技术领域technical field
本发明涉及相变材料技术领域，尤其涉及一种相变材料及其制备方法。The invention relates to the technical field of phase change materials, in particular to a phase change material and a preparation method thereof.
背景技术Background technique
相变材料(Phase Change Materials，简称：PCMs)是指随温度变化而改变物质状态并能提供潜热的物质。材料转变物理性质的过程称为相变过程，在特定的温度变化范围内，材料的相态发生转变，会对环境自动的吸收或者放出大量的潜热，环境温度就会随着变化。随着外界环境温度的升高，相变储能材料的相态发生变化时，可以从环境中吸收大量的热量使得环境温度恒定；外界环境开始降温后，材料可以放出热量，使得环境温度可以维持在稳定的状态，从而材料可以恢复到最初的相态结构。Phase change materials (PCMs for short) refer to substances that change the state of matter and provide latent heat as the temperature changes. The process of changing the physical properties of materials is called the phase change process. Within a specific temperature range, the phase state of the material changes, and it will automatically absorb or release a large amount of latent heat to the environment, and the ambient temperature will change accordingly. As the temperature of the external environment increases, when the phase state of the phase change energy storage material changes, it can absorb a large amount of heat from the environment to keep the ambient temperature constant; when the external environment begins to cool down, the material can release heat so that the ambient temperature can be maintained. In a stable state, the material can return to its original phase structure.
传统的相变材料一般多为固-液类相变材料，固-液类相变材料在相变的过程中会出现液体泄漏现象，因此需要找到合适的容器进行封装。而固-固类相变储能材料在相变过程中的塑晶现象比较明显，且使用时温度高，也需适宜的封装处理。然而，封装结构的设置无形中增加了操作难度和生产成本，使其在日常中的应用受到了限制。Traditional phase change materials are generally solid-liquid phase change materials, and solid-liquid phase change materials will leak liquid during the phase change process, so it is necessary to find a suitable container for packaging. However, solid-solid phase change energy storage materials have obvious plastic crystal phenomenon during the phase change process, and the temperature is high when used, and appropriate packaging treatment is also required. However, the setting of the packaging structure virtually increases the difficulty of operation and production cost, which limits its application in daily life.
发明内容Contents of the invention
本发明的目的在于提供一种相变材料及其制备方法，本发明提供的相变材料为固-固相变材料，在使用时无需任何的封装结构进行封装，操作简单、节约成本。The object of the present invention is to provide a phase change material and a preparation method thereof. The phase change material provided by the present invention is a solid-solid phase change material, which does not need any packaging structure for packaging during use, and is easy to operate and cost-saving.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种相变材料的制备方法，包含如下步骤：The invention provides a preparation method of a phase change material, comprising the following steps:
将羧甲基纤维素钠和氯化锂在第一有机溶剂条件下进行溶解，得到溶解体系；dissolving sodium carboxymethylcellulose and lithium chloride in the first organic solvent to obtain a dissolved system;
将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物与所述溶解体系进行反应，得到月桂酸羧甲基纤维素酯；reacting a mixture comprising lauric acid, p-toluenesulfonyl chloride and a second organic solvent with the dissolving system to obtain carboxymethyl cellulose laurate;
将所述月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到相变材料。Composite the carboxymethyl cellulose laurate and polylactic acid to obtain a phase change material.
优选的，所述羧甲基纤维素钠和氯化锂的质量比为(1.5～2):(6～7)；Preferably, the mass ratio of the sodium carboxymethylcellulose and lithium chloride is (1.5～2):(6～7);
所述羧甲基纤维素钠的质量和第一有机溶剂的体积之比为 (1.5～2)g:(70～80)mL。The ratio of the quality of the sodium carboxymethyl cellulose to the volume of the first organic solvent is (1.5～2)g:(70～80)mL.
优选的，所述溶解的时间为8～13小时。Preferably, the dissolution time is 8-13 hours.
优选的，所述月桂酸和对甲苯磺酰氯的质量比为(3～4):(3～4)；Preferably, the mass ratio of said lauric acid and p-toluenesulfonyl chloride is (3～4):(3～4);
所述羧甲基纤维素钠的重复单元和月桂酸的摩尔比为1:(2～2.5)；The repeating unit of the sodium carboxymethylcellulose and the mol ratio of lauric acid are 1:(2～2.5);
所述月桂酸的质量和第二有机溶剂的体积之比为(3～4)g:(25～35)mL。The ratio of the mass of the lauric acid to the volume of the second organic solvent is (3-4) g:(25-35) mL.
优选的，所述反应的温度为75～85℃，反应时间为25～35小时。Preferably, the reaction temperature is 75-85°C, and the reaction time is 25-35 hours.
优选的，所述第一有机溶剂和第二有机溶剂独立的为N,N-二甲基乙酰胺或N-甲基吗啉氧化物，Preferably, the first organic solvent and the second organic solvent are independently N,N-dimethylacetamide or N-methylmorpholine oxide,
或多聚甲醛和二甲基亚砜的混合物，or a mixture of paraformaldehyde and dimethylsulfoxide,
或四氧化二氮和二甲基亚砜的混合物，or a mixture of dinitrogen tetroxide and dimethyl sulfoxide,
或二甲基亚砜和四乙基氯化铵的混合物，or a mixture of dimethylsulfoxide and tetraethylammonium chloride,
或氨和硫氰酸铵的混合物。Or a mixture of ammonia and ammonium thiocyanate.
优选的，所述月桂酸羧甲基纤维素酯和聚乳酸的质量比为(0,15]:[85,100)。Preferably, the mass ratio of carboxymethyl cellulose laurate to polylactic acid is (0,15]:[85,100).
优选的，所述复合的温度为75～85℃，时间为25～35小时。Preferably, the compounding temperature is 75-85° C., and the time is 25-35 hours.
本发明还提供了一种上述技术方案任意一项所述的制备方法得到的相变材料，以聚乳酸作为基体，以月桂酸羧甲基纤维素酯为相变剂，所述月桂酸羧甲基纤维素酯和聚乳酸的质量比为(0,15]:[85,100)。The present invention also provides a phase change material obtained by the preparation method described in any one of the above technical solutions, using polylactic acid as a matrix, and carboxymethyl cellulose laurate as a phase change agent, and the carboxymethyl laurate The mass ratio of base cellulose ester to polylactic acid is (0,15]:[85,100).
本发明提供了一种相变材料。本发明将对甲苯磺酰氯作为共反应剂，先与月桂酸反应得到更高反应活性的混合酸酐中间产物，中间产物再与羧甲基纤维素反应生成月桂酸羧甲基纤维素酯，然后将月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到定型相变材料。根据实施例的实验结果可知，本发明提供的相变材料以月桂酸羧甲基纤维素酯作为相变剂，以聚乳酸作为基体，在相变过程中一直保持固态，无液体泄漏。The invention provides a phase change material. The present invention uses p-toluenesulfonyl chloride as a co-reactant, first reacts with lauric acid to obtain a higher reactivity mixed anhydride intermediate product, then reacts the intermediate product with carboxymethyl cellulose to generate carboxymethyl cellulose laurate, and then Carboxymethyl cellulose laurate is compounded with polylactic acid to obtain a shaped phase change material. According to the experimental results of the examples, it can be seen that the phase change material provided by the present invention uses carboxymethyl cellulose laurate as a phase change agent and polylactic acid as a matrix, and keeps solid during the phase change process without liquid leakage.
本本发明还提供了一种相变材料的制备方法，将羧甲基纤维素钠和氯化锂在第一有机溶剂条件下进行溶解，得到溶解体系；将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物与所述溶解体系进行反应，得到月桂酸羧甲基纤维素酯；将所述月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到相变材料。本发明提供的制备方法，操作简单，易于实行。The present invention also provides a preparation method of a phase change material, dissolving sodium carboxymethyl cellulose and lithium chloride under the condition of the first organic solvent to obtain a dissolved system; comprising lauric acid, p-toluenesulfonyl chloride and the The mixture of two organic solvents is reacted with the dissolving system to obtain carboxymethyl cellulose laurate; the compound of carboxymethyl cellulose laurate and polylactic acid is compounded to obtain a phase change material. The preparation method provided by the invention is simple in operation and easy to implement.
附图说明Description of drawings
图1为本发明制备相变材料的过程示意图；Fig. 1 is the schematic diagram of the process of preparing phase change material of the present invention;
图2为本发明实施例1中CMC及LACCE的FTIR谱图；Fig. 2 is the FTIR spectrogram of CMC and LACCE in the embodiment of the present invention 1;
图3为本发明实施例1中LACCE的核磁氢谱；Fig. 3 is the proton nuclear magnetic spectrum of LACCE in the embodiment 1 of the present invention;
图4为本发明实施例1中CMC的XRD谱图；Fig. 4 is the XRD spectrogram of CMC in the embodiment of the present invention 1;
图5为本发明实施例1中LACCE的XRD谱图；Fig. 5 is the XRD spectrogram of LACCE in the embodiment 1 of the present invention;
图6为本发明实施例1中CMC的断裂面SEM图；Fig. 6 is the fracture surface SEM figure of CMC in the embodiment 1 of the present invention;
图7为本发明实施例1中LACCE的断裂面SEM图；Fig. 7 is the fracture surface SEM figure of LACCE in the embodiment 1 of the present invention;
图8为本发明实施例1中PLA的断裂面SEM图；Fig. 8 is the SEM diagram of the fracture surface of PLA in Example 1 of the present invention;
图9为本发明实施例1中LACCE-PLA的断裂面SEM图；Fig. 9 is the fracture surface SEM figure of LACCE-PLA in the embodiment 1 of the present invention;
图10为本发明实施例2中LACCE-PLA的力学性能数据图；Fig. 10 is the mechanical property data figure of LACCE-PLA in the embodiment 2 of the present invention;
图11为本发明实施例3中LACCE循环前后的DSC曲线；Fig. 11 is the DSC curve before and after the LACCE cycle in the embodiment of the present invention 3;
图12为本发明实施例3中LACCE-PLA循环前后的DSC曲线；Fig. 12 is the DSC curve before and after LACCE-PLA cycle in the embodiment of the present invention 3;
图13为本发明实施例4中材料的TG曲线；Fig. 13 is the TG curve of the material in the embodiment of the present invention 4;
图14为本发明实施例4中材料的DTG曲线；Fig. 14 is the DTG curve of the material in the embodiment of the present invention 4;
图15为本发明实施例5中相变前相变材料的状态；Figure 15 is the state of the phase change material before the phase change in Example 5 of the present invention;
图16为本发明实施例5中相变后相变材料的状态。Fig. 16 is the state of the phase change material after the phase change in Example 5 of the present invention.
具体实施方式Detailed ways
本发明提供了一种相变材料的制备方法，包含如下步骤：The invention provides a preparation method of a phase change material, comprising the following steps:
将羧甲基纤维素钠和氯化锂在第一有机溶剂条件下进行溶解，得到溶解体系；dissolving sodium carboxymethylcellulose and lithium chloride in the first organic solvent to obtain a dissolved system;
将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物与所述溶解体系进行反应，得到月桂酸羧甲基纤维素酯；reacting a mixture comprising lauric acid, p-toluenesulfonyl chloride and a second organic solvent with the dissolving system to obtain carboxymethyl cellulose laurate;
将所述月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到相变材料。Composite the carboxymethyl cellulose laurate and polylactic acid to obtain a phase change material.
本发明将羧甲基纤维素钠和氯化锂在第一有机溶剂条件下进行溶解，得到溶解体系。在本发明中，所述羧甲基纤维素钠和氯化锂具体的为本领域技术人员所熟知的市售的羧甲基纤维素钠和氯化锂。在本发明中，所述第一有机溶剂优选为N,N-二甲基乙酰胺或N-甲基吗啉氧化物，或多聚甲醛和二甲基亚砜的混合物，或四氧化二氮和二甲基亚砜的混合物，或二甲基亚砜和四乙基氯化铵的混合物，或氨和硫氰酸铵的混合物。在本发明中，当所述第一有机溶剂优选为两种物质的混合物时，两种组分的质量优选相等。In the present invention, sodium carboxymethyl cellulose and lithium chloride are dissolved under the condition of the first organic solvent to obtain a dissolution system. In the present invention, the sodium carboxymethylcellulose and lithium chloride are specifically commercially available sodium carboxymethylcellulose and lithium chloride well known to those skilled in the art. In the present invention, the first organic solvent is preferably N,N-dimethylacetamide or N-methylmorpholine oxide, or a mixture of paraformaldehyde and dimethyl sulfoxide, or dinitrogen tetroxide and dimethyl sulfoxide, or a mixture of dimethyl sulfoxide and tetraethylammonium chloride, or a mixture of ammonia and ammonium thiocyanate. In the present invention, when the first organic solvent is preferably a mixture of two substances, the masses of the two components are preferably equal.
本发明对所述羧甲基纤维素钠、氯化锂和第一有机溶剂的混合方式没有任何的特殊要求，三者可以按照任意的顺序进行混合。The present invention does not have any special requirements on the mixing method of the sodium carboxymethyl cellulose, lithium chloride and the first organic solvent, and the three can be mixed in any order.
本发明优选先将羧甲基纤维素钠溶于第一有机溶剂中，然后再与氯化锂混合。本发明优选对上述方案得到的羧甲基纤维素钠的第一有机溶剂溶液进行回流处理。在本发明中，所述回流的温度与具体选择的第一有机溶剂的种类相关，不同种类的第一有机溶剂有其相应的回流温度，所设置的回流温度能够满足回流条件即可。在本发明中，当所述第一有机溶剂为N,N-二甲基乙酰胺时，所述回流的温度优选为150～170℃，更优选为155～165℃，最优选为 160℃。在本发明中，所述回流的时间优选为1～5小时，具体的可以为1小时、 2小时、3小时、4小时或5小时。在本发明中，所述回流能够避免羧甲基纤维素钠损耗，充分利用羧甲基纤维素钠组分。The present invention preferably dissolves sodium carboxymethyl cellulose in the first organic solvent, and then mixes it with lithium chloride. The present invention preferably carries out reflux treatment to the first organic solvent solution of sodium carboxymethylcellulose obtained by the above scheme. In the present invention, the reflux temperature is related to the type of first organic solvent selected specifically, different types of first organic solvents have their corresponding reflux temperatures, and the set reflux temperature only needs to meet the reflux conditions. In the present invention, when the first organic solvent is N,N-dimethylacetamide, the reflux temperature is preferably 150-170°C, more preferably 155-165°C, most preferably 160°C. In the present invention, the reflux time is preferably 1-5 hours, specifically 1 hour, 2 hours, 3 hours, 4 hours or 5 hours. In the present invention, the reflux can avoid the loss of sodium carboxymethyl cellulose and make full use of the sodium carboxymethyl cellulose component.
本发明优选在所述回流结束后，将所述回流体系的温度降至95～105℃，更优选降至98～103℃，最优选降至100℃。本发明优选将氯化锂加入到上述降温后的回流体系中。In the present invention, preferably after the reflux is completed, the temperature of the reflux system is reduced to 95-105°C, more preferably to 98-103°C, most preferably to 100°C. In the present invention, lithium chloride is preferably added to the above-mentioned reflux system after cooling.
在本发明中，所述羧甲基纤维素钠和氯化锂的质量比优选为 (1.5～2):(6～7)，更优选为(1.6～1.9):(6.2～6.8)，最优选为1.8:6.5；所述羧甲基纤维素钠的质量和第一有机溶剂的体积之比优选为(1.5～2)g:(70～80)mL，更优选为(1.6～1.8)g:(72～78)mL，最优选为1.7g:(74～76)mL。In the present invention, the mass ratio of sodium carboxymethylcellulose to lithium chloride is preferably (1.5～2):(6～7), more preferably (1.6～1.9):(6.2～6.8), most preferably Preferably 1.8:6.5; the ratio of the quality of the sodium carboxymethylcellulose to the volume of the first organic solvent is preferably (1.5～2)g:(70～80)mL, more preferably (1.6～1.8)g : (72～78) mL, most preferably 1.7g: (74～76) mL.
在本发明中，所述溶解优选在室温下进行；所述溶解的时间优选为8～13 小时，具体的可以为8小时、9小时、10小时、11小时、12小时或13小时。在本发明中，所述氯化锂和第一有机溶剂是溶解羧甲基纤维素钠(CMC)的溶剂体系，LiCl还是亲核离子，能够打开CMC分子内和分子间的氢键。In the present invention, the dissolution is preferably carried out at room temperature; the dissolution time is preferably 8-13 hours, specifically 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or 13 hours. In the present invention, the lithium chloride and the first organic solvent are solvent systems for dissolving sodium carboxymethylcellulose (CMC), and LiCl is also a nucleophilic ion capable of opening hydrogen bonds within and between molecules of CMC.
得到所述溶解体系后，本发明将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物与所述溶解体系进行反应，得到月桂酸羧甲基纤维素酯。在本发明中，所述月桂酸和对甲苯磺酰氯具体的为本领域技术人员所熟知的市售的月桂酸和对甲苯磺酰氯。在本发明中，所述第二有机溶剂独立的与所述第一有机溶剂的要求相同，在此不再进行赘述。After the dissolution system is obtained, the present invention reacts the mixture comprising lauric acid, p-toluenesulfonyl chloride and a second organic solvent with the dissolution system to obtain carboxymethylcellulose laurate. In the present invention, the lauric acid and p-toluenesulfonyl chloride are specifically commercially available lauric acid and p-toluenesulfonyl chloride well known to those skilled in the art. In the present invention, the requirements of the second organic solvent are independently the same as those of the first organic solvent, which will not be repeated here.
本发明对所述月桂酸、对甲苯磺酰氯和第二有机溶剂的混合顺序没有任何的特殊要求，三者可以按照任意的顺序进行混合。本发明优选将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物加入到所述溶解体系中进行反应。The present invention has no special requirement on the mixing order of the lauric acid, p-toluenesulfonyl chloride and the second organic solvent, and the three can be mixed in any order. In the present invention, preferably, a mixture comprising lauric acid, p-toluenesulfonyl chloride and a second organic solvent is added to the dissolution system for reaction.
在本发明中，所述月桂酸和对甲苯磺酰氯的质量比优选为(3～4):(3～4)，更优选为(3.2～3.8):(3～4)，最优选为3.5:(3.4～3.6)；所述羧甲基纤维素钠的重复单元和月桂酸的摩尔比优选为1:(2～2.5)，更优选为1:(2.1～2.4)，最优选为 1:(2.2～2.3)；所述月桂酸的质量和第二有机溶剂的体积之比优选为 (3～4)g:(25～35)mL，更优选为(3.2～3.8)g:(28～33)mL，最优选为(3.4～3.6)g:30mL。In the present invention, the mass ratio of said lauric acid to p-toluenesulfonyl chloride is preferably (3～4):(3～4), more preferably (3.2～3.8):(3～4), most preferably 3.5 :(3.4～3.6); The repeating unit of the sodium carboxymethylcellulose and the mol ratio of lauric acid are preferably 1:(2～2.5), more preferably 1:(2.1～2.4), most preferably 1: (2.2～2.3); The ratio of the quality of described lauric acid and the volume of the second organic solvent is preferably (3～4) g:(25～35) mL, more preferably (3.2～3.8) g:(28～ 33) mL, most preferably (3.4-3.6) g: 30 mL.
在本发明中，所述反应的温度优选为75～85℃，更优选为78～83℃，最优选为80℃；所述反应的时间优选为25～35小时，更优选为28～33小时，最优选为30小时。In the present invention, the reaction temperature is preferably 75-85°C, more preferably 78-83°C, most preferably 80°C; the reaction time is preferably 25-35 hours, more preferably 28-33 hours , most preferably 30 hours.
在本发明中，所述反应具体的为：对甲苯磺酰氯作为共反应剂，先与月桂酸反应得到更高反应活性的混合酸酐中间产物，中间产物再与羧甲基纤维素反应生成月桂酸羧甲基纤维素酯。In the present invention, the specific reaction is as follows: p-toluenesulfonyl chloride is used as a co-reactant, first reacts with lauric acid to obtain a higher reactivity mixed anhydride intermediate product, and the intermediate product reacts with carboxymethyl cellulose to generate lauric acid Carboxymethyl cellulose ester.
在本发明中，所述甲苯磺酰氯与月桂酸反应的过程具体为：In the present invention, the process of said toluenesulfonyl chloride and lauric acid reaction is specifically:
在本发明中，所述中间产物与羧甲基纤维素反应生成月桂酸羧甲基纤维素酯的过程具体为：In the present invention, the process of generating carboxymethyl cellulose laurate by reacting the intermediate product with carboxymethyl cellulose is specifically:
其中，代表羧甲基纤维素钠，R为in, Represents sodium carboxymethyl cellulose, R is
本发明优选将所述反应得到的产物体系在水中进行沉淀，具体的将得到的产物体系置于过量的水中即可。In the present invention, the product system obtained by the reaction is preferably precipitated in water, specifically, the obtained product system can be placed in excess water.
所述沉淀结束后，本发明优选对得到的沉淀进行洗涤；所述洗涤用洗涤剂优选为无水乙醇。After the precipitation is finished, the present invention preferably washes the obtained precipitation; the washing detergent is preferably absolute ethanol.
所述洗涤之后，本发明优选对洗涤后的产物进行干燥，得到干燥的月桂酸羧甲基纤维素酯。本发明对所述干燥的温度和时间没有任何的特殊要求，能够将洗涤用洗涤剂蒸发干净即可。After the washing, the present invention preferably dries the washed product to obtain dry carboxymethyl cellulose laurate. The present invention does not have any special requirements on the drying temperature and time, as long as the washing detergent can be evaporated cleanly.
得到所述月桂酸羧甲基纤维素酯后，本发明将所述月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到相变材料。在本发明中，所述月桂酸羧甲基纤维素酯和聚乳酸的质量比优选为(0,15]:[85,100)，更优选为(5～10):(90～95)，最优选为(6～8):(92～94)。After the carboxymethyl cellulose laurate is obtained, the present invention composites the carboxymethyl cellulose laurate with polylactic acid to obtain a phase change material. In the present invention, the mass ratio of carboxymethyl cellulose laurate to polylactic acid is preferably (0,15]:[85,100), more preferably (5-10):(90-95), most preferably It is (6～8): (92～94).
在本发明中，所述复合的温度优选为75～85℃，更优选为78～83℃，最优选为80℃；所述复合的时间优选为25～35小时，更优选为28～33小时，最优选为30小时。In the present invention, the compounding temperature is preferably 75-85°C, more preferably 78-83°C, most preferably 80°C; the compounding time is preferably 25-35 hours, more preferably 28-33 hours , most preferably 30 hours.
本发明制备相变材料的过程示意图如图1所示。The schematic diagram of the process of preparing the phase change material in the present invention is shown in FIG. 1 .
本发明还提供了一种上述技术方案任意一项所述的制备方法得到的相变材料，以聚乳酸作为基体，以月桂酸羧甲基纤维素酯为相变剂，所述月桂酸羧甲基纤维素酯和聚乳酸的质量比为(0,15]:[85,100)。The present invention also provides a phase change material obtained by the preparation method described in any one of the above technical solutions, using polylactic acid as a matrix, and carboxymethyl cellulose laurate as a phase change agent, and the carboxymethyl laurate The mass ratio of base cellulose ester to polylactic acid is (0,15]:[85,100).
在本发明中，所述相变材料在进行性能测试前优选进行熔融共混处理，以使得相变材料混合的更加均匀。在本发明中，所述熔融共混处理优选在转矩流变仪中进行；所述熔融共混的温度优选为170～190℃，更优选为 175～185℃，最优选为180℃；所述熔融共混的时间优选为5～8分钟，具体的可以为5分钟、6分钟、7分钟或8分钟。In the present invention, the phase change material is preferably melt-blended before the performance test, so that the phase change material can be mixed more uniformly. In the present invention, the melt blending treatment is preferably carried out in a torque rheometer; the temperature of the melt blending is preferably 170-190°C, more preferably 175-185°C, most preferably 180°C; The above melt blending time is preferably 5-8 minutes, specifically 5 minutes, 6 minutes, 7 minutes or 8 minutes.
在本发明实施例中，所述转矩流变仪的参数具体为：一区温度(T1)＝ 180℃，二区温度(T2)＝180℃，三区温度(T3)＝180℃，电机转速(Sp) ＝50rpm，转矩＝0.3N·m。In the embodiment of the present invention, the parameters of the torque rheometer are specifically: the first zone temperature (T1)=180°C, the second zone temperature (T2)=180°C, the third zone temperature (T3)=180°C, the motor Rotation speed (Sp) = 50 rpm, torque = 0.3 N·m.
本发明优选对熔融共混后的相变材料进行压片处理。在本发明中，所述压片的尺寸根据具体所要进行的测试进行设定。在本发明实施例中，对相变材料进行拉伸性能测试时，按照GB/T1040-2006标准，将相变材料制成标准样条，长100.0mm，宽10.0mm，厚4.0mm，试验速度为5mm/min；对相变材料进行弯曲性能测试时，按照GB/T9341-2008标准，将试样制成标准样条，长80.0mm，宽10.0mm，厚4mm，拉伸速度为2mm/min。In the present invention, the melt-blended phase change material is preferably subjected to tableting treatment. In the present invention, the size of the compressed tablet is set according to the specific test to be performed. In the embodiment of the present invention, when testing the tensile properties of the phase change material, according to the GB/T1040-2006 standard, the phase change material is made into a standard sample, with a length of 100.0 mm, a width of 10.0 mm, and a thickness of 4.0 mm. The test speed 5mm/min; when testing the bending properties of phase change materials, according to the GB/T9341-2008 standard, the sample is made into a standard sample, with a length of 80.0mm, a width of 10.0mm, a thickness of 4mm, and a tensile speed of 2mm/min .
在本发明实施例中，所述压片优选在SL-6型塑料压力成型机上进行：上板温度＝180℃，下板温度＝180℃，耐震压力＝1000MPa。In the embodiment of the present invention, the tableting is preferably carried out on an SL-6 plastic pressure molding machine: upper plate temperature = 180°C, lower plate temperature = 180°C, shock resistance pressure = 1000MPa.
下面结合实施例对本发明提供的一种相变材料及其制备方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。A phase change material provided by the present invention and its preparation method will be described in detail below in conjunction with examples, but they should not be construed as limiting the protection scope of the present invention.
实施例1Example 1
称取烘干的羧甲基纤维素钠(CMC)2g，N,N-二甲基乙酰胺75mL，加入到三口瓶中，搅拌，160℃下回流3个小时。Weigh 2 g of dried sodium carboxymethylcellulose (CMC) and 75 mL of N,N-dimethylacetamide, add them into a three-necked flask, stir, and reflux at 160°C for 3 hours.
降温到100℃，向三口瓶中放入7g经过烘干后的无水氯化锂，降到室温继续搅拌10个小时，最终形成均匀的羧甲基纤维素钠LiCl/DMAc溶液。Cool down to 100°C, put 7g of dried anhydrous lithium chloride into the three-necked flask, cool down to room temperature and continue stirring for 10 hours, finally forming a uniform sodium carboxymethylcellulose LiCl/DMAc solution.
将3.770g月桂酸和3.588g对甲苯磺酰氯在30mLN,N-二甲基乙酰胺中溶解，将该溶解后的溶液加入到上述制备的均相溶液中，搅拌，80℃下反应30 小时。反应完成后的溶液用150mL蒸馏水进行沉淀，抽滤，无水乙醇洗涤，干燥，得到月桂酸羧甲基纤维素酯(LACCE)。Dissolve 3.770g of lauric acid and 3.588g of p-toluenesulfonyl chloride in 30mL of N,N-dimethylacetamide, add the dissolved solution to the homogeneous solution prepared above, stir, and react at 80°C for 30 hours. After the reaction, the solution was precipitated with 150 mL of distilled water, filtered with suction, washed with absolute ethanol, and dried to obtain carboxymethyl cellulose laurate (LACCE).
将85质量份聚乳酸(PLA)和15质量份制备的月桂酸羧甲基纤维素酯在 80℃烘箱中干燥2小时，得到相变材料。85 parts by mass of polylactic acid (PLA) and 15 parts by mass of carboxymethyl cellulose laurate were dried in an oven at 80°C for 2 hours to obtain a phase change material.
本发明分别对CMC及制备的LACCE进行了FTIR分析，结果如图2所示。图2中，A为CMC的红外谱图，B为LACCE的红外谱图。在A谱图中羟基的伸缩振动特征峰在3437.72cm-1处；相对应的，B中3750cm-1到3250cm-1的吸收峰有明显大幅度的减弱，这是由于LA(月桂酸)与CMC发生了酯化反应，取代了大部分的羟基。在B图中2919.19cm-1以及2850.87cm-1处形成的双峰即为LA长链上的C-H伸缩振动吸收峰，其强度大幅度增加，反映了烷烃结构的增加；1701.78cm-1是LACCE中C＝O基团的伸缩振动特征峰，这是新出现的较强的吸收峰；1619.91cm-1是羧甲基中-COO基团的吸收特征峰。产物LACCE的红外光谱中并没有在1800cm-1处形成吸收峰，说明产品中没有酰氯的存在。图2所示的红外光谱证明了月桂酸与羧甲基纤维素钠发生了酯化反应，且合成的产物并没有反应物以及杂质的存在。The present invention has carried out FTIR analysis to CMC and prepared LACCE respectively, and the result is shown in Figure 2. In Fig. 2, A is the infrared spectrum of CMC, and B is the infrared spectrum of LACCE. In spectrum A, the characteristic peak of stretching vibration of hydroxyl is at 3437.72cm-1 ; correspondingly, the absorption peak from 3750cm-1 to 3250cm-1 in B is significantly weakened, which is due to LA (lauric acid) and CMC undergoes an esterification reaction and replaces most of the hydroxyl groups. In Figure B, the double peaks formed at 2919.19cm-1 and 2850.87cm-1 are the CH stretching vibration absorption peaks on the LA long chain, and its intensity increases greatly, reflecting the increase of the alkane structure; 1701.78cm-1 is the LACCE The characteristic peak of the stretching vibration of the C=O group in the carboxymethyl group is a new strong absorption peak; 1619.91cm-1 is the characteristic absorption peak of the -COO group in the carboxymethyl group. In the infrared spectrum of the product LACCE, no absorption peak is formed at 1800 cm-1 , indicating that there is no acid chloride in the product. The infrared spectrum shown in Figure 2 proves that the esterification reaction between lauric acid and sodium carboxymethyl cellulose has taken place, and the synthesized product does not have the presence of reactants and impurities.
在本发明中，酯化后的LACCE的氢核磁谱图如图3所示。首先，δ＝2.497 ppm是二甲基亚砜(DMSO)溶剂的化学位移；δ＝0.88ppm是甲基质子的化学位移；δ＝1.26～1.60ppm是LA中亚甲基质子的化学位移；δ＝2.17～3.06ppm是次甲基质子的化学位移，每一个峰值都可以说明酯化接枝的产物结构。另外，图3中在δ＝6～7ppm和δ＝10～11ppm处没有化学位移，证明产物中并没有残留的苯环以及羧酸。核磁共振谱说明了月桂酸与羧甲基纤维素钠发生了酯化反应，且产物中不存在其他的物质。In the present invention, the proton magnetic spectrum of LACCE after esterification is shown in FIG. 3 . First, δ=2.497 ppm is the chemical shift of dimethylsulfoxide (DMSO) solvent; δ=0.88ppm is the chemical shift of methyl proton; δ=1.26～1.60ppm is the chemical shift of methylene proton in LA; δ =2.17～3.06ppm is the chemical shift of the methine proton, and each peak can explain the structure of the product of esterification grafting. In addition, there are no chemical shifts at δ=6-7ppm and δ=10-11ppm in Figure 3, which proves that there are no residual benzene rings and carboxylic acids in the product. The NMR spectrum shows that the esterification reaction between lauric acid and sodium carboxymethyl cellulose occurs, and there are no other substances in the product.
CMC和LACCE的XRD谱图分别如图4和图5所示，对应的结晶度指数和结晶尺寸大小的数据如表1所示。很多葡萄糖分子在纤维素链中是高度结晶的，对于纤维素的晶体结构，特征峰的位置在2θ＝20.5°(002)时，在图4和图5的衍射谱图中都有出现。2θ＝18°的峰值代表了纤维素的无定形区域。CMC 和LACCE的结晶度指数(Icr)分别为32.4％和40.9％，特征衍射峰2θ＝20.5°时，这个峰值用来估测结晶的大小，而CMC和LACCE的晶体尺寸分别为7.9nm和23.2nm。因为月桂酸分子酯化后接枝到管状的羧甲基纤维素链上，管状的结构被破坏了导致不再是原有的结晶度，而月桂酸的长链结构使得合成的LACCE的结晶尺寸增大了。图5中，当2θ＝32°、46°和56.5°时，这三个特征峰归属于氯化钠，是CMC中的钠离子和氯化锂中的氯离子而产生的该峰值。The XRD patterns of CMC and LACCE are shown in Figure 4 and Figure 5, respectively, and the corresponding crystallinity index and crystal size data are shown in Table 1. Many glucose molecules are highly crystalline in the cellulose chain. For the crystalline structure of cellulose, the position of the characteristic peak is at 2θ=20.5°(002), which appears in the diffraction spectra of Fig. 4 and Fig. 5 . The peak at 2θ=18° represents the amorphous region of cellulose. The crystallinity index (Icr) of CMC and LACCE is 32.4% and 40.9% respectively, when the characteristic diffraction peak 2θ=20.5°, this peak is used for estimating the size of crystal, and the crystal size of CMC and LACCE is 7.9nm and 23.2nm respectively. nm. Because the lauric acid molecule is esterified and grafted to the tubular carboxymethyl cellulose chain, the tubular structure is destroyed, resulting in no longer the original crystallinity, and the long chain structure of lauric acid makes the crystal size of the synthesized LACCE increased. In Fig. 5, when 2θ=32°, 46° and 56.5°, these three characteristic peaks belong to sodium chloride, which are the peaks produced by sodium ions in CMC and chloride ions in lithium chloride.
表1 CMC和LACCE的结晶度指数和结晶尺寸Table 1 Crystallinity index and crystal size of CMC and LACCE
CMC和LACCE的SEM形貌分别如图6～9所示，其中，图6为CMC的断裂面SEM图；图7为LACCE的断裂面SEM图；图8为PLA的断裂面SEM 图；图9为LACCE-PLA的断裂面SEM图。从图6中可以看出，CMC的纤维束像管状物相互交错着，管状物与管状物之间存在着一些空间可以使得酯化反应得以进行；在图7中，管状物的表面比较粗糙，这是因为LA通过酯化反应接枝到了CMC的表面，进一步说明成功制备了LACCE相变材料；在图 8中，PLA有着光滑的表面且粒度大小分散的很均匀，当与LACCE进行共混时，纤维束穿绕在其中，如图9中黑色椭圆标记处。图6～9表明，适当的LACCE 可以均匀的分散于PLA基质，从而形成复合相变材料。The SEM morphologies of CMC and LACCE are shown in Figures 6-9, respectively, where Figure 6 is the SEM image of the fracture surface of CMC; Figure 7 is the SEM image of the fracture surface of LACCE; Figure 8 is the SEM image of the fracture surface of PLA; Figure 9 It is the SEM image of the fracture surface of LACCE-PLA. It can be seen from Figure 6 that the fiber bundles of CMC are interlaced like tubes, and there are some spaces between the tubes to allow the esterification reaction to proceed; in Figure 7, the surface of the tubes is relatively rough, This is because LA was grafted onto the surface of CMC through esterification reaction, further indicating that the LACCE phase change material was successfully prepared; in Figure 8, PLA has a smooth surface and the particle size is uniformly dispersed. When blended with LACCE , where the fiber bundles are wound, as shown in the black ellipse marks in Figure 9. Figures 6-9 show that appropriate LACCE can be uniformly dispersed in the PLA matrix to form a composite phase change material.
实施例2Example 2
本实施例和实施例1的方法一致，唯一的区别为：LACCE在相变材料中的添加量分别为0wt％、5wt％、10wt％、15wt％和20wt％，LACCE与PLA 相加的总量为100％。The method of this embodiment is the same as that of Example 1, the only difference is: the amount of LACCE added to the phase change material is 0wt%, 5wt%, 10wt%, 15wt% and 20wt%, respectively, and the total amount of LACCE and PLA added is 100%.
在本实施例中，得到的相变材料的力学性能的测试结果如图10所示。由图10可知，随着LACCE添加量的增加，LACCE-PLA的拉伸性能和弯曲性能也随之稳步的下降。原因在于聚乳酸本身属于疏水性的高分子材料，尽管接枝的月桂酸为疏水性的基团，但是纤维素的长分子链中仍然含有醚类取代基，以及一部分未反应的羟基，这些结构都属于亲水性的基团，使得月桂酸羧甲基纤维素酯的疏水性降低，从而影响了二者的界面相容性，降低了其间的相互作用力。当LACCE的添加量为20％时，LACCE-PLA的拉伸强度和弯曲强度分别为19.16MPa和34.34MPa，在转矩加工中出现烧焦的糖味；和纯的PLA相比，LACCE添加量为20％的LACCE-PLA的力学性能下降超过了 50％。当LACCE的含量进一步增加时，热量的聚集会引起物质的过热化和 PLA基质的碳化。虽然力学性能有所下降，但是LACCE-PLA复合材料有着良好的相变性能和可降解性能。In this embodiment, the test results of the mechanical properties of the obtained phase change material are shown in FIG. 10 . It can be seen from Figure 10 that with the increase of the addition amount of LACCE, the tensile and bending properties of LACCE-PLA also decrease steadily. The reason is that polylactic acid itself is a hydrophobic polymer material. Although the grafted lauric acid is a hydrophobic group, the long molecular chain of cellulose still contains ether substituents and some unreacted hydroxyl groups. These structures Both belong to hydrophilic groups, which reduces the hydrophobicity of carboxymethyl cellulose laurate, thereby affecting the interfacial compatibility of the two and reducing the interaction force between them. When the addition of LACCE was 20%, the tensile strength and flexural strength of LACCE-PLA were 19.16MPa and 34.34MPa, respectively, and a burnt sugar taste appeared during torque processing; compared with pure PLA, the addition of LACCE The mechanical properties of 20% LACCE-PLA decreased by more than 50%. When the content of LACCE is further increased, the accumulation of heat will cause superheating of the material and carbonization of the PLA matrix. Although the mechanical properties have declined, the LACCE-PLA composite has good phase transition properties and degradable properties.
实施例3Example 3
将实施例1得到的复合相变储能材料置于-20℃冰箱中恒温20min，然后转移到50℃烘箱中恒温20min，以此作为一个完整热循环，重复100次。 LACCE和LACCE-PLA的循环前后的DSC曲线分别如图11和图12所示，相应的相变温度和相变潜热焓值如表2所示。经过热循环之后，LACCE和 LACCE-PLA的相变温度分别降低了0.61℃和0.46℃，相变潜热焓值分别降低了1.43J/g和0.62J/g。The composite phase change energy storage material obtained in Example 1 was placed in a -20°C refrigerator at a constant temperature for 20 minutes, and then transferred to a 50°C oven at a constant temperature for 20 minutes. This was regarded as a complete thermal cycle and repeated 100 times. The DSC curves of LACCE and LACCE-PLA before and after the cycle are shown in Figure 11 and Figure 12, respectively, and the corresponding phase transition temperature and phase transition latent enthalpy are shown in Table 2. After thermal cycling, the phase transition temperatures of LACCE and LACCE-PLA decreased by 0.61°C and 0.46°C, respectively, and the latent enthalpy values of phase transition decreased by 1.43J/g and 0.62J/g, respectively.
热循环试验结果表明：在100次的热循环后相变材料的相变温度和相变潜热焓值没有明显的变化，具有良好的热稳定性，可以制备出LACCE-PLA 复合相变材料用于存储热量。因为LACCE的添加量为15％，导致相变潜热有些小，但是把LACCE的百分含量转化为100％时，材料的相变潜热焓值为 86.40J/g。在LACCE中LA占有56.94％，酯化反应后的LA的焓值为153.06J/g，这是由于纤维素分子链对月桂酸的牵制作用，导致其结晶的完整性降低，从而使得相变焓降低。The thermal cycle test results show that the phase change temperature and latent enthalpy of the phase change material do not change significantly after 100 thermal cycles, and have good thermal stability. LACCE-PLA composite phase change materials can be prepared for use in Store heat. Because the addition of LACCE is 15%, the latent heat of phase change is somewhat small, but when the percentage of LACCE is converted to 100%, the latent heat of phase change of the material is 86.40J/g. In LACCE, LA occupies 56.94%, and the enthalpy value of LA after esterification reaction is 153.06J/g, which is due to the restraining effect of cellulose molecular chain on lauric acid, which reduces the integrity of its crystallization, thus making the phase change enthalpy reduce.
表2相变材料的性能数据Table 2 Performance data of phase change materials
*：归一化后的相变潜热焓值；*: Normalized latent heat enthalpy of phase transition;
a：LA归一化后的相变焓值；a: LA normalized phase transition enthalpy;
b：LACCE归一化后的相变焓值。b: Phase transition enthalpy after LACCE normalization.
实施例4Example 4
复合相变材料的热稳定性能通过TGA和DTG分析可以测试出来， LACCE、LACCE-PLA和PLA的TGA和DTG测试结果分别如图13和图14 所示，而质量损失5％时的热分解温度(T5％)和最大热降解时的温度(Tmax1 and Tmax2)如表3所示。DTG曲线表明了LACCE和LACCE-PLA的两个主要的热降解步骤。LACCE-PLA的热分解温度相对于LACCE提高了77℃，但是比纯的PLA的热分解温度要低。但是对于一般复合相变材料而言，LACCE-PLA 复合相变材料仍然保持着高的热分解温度。对于LACCE，第一步的热分解是 LA，第二步的热分解是CMC。而对于LACCE-PLA，第一次失重是在332.1℃，这是由于少量的LACCE的热分解，第二次的失重是在366.6℃是因为PLA 的热分解。在LACCE-PLA中，LACCE的最佳添加量为15％，热分解温度提高了热稳定性随之提高，因为PLA的基质的增加确保了复合相变材料的稳定性。The thermal stability of composite phase change materials can be tested by TGA and DTG analysis. The TGA and DTG test results of LACCE, LACCE-PLA and PLA are shown in Figure 13 and Figure 14 respectively, and the thermal decomposition temperature when the mass loss is 5% (T5% ) and the maximum thermal degradation temperature (Tmax1 and Tmax2 ) are shown in Table 3. The DTG curves indicated two main thermal degradation steps of LACCE and LACCE-PLA. The thermal decomposition temperature of LACCE-PLA is 77℃ higher than that of LACCE, but lower than that of pure PLA. But for general composite phase change materials, LACCE-PLA composite phase change materials still maintain a high thermal decomposition temperature. For LACCE, the thermal decomposition of the first step is LA, and the thermal decomposition of the second step is CMC. For LACCE-PLA, the first weight loss was at 332.1 °C, which was due to the thermal decomposition of a small amount of LACCE, and the second weight loss was at 366.6 °C, which was due to the thermal decomposition of PLA. In LACCE-PLA, the optimal addition amount of LACCE is 15%, and the thermal stability increases as the thermal decomposition temperature increases, because the increase of PLA matrix ensures the stability of the composite phase change material.
表3材料的热性能数据Table 3 thermal performance data of materials
实施例5Example 5
本实施例将实施例1得到的相变材料进行干燥处理，将干燥的相变材料置于滤纸上后放入表面皿中，然后放入80℃的烘箱中，恒温12小时后从烘箱中取出并冷却至室温，相变材料在升温和降温过程中一直保持固体状态。其中，刚置于烘箱前的状体如图15所示，冷却后的状态如图16所示，观察滤纸表面并没有液体渗漏。In this example, the phase change material obtained in Example 1 is dried, and the dried phase change material is placed on a filter paper and placed in a watch glass, and then placed in an oven at 80°C, and taken out of the oven after a constant temperature of 12 hours. And cooled to room temperature, the phase change material remains in a solid state during the heating and cooling process. Wherein, the shape just before being placed in the oven is shown in Figure 15, and the state after cooling is shown in Figure 16, and there is no liquid leakage on the surface of the filter paper.
由以上实施例可知，本发明提供了一种相变材料。本发明将对甲苯磺酰氯作为共反应剂，先与月桂酸反应得到更高反应活性的混合酸酐中间产物，中间产物再与羧甲基纤维素反应生成月桂酸羧甲基纤维素酯，然后将月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到定型相变材料。根据实施例的实验结果可知，本发明提供的相变材料以月桂酸羧甲基纤维素酯作为相变剂，以聚乳酸作为基体，在相变过程中一直保持固态，无液体泄漏。It can be known from the above embodiments that the present invention provides a phase change material. The present invention uses p-toluenesulfonyl chloride as a co-reactant, first reacts with lauric acid to obtain a higher reactivity mixed anhydride intermediate product, then reacts the intermediate product with carboxymethyl cellulose to generate carboxymethyl cellulose laurate, and then Carboxymethyl cellulose laurate is compounded with polylactic acid to obtain a shaped phase change material. According to the experimental results of the examples, it can be seen that the phase change material provided by the present invention uses carboxymethyl cellulose laurate as a phase change agent and polylactic acid as a matrix, and keeps solid during the phase change process without liquid leakage.
本发明还提供了一种相变材料的制备方法，将羧甲基纤维素钠和氯化锂在第一有机溶剂条件下进行溶解，得到溶解体系；将包含月桂酸、对甲苯磺酰氯和第二有机溶剂的混合物与所述溶解体系进行反应，得到月桂酸羧甲基纤维素酯；将所述月桂酸羧甲基纤维素酯与聚乳酸进行复合，得到相变材料。本发明提供的制备方法，操作简单，易于实行。The present invention also provides a preparation method of a phase change material, dissolving sodium carboxymethyl cellulose and lithium chloride under the condition of the first organic solvent to obtain a dissolution system; comprising lauric acid, p-toluenesulfonyl chloride and the second The mixture of two organic solvents is reacted with the dissolving system to obtain carboxymethyl cellulose laurate; the compound of carboxymethyl cellulose laurate and polylactic acid is compounded to obtain a phase change material. The preparation method provided by the invention is simple in operation and easy to implement.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.
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| CN115594618B (en)* | 2022-09-27 | 2024-04-02 | 山东农业大学 | A high conductivity anion-doped plastic crystal solid electrolyte material and preparation method thereof |
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| CN102321452A (en)* | 2011-06-22 | 2012-01-18 | 新疆大学 | Method for preparing cross-linked solid-solid phase change energy storage material |
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| 脂肪酸羧甲基纤维素钠相变材料的制备及性能研究;苗扬;《万方学位论文数据库》;万方数据;20190118(第1期);第1-59页* |
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