic wall phase change microcapsule-containing fiber is 10-30 J / g, and the elastic recovery rate is 85% or more (@10%).

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

[0010] The polyimide aerogel mentioned above can be prepared by conventional freeze drying or supercritical drying to obtain a block material, which 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 embodiment, the elastic wall phase change microcapsules are distributed in the fiber substrate, and the mass ratio of the elastic wall phase change microcapsules to the fiber substrate is (5-30):100.

[0013] In one embodiment, the raw material of the fiber substrate includes polyamide 6 / 66 copolymer and polyamide 6, and the complex ratio of the polyamide 6 / 66 copolymer to the 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 polyamide 6 / 66 copolymer is 100, and the weight parts of PA6 changes from 80 to 85, and the weight parts of PA66 changes correspondingly from 20 to 15, so the copolymerization ratio of PA6 and 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 application also provides a preparation method of the fiber, comprising the following steps:

[0018] Preparation of elastic wall phase change microcapsules: mixing adipic acid and hexamethylene diamine under a protective atmosphere, heating, cooling, and obtaining a polyamide 66 precursor; adding polyethylene glycol and a catalyst, and heating to a polymerization temperature to perform a polymerization reaction, and obtaining a wall material; mixing raw materials of a core material under high-temperature vacuum conditions to obtain the 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 the elastic wall phase change microcapsules;

[0019] Preparation of the fiber: mixing the elastic wall phase change microcapsules and raw materials of the fiber matrix, and performing spinning to obtain the fiber 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 conditions of spinning through the high-elastic state of the fiber matrix, and do not break, and form a strip-shaped distribution in the fiber in situ.

[0021] In one embodiment, the molecular weight of the polyamide 66 precursor ranges from 1000 g / mol to 10000 g / mol, and the molecular weight of the polyethylene glycol ranges from 200 g / mol to 800 g / mol.

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

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

[0024] In one of the embodiments, in the step of preparing the fiber, the mixing of the elastic wall phase change microcapsule and the raw material of the fiber base, the spinning is realized by adding melt spinning through blending.

[0025] In one of the embodiments, the adding melt spinning through blending comprises the following steps: blending the elastic wall phase change microcapsule, the polyamide 6 / 66 copolymer and the polyamide 6 slice, blending one of the polyamide 6 / 66 copolymer and the polyamide 6 with the elastic wall phase change microcapsule to obtain a blend, adding the blend and the remaining raw material of the fiber base into two spinning screw extruders of a parallel composite spinning assembly respectively to melt and homogenize, extruding from the parallel composite spinning assembly, solidifying through cooling, two-step drawing and heat setting process, oiling to obtain the fiber containing the elastic wall phase change microcapsule.

[0026] In one of the embodiments, the adding melt spinning through blending comprises the following steps: blending the elastic wall phase change microcapsule, the polyamide 6 / 66 copolymer and the polyamide 6 slice, blending one of the polyamide 6 / 66 copolymer and the polyamide 6 with the elastic wall phase change microcapsule to obtain a blend, adding the blend and the remaining raw material of the fiber base into two spinning screw extruders of a parallel composite spinning assembly respectively to melt and homogenize, extruding from the parallel composite spinning assembly, solidifying through cooling, two-step drawing and heat setting process, oiling to obtain the fiber containing the elastic wall phase change microcapsule.

[0027] The above adding melt spinning through blending is simple and easy to operate, and makes the elastic wall phase change microcapsule uniformly distributed in the raw material of the fiber base.

[0028] The application further provides a fabric prepared from the fiber.

[0029] The application further provides an application of the fiber in preparing clothes, home textiles, building materials, automotive interiors and nursing supplies.

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

[0031] The present application relates to a kind of elastic wall phase change microcapsule-containing fiber and its preparation method and application, the wall material of the elastic wall phase change microcapsule has self-adapting deformation characteristics, can produce deformation at high temperature, can maintain deformation after cooling without destroying wall surface, so that phase change material in core material is stable, with higher potential economic value, the fiber containing the elastic wall phase change microcapsule, can overcome the problems that microcapsule used in the phase change polyamide fiber in the prior art is difficult to deform, particle size size requirement is strict, and then leading to core material is easily leaked, and the compatibility of raw material of fiber matrix is poor.The resilience of the fiber can be up to 92%, and the elasticity is provided by the morphology of the parallel composite fiber itself, without chemical structure design.In addition, the fiber also has the potential of phase change temperature control, and can be woven and applied in clothing, medical, automobile and other industries. DETAILED DESCRIPTION

[0032] In order to facilitate the understanding of the present application, the present application will be described more fully below with reference to relevant examples.However, the present application can be realized in many different forms, and is not limited to the embodiments described herein.Those embodiments are provided only to make the disclosure of the present application more thorough and comprehensive.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs.Any use of section headings is for organizational purposes only and is not intended to limit the scope of the present application.

[0034] Source:

[0035] The reagents, materials and equipment used in this example are commercially available unless otherwise specified; the test method is the conventional test method in the art unless otherwise specified.

[0036] Definition:

[0037] The resilience of the polyamide fiber in the present application is tested at room temperature by using ASTM D4964-2016 method, by WDW3020 tensile testing machine under the condition of 10mm / min, 50N;The resilience of each sample is calculated by 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 average value is taken.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 hexamethylene diamine (0.1 mol, 11.62 g) were added to a reaction kettle, and in this embodiment, the molar ratio of adipic acid to hexamethylene diamine was 1:1. The mixture was heated to 240°C, and after 6 hours of reaction, it was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (500 g) and the polyamide 66 precursor (250 g) were added together to the above reaction kettle, and in this embodiment, the copolymerization ratio of polyamide 66 to PEG was 2:1. The temperature was raised to 230°C, and the reaction was carried out 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 was mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 1 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this embodiment, the mass percentage of polyimide aerogel in the core material was 0.50%. The polyamide 66 / polyethylene glycol copolymer (1.5 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture was coated with the polyamide 66 / polyethylene glycol copolymer (wall material) by spray drying, and then the elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 51%.

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

[0045] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) were compounded and spun in a compound ratio of 50:50, and the proportion of the added elastic wall phase change microcapsules was 20% of the mass of the fiber matrix (i.e., the sum of the masses of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules were blended with polyamide 6 / 66, they were respectively melt-spun by a parallel compound spinning machine.

[0046] The specific operation includes the following steps: after the elastic wall phase change microcapsules and polyamide 6 / 66 chips are sufficiently mixed, they are added into a 1 -spindle extruder for composite spinning, melted and homogenized to obtain a blend. The polyamide 6 is directly added into a second 1 -spindle extruder in the composite spinning machine, melted and homogenized; the melts (i.e. the melt of the blend and the melt of the polyamide 6) after homogenization are extruded through a parallel composite spinning assembly, and fibers are formed through a parallel composite spinning spinneret, with a spinning temperature of 240°C. After cooling and solidification, 2-step drawing and heat setting processes, oiling, a fiber containing elastic wall phase change microcapsules is obtained.

[0047] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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 such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, thereby being distributed in the interior of the fiber.

[0048] The elastic polyamide fiber prepared in this example has a resilience rate 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 hexamethylene diamine (0.1 mol, 11.62 g) were added to a reaction kettle, and in this example, the molar ratio of adipic acid to hexamethylene diamine was 1:1. The mixture was heated to 240°C, and after 8h of reaction, it was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 7000 g / mol. PEG400 (700 g) and the polyamide 66 precursor (300 g) were added together into the above reaction kettle, and the copolymerization ratio of the polyamide 66 to PEG was 7:3. The temperature was raised to 230°C, and the mixture was reacted for 8h. 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 for preparing the core material was mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 0.1 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this example, the mass percentage of the polyimide aerogel in the core material was 0.99%; the polyamide 66 / polyethylene glycol copolymer (1.5 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture was coated on the polyimide aerogel powder and PEG composite (core material) by spray drying to achieve coating of the polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG composite (core material), and then elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 70% of the elastic wall phase change microcapsules.

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

[0054] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) were compounded and spun at a compound ratio of 50:50, and the added elastic wall phase change microcapsules accounted for 30% of the mass of the fiber matrix (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules were mixed with polyamide 6 / 66 and polyamide 6, respectively, and spun by melt spinning through blending.

[0055] The specific operation included the following steps: the total amount of 30% of the elastic wall phase change microcapsules, polyamide 6 / 66, and polyamide 6 chips were mixed, and the elastic wall phase change microcapsules were mixed with polyamide 6 / 66 and polyamide 6, respectively, to obtain polyamide 6 / 66 blends and polyamide 6 blends, which were respectively added to two spinning screw extruders for melting and homogenization to obtain a melt; the melt of the polyamide 6 / 66 blend and the melt of the polyamide 6 blend were extruded by a side-by-side compound spinning assembly, and the fiber was formed by a side-by-side compound spinning spinneret at a spinning temperature of 240°C. After cooling and solidification, 2-step drawing and heat setting processes, and oiling, the fibers containing elastic wall phase change microcapsules were obtained.

[0056] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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, such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, and thus are distributed in the interior of the fiber.

[0057] The resilience rate of the elastic polyamide fibers prepared in this example was 80%, and the fiber phase change enthalpy was 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 hexamethylene diamine (0.1 mol, 11.62 g) were added to a reaction kettle, and in this embodiment, the molar ratio of adipic acid to hexamethylene diamine was 1:1. The mixture was heated to 230°C, and after 4 hours of reaction, it was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 4000 g / mol. PEG800 (250 g) and the polyamide 66 precursor (500 g) were added together to the above reaction kettle, and in this embodiment, the copolymerization ratio of polyamide 66 to PEG was 1:2. The temperature was raised to 240°C, and the reaction was carried out 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 was mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 0.5 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this embodiment, the mass percentage of polyimide aerogel in the core material was 0.40%. The polyamide 66 / polyethylene glycol copolymer (1 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture was coated on the polyimide aerogel powder and PEG composite (core material) by spray drying, and then elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 80%.

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

[0063] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.6) and polyamide 6 (relative viscosity 2.8) were compounded and spun in a compound ratio of 50:50, and the proportion of the added elastic wall phase change microcapsules was 30% of the mass of the fiber matrix (i.e., the sum of the masses of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules were mixed with polyamide 6 / 66 and polyamide 6, respectively, and spun by melt spinning through blending.

[0064] The specific operation comprises the following steps: adding 30% of the total amount of elastic wall phase change microcapsules, polyamide 6 / 66, polyamide 6 chips, mixing the elastic wall phase change microcapsules with the polyamide 6 / 66 and the polyamide 6 respectively to obtain a polyamide 6 / 66 blend and a polyamide 6 blend, and adding the blends into two spinning screw extruders for melting and homogenizing to obtain a melt; extruding the melt of the polyamide 6 / 66 blend and the melt of the polyamide 6 blend from a parallel composite spinning assembly, forming fibers through a parallel composite spinning spinneret, and setting the spinning temperature to 250 DEG C. After cooling, solidification, two-step drawing, heat setting, oiling, a fiber containing elastic wall phase change microcapsules is obtained. The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the viscous flow state at 250 DEG C, and can be deformed under the action of shear force, but the inner and outer layers of the microcapsules will not be damaged, such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, and are thus distributed in the interior of the fiber.

[0065] The resilience of the elastic polyamide fiber prepared in this example is 85%, and the fiber phase change enthalpy is 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 hexamethylene diamine (0.1 mol, 11.62 g) are added to a reaction kettle, and in this example, the molar ratio of adipic acid to hexamethylene diamine is 1:1. The mixture is heated to 240 DEG C, and after 2 h of reaction, it is cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 1000 g / mol. PEG200 (250 g) and the polyamide 66 precursor (500 g) are added together into the above reaction kettle, and the copolymerization ratio of the polyamide 66 to the PEG is 1:2. The temperature is raised to 230 DEG C, and the mixture is reacted for 8 h. A polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.6 is obtained.

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

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

[0071] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.6) and polyamide 6 (relative viscosity 2.6) were compounded and spun in a compound ratio of 50:50, and the proportion of the added elastic wall phase change microcapsules was 30% of the mass of the fiber matrix (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules were blended and mixed with the polyamide 6 / 66 fibers, the polyamide 6 was respectively melt-spun through a side-by-side compound spinning machine.

[0072] The specific operation included the following steps: the elastic wall phase change microcapsules and polyamide 6 / 66 chips were thoroughly mixed and then added to a 1 -spindle extruder for compound spinning, which was melt and homogenized to obtain a blend. The polyamide 6 was directly added to a second 1 -spindle extruder in the compound spinning machine, which was melt and homogenized; the melt of each (i.e., the melt of the blend and the melt of the polyamide 6) was extruded through a side-by-side compound spinning assembly and formed into fibers through a side-by-side compound spinning spinneret, and the spinning temperature was 240°C. After cooling and solidification, 2-step drawing and heat setting processes, oiling, the fibers containing elastic wall phase change microcapsules were obtained.

[0073] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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, such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, and thus are distributed in the interior of the fibers.

[0074] The resilience rate of the elastic polyamide fibers prepared in this example was 80%, and the fiber phase change enthalpy was 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 hexamethylene diamine (0.1 mol, 11.62 g) were added into a reaction kettle, and in this embodiment, the molar ratio of adipic acid to hexamethylene diamine was 1:1. The mixture was heated to 250°C, and after 8 hours of reaction, it was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 8000 g / mol. PEG200 (500 g) and the polyamide 66 precursor (250 g) were added together into the above-mentioned reaction kettle, and in this embodiment, the copolymerization ratio of polyamide 66 to PEG was 2:1. The temperature was raised to 240°C, and the mixture was 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 was mixed with the polyethylene glycol phase change material (molecular weight 2000 g / mol, 1 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this embodiment, the mass percentage of polyimide aerogel in the core material was 0.50%. The polyamide 66 / polyethylene glycol copolymer (1.5 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture was coated on the polyimide aerogel powder and PEG composite (core material) by spray drying, and then elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 60%.

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

[0080] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) were compounded and spun in a form of a compound ratio of 50:50, and the added microcapsule ratio was 20% of the mass of the fiber substrate (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules were blended with polyamide 6 / 66, they were respectively melt-spun by a parallel compound spinning machine.

[0081] The specific operation includes the following steps: after the elastic wall phase change microcapsules and polyamide 6 / 66 chips are sufficiently mixed, they are added into a 1 -spindle extruder for composite spinning, melted and homogenized to obtain a blend. The polyamide 6 is directly added into a second 1 -spindle extruder in the composite spinning machine, melted and homogenized; the melts (i.e. the melt of the blend and the melt of the polyamide 6) after homogenization are extruded through a parallel composite spinning assembly, and fibers are formed through a parallel composite spinning spinneret, with a spinning temperature of 240°C. After cooling and solidification, 2-step drawing and heat setting processes, oiling, a fiber containing elastic wall phase change microcapsules is obtained.

[0082] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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 such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, so as to be distributed in the interior of the fiber.

[0083] The elastic polyamide fiber prepared in this example has a resilience rate of 87%, and the fiber phase change enthalpy is 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 hexamethylene diamine (0.1 mol, 11.62 g) were added to a reaction kettle, and in this example, the molar ratio of adipic acid to hexamethylene diamine was 1:1. After heating to 240°C and reacting for 6 h, the reaction was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (500 g) and the polyamide 66 precursor (500 g) were added together into the above reaction kettle, and the copolymerization ratio of polyamide 66 to PEG was 1:1. After heating to 240°C and reacting for 8 h, 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 for preparing the core material was mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 1 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this example, the mass percentage of the polyimide aerogel in the core material was 0.10%; the polyamide 66 / polyethylene glycol copolymer (2.0 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 10%. The wall material mixture was subjected to spray drying to achieve coating of the polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG composite (core material), and then elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 70%.

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

[0089] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) were compounded and spun at a compound ratio of 50:50, and the added elastic wall phase change microcapsules accounted for 30% of the mass of the fiber matrix (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). The elastic wall phase change microcapsules were mixed with polyamide 6 / 66 and polyamide 6, respectively, and were spun by melt spinning through blending.

[0090] The specific operation included the following steps: the total amount of added elastic wall phase change microcapsules was 30%, and polyamide 6 / 66 and polyamide 6 chips were used; the elastic wall phase change microcapsules were mixed with polyamide 6 / 66 and polyamide 6, respectively, to obtain polyamide 6 / 66 blends and polyamide 6 blends; the blends were melted and homogenized by being added to two spinning screw extruders for compound spinning; the melt of the polyamide 6 / 66 blend and the melt of the polyamide 6 blend were extruded by a side-by-side compound spinning assembly and were formed into fibers by a side-by-side compound spinning spinneret at a spinning temperature of 240°C; and the fibers were obtained after cooling and solidification, two-step drawing, heat setting, and oiling.

[0091] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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, such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, and are thus distributed in the interior of the fibers.

[0092] The resilience of the elastic polyamide fibers prepared in this example was 88%, and the fiber phase change enthalpy was 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 hexamethylene diamine (0.1 mol, 11.62 g) were added to a reaction kettle, and in this embodiment, the molar ratio of adipic acid to hexamethylene diamine was 1:1. The mixture was heated to 240°C, and after 6 hours of reaction, it was cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 5000 g / mol. PEG200 (700 g) and the polyamide 66 precursor (300 g) were added together to the above reaction kettle, and in this embodiment, the copolymerization ratio of polyamide 66 to PEG was 7:3. The temperature was raised to 220°C, and the reaction was carried out 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 was mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 1 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this embodiment, the mass percentage of polyimide aerogel in the core material was 0.05%. The polyamide 66 / polyethylene glycol copolymer (2 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 5%. The wall material mixture was coated on the polyimide aerogel powder and PEG composite (core material) by spray drying, and then elastic wall phase change microcapsules were obtained. The core material accounted for 60% of the mass percentage of the elastic wall phase change microcapsules.

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

[0098] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 85:15, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.0) were compounded and spun in a compound ratio of 50:50, and the proportion of the added elastic wall phase change microcapsules was 30% of the mass of the fiber matrix (i.e., the sum of the masses of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules were blended with polyamide 6 / 66, they were respectively melt-spun by a parallel compound spinning machine.

[0099] The specific operation includes the following steps: the elastic wall phase change microcapsules and polyamide 6 / 66 chips are mixed sufficiently, and then are added into a 1 -spindle extruder for composite spinning to be melted and homogenized to obtain a blend. The polyamide 6 is directly added into a 2-spindle extruder in the composite spinning machine to be melted and homogenized; the melts (i.e. the melt of the blend and the melt of the polyamide 6) after homogenization are extruded through a parallel composite spinning assembly, and the fibers are formed through a parallel composite spinning spinneret at a spinning temperature of 220°C. After cooling and solidification, 2-step drawing and heat setting processes, oiling, the fiber containing the elastic wall phase change microcapsules is obtained.

[0100] The elastic wall phase change microcapsules can be in a transition state between the high-elastic state and the 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 such as cracking. At this temperature, the microcapsules gradually tend to be strip-shaped fusiform under the action of shear force, and are thus distributed in the interior of the fiber.

[0101] The elastic polyamide fiber prepared in this example has a resilience rate of 88%, and the fiber phase change enthalpy is 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 hexamethylene diamine (0.1 mol, 11.62 g) are added into a reaction kettle, and in this example, the molar ratio of adipic acid to hexamethylene diamine is 1:1. The mixture is heated to 240°C, and after reaction for 3 h, it is cooled to room temperature to obtain a polyamide 66 precursor with a molecular weight of 1500 g / mol. PEG200 (500 g) and the polyamide 66 precursor (500 g) are added together into the above reaction kettle, and the copolymerization ratio of the polyamide 66 to PEG is 1:1. The mixture is heated to 240°C, and after reaction for 8 h, a polyamide 66 / polyethylene glycol copolymer (wall material) with a relative viscosity of 2.8 is obtained.

[0105] The polyimide aerogel powder (average particle size 30 microns, 1 mg) used for preparing the core material was mixed with the polyethylene glycol phase change material (molecular weight 1000 g / mol, 0.5 g) at 100°C under high-temperature vacuum conditions of -0.1 MPa to obtain a polyimide aerogel powder and PEG composite (core material), and in this example, the mass percentage of the polyimide aerogel in the core material was 0.20%; the polyamide 66 / polyethylene glycol copolymer (1 g) was dissolved in a hexafluoroisopropanol solution to prepare a wall material solution with a mass concentration of 15%. The wall material mixture was subjected to spray drying to realize coating of the polyamide 66 / polyethylene glycol copolymer (wall material) on the polyimide aerogel powder and PEG composite (core material), and then elastic wall phase change microcapsules were obtained. The mass percentage of the core material in the elastic wall phase change microcapsules was 70%.

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

[0107] The processing steps of the polyamide elastic fibers were as follows: polyamide 6 / 66 (copolymerization ratio 80:20, relative viscosity 2.4) and polyamide 6 (relative viscosity 2.4) were compounded and spun in a compound ratio of 50:50, and the proportion of the added elastic wall phase change microcapsules was 30% of the mass of the fiber matrix (i.e., the sum of the mass of polyamide 6 / 66 and polyamide 6). After the elastic wall phase change microcapsules were blended with polyamide 6 / 66, they were respectively subjected to melt spinning through a side-by-side compound spinning machine together with polyamide 6.

[0108] The specific operation included the following steps: the elastic wall phase change microcapsules and polyamide 6 / 66 chips were thoroughly mixed and then fed into a spinning screw extruder for melting and homogenization to obtain a blend. The polyamide 6 was directly fed into a second spinning screw extruder in the compound spinning machine for melting and homogenization; the melts (i.e., the melt of the blend and the melt of polyamide 6) after homogenization were extruded through a side-by-side compound spinning assembly and formed into fibers through a side-by-side compound spinning spinneret at a spinning temperature of 240°C. After cooling and solidification, 2-step drawing and heat setting processes, oiling, the fibers containing elastic wall phase change microcapsules were obtained.

[0109] The elastic wall phase change microcapsules could be in a transition state between the high-elastic state and the viscous flow state at 240°C and could be deformed under the action of shear force, but the inner and outer layers of the microcapsules would not be damaged, such as cracking. At this temperature, the microcapsules gradually tended to be strip-shaped fusiform under the action of shear force, thereby being distributed in the interior of the fibers.

[0110] The resilience rate of the elastic polyamide fibers prepared in this example was 86%, and the fiber phase change enthalpy was 22 J / g.

[0111] In summary, in the prior art, the process route for preparing the polymer fiber containing phase change microcapsules is generally complex, and the prepared polymer fiber generally does not have good elasticity. The preparation route of some technologies is relatively complicated, and the self-adaptive deformation between the wall material and the core material is not designed. Some technologies have volatile substances such as peppermint oil in the cool microcapsules, which is difficult to ensure the long-term stability of the material.

[0112] Compared with the stability of microcapsules in the product and the additional functions of the polymer fiber in the prior art, the preparation route of the present application is more simple, the design of the wall material adopts the copolymerization design idea, and the core material is designed by adjusting the thermal stability of the polyimide aerogel and the common PEG phase change material. The elasticity of the fiber is derived from the parallel processing method adopted in the spinning process, rather than the design idea of chemical structure elastomer. The microcapsules prepared by the present application have similar chemical polarity between the wall material and the core material, and are compatible, dispersed more uniformly when spraying. Secondly, through high temperature processing, the fluid characteristics give the microcapsules self-adaptive deformation characteristics without damaging the capsules, avoiding the risk of phase change core material leakage. Specifically, the microcapsules are not directly used for spinning, but are added to the polymer matrix. Since the melting 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 processing without melt flow, thereby achieving the purpose of the present application

[0113] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description simple, all possible combinations of the technical features in the above-mentioned embodiments are not described, but as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present application.

[0114] The above-mentioned embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of protection of the present application should be subject to the appended claims.

Claims

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

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 claim 1, characterized in that The copolymerization ratio of PA6 to PA66 in the polyamide 6 / 66 copolymer is (80-85): (20-15).

6. The method for preparing the fiber according to any one of claims 1 to 5, characterized in that: The following steps are involved: Preparation of elastic wall phase change microcapsules: Adipic acid and hexamethylenediamine are mixed under a protective atmosphere, heated, and cooled to obtain a polyamide 66 precursor; polyethylene glycol and a catalyst are added, the temperature is raised to a polymerization temperature, and a polymerization reaction is carried out to obtain a wall material; raw materials of a core material are mixed under high temperature vacuum conditions to obtain a core material; the wall material is dissolved in a polar solvent to obtain a wall material solution; the core material is added to the wall material solution, and dried 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.

7. The preparation method according to claim 6, 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 2-8 hours; the polymerization temperature is 180-250°C, and the polymerization reaction time is 2-8 hours; the high temperature vacuum conditions are 95-105°C, -0.15 to -0.05MPa; and the drying includes spray drying.

8. A fabric, characterized in that: The fiber is prepared by using the fiber according to any one of claims 1 to 5.

9. Use of the fiber according to any one of claims 1 to 5 in the preparation of clothing, home textiles, building materials, automobile interiors, and care products.

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