阅读说明：本技术 一种纺织上应用的多层蓄热保温微胶囊及制备方法 (Multilayer heat-storage heat-preservation microcapsule applied to textile and preparation method thereof ) 是由 翁朝阳 于 2020-05-29 设计创作，主要内容包括：本发明属于储能材料技术领域,具体是一种纺织上应用的多层蓄热保温微胶囊及制备方法,所述多层蓄热保温微胶囊由内核、内层壳层、中间壳层和外层壳层组成,内层壳层置于内核和中间壳层之间,中间壳层置于内层壳层和外层壳层之间,外层壳层置于微胶囊的最外层；内核为相变储能材料,内层壳层为1,3,5-均苯三甲酰氯和N,N’-(1,2-二羟基乙烯)双丙烯酰反应产生的交联物,中间壳层为乙烯基和2,3-二巯基丁二酸反应产生的交联物,外层壳层为羧基和氮丙啶交联剂反应产生的交联物。本发明的多层蓄热保温微胶囊的外壳具有较高的厚度和强度,在纺织上应用时具有较好的稳定性。(The invention belongs to the technical field of energy storage materials, and particularly relates to a multilayer heat-storage heat-preservation microcapsule applied to textile and a preparation method thereof, wherein the multilayer heat-storage heat-preservation microcapsule consists of an inner core, an inner shell layer, an intermediate shell layer and an outer shell layer, the inner shell layer is arranged between the inner core and the intermediate shell layer, the intermediate shell layer is arranged between the inner shell layer and the outer shell layer, and the outer shell layer is arranged on the outermost layer of the microcapsule; the core is a phase-change energy storage material, the inner shell layer is a cross-linking product generated by the reaction of 1,3, 5-trimesoyl chloride and N, N' - (1, 2-dihydroxyethylene) diacryloyl, the middle shell layer is a cross-linking product generated by the reaction of vinyl and 2, 3-dimercaptosuccinic acid, and the outer shell layer is a cross-linking product generated by the reaction of carboxyl and an aziridine cross-linking agent. The shell of the multilayer heat-storage heat-preservation microcapsule has higher thickness and strength, and has better stability when being applied to textiles.)

1. A multilayer heat accumulation heat preservation microcapsule who uses in weaving characterized in that: the microcapsule comprises an inner core, an inner shell layer, an intermediate shell layer and an outer shell layer, wherein the inner shell layer is arranged between the inner core and the intermediate shell layer, the intermediate shell layer is arranged between the inner shell layer and the outer shell layer, and the outer shell layer is arranged on the outermost layer of the microcapsule; the core is a phase-change energy storage material, the inner shell layer is a cross-linked product generated by the reaction of 1,3, 5-trimesoyl chloride and N, N' - (1, 2-dihydroxyethylene) diacryloyl, the middle shell layer is a cross-linked product generated by the reaction of vinyl and 2, 3-dimercaptosuccinic acid, and the outer shell layer is a cross-linked product generated by the reaction of carboxyl and an aziridine cross-linking agent.

2. The multilayer heat-storage heat-preservation microcapsule according to claim 1, characterized in that: the phase change energy storage material is at least one of n-octadecane, n-eicosane, n-docosane, paraffin and butyl stearate.

3. A method for preparing multilayer heat-storage heat-preservation microcapsules applied to textiles according to claim 1 or 2, which is characterized by comprising the following steps: the method comprises the following steps:

s1, mixing the 1,3, 5-benzene trimethyl acyl chloride, the phase change energy storage material and an emulsifier, heating to form liquid, and adding deionized water with the same temperature under high-speed stirring to form emulsion;

s2, adding the N, N' - (1, 2-dihydroxyethylene) diacryloyl into the emulsion obtained in the step S1, stirring for 0.5-5 hours, separating and washing with water to obtain a single-layer microcapsule;

s3, dispersing the single-layer microcapsule obtained in the step S2 in deionized water, adding the 2, 3-dimercaptosuccinic acid and the water-soluble photoinitiator, irradiating the mixture for 2-10 minutes by using ultraviolet light with the dominant wavelength of 365nm and the light intensity of 1-10mW/cm, separating and washing the mixture to obtain a double-layer microcapsule;

s4, dispersing the double-layer microcapsule obtained in the step S3 in deionized water, adding the aziridine crosslinking agent, stirring for 0.5-5 hours, separating, washing with water, and drying to obtain the multilayer phase change energy storage microcapsule.

4. The production method according to claim 3, characterized in that: in the step S1, the weight ratio of the 1,3, 5-benzene trimethyl acyl chloride, the phase change energy storage material, the emulsifier and the deionized water is (0.1-2): 10, (0.5-2): 10-30).

5. The production method according to claim 3, characterized in that: in the step S1, the temperature of the heated liquid is 5-15 ℃ higher than the melting point of the phase change energy storage material, but not higher than 90 ℃.

6. The production method according to claim 3, characterized in that: in the step S2, the weight ratio of the emulsion to the N, N' - (1, 2-dihydroxyethylene) diacryloyl is 1 (0.005-0.1).

7. The production method according to claim 3, characterized in that: in step S3, the weight ratio of the single-layer microcapsule, the deionized water, the 2, 3-dimercaptosuccinic acid and the water-soluble photoinitiator is 1 (1-10): (0.001-0.1): 0.001-0.005).

8. The method of claim 7, wherein: the weight ratio of the single-layer microcapsule, the deionized water, the 2, 3-dimercaptosuccinic acid and the water-soluble photoinitiator is 1 (1.5-7): (0.01-0.15): 0.002-0.004.

9. The production method according to claim 3, characterized in that: in the step S4, the weight ratio of the double-layer microcapsule, the deionized water and the aziridine crosslinking agent is 1 (1-10) to 0.05-0.2.

10. The method of claim 9, wherein: the weight ratio of the double-layer microcapsule, the deionized water and the aziridine crosslinking agent is 1 (1.5-8) to 0.08-0.15.

Technical Field

The invention relates to the technical field of energy materials, in particular to the technical field of energy storage materials, and relates to a multilayer heat storage and insulation microcapsule applied to textile and a preparation method thereof.

Background

The heat storage and preservation microcapsule is a structure formed by coating a phase change energy storage material with a material to form a core made of the phase change energy storage material and a shell made of a coating material, and when the microcapsule is applied to textiles, the microcapsule can store heat at a higher ambient temperature, so that the cool property is improved, the stored heat is released when the ambient temperature is reduced, and the heat preservation property is improved, so that the microcapsule has the characteristics of energy conservation and environmental protection.

At present, the heat storage and preservation microcapsule is generally prepared by emulsifying a phase change energy storage material and then forming a cross-linked polymer at an oil-water interface through a cross-linking reaction between an oil phase compound and a water phase compound. The method adopted in the prior art comprises the reaction of trimesoyl chloride and polyamino compounds, the reaction of isocyanate compounds and polyamino compounds, interfacial free radical polymerization and the like, but mainly forms a single-shell structure, and the shell formed by the general formula can block the contact of oil-phase and water-phase compounds, so that the reaction can not be continuously carried out, and the problems of thin shell thickness, insufficient strength, insufficient coating performance, leakage and the like caused when the microcapsule is applied to a textile forming process are caused.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, and provides a multilayer heat-storage heat-preservation microcapsule applied to textile, wherein the shell has higher thickness and strength, and the problem that the leakage of a core phase-change energy-storage material occurs in the use process of the microcapsule due to insufficient shell thickness and insufficient strength of the existing heat-storage heat-preservation microcapsule is solved.

The invention also aims to provide a preparation method of the multilayer heat-storage heat-preservation microcapsule applied to textile, three crosslinking layers are built on the shell of the microcapsule layer by layer through three different crosslinking methods, the thickness and the strength of the shell are improved, and the practicability of the heat-storage heat-preservation microcapsule is enhanced.

The invention adopts the following technical scheme:

a multilayer heat-storage heat-preservation microcapsule applied to textile comprises an inner core, an inner shell layer, an intermediate shell layer and an outer shell layer, wherein the inner shell layer is arranged between the inner core and the intermediate shell layer, the intermediate shell layer is arranged between the inner shell layer and the outer shell layer, and the outer shell layer is arranged on the outermost layer of the microcapsule; the core is a phase-change energy storage material, the inner shell layer is a cross-linked product generated by the reaction of 1,3, 5-trimesoyl chloride and N, N' - (1, 2-dihydroxyethylene) diacryloyl, the middle shell layer is a cross-linked product generated by the reaction of vinyl and 2, 3-dimercaptosuccinic acid, and the outer shell layer is a cross-linked product generated by the reaction of carboxyl and an aziridine cross-linking agent.

Preferably, the phase change energy storage material is selected from at least one of n-octadecane, n-eicosane, n-docosane, paraffin and butyl stearate.

A method for preparing a multilayer heat-storage heat-preservation microcapsule applied to textile in any embodiment comprises the following steps:

s1, mixing the 1,3, 5-benzene trimethyl acyl chloride, the phase change energy storage material and an emulsifier, heating to form liquid, and adding deionized water with the same temperature under high-speed stirring to form emulsion;

s2, adding the N, N' - (1, 2-dihydroxyethylene) diacryloyl into the emulsion obtained in the step S1, stirring for 0.5-5 hours, separating and washing with water to obtain a single-layer microcapsule;

s3, dispersing the single-layer microcapsule obtained in the step S2 in deionized water, adding the 2, 3-dimercaptosuccinic acid and a water-soluble photoinitiator, irradiating for 2-10 minutes by using ultraviolet light with the dominant wavelength of 365nm and the light intensity of 1-10mW/cm, separating and washing with water to obtain a double-layer microcapsule;

s4, dispersing the double-layer microcapsule obtained in the step S3 in deionized water, adding the aziridine crosslinking agent, stirring for 0.5-5 hours, separating, washing with water, and drying to obtain the multilayer phase change energy storage microcapsule.

Preferably, the weight ratio of the 1,3, 5-benzene tricarboxy chloride, the phase change energy storage material, the emulsifier and the deionized water in the step S1 is (0.1-2): 10, (0.5-2): 10-30).

Preferably, the temperature of the heated liquid in the step S1 is 5 to 15 ℃ higher than the melting point of the phase change energy storage material, but not higher than 90 ℃.

Preferably, the weight ratio of the emulsion to the N, N' - (1, 2-dihydroxyethylene) bisacryloyl in the step S2 is 1 (0.005-0.1).

The emulsifier of the invention can beOf the formula R¹(OCH₂CH₂)_nNonionic emulsifiers of OH, where R¹Is C6-C18 alkyl or acylalkyl, and n is 3-20; or of the general formula R²(OCH₂CH₂)_mOSO₃M¹The anionic emulsifier of (1), wherein R²Is C8-C18 alkyl or acylalkyl, M is 3-10, M¹Is sodium, potassium or ammonium; or of the general formula R³SO₃M²Anionic emulsifiers of, R³Is C8-C18 alkyl or phenyl-containing C8-C18 alkyl, M²Is sodium, potassium or ammonium; or of the general formula R⁴OSO₃M³Anionic emulsifiers of, R⁴Is C8-C18 alkyl or phenyl-containing C8-C18 alkyl, M³Is sodium, potassium or ammonium; or a combination of the above nonionic emulsifiers and anionic emulsifiers.

Preferably, the weight ratio of the single-layer microcapsule, the deionized water, the 2, 3-dimercaptosuccinic acid and the water-soluble photoinitiator in the step S3 is 1 (1-10): (0.001-0.1): 0.001-0.005).

More preferably, the weight ratio of the single-layer microcapsule, the deionized water, the 2, 3-dimercaptosuccinic acid and the water-soluble photoinitiator is 1 (1.5-7): (0.01-0.15): 0.002-0.004).

Preferably, the weight ratio of the double-layer microcapsule, the deionized water and the aziridine crosslinking agent in the step S4 is 1 (1-10) to 0.05-0.2.

More preferably, the weight ratio of the double-layer microcapsule, the deionized water and the aziridine crosslinking agent is 1 (1.5-8) to 0.08-0.15.

The invention has the beneficial effects that:

(1) according to the invention, the shell composed of three different crosslinking compounds is constructed in the heat storage and insulation microcapsule by a method of constructing crosslinking layers layer by layer, and compared with a single-layer shell or a double-layer shell, the shell has higher thickness and strength, the stability of the shell in the use process of the microcapsule in application in textile is improved, and the leakage of the core phase change energy storage material is avoided.

(2) The three crosslinking reaction methods used by the shell have higher reaction activity, so the crosslinking reaction efficiency is higher, the practicability is better, and the application prospect is wide.

Drawings

Fig. 1 is a schematic representation of a multilayer phase change energy storage microcapsule of the present invention.

Wherein, 1-inner core, 2-inner shell, 3-middle shell, and 4-outer shell.

Detailed Description

The technical solution of the present invention is further illustrated and described by the following detailed description.

Unless otherwise specified, the parts in the following examples are parts by weight.