Automatic temperature control down feather preparation method based on protein activated microspheres

Abstract

The invention relates to the field of down feather, and discloses an automatic temperature control down feather preparation method based on protein activated microspheres, which comprises the following steps: S1, preparing organic phase change microspheres through chemical synthesis methods such as interfacial polymerization, in-situ polymerization or Pickering emulsion polymerization; s2, mixing the prepared microspheres with a collagen solution, and enabling fiber collagen to firmly coat the surfaces of the microspheres through physical adsorption and chemical cross-linking reaction, so as to prepare protein activated microspheres; s3, uniformly distributing and grafting the protein activated microspheres into the down feather material to obtain a self-temperature-control down feather product; according to the invention, the protein activated microspheres are embedded and grafted into the down feather filler, and the temperature response characteristics of the protein microspheres are combined, so that the automatic temperature control regulation of the down feather material at different environment temperatures is realized, and the technical problems of the current down feather material in the aspects of temperature control precision, comfort, temperature control stability and the like are effectively solved.

Description

Technical Field

[0001] The invention relates to the field of down, and more specifically to a method for preparing self-temperature-controlled down based on protein activated microspheres. Background Art

[0002] As people's requirements for clothing comfort and functionality continue to increase, although traditional down clothing has excellent thermal insulation performance, it cannot adaptively adjust the temperature under different ambient temperatures, causing the wearer to feel overheated in high-temperature environments and insufficient insulation in low-temperature environments. In addition, existing down materials often rely on static filling structures to achieve thermal insulation and lack dynamic adjustment functions, so they cannot meet the higher requirements for temperature control accuracy.

[0003] The reason for the above problems is that the structure and performance of traditional down materials are difficult to adapt to changes in ambient temperature. Existing technologies have not fully utilized the characteristics of smart materials to achieve temperature control. Protein-activated microspheres have excellent environmental response characteristics and can automatically adjust their morphology and functions according to changes in external temperature, thereby achieving a self-controlling temperature effect. Therefore, how to combine protein-activated microspheres with down materials to form a stable composite material with self-controlling temperature function is a key problem that needs to be solved in current technology. Summary of the invention

[0004] The present invention provides a method for preparing self-temperature-controlling down based on protein activated microspheres, aiming to solve the technical problems of current down materials in temperature control accuracy, comfort and temperature control stability.

[0005] The present invention provides a method for preparing self-temperature-controlled down based on protein activated microspheres, comprising the following steps:

[0006] S1: Preparation of organic phase change microspheres by interfacial polymerization, in situ polymerization or Pickering emulsion polymerization chemical synthesis method;

[0007] S2: mixing the prepared microspheres with the collagen solution, and making the fibrous collagen firmly coated on the surface of the microspheres through physical adsorption and chemical cross-linking reaction to obtain protein activated microspheres;

[0008] S3: The protein activated microspheres are evenly distributed and grafted into the down material to obtain a self-temperature-regulating down product.

[0009] Preferably: in step S2, collagen is used to activate the phase change microspheres to make them have stronger functional activity.

[0010] Preferably, the activating agent is type I, type II or other collagen, and is used in combination with a hydroxylated or amidated cross-linking agent.

[0011] Preferably, in step S3, the protein activated microspheres are evenly distributed in the down material by spraying, dipping or rolling, so that the activated microspheres are firmly combined with the surface of the down.

[0012] Preferably, the protein activated microspheres are composed of three parts: a core phase change material, a phase change microsphere skeleton and a coated activated protein.

[0013] Preferably, the phase change material includes paraffinic alkanes (such as n-octadecane and n-eicosane), fatty acids and their esters, polyols (such as tetradecanol and octadecyl alcohol), and high molecular polymers.

[0014] Preferably, the phase-change microsphere skeleton is a polymer material with temperature responsiveness, including but not limited to polyvinyl alcohol, poly-N-isopropylacrylamide, polyurethane, and polymethacrylate.

[0015] Preferably, the activation protein is fibroblast collagen, mainly including collagen types I, II, III, XI and X, which imparts biocompatibility and functional grafting properties to the microspheres.

[0016] The beneficial effect of the present invention is that the present invention embeds and grafts protein-activated phase change microspheres into down fillings, combines the temperature response characteristics of the protein microspheres, and realizes self-control temperature regulation of the down material under different ambient temperatures, thereby effectively solving the current technical problems of down materials in terms of temperature control accuracy, comfort and temperature control stability.

[0017] The present invention successfully realizes a method for preparing down with self-temperature control performance by accurately selecting basic materials, designing optimized microsphere structures, and combining protein activation and grafting technology. The method is simple in process, low in cost, and has a significant and stable temperature control effect, and is suitable for the production of various thermal insulation down products.

[0018] Through the self-controlling temperature mechanism, down jackets can automatically adjust the insulation effect according to the changes in ambient temperature, so that the wearer can always maintain a comfortable temperature state under different environmental conditions. More importantly, since the microspheres can release or absorb heat according to the changes in the external temperature, this allows down jackets to provide the most suitable warmth effect in extremely cold or warm environments, avoiding the overheating or overcooling problems that traditional down jackets are prone to. Compared with traditional down jackets that rely on external heat sources or manual adjustment, self-controlling temperature down jackets can reduce the need for artificial heating and have higher energy efficiency and environmental protection. In addition, the structural stability of activated protein-coated microspheres and the regulating effect of phase change materials can improve the durability of down jackets, extend the service life of clothing, and reduce the need for replacement and maintenance. In short, the self-controlling temperature down technology based on protein-activated microspheres can provide more accurate and intelligent temperature control, significantly improve the comfort and safety of the wearer in various environments, and has broad market application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic diagram of the preparation process of the protein activated microspheres in the present invention;

[0020] Figure 2 It is a schematic diagram of grafting protein activated microspheres and down in the present invention;

[0021] Figure 3 This is a characteristic diagram of the microscopic morphology of the protein activated microspheres of the present invention;

[0022] Figure 4 is the DSC curve of the protein activated microspheres of the present invention and the traditional phase change microcapsules;

[0023] Figure 5 This is a microscopic morphological characteristic diagram of the self-temperature-controlling down in the present invention;

[0024] Figure 6 1 is the DSC curve of the self-temperature-controlling down feather Example 1 and Example 2 of the present invention;

[0025] Figure 7 It is an example diagram of the analysis of phase change temperature and enthalpy value ΔHm of traditional phase change microcapsules and protein activated microspheres in the present invention.

[0026] Figure 8 It is an example diagram of the analysis of the phase change temperature and enthalpy value ΔHm of the protein activated phase change microspheres and the self-temperature controlling down in the present invention. DETAILED DESCRIPTION

[0027] The subject matter described herein will now be discussed with reference to example implementations. It should be emphasized that the purpose of discussing these implementations is to help those skilled in the art better understand and implement the contents described herein. Without exceeding the scope of protection of this specification, the functions and arrangements of the elements discussed may be appropriately adjusted. The processes or components in each example may be omitted, substituted or added as needed. In addition, the features in some examples may also be combined in other examples.

[0028] At least one embodiment of the present invention discloses a method for preparing self-temperature-controlled down based on protein-activated microspheres, comprising the following steps:

[0029] S1: Preparation of organic phase change microspheres by interfacial polymerization, in situ polymerization or Pickering emulsion polymerization chemical synthesis method;

[0030] S2: mixing the prepared microspheres with the collagen solution, and making the fibrous collagen firmly coated on the surface of the microspheres through physical adsorption and chemical cross-linking reaction to obtain protein activated microspheres;

[0031] S3: The protein activated microspheres are evenly distributed and grafted into the down material to obtain a self-temperature-regulating down product.

[0032] in:

[0033] In step S2, the phase change microspheres are activated with an activation reagent collagen to make them more functionally active. The activation reagent is type I, type II, etc. collagen, and is used in combination with a hydroxylated or amidated crosslinking agent.

[0034] In step S3, the protein activated microspheres are evenly distributed in the down material by spraying, dipping or rolling, so that the activated microspheres are firmly combined with the surface of the down.

[0035] Protein activated microspheres are composed of three parts: core phase change material, phase change microsphere skeleton and coated activated protein.

[0036] Phase change materials include paraffinic alkanes (such as n-octadecane and n-eicosane), fatty acids and their esters, polyols (such as tetradecanol and octadecyl alcohol), and high molecular polymers.

[0037] The phase change microsphere skeleton is a temperature-responsive polymer material, including polyvinyl alcohol, poly (N-isopropylacrylamide), polyurethane, and polymethacrylate.

[0038] The activating protein is fibroblast collagen, mainly including collagen types I, II, III, XI and X, which endows the microspheres with biocompatibility and functional grafting properties.

[0039] This embodiment solves the technical problem that down jackets cannot be adaptively adjusted under different ambient temperatures by using self-controlling down technology based on protein activated microspheres. The microspheres are filled with phase change materials (such as paraffin alkanes, fatty acids and their esters, polyols and high molecular polymers, etc.), the phase change microsphere skeleton uses temperature-sensitive high molecular materials (such as polyvinyl alcohol, poly N-isopropyl acrylamide, polyurethane, polymethacrylate, etc.), and the microsphere activation layer uses fibrous collagen (such as collagen types I, II, III, XI and X, etc.), giving the microspheres biocompatibility and functional grafting characteristics. Self-controlling down technology, that is, when the external temperature changes, the phase change material of the microspheres can actively absorb or release heat, thereby adjusting the temperature control effect of the down jacket and realizing the self-controlling function.

[0040] The preparation process of the protein activated microspheres in this example is as follows Figure 1 As shown, reasonable process design can ensure that the microspheres have sufficient load capacity to effectively wrap the phase change material and ensure that the functional activity of the protein is not destroyed. The structure of the microspheres must not only have sufficient strength to withstand the physical pressure of the down material, but also ensure good thermal response performance so that it can produce obvious expansion or contraction effects when the temperature changes.

[0041] In this embodiment, the preparation of microspheres adopts interfacial polymerization or Pickering emulsion polymerization chemical synthesis method, and the particle size, pore structure and surface characteristics of the microspheres are adjusted by precisely controlling the reaction conditions. By optimizing the process parameters, the thermal response temperature range of the microspheres can be precisely adjusted to ensure that it matches the thermal insulation performance of down. The surface of the microspheres can be chemically modified to introduce functional groups such as amino groups and carboxyl groups, thereby achieving effective binding with proteins and enhancing the fixation and stability of proteins.

[0042] Finally, the protein activation of phase change microspheres and grafting of down are equally critical. First, the prepared microspheres are mixed with collagen solution, and the fibrous collagen is firmly coated on the surface of the microspheres through physical adsorption and chemical cross-linking reactions. During the activation process, the activation reagent collagen can be used to activate the phase change microspheres to make them have stronger functional activity. The activation reagent is type I, type II and other collagens, and is used in combination with hydroxylated or amidated cross-linking agents to form a stable protein-phase change microsphere complex, such as Figure 2 Then, the protein activated microspheres are evenly distributed in the down material by spraying, dipping or padding, so that the activated microspheres are firmly bonded to the surface of the down. In this way, the temperature control function of the phase change microspheres can be effectively transferred to the down material, achieving the self-temperature control effect of the down. The temperature control performance of the microspheres and the thermal insulation properties of the down work together to ensure that the down material can automatically adjust its thermal insulation performance according to the ambient temperature, thereby improving the comfort of the wearer.

[0043] Existing relevant experimental studies have shown that phase change materials can release or absorb heat under different temperature conditions, thereby regulating the ambient temperature. Temperature-responsive polymer materials (such as PNIPAM) can undergo significant physical changes when the temperature changes. They will expand when the temperature is lower than their interface temperature and shrink when the critical temperature is exceeded. This fully proves the feasibility of the microsphere structure in regulating the temperature control effect. In addition, protein coating technology has been widely used in many fields of biomedical materials, verifying its effectiveness in improving biocompatibility and functionality.

[0044] Example 1

[0045] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the phase change material paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0046] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of cross-linking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h. After the fibrous collagen was firmly coated on the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0047] (3) Composite of self-controlling temperature down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein activated microsphere (solid content 0.15g) suspension in step (2), and the temperature is controlled at 50°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-controlling temperature down and the stability of the microspheres.

[0048] Example 2

[0049] (1) Preparation of phase change microspheres (emulsion polymerization method): Weigh 1 g of TiO2 nanoparticles modified with methacryloxypropyltrimethoxysilane (KH-570) and disperse them in 80 mL of water, ultrasonicate for 30 min, and then stir at 6000 rpm for 20 min to obtain an aqueous TiO2 suspension. At the same time, weigh 0.6 g of phase change material paraffin and 0.6 g of toluene 2,4-diisocyanate (2,4-TDI), and stir vigorously at 50 ° C for 30 min as the oil phase system. Slowly add the oil phase to the aqueous TiO2 suspension, control the temperature at 50 ° C, and stir at 10000 rpm for 20 min to form an O / W Pickering suspension. Subsequently, slowly add an acetone solution of phenolic resin (10wt%, 20 mL) to the Pickering suspension, control the temperature at 45 ° C, and continue the reaction at 500 rpm for 20 h. After the reaction, the hybrid phase change microspheres were collected by filtration and washed three times with 60°C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, they were placed in a vacuum freeze dryer and dried for 12 hours to obtain white powder, which was the hybrid phase change microspheres.

[0050] (2) Protein activation of phase change microspheres: The prepared phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of cross-linking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h. After the fibrous collagen firmly coated the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0051] (3) Composite of self-controlling temperature down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein activated microsphere (solid content 0.15g) suspension in step (2), and the temperature is controlled at 50°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-controlling temperature down and the stability of the microspheres.

[0052] Example 3

[0053] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0054] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 20 mg / mL type I collagen solution and stirred at 300 rpm at room temperature for 2 h. Then, an appropriate amount of cross-linking agent glutaraldehyde was added and stirred at room temperature for 2 h. After the fibrous collagen firmly coated the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0055] (3) Composite of self-controlling temperature down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein activated microsphere (solid content 0.15g) suspension in step (2), and the temperature is controlled at 50°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-controlling temperature down and the stability of the microspheres.

[0056] Example 4

[0057] (1) Preparation of phase change microspheres: Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0058] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 2 h. Then, an appropriate amount of cross-linking agent 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) was added and stirred at room temperature for 1 h. After the fibrous collagen firmly coated the surface of the phase change microspheres through physical adsorption and chemical cross-linking reactions, a protein-activated microsphere emulsion was obtained.

[0059] (3) Composite of self-controlling temperature down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein activated microsphere (solid content 0.15g) suspension in step (2), and the temperature is controlled at 50°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-controlling temperature down and the stability of the microspheres.

[0060] Example 5

[0061] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0062] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of temperature-sensitive crosslinking agent poly (N-isopropylacrylamide) (PNIPAM) was added and stirred at room temperature for 3 h. After the fibrous collagen firmly coated the surface of the phase change microspheres through physical adsorption and chemical crosslinking reactions, a protein-activated microsphere emulsion was obtained.

[0063] (3) Composite of self-controlling temperature down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein activated microsphere (solid content 0.15g) suspension in step (2), and the temperature is controlled at 50°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-controlling temperature down and the stability of the microspheres.

[0064] Example 6

[0065] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0066] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of cross-linking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h. After the fibrous collagen was firmly coated on the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0067] (3) Composite of self-temperature-controlled down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein-activated microsphere suspension (solid content 0.30g) in step (2), and the temperature is controlled at 40°C and stirred at 500rpm for 5h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0068] Comparative Example 1 (the difference between Comparative Example 1 and Example 1 is only whether the microspheres are activated with collagen in step (2))

[0069] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0070] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were directly dispersed in collagen-free water and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of crosslinking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h to obtain a microsphere suspension that was not protein activated.

[0071] (3) Composite of self-temperature-controlled down material: Preferably, 1 g of clean down is immersed and evenly dispersed in 80 mL of microsphere suspension (solid content 0.15 g) in step (2), the temperature is controlled at 50°C, and stirred at 500 rpm for 3 hours. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12 hours, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0072] Comparative Example 2 (Comparative Example 2 differs from Example 1 only in that different activated proteins are used in step (2))

[0073] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0074] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL dopamine solution and stirred at 300 rpm for 1 h at room temperature. Then, an appropriate amount of crosslinking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h to obtain a phase change microsphere suspension.

[0075] (3) Composite of self-temperature-controlled down material: Preferably, 1 g of clean down is immersed and evenly dispersed in 80 mL of microsphere suspension (solid content 0.15 g) in step (2), the temperature is controlled at 50°C, and stirred at 500 rpm for 3 hours. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12 hours, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0076] Comparative Example 3 (Comparative Example 3 differs from Example 1 only in the type and content of collagen used in step (2))

[0077] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0078] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 20 mg / mL type I collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of crosslinking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h to obtain a protein-activated microsphere suspension.

[0079] (3) Composite of self-temperature-controlled down material: Preferably, 1 g of clean down is immersed and evenly dispersed in 80 mL of protein-activated microsphere suspension (solid content 0.15 g) in step (2), the temperature is controlled at 50°C, and the mixture is stirred at 500 rpm for 3 hours. After the reaction is completed, the liquid is filtered out, the mixture is washed with clean water 3 times, freeze-dried for 12 hours, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0080] Comparative Example 4 (Comparative Example 4 differs from Example 1 only in that no cross-linking agent is used in step (2))

[0081] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0082] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm for 3 h at room temperature to obtain a protein activated microsphere suspension.

[0083] (3) Composite of self-temperature-controlled down material: Preferably, 1 g of clean down is immersed and evenly dispersed in 80 mL of protein-activated microsphere suspension (solid content 0.15 g) in step (2), the temperature is controlled at 50°C, and the mixture is stirred at 500 rpm for 3 hours. After the reaction is completed, the liquid is filtered out, the mixture is washed with clean water 3 times, freeze-dried for 12 hours, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0084] Comparative Example 5 (Comparative Example 5 differs from Example 1 in that the solid content in the protein activated microsphere suspension and the reaction temperature in step (3) are different)

[0085] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0086] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of cross-linking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h. After the fibrous collagen was firmly coated on the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0087] (3) Composite of self-temperature-controlled down material: Preferably, 1g of clean down is immersed and evenly dispersed in 80mL of protein-activated microsphere (solid content 0.10g) suspension in step (2), and the temperature is controlled at 30°C and stirred at 500rpm for 3h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres.

[0088] Comparative Example 6 (Comparative Example 6 differs from Example 1 in that the mixing and compounding time of the phase change microspheres and the down material in step (3) is different)

[0089] (1) Preparation of phase change microspheres (interfacial polymerization method): Weigh 0.6 g of the paraffin nanoparticles prepared in the previous step and place them in a reaction bottle, and disperse them in 250 mL of acetone solution. Add 0.6 g of toluene 2,4-diisocyanate (2,4-TDI) and stir at room temperature for 10 h at 800 rpm. After 2,4-TDI fully modifies the nanoparticles, ultrasonically disperse them for 10 min. Then slowly add 50 mL of acetone solution containing 1.5 g of phenolic resin, and continue to stir stably at 45 °C for 20 h. After the shelling reaction is completed, filter and collect the organic phase change microspheres, and wash them three times with 60 °C anhydrous ethanol and deionized water to remove impurities and unencapsulated phase change materials. Finally, place them in a vacuum freeze dryer and dry them for 12 h to obtain a white powder, which is the organic phase change microspheres.

[0090] (2) Protein activation of phase change microspheres: The prepared organic phase change microspheres were mixed with 15 mg / mL type II collagen solution and stirred at 300 rpm at room temperature for 1 h. Then, an appropriate amount of cross-linking agent diphenylmethane diisocyanate (MDI) was added and stirred at room temperature for 2 h. After the fibrous collagen was firmly coated on the surface of the phase change microspheres through physical adsorption and chemical cross-linking reaction, a protein-activated microsphere emulsion was obtained.

[0091] (3) Composite of self-temperature-controlled down material: preferably 1g of clean down is immersed and evenly dispersed in 80mL of protein-activated microsphere (solid content 0.15g) suspension in step (2), the temperature is controlled at 50°C, and stirred at 500rpm for 7h to ensure that the microspheres are evenly and firmly attached to the down fibers. After the reaction is completed, the liquid is filtered out, washed with clean water 3 times, freeze-dried for 12h, and then gently dried at 50°C to ensure the fluffiness of the self-temperature-controlled down and the stability of the microspheres. Wherein:

[0092] In step (1), the preparation of phase change microcapsules mainly includes chemical synthesis methods such as interfacial polymerization, in situ polymerization and Pickering emulsion polymerization. The phase change materials used include paraffin alkanes (such as n-octadecane, n-eicosane), fatty acids and their esters, polyols (such as tetradecanol, octadecyl alcohol, etc.) and high molecular polymers. The prepared microsphere skeleton is a polymer material with temperature responsiveness, and the polymer material includes but is not limited to polyvinyl alcohol (PVA), poly (N-isopropylacrylamide), polyurethane, polymethacrylate. The preparation process of phase change microspheres in step (1) is as follows: Figure 1 As shown in Figure 2, the microstructure of the prepared phase change microspheres is as follows Figure 3 As shown, the spheres are full and uniform. Figure 4 ), the melting point of the obtained phase change microspheres is 33.6℃, ​​the enthalpy is 276J / g, and the heat storage performance is significantly higher than that of traditional phase change microcapsules (265J / g).

[0093] In step (2), the protein activated microspheres are mainly composed of three parts: core phase change material, phase change microsphere skeleton and coated activated protein. The activated protein used is animal protein from livestock and poultry, involving type I and type ⅠⅠ collagen, basement membrane collagen, microfibril collagen, anchoring collagen, hexagonal mesh collagen, fibrin, etc., according to the structure, to enhance the biocompatibility and functional grafting properties of the microspheres. The protein activation mechanism of phase change microspheres is as follows Figure 2 shown.

[0094] In step (3), the activation and grafting of down and microspheres are further completed based on the protein activated microsphere emulsion formed in step (2). The functional grafting mechanism diagram is shown in FIG. Figure 2 The microscopic morphology of the self-temperature-controlled down is shown in Figure 5 As shown in Figure 2, the activated phase change microspheres can be well embedded and grafted onto the down fibers. Figure 6 ), the melting temperature of the self-controlling down was 33.4℃, and the enthalpy was 93.7J / g. After repeated rinsing for 20 times, the self-controlling down still maintained a thermal enthalpy of 81.6J / g (Table 2).

[0095] This embodiment solves the technical problem that down jackets cannot be adaptively adjusted under different ambient temperatures by using self-controlling down technology based on protein activated microspheres. The microspheres are filled with phase change materials (such as paraffin alkanes, fatty acids and their esters, polyols and high molecular polymers, etc.), the phase change microsphere skeleton uses temperature-sensitive high molecular materials (such as polyvinyl alcohol, poly N-isopropyl acrylamide, polyurethane, polymethacrylate, etc.), and the microsphere activation layer uses fibrous collagen (such as collagen types I, II, III, XI and X, etc.), giving the microspheres biocompatibility and functional grafting characteristics. Self-controlling down technology, that is, when the external temperature changes, the phase change material of the microspheres can actively absorb or release heat, thereby adjusting the temperature control effect of the down jacket and realizing the self-controlling function.

[0096] The preparation process of the protein activated microspheres in this example is as follows Figure 1 As shown, reasonable process design can ensure that the microspheres have sufficient load capacity to effectively wrap the phase change material and ensure that the functional activity of the protein is not destroyed. The structure of the microspheres must not only have sufficient strength to withstand the physical pressure of the down material, but also ensure good thermal response performance so that it can produce obvious expansion or contraction effects when the temperature changes.

[0097] In this embodiment, the preparation of microspheres adopts interfacial polymerization or Pickering emulsion polymerization chemical synthesis method, and the particle size, pore structure and surface characteristics of the microspheres are adjusted by precisely controlling the reaction conditions. By optimizing the process parameters, the thermal response temperature range of the microspheres can be precisely adjusted to ensure that it matches the thermal insulation performance of down. The surface of the microspheres can be chemically modified to introduce functional groups such as amino groups and carboxyl groups, thereby achieving effective binding with proteins and enhancing the fixation and stability of proteins.

[0098] Finally, the protein activation of phase change microspheres and grafting of down are equally critical. First, the prepared microspheres are mixed with collagen solution, and the fibrous collagen is firmly coated on the surface of the microspheres through physical adsorption and chemical cross-linking reactions. During the activation process, the activation reagent collagen can be used to activate the phase change microspheres to make them have stronger functional activity. The activation reagent is type I, type II and other collagens, and is used in combination with hydroxylated or amidated cross-linking agents to form a stable protein-phase change microsphere complex, such as Figure 2 Then, the protein activated microspheres are evenly distributed in the down material by spraying, dipping or padding, so that the activated microspheres are firmly bonded to the surface of the down. In this way, the temperature control function of the phase change microspheres can be effectively transferred to the down material, achieving the self-temperature control effect of the down. The temperature control performance of the microspheres and the thermal insulation properties of the down work together to ensure that the down material can automatically adjust its thermal insulation performance according to the ambient temperature, thereby improving the comfort of the wearer.

[0099] The protein activated microspheres prepared by the present invention have uniform morphology and can be stably grafted onto the down core. Figure 5 Protein-activated phase-change microspheres have more advantages than traditional phase-change microcapsules. The latent heat ΔHm is larger, about 276 J / g, and after 30 cycles of heat storage and release, more than 95% of the latent heat performance can still be retained. Figure 4 and Figure 7 Table 1. Similarly, differential scanning calorimetry studies were performed (see Figure 6 ), the melting point of the self-controlled temperature down is 33.4℃, and the enthalpy is 93.7J / g. After repeated rinsing for 20 times, the self-controlled temperature down (81.6J / g) can still retain more than 87% of the microspheres. Figure 8 Table 2 in .

[0100] The experimental results of the present invention show that the protein activated microspheres can maintain a constant temperature effect for a long time under different temperature environments, and have good durability and stability. Compared with ordinary down, the prepared self-controlling temperature down has better temperature control performance and comfort. At the same time, the stable grafting of activated proteins helps the temperature regulating textiles to avoid the problem of temperature control effect attenuation during long-term use. Therefore, the present invention has strong industrial application potential and is particularly suitable for the production of high-performance down and other textiles.

[0101] In summary, the embodiments of the present invention have been described above, but this embodiment is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Ordinary technicians in this field can also make many forms inspired by this embodiment, all of which are within the protection of this embodiment.

Claims

1. A method for preparing self-temperature-controlled down based on protein activated microspheres, characterized in that: The steps include: S1: Preparation of organic phase change microspheres by interfacial polymerization, in situ polymerization or Pickering emulsion polymerization chemical synthesis method; S2: mixing the prepared microspheres with the collagen solution, and making the fibrous collagen firmly coated on the surface of the microspheres through physical adsorption and chemical cross-linking reaction to obtain protein activated microspheres; S3: The protein activated microspheres are evenly distributed and grafted into the down material to obtain a self-temperature-regulating down product.

2. The method for preparing self-temperature-controlled down based on protein-activated microspheres according to claim 1, characterized in that: In step S2, collagen is used to activate the phase change microspheres to make them have stronger functional activity.

3. The method for preparing self-temperature-controlled down based on protein activated microspheres according to claim 1, characterized in that: The activating agent is type I, type II and other collagens, and is used in combination with a hydroxylated or amidated cross-linking agent.

4. The method for preparing self-temperature-controlled down based on protein activated microspheres according to claim 1, characterized in that: In step S3, the protein activated microspheres are evenly distributed in the down material by spraying, dipping or rolling, so that the activated microspheres are firmly combined with the surface of the down.

5. The method for preparing self-temperature-controlled down based on protein activated microspheres according to claim 1, characterized in that: Protein activated microspheres are composed of three parts: core phase change material, phase change microsphere skeleton and coated activated protein.

6. The method for preparing self-temperature-controlled down based on protein-activated microspheres according to claim 5, characterized in that: Phase change materials include paraffinic alkanes (such as n-octadecane and n-eicosane), fatty acids and their esters, polyols (such as tetradecanol and octadecyl alcohol), and high molecular polymers.

7. The method for preparing self-temperature-controlled down based on protein activated microspheres according to claim 5, characterized in that: The phase change microsphere skeleton is a temperature-responsive polymer material, including polyvinyl alcohol, poly (N-isopropylacrylamide), polyurethane, and polymethacrylate.

8. The method for preparing self-temperature-controlled down based on protein-activated microspheres according to claim 5, characterized in that: The activation protein is fibroblast collagen, mainly including type I, II, III, XI and X collagen, which endows the microspheres with biocompatibility and functional grafting characteristics.

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