阅读说明：本技术 一种新型固-固相变储能材料的制备方法 (Preparation method of novel solid-solid phase change energy storage material ) 是由 陆少锋 师文钊 徐成书 谢艳 王海珠 展雄威 于 2020-10-30 设计创作，主要内容包括：本发明公开了一种新型固-固相变储能材料的制备方法,在反应器内加入适量聚醚多元醇,进行高温抽真空脱水处理；将反应器的温度降至50℃,加入适量二异氰酸酯,保温反应1h,而后升温至80℃,保温反应2～3h,得到聚氨酯预聚体；在反应器中加入适量小分子扩链剂进行扩链,并于80℃保温反应2h；将反应器温度降至室温,加水乳化均匀,得到新型固-固相变储能材料。本发明一种新型固-固相变储能材料的制备方法,解决了现有技术中存在的聚氨酯固-固相变储能材料相变焓高的问题。(The invention discloses a preparation method of a novel solid-solid phase change energy storage material, which comprises the steps of adding a proper amount of polyether glycol into a reactor, and carrying out high-temperature vacuum-pumping dehydration treatment; reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 2-3 h to obtain a polyurethane prepolymer; adding a proper amount of micromolecular chain extender into a reactor for chain extension, and carrying out heat preservation reaction for 2 hours at 80 ℃; and (3) cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The invention relates to a preparation method of a novel solid-solid phase change energy storage material, which solves the problem of high phase change enthalpy of a polyurethane solid-solid phase change energy storage material in the prior art.)

1. A preparation method of a novel solid-solid phase change energy storage material is characterized by comprising the following steps:

step 1, adding a proper amount of polyether polyol into a reactor, and performing high-temperature vacuum-pumping dehydration treatment;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1 hour, then heating to 80 ℃, and carrying out heat preservation reaction for 2-3 hours to obtain a polyurethane prepolymer;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material.

2. The preparation method of the novel solid-solid phase change energy storage material according to claim 1, wherein the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 1-9: 1.

3. the method for preparing the novel solid-solid phase change energy storage material according to claim 1, wherein the diisocyanate is isophorone diisocyanate.

4. The preparation method of the novel solid-solid phase change energy storage material as claimed in claim 1, wherein the molar ratio of the diisocyanate to the polyether polyol is 1.3-3: 1.

5. the method for preparing the novel solid-solid phase change energy storage material as claimed in claim 1, wherein the small molecule chain extender comprises glycerol.

6. The preparation method of the novel solid-solid phase change energy storage material according to claim 1, wherein the molar ratio of the small-molecule chain extender to the polyether polyol is 0.3-2: 1.

Technical Field

The invention relates to the technical field of phase change energy storage material preparation, in particular to a preparation method of a novel solid-solid phase change energy storage material.

Background

The clothes made of the phase-change energy storage material can keep a human body in a comfortable temperature environment through the specific heat preservation performance of the phase-change material during heat absorption and heat release. When the temperature rises, the phase-change material undergoes crystallization-melting phase change to absorb heat; when the temperature is reduced, the phase-change material undergoes melting-crystallization phase change, heat is released, and the effect of adjusting the temperature is achieved through the absorption and the release of energy.

At present, microencapsulated phase change materials are mostly used in the field of temperature-regulating textiles. The phase change material microcapsules have many advantages such as increased heat transfer area, reduced reactivity of the phase change material with the external environment, and controlled volume change of the energy storage material when phase change occurs. But the application of the phase-change material microcapsule in the field of textile and clothing also has defects, namely, the microcapsule phase-change material has the problems of shell breakage and core material leakage in use; and secondly, the microcapsule phase change material has no affinity with textile fibers, can be firmly fixed on the fabric only under the action of an adhesive, and has great influence on the hand feeling, the air permeability and the like of the fabric.

The polyurethane solid-solid phase change material is a phase change from solid to solid, the phase change mechanism is essentially a process that a soft section in a molecular structure partially undergoes phase change and is changed from a crystalline state to an amorphous state, and the phase change process can realize the storage and release of energy through heat absorption and heat release. The phase transition process from solid state to solid state has the advantages of good volume stability, small expansion coefficient, small volume change and convenient use, and the application range of the phase transition material is greatly expanded. Compared with the microcapsule phase change material, the phase change material does not leak, and does not need adhesive adhesion, and the polyurethane can form a film on the surface of the fiber and has excellent fixation performance. However, the phase-change temperature of the phase-change material is generally higher and basically higher than 50 ℃, so that the application of the phase-change material in the field of textile and clothing is limited.

Disclosure of Invention

The invention aims to provide a preparation method of a novel solid-solid phase change energy storage material, which solves the problem of high phase change enthalpy of a polyurethane solid-solid phase change energy storage material in the prior art.

The technical scheme adopted by the invention is a preparation method of a novel solid-solid phase change energy storage material, which is implemented according to the following steps:

step 1, adding a proper amount of polyether polyol into a reactor, and performing high-temperature vacuum-pumping dehydration treatment;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1 hour, then heating to 80 ℃, and carrying out heat preservation reaction for 2-3 hours to obtain a polyurethane prepolymer;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material.

The invention is also characterized in that:

the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 1-9: 1.

the diisocyanate is isophorone diisocyanate.

The molar ratio of diisocyanate to polyether polyol is 1.3-3: 1.

the micromolecular chain extender is glycerol.

The mole ratio of the micromolecule chain extender to the polyether polyol is 0.3-2: 1.

the invention has the beneficial effects that:

the preparation method of the novel solid-solid phase change energy storage material provided by the invention has the advantages that the series of solid-solid phase change energy storage materials with the phase change temperature of 20-37 ℃ and high phase change enthalpy are prepared, and the temperature regulation requirements of the solid-solid phase change energy storage materials on the aspects of textiles and clothing can be met; the preparation method of the novel solid-solid phase change energy storage material ensures the hydrophilicity of the chain segment, enables the prepared phase change energy storage material to have proper phase change enthalpy, and overcomes the problem that the phase change enthalpy of the phase change energy storage material prepared by only taking PEG as polyether glycol is lower; according to the preparation method of the novel solid-solid phase change energy storage material, disclosed by the invention, the glycerol is used as the chain extender, so that the phase change temperature of the prepared phase change energy storage material can be reduced, and the application requirement of the phase change energy storage material in the field of textile and clothing is met.

Drawings

FIG. 1 is a DSC of the novel solid-solid phase change energy storage material prepared in example 1 of the present invention.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

The invention provides a preparation method of a novel solid-solid phase change energy storage material, which is implemented according to the following steps:

step 1, adding a proper amount of polyether polyol into a reactor, and performing high-temperature vacuum-pumping dehydration treatment;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1 hour, then heating to 80 ℃, and carrying out heat preservation reaction for 2-3 hours to obtain a polyurethane prepolymer;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material.

The polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 1-9: 1; the molecular weight of polyethylene glycol is 2000, and the molecular weight of polytetrahydrofuran ether glycol is 2000.

Preferably, the diisocyanate is isophorone diisocyanate.

Preferably, the molar ratio of diisocyanate to polyether polyol is 1.3-3: 1.

preferably, the small molecule chain extender comprises glycerol.

Preferably, the molar ratio of the small-molecule chain extender to the polyether polyol is 0.3-2: 1.

example 1

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 9: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 3h to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 1.3: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecular chain extender to the polyether polyol is 0.3: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Example 2

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 1: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 2: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecule chain extender to the polyether polyol is 2: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Example 3

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 6: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1 hour, then heating to 80 ℃, and carrying out heat preservation reaction for 2.5 hours to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 2: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecular chain extender to the polyether polyol is 1: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Example 4

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 9: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 3: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecule chain extender to the polyether polyol is 2: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Example 5

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 3: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 3h to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 2.2: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecular chain extender to the polyether polyol is 1.3: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Example 6

A preparation method of a novel solid-solid phase change energy storage material is implemented according to the following steps:

step 1, adding a proper amount of polyether glycol into a reactor, and vacuumizing and dehydrating for 2 hours at the temperature of 110 ℃ under a vacuum condition; the polyether polyol is a compound of polyethylene glycol and polytetrahydrofuran ether glycol, and the mass ratio of the polyethylene glycol to the polytetrahydrofuran ether glycol is 7: 1; the molecular weight of the polyethylene glycol is 2000, and the molecular weight of the polytetrahydrofuran ether glycol is 2000;

step 2, reducing the temperature of the reactor to 50 ℃, adding a proper amount of diisocyanate, carrying out heat preservation reaction for 1h, then heating to 80 ℃, and carrying out heat preservation reaction for 2h to obtain a polyurethane prepolymer;

wherein the diisocyanate is isophorone diisocyanate; the molar ratio of diisocyanate to polyether polyol is 1.7: 1;

step 3, adding a proper amount of micromolecule chain extender into the reactor for chain extension, and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃;

wherein the small molecule chain extender comprises glycerol; the molar ratio of the micromolecular chain extender to the polyether polyol is 0.7: 1;

and 4, cooling the temperature of the reactor to room temperature, adding water, and emulsifying uniformly to obtain the novel solid-solid phase change energy storage material. The water addition amount is preferably 30 percent of the solid content of the novel solid-solid phase change energy storage material.

Best mode for carrying out the invention example 1. A DSC diagram of the novel solid-solid phase change energy storage material prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the melting phase change temperature of the novel solid-solid phase change energy storage material prepared in the present invention is 32 ℃, which is greatly reduced compared with the phase change temperature of pure polyethylene glycol 2000, and the melting enthalpy is as high as 77.6J/g, which indicates that the novel solid-solid phase change energy storage material prepared in the present invention can meet the temperature regulation requirement in the field of textile and clothing.