CN111423857A - Maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material and preparation method thereof - Google Patents
Maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material and a preparation method thereof. The phase-change material is prepared from the following raw materials in parts by weight: the phase-change material is prepared from the following raw materials in parts by weight: 1 to 5 parts of maleic anhydride copolymer, 5 to 20 parts of fatty acid, and 0.15 to 0.75 part of IIA group or IIB group metal oxide or hydroxide. The solid-solid phase change material has the melting enthalpy of 65-135J/g and the melting temperature of 18-70 ℃, has excellent thermal stability, cycle durability and shape retention capacity, and has a good application prospect in the textile and building industries. Meanwhile, the preparation method of the material is simple, the operation is simple and convenient, the post-treatment is not needed, the production cost is low, and the large-scale industrial production is easy to realize.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage, and particularly relates to a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material and a preparation method thereof.
Background
With the continuous progress of human society and the increasing energy demand, the existing fossil energy can not meet the requirements of people, and people begin to face an unprecedented energy crisis. Meanwhile, human beings generate a great deal of pollution in the process of developing and utilizing fossil energy, and a series of environmental problems are caused. Therefore, the development of a new energy source and the effective utilization of the existing energy source are always important directions for the development of the industry.
The phase-change material has received great attention because of constant temperature and repeated storage and release of heat energy in the phase-change process, and can be used for relieving energy crisis and environmental pollution as a heat energy storage material with potential application value. At present, phase change energy storage materials are widely applied in the fields of solar energy utilization, phase change energy storage type air conditioners, heat preservation clothes, energy storage cookers and the like. The phase-change material specifically comprises four phase-change materials of solid-gas, liquid-gas, solid-solid and solid-liquid. The volume change of the former two is large in the phase change process and gas is generated, so that the requirements of practical application are difficult to meet. The solid-liquid phase change material is a mature phase change energy storage material, but the solid-liquid phase change material is easy to leak in the phase change process, has the hidden trouble of polluting the surrounding environment, and greatly limits the practical application range. The solid-solid phase change material has the advantages of no liquid or gas generation, stable shape, less possibility of leakage and the like in the using process, and is receiving more and more attention. Currently, the solid-solid phase change material preparation methods mainly include physical methods and chemical methods. The solid-solid phase change material prepared by a physical method greatly reduces the mechanical property of the material, is easy to age and leak, pollutes the environment and limits the application range of the material. The solid-solid phase change material synthesized by the chemical method can keep the macroscopic shape stable in the phase change process, can realize the regulation and control of the phase change temperature and the phase change enthalpy by controlling the reaction conditions, and has wide application prospect. However, the solid-solid phase change materials prepared by the chemical method still face a plurality of problems to be solved.
Chinese patent (CN104356306) discloses a comb-like polymer phase-change energy storage material obtained by taking polyethylene grafted maleic anhydride as a supporting skeleton, and taking alcohol with a hydroxyl active group at the end group, ether with a hydroxyl active group at the end group or mercaptan with a mercapto active group at the end group as a phase-change material through a grafting reaction. The method has complex preparation process, needs a large amount of solvents such as benzene, toluene and the like, is not beneficial to environmental protection, and has low grafting efficiency of the phase-change material. Chinese patent (CN108456948) discloses a heat storage and temperature regulation fiber with a skin-core structure, which takes comb-shaped high-molecular phase change material poly (styrene-co-maleic anhydride) -g-n-alkanol as a core layer and takes fiber-forming polymer as a skin layer. The preparation process of the heat-storage temperature-regulating fiber relates to the reaction of grafting two kinds of n-alkanol with different carbon atoms by poly (styrene-co-maleic anhydride), and has the disadvantages of complex process and low heat absorption capacity. Chinese patent (CN108265348) discloses a heat storage and temperature regulation fiber with a skin-core structure, which takes comb-shaped high-molecular phase change material poly (ethylene-g-maleic anhydride) -g-n-alkanol as a core layer and takes fiber-forming polymer as a skin layer. Also, the preparation process of the heat-storage temperature-regulating fiber involves the reaction of grafting two kinds of normal alkanol with different carbon atoms by poly (ethylene-g-maleic anhydride), the process is complex, and the grafting rate of the normal alkanol is low. Therefore, the preparation processes of the various solid-solid phase change materials all involve complex chemical reactions, various toxic and harmful reaction solvents are required, the environment is not protected, and the prepared solid-solid phase change materials have low phase change enthalpy.
Disclosure of Invention
In view of the problems in the background art, the present invention is directed to a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material and a method for preparing the same. The solid-solid phase change material with a mutual crosslinking framework structure is prepared by taking maleic anhydride copolymer as a framework supporting structure, taking fatty acid as a phase change material and taking metal oxide or hydroxide of IIA group or IIB group as an active crosslinking center. The method has the advantages of simple preparation process, no participation of reaction solvent, high phase change enthalpy value of the prepared solid-solid phase change material, strong shape retention capacity and good application prospect.
In order to achieve the purpose, the invention provides the following technical scheme:
the maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material is prepared from the following raw materials in parts by weight: 1 to 5 parts of maleic anhydride copolymer, 5 to 20 parts of fatty acid, and 0.15 to 0.75 part of IIA group or IIB group metal oxide or hydroxide.
As a preferable mode, the maleic anhydride copolymer is selected from any one of polymaleic anhydride-alt-1-octadecene, isobutylene-maleic anhydride copolymer, maleic anhydride-acrylic acid copolymer, polyisoprene-graft-maleic anhydride, polypropylene-graft-maleic anhydride, polyethylene-alt-maleic anhydride, polymethylvinylether maleic anhydride, and polystyrene-co-maleic anhydride.
As a preferable mode, the fatty acid is any one or a mixture of two or more of capric acid, lauric acid, myristic acid, palmitic acid and stearic acid.
As a preferred embodiment, the group IIA or IIB metal oxide or hydroxide is selected from MgO, Mg (OH)2、CaO、Ca(OH)2、ZnO、Zn(OH)2Any one of the above.
A method of making a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material as described above, the method comprising the steps of:
step (1): respectively weighing the maleic anhydride copolymer and the fatty acid in corresponding parts by weight, placing the maleic anhydride copolymer and the fatty acid in a stainless steel container, and heating and stirring the maleic anhydride copolymer and the fatty acid to enable the maleic anhydride copolymer and the fatty acid to be melted and mixed uniformly to obtain a melted mixture;
step (2): adding corresponding parts by weight of IIA group or IIB group metal oxide or hydroxide into the molten mixture obtained in the step (1), heating, and continuously mechanically stirring until the color of the molten mixture is changed from white to yellow; the final temperature of heating is 120-150 ℃;
and (3): and (3) pouring the molten blend obtained in the step (2) into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
Preferably, in the step (1), the heating temperature is 70 to 110 ℃.
As a preferable mode, in the step (1), the mixture is heated and stirred for 30 minutes.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method utilizes IIA group or IIB group metal oxide or hydroxide as a crosslinking center, and firstly performs acid-base reaction with carboxyl in fatty acid to generate basic salt; then, the basic salt or the copolymer of the basic salt and maleic anhydride and the fatty acid are further dehydrated to generate crosslinking; meanwhile, metal ions in the basic salt can be coordinated with oxygen atoms on carbonyl groups in the maleic anhydride copolymer and the fatty acid to generate further crosslinking, and finally the solid-solid phase change material with a firm mutual crosslinking network structure is formed, so that the problem of leakage of the fatty acid in a molten state is solved.
(2) The solid-solid phase change material prepared by the method has the melting enthalpy of 65-135J/g and the melting temperature of 18-70 ℃, and has a good application prospect in the textile and building industries.
(3) The solid-solid phase change material prepared by the invention has excellent thermal stability and shape retention capability.
(4) The solid-solid phase change material prepared by the invention has excellent cycle durability.
(5) The preparation method is simple, simple and convenient to operate, free of solvent participation, environment-friendly, low in production cost and easy for large-scale industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the solid-solid phase change material of example 1 (FIG. 1a) and example 3 (FIG. 1 b);
FIG. 2 is a DSC curve of the solid-solid phase change material of example 3;
FIG. 3 is a DSC curve of the solid-solid phase change material of example 3 after 200 cycles without cycles;
FIG. 4 is a thermogravimetric analysis curve of the solid-solid phase change material and palmitic acid of example 3.
Detailed Description
The following examples are given to illustrate specific embodiments of the present invention in detail. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The melting enthalpy value test method of the maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material comprises the following steps: a differential scanning calorimeter DSC2500 of American TA company is adopted, the test temperature range is-70-100 ℃, the temperature rise and temperature drop rate is 10 ℃/min in a nitrogen atmosphere.
Example 1
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed uniformly, 0.15g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 131.1J/g and a melting temperature of 63.5 ℃ through DSC test; the enthalpy of crystallization was 128.8J/g and the crystallization temperature was 53.4 ℃.
Example 2
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed uniformly, 0.35g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 106.7J/g and a melting temperature of 62.0 ℃ through DSC test; the enthalpy of crystallization was 101.7J/g and the crystallization temperature was 54.3 ℃.
Example 3
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 104.5J/g and a melting temperature of 62.0 ℃ through DSC test; the enthalpy of crystallization was 104.0J/g and the crystallization temperature was 55.0 ℃.
Fig. 1 is a scanning electron micrograph of the solid-solid phase change material in example 1 (fig. 1a) and example 3 (fig. 1b), which illustrates that as the amount of MgO incorporated increases, the degree of crosslinking increases and the inter-crosslinked network structure in the solid-solid phase change material becomes more and more dense, which is more favorable for the solid-solid phase change material to maintain a stable shape during use.
FIG. 2 is a DSC curve of the solid-solid phase change material of example 3.
Fig. 3 is a DSC curve of the solid-solid phase change material of example 3 after 200 cycles without cycling, which illustrates that the prepared solid-solid phase change material still has higher heat storage density and excellent cycling durability after 200 cycles.
FIG. 4 is a thermogravimetric analysis plot of the solid-solid phase change material with palmitic acid of example 3, illustrating that the prepared solid-solid phase change material has better thermal stability than palmitic acid.
Example 4
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed uniformly, 0.75g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 99.8J/g and a melting temperature of 63.7 ℃ through DSC test; the enthalpy of crystallization was 97.7J/g and the crystallization temperature was 54.1 ℃.
Example 5
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 20g of capric acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the capric acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 98.4J/g and a melting temperature of 30.8 ℃ through DSC test; the enthalpy of crystallization was 95.4J/g and the crystallization temperature was 21.7 ℃.
Example 6
First, 5g of poly (maleic anhydride-alt-1-octadecene) and 5g of lauric acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the lauric acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 66.5J/g and a melting temperature of 39.4 ℃ through DSC test; the enthalpy of crystallization was 62.1J/g and the crystallization temperature was 30.3 ℃.
Example 7
First, 3g of poly (maleic anhydride-alt-1-octadecene) and 13g of myristic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and myristic acid were mixed well, 0.55g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 102.3J/g and a melting temperature of 50.2 ℃ through DSC test; the enthalpy of crystallization was 97.9J/g and the crystallization temperature was 38.9 ℃.
Example 8
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of stearic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and stearic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 108.4J/g and a melting temperature of 58.9 ℃ through DSC test; the enthalpy of crystallization was 107.6J/g and the crystallization temperature was 49.1 ℃.
Example 9
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed well, 0.55g of Mg (OH) was added2The temperature is increased to 135 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 105.0J/g and a melting temperature of 61.4 ℃ through DSC test; the enthalpy of crystallization was 102.7J/g and the crystallization temperature was 55.4 ℃.
Example 10
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the palmitic acid are mixed uniformly, 0.55g of CaO is added, the temperature is raised to 150 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 105.8J/g and a melting temperature of 61.7 ℃ through DSC test; the enthalpy of crystallization was 104.6J/g and the crystallization temperature was 55.1 ℃.
Example 11
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 70 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed well, 0.55g of Ca (OH) was added2The temperature is increased to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 101.4J/g and a melting temperature of 62.4 ℃ through DSC test; the enthalpy of crystallization was 102.1J/g and the crystallization temperature was 56.2 ℃.
Example 12
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 90 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed uniformly, 0.55g of ZnO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 103.5J/g and a melting temperature of 63.2 ℃ through DSC test; the enthalpy of crystallization was 102.5J/g and the crystallization temperature was 55.8 ℃.
Example 13
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 9.5g of palmitic acid were heated to a molten state at 110 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and palmitic acid were mixed well, 0.55g of Zn (OH) was added2The temperature is increased to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 98.9J/g and a melting temperature of 62.6 ℃ through DSC test; the enthalpy of crystallization was 97.3J/g and the crystallization temperature was 55.4 ℃.
Example 14
First, 1.5g of an isobutylene-maleic anhydride copolymer and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polyisobutylene-maleic anhydride copolymer and palmitic acid were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and stirring was continued until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 104.6J/g and a melting temperature of 64.1 ℃ through DSC test; the enthalpy of crystallization was 103.1J/g and the crystallization temperature was 56.2 ℃.
Example 15
First, 1.5g of maleic anhydride-acrylic acid copolymer and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polymaleic anhydride-acrylic acid copolymer and the palmitic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 94.1J/g and a melting temperature of 61.2 ℃ through DSC test; the enthalpy of crystallization was 91.2J/g and the crystallization temperature was 54.4 ℃.
Example 16
First, 1.5g of polyisoprene-graft-maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polyisoprene-graft-maleic anhydride and the palmitic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 101.9J/g and a melting temperature of 63.4 ℃ through DSC test; the enthalpy of crystallization was 98.9J/g and the crystallization temperature was 55.9 ℃.
Example 17
First, 1.5g of polypropylene-graft-maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polypropylene-graft-maleic anhydride and the palmitic acid are uniformly mixed, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 105.4J/g and a melting temperature of 64.5 ℃ through DSC test; the enthalpy of crystallization was 103.9J/g and the crystallization temperature was 54.8 ℃.
Example 18
First, 1.5g of polyethylene-graft-maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polyethylene-graft-maleic anhydride and the palmitic acid are uniformly mixed, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 103.3J/g and a melting temperature of 64.2 ℃ through DSC test; the enthalpy of crystallization was 103.5J/g and the crystallization temperature was 55.3 ℃.
Example 19
First, 1.5g of polyethylene-alt-maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polyethylene-alt-maleic anhydride and the palmitic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 102.1J/g and a melting temperature of 64.9 ℃ through DSC test; the enthalpy of crystallization was 103.1J/g and the crystallization temperature was 55.9 ℃.
Example 20
First, 1.5g of polymethyl vinyl ether maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polymethyl vinyl ether maleic anhydride and the palmitic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 98.7J/g and a melting temperature of 64.3 ℃ through DSC test; the enthalpy of crystallization was 100.2J/g and the crystallization temperature was 55.3 ℃.
Example 21
First, 1.5g of polystyrene-co-maleic anhydride and 9.5g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the polystyrene-co-maleic anhydride and the palmitic acid are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture changes from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 95.6J/g and a melting temperature of 63.6 ℃ through DSC test; the enthalpy of crystallization was 92.5J/g and the crystallization temperature was 54.7 ℃.
Example 22
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 7.77g of lauric acid and 3.33g of stearic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 109.2J/g and a melting temperature of 27.8 ℃ through DSC test; the enthalpy of crystallization was 107.4J/g and the crystallization temperature was 17.9 ℃.
Example 23
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 6.70g of n-decanoic acid and 3.30g of lauric acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 89.7J/g and a melting temperature of 20.7 ℃ through DSC test; the enthalpy of crystallization was 83.6J/g and the crystallization temperature was 18.5 ℃.
Example 24
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 7.30g of n-decanoic acid and 2.80g of myristic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 72.7J/g and a melting temperature of 23.1 ℃ through DSC test; the enthalpy of crystallization was 68.9J/g and the crystallization temperature was 22.6 ℃.
Example 25
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 7.30g of n-decanoic acid and 2.80g of myristic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 72.7J/g and a melting temperature of 23.1 ℃ through DSC test; the enthalpy of crystallization was 68.9J/g and the crystallization temperature was 22.6 ℃.
Example 26
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 7.70g of n-decanoic acid and 2.30g of stearic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 63.2J/g and a melting temperature of 24.4 ℃ through DSC test; the enthalpy of crystallization was 61.2J/g and the crystallization temperature was 22.3 ℃.
Example 27
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) was heated to a molten state with 5.80g of lauric acid and 4.2g of myristic acid at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the two fatty acids were mixed uniformly, 0.55g of MgO was added, the temperature was raised to 120 ℃ and the mixture was stirred until the color of the mixture changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 91.6J/g and a melting temperature of 32.6 ℃ through DSC test; the enthalpy of crystallization was 90.7J/g and the crystallization temperature was 30.7 ℃.
Example 28
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 2.0g of myristic acid and 8.0g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the three fatty acids are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 96.7J/g and a melting temperature of 53.8 ℃ through DSC test; the enthalpy of crystallization was 93.4J/g and the crystallization temperature was 50.9 ℃.
Example 29
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 6.84g of lauric acid, 2.71g of palmitic acid and 1.45g of stearic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the three fatty acids are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 68.9J/g and a melting temperature of 29.5 ℃ through DSC test; the enthalpy of crystallization was 66.3J/g and the crystallization temperature was 27.7 ℃.
Example 30
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) and 5.52g of lauric acid, 2.97g of myristic acid and 1.51g of palmitic acid were heated to a molten state at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the three fatty acids are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 81.5J/g and a melting temperature of 29.8 ℃ through DSC test; the enthalpy of crystallization was 80.7J/g and the crystallization temperature was 27.7 ℃.
Example 31
First, 1.5g of poly (maleic anhydride-alt-1-octadecene) was heated to a molten state with 5.22g of myristic acid, 2.94g of palmitic acid and 1.84g of stearic acid at 100 ℃ and mechanically stirred for 30 minutes. After the poly (maleic anhydride-alt-1-octadecene) and the three fatty acids are mixed uniformly, 0.55g of MgO is added, the temperature is raised to 120 ℃, and the mixture is continuously stirred until the color of the mixture is changed from white to yellow. And finally, pouring the yellow molten mixture into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
The solid-solid phase change material obtained in the embodiment has a phase melting enthalpy of 82.3J/g and a melting temperature of 40.1 ℃ through DSC test; the enthalpy of crystallization was 77.4J/g and the crystallization temperature was 38.3 ℃.
Claims (7)
1. The maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material is characterized by being prepared from the following raw materials in parts by weight: 1 to 5 parts of maleic anhydride copolymer, 5 to 20 parts of fatty acid, and 0.15 to 0.75 part of IIA group or IIB group metal oxide or hydroxide.
2. The maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material of claim 1, wherein the maleic anhydride copolymer is selected from any one of polymaleic anhydride-alt-1-octadecene, isobutylene-maleic anhydride copolymer, maleic anhydride-acrylic acid copolymer, polyisoprene-graft-maleic anhydride, polypropylene-graft-maleic anhydride, polyethylene-alt-maleic anhydride, polymethylvinylether maleic anhydride, polystyrene-co-maleic anhydride.
3. The maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material according to claim 1, wherein the fatty acid is any one or a mixture of two or more selected from capric acid, lauric acid, myristic acid, palmitic acid and stearic acid.
4. The maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material of claim 1, wherein the group IIA or IIB metal oxide or hydroxide is selected from MgO, Mg (OH)2、CaO、Ca(OH)2、ZnO、Zn(OH)2Any one of the above.
5. A method for preparing a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material according to any of claims 1 to 4, comprising the steps of:
step (1): respectively weighing the maleic anhydride copolymer and the fatty acid in corresponding parts by weight, placing the maleic anhydride copolymer and the fatty acid in a stainless steel container, and heating and stirring the maleic anhydride copolymer and the fatty acid to enable the maleic anhydride copolymer and the fatty acid to be melted and mixed uniformly to obtain a melted mixture;
step (2): adding corresponding parts by weight of IIA group or IIB group metal oxide or hydroxide into the molten mixture obtained in the step (1), heating, and continuously mechanically stirring until the color of the molten mixture is changed from white to yellow; the final temperature of heating is 120-150 ℃;
and (3): and (3) pouring the molten blend obtained in the step (2) into a stainless steel mold, and cooling to room temperature to obtain the solid-solid phase change material.
6. The method for preparing a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material according to claim 5, wherein the heating temperature in step (1) is 70 to 110 ℃.
7. The method for preparing a maleic anhydride copolymer/fatty acid crosslinked solid-solid phase change material according to claim 5, wherein in the step (1), the mixture is heated and stirred for 30 minutes.
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| CN101519581A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院化学研究所 | Phase change energy storage material and preparation method thereof |
| CN104356306A (en) * | 2014-11-12 | 2015-02-18 | 天津工业大学 | Preparation method of comb-shaped polymer phase change energy storage material |
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| CN108102614A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of organic composite shaping phase-change material and preparation method thereof |
| CN108102613A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of anti-mildew organic composite shaping phase-change material and preparation method thereof |
| CN108285502A (en) * | 2018-02-02 | 2018-07-17 | 天津工业大学 | The preparation method of comb-type polymer phase change energy storage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101519581A (en) * | 2008-02-29 | 2009-09-02 | 中国科学院化学研究所 | Phase change energy storage material and preparation method thereof |
| CN104356306A (en) * | 2014-11-12 | 2015-02-18 | 天津工业大学 | Preparation method of comb-shaped polymer phase change energy storage material |
| CN108048045A (en) * | 2017-11-28 | 2018-05-18 | 大连理工大学 | A kind of enhanced thermal conduction organic composite shaping phase-change material and preparation method thereof |
| CN108102614A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of organic composite shaping phase-change material and preparation method thereof |
| CN108102613A (en) * | 2017-11-28 | 2018-06-01 | 大连理工大学 | A kind of anti-mildew organic composite shaping phase-change material and preparation method thereof |
| CN108285502A (en) * | 2018-02-02 | 2018-07-17 | 天津工业大学 | The preparation method of comb-type polymer phase change energy storage |
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