CN110372824B - 一种用于室温热能储存固-固相变材料及其制备方法 - Google Patents
一种用于室温热能储存固-固相变材料及其制备方法 Download PDFInfo
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Abstract
本发明提供一种用于室温型热能储存固‑固相变材料及其制备方法。先制备得双键改性的水性聚氨酯,然后将双键改性的水性聚氨酯与丙烯酸单体进行自由基共聚,然后通过溶液混合法将相变单体与上述乳液进行混合,得到用于室温热能储存的固‑固相变储能材料。本发明所阐述的室温型固‑固相变储能材料可应用于衣物保暖,建筑保温防冻,并具有反应过程简单易控,无单体残留,不使用乳化剂,环境友好的优点。
Description
技术领域
本发明涉及一种用于室温热能储存的固-固相变材料及其制备方法,属于复合材料的领域。
背景技术
随着时代的更迭,科技的进步,人类的发展越来越受到能源的制约,开发可再生能源成为了研究人员的目标,相变储能材料(这里简称PCM,下文用PCM代替)很好的满足了人们的对于能源的需求。PCM是指一种随温度变化而产生物质态变化从而吸收或者释放能量的一种材料,按照相变形式主要分为固-固PCM、固-液PCM、固-气PCM、液-气PCM。按照相变温度又可分为低温PCM、室温PCM、高温PCM;低温PCM以及高温PCM具有颇多研究,而室温型相变材料研究较少,将其与性能优异的固-固相变材料相结合,其方向颇具研究前景。
固-固PCM通过采用聚合物材料(如聚氨酯,聚丙烯酸酯、聚烯烃、苯乙烯嵌段共聚物、多糖)抑或是无机材料(如膨胀石墨)等作为PCM的载体,再通过诸如化学接枝、交联反应、熔融混合、原位聚合等方式,将相变材料与载体相结合形成耐化学性质好、强度高的PCM。而溶剂型聚氨酯由于大量使用有机溶剂对环境产生危害故逐渐被水性聚氨酯所取代,并且由于其化学键的固定作用,导致相变单元被限制在了聚合物结构中,从而导致在相变温度点相变单元的链段运动受到限制,结晶能力下降,其相变焓受到了很大的影响。
本文通过选择溶液混合法将室温型相变单体与丙烯酸改性的水性聚氨酯结合,在脱除水分的过程利用氢键结合作用将相变单体跟改性水性聚氨酯相结合达到更高的相变焓以此更好的应用于衣物保暖等领域。
发明内容
本发明目的在于克服现有聚氨酯固-固相变储能材料的不足之处,通过使用溶液混合法将室温型相变单体与丙烯酸改性的水性聚氨酯结合,以此提高相变焓热和材料稳定性。提供了一种用于室温热能储存固-固相变材料的制备方法,
其步骤包括:
(1)将大分子二元醇于120℃真空干燥4h,降温至30~50℃,加入一定量的二异氰酸酯在50~70℃下反应2~6h,反应过程中加入小分子二元醇、含双键小分子单元醇、亲水扩链剂和催化剂,制得预聚体,粘度过大适量加入溶剂。降至室温加入碱中和以及去离子水乳化,制得含双键的聚氨酯分散液,留待备用;
(2)取步骤(1)中制得的含双键的聚氨酯分散液于三口烧瓶中,加入一定量丙烯酸单体,室温搅拌30~45min,加入引发剂溶液以及剩余丙烯酸单体混合液升温至60~80℃,反应2~5h,得到丙烯酸改性聚氨酯(PUA)的乳液;
其中丙烯酸单体与含双键小分子单元醇质量比(2~5):1,引发剂质量为丙烯酸单体总质量的0.1%~0.8%;
(3)将上述PUA乳液与相变材料进行溶液混合,温度为30~50℃,反应时间为1h~1.5h,制得含相变材料的丙烯酸改性聚氨酯乳液;其中,相变材料的质量是储能材料总质量的20%~100%。
进一步,步骤(1)中大分子二元醇与二异氰酸酯的摩尔比为-OH:-NCO=1:(2~6);
小分子二元醇、含双键小分子单元醇与大分子二元醇的质量比为1:(1.2~3):(10~20);
所述亲水扩链剂质量为含大分子二元醇、二异氰酸酯的总质量的3%~7%;
催化剂质量为大分子二元醇、二异氰酸酯、扩链剂、含双键单元醇总质量的0.01%~0.1%,
溶剂的质量为单体总质量的10%~100%;
进一步,步骤(1)中所述的二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯;
所述大分子二元醇为聚乙二醇、聚丙二醇、聚四亚甲基醚二醇、聚己内酯二醇、聚己二酸丁二醇酯二醇、聚碳酸酯二醇或聚氧化丙烯二醇,分子量为1000~10000;
所述小分子二元醇为乙二醇、丙二醇、一缩二乙二醇、1,4-丁二醇、丁二醇、己二醇、异戊二醇或新戊二醇;
所述含双键小分子单元醇为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯或甲基丙烯酸羟丙酯;
所述催化剂为二月桂酸二丁基锡、辛酸亚锡或异辛酸锡;
所述碱为三乙胺、三乙醇胺、N,N-二甲基乙醇胺、乙醇胺、N,N-二异丙基乙胺中的一种或多种;
所述溶剂为丙酮、甲苯、乙酸乙酯、N,N-二甲基甲酰胺或二甲苯。
进一步,步骤(2)所述丙烯酸单体为甲基丙烯酸甲酯和甲基丙烯酸丁酯、丙烯酸甲酯和丙烯酸丁酯;
所述引发剂为偶氮二异丁腈、过硫酸钾、过硫酸铵或过氧化苯甲酰。
进一步,步骤(3)所述相变材料室温型有机相变物质,具体为十二醇、十四醇、十六烷或十八烷。
上述制备方法的反应式如下:
其中R1为二异氰酸酯:
R2为亲水扩链剂:二羟甲基丙酸;
R3为含双键小分子单元醇,具体为:甲基丙烯酸羟乙酯;成盐剂是三乙胺;相变单体可以是十二醇、十四醇、十六烷、十八烷。
与现有技术相比,本申请的有益效果为:
本发明以改性的水性聚氨酯为聚合物基体来制备形状稳定的储能材料,通过溶液混合法将室温型的相变材料与水性聚氨酯聚合物基体结合,从而达到使用目的。
本发明通过溶液混合法制备了以丙烯酸改性水性聚氨酯为聚合物基质的形状稳定的储能材料,相变材料均匀的分散在具有一定交联结构的聚合物基体中。本发明制备的固-固相变储能材料并非是核壳结构,而且得到包裹相变材料螺旋状的相变储能材料,在结构稳定的同时不会使相变单元的链段运动受到限制,有利于相变焓的提高。相比于传统的核壳结构,该实施成本低,并且核壳结构由于壳的限制会影响相变材料的使用。
附图说明
图1分别为实施例1中制备的储能材料与十四醇的FTIR图。
其中(a)是相变单体十四醇的红外谱图,(b)是实施例1中制备的储能材料的红外谱图。谱图上吸收峰位置分别为:1724cm-1是聚氨酯中氨基甲酸酯的C=O伸缩振动峰,1538cm-1是苯环上-CH的伸缩振动峰,1239cm-1和1146cm-1分别是丙烯酸酯中C-O键与氨基甲酸酯中C-O键的伸缩振动峰。这说明本发明成功合成制备处丙烯酸改性聚氨酯的相变材料。
图2分别为实施例1、实施例2和实施例3制备的储能材料的DSC熔融曲线图。
其中实施例1中十四醇的含量为37%,实施例2中十四醇的含量为46%,3中十四醇的含量为43%,根据数据可以得出,实施例1制备的储能材料的相变潜热为44.36J/g,主要是由于相变单体与聚合物基体的混合比例差距较大,仅占37%,故而潜热焓变较小,而实施例2与实施例3制备的储能材料的的相变潜热分别达到了140J/g和123J/g,通过增加相变单体的含量,相变焓也随之增加。
图3为实施例4制备的储能材料的XRD曲线图。
其中分别是纯的十二醇以及实施例4十二醇制得的固-固储能材料的衍射峰,从图中曲线可以看出,经过溶液混合法制备的十二醇相变材料,其结晶性能较之纯的十二醇有了提高。说明采用实施例4溶液混合法制得的储能材料结晶效果好,这说明了本发明的储能材料储能效果更佳。
图4分别为实施例1和实施例2制备的储能材料的热失重曲线图。
从图上可以看出在150~220℃是第一段热失重区间,这是由于相变材料十四醇的降解所引起的;第二段热失重区间为360~450℃,这是丙烯酸改性水性聚氨酯的降解所引起的;合成的储能材料降解温度对于5%质量损失来说大约为161℃,并且对于90%的质量损失来说为446℃,其中最大热失重速率分解温度为420℃。通过TG曲线的斜率最大处可以得到。累计质量变化最大时的温度是在460度左右,即图中分解质量不再变化时对应的温度。
图5为本申请制备丙烯酸改性聚氨酯的相变材料的简单结构形式图。
具体实施方式
下面通过实施例对本发明作进一步说明。在此有必要指出的是以下实施例只是用于本发明进一步说明,不能理解为对本发明保护范围的限制。
实施例1:
(1)聚氨酯分散液的制备
将5g(0.0025moL)聚醚220(Mn=2000)通过循环式水泵真空120℃干燥4h,降至50℃,加入2.5g二苯基甲烷二异氰酸酯(0.01moL),反应2h,再加入0.335g(0.0025moL)经80℃真空烘箱干燥2h的二羟甲基丙酸和3滴二月桂酸二丁基锡,升温至75℃反应2h,降温至50℃,加入1.589g(0,012moL)甲基丙烯酸羟乙酯和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的丙酮溶液;降至室温加入0.2525g三乙胺中和10min,然后加入去离子水22g自乳化,得到含双键的聚氨酯分散液;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述含双键的聚氨酯分散液于三口烧瓶,加入1.25g甲基丙烯酸甲酯(MMA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.027g的AIBN丙酮溶液以及1.25gMMA和0.625g BMA混合液分别滴加至反应液,滴完升温至80℃反应2h。
(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含8g十四醇的丙酮溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料(其中十四醇在总相变储能材料的质量含量为37%)。
实施例2:
(1)聚氨酯分散液的制备
将5g(0.0025moL)聚醚220(Mn=2000)通过循环式水泵真空120℃干燥4h,降温至50℃,加入2.5g二苯基二异氰酸酯(0.01moL),反应2h,然后加入0.82g(0.006moL)经80℃真空烘箱干燥2h的二羟甲基丙酸和3滴二月桂酸二丁基锡,反应2h,加入2.918g甲基丙烯酸羟乙酯(0.022moL)和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的丙酮溶液;降至室温加入0.2525g三乙胺中和10min,然后加入去离子水43g自乳化,得到聚氨酯分散液;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述聚氨酯分散液于三口烧瓶,加入1.25g甲基丙烯酸甲酯(MMA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.033g的AIBN丙酮溶液以及1.25g MMA和0.625gBMA混合液分别滴加至反应液,滴完升温至80℃反应2h。
(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含13g十四醇的丙酮溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料,其中十四醇在相变储能材料的质量含量为46%。
实施例3:
(1)聚氨酯分散液的制备
将5g(0.0025moL)聚醚220和0.335g(0.0025moL)二羟甲基丙酸120℃真空干燥4h,降至90℃,加入2.2g异佛尔酮二异氰酸酯(0.01moL)和3滴二月桂酸二丁基锡,反应4h,降温至50℃,加入1.589g甲基丙烯酸羟乙酯(0.012moL)和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的甲苯溶液;降至室温加入0.2525g三乙胺中和10min,然后加入去离子水22g自乳化,得到聚氨酯分散液;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述聚氨酯分散液于三口烧瓶,加入1.25g甲基丙烯酸甲酯(MMA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.027g的AIBN丙酮溶液以及1.25g MMA和0.625gBMA混合液分别滴加至反应液,滴完升温至80℃反应2h。
(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含10g十四醇的甲苯溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料,其中十四醇在相变储能材料的质量含量为43%。
实施例4:
(1)聚氨酯分散液的制备
将5g(0.0025moL)聚乙二醇(Mn=2000)和0.335g(0.0025moL)二羟甲基丙酸120℃真空干燥4h,降至90℃,加入2.2g异佛尔酮二异氰酸酯(0.01moL)和3滴二月桂酸二丁基锡,反应4h,降温至50℃,加入1.392g丙烯酸羟乙酯(0.012moL)和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的甲苯溶液;降至室温加入0.2525g三乙胺中和10min,然后加入去离子水22g自乳化,得到聚氨酯分散液;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述聚氨酯分散液于三口烧瓶,加入1.25g丙烯酸甲酯(MA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.026g的AIBN甲苯溶液以及1.25g MA和0.625g BMA混合液分别滴加至反应液,滴完升温至80℃反应2h。(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含13g十二醇的甲苯溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料。经DSC测试,其复合材料的相变焓数据达到了71J/g,而经TGA分析,最大热失重分解速率峰在411℃。
实施例5:
(1)聚氨酯分散液的制备
将5g(0.0025moL)聚醚220和0.335g(0.0025moL)二羟甲基丙酸120℃真空干燥4h,降至90℃,加入2.2g异佛尔酮二异氰酸酯(0.01moL)和3滴二月桂酸二丁基锡,反应4h,降温至50℃,加入1.589g甲基丙烯酸羟乙酯(0.012moL)和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的甲苯溶液;降至室温加入0.2525g三乙胺中和10min,然后加入去离子水22g自乳化,得到聚氨酯分散液;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述聚氨酯分散液于三口烧瓶,加入1.25g甲基丙烯酸甲酯(MMA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.027g的AIBN丙酮溶液以及1.25g MMA和0.625gBMA混合液分别滴加至反应液,滴完升温至80℃反应2h。
(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含15g十六烷的丙酮溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料。
经DSC测试,其复合材料的相变焓数据达到了110J/g,而经TGA分析,最大热失重分解速率峰在425℃。
实施例6:
(1)聚氨酯分散液的制备
将0.848g(0.008moL)一缩二乙二醇和0.536g(0.004moL)二羟甲基丙酸于120℃三口烧瓶除水2h,降至95℃,加入8g异佛尔酮二异氰酸酯(0.036moL)和3滴二月桂酸二丁基锡,反应4h,降温至50℃,1.56g甲基丙烯酸羟乙酯(0.012moL)和3滴二月桂酸二丁基锡,反应2h,得聚氨酯预聚体,过程中因粘度增大,加入共5g的甲苯溶液;降至室温加入0.404g三乙胺中和10min,然后加入去离子水44g自乳化,得到聚氨酯预聚体分散液,待乳化完毕,将2.58g的哌嗪溶于10g水溶液逐滴加到上述溶液,反应得到聚氨酯;
(2)聚氨酯-丙烯酸酯乳液的制备
取上述聚氨酯分散液于三口烧瓶,加入1.25g甲基丙烯酸甲酯(MMA)、0.625g甲基丙烯酸丁酯(BMA),低速搅拌30min,然后将0.027g的AIBN甲苯溶液以及1.25g MMA和0.625gBMA混合液分别滴加至反应液,滴完升温至80℃反应2h。
(3)聚氨酯-丙烯酸酯相变储能材料的制备
待上述共聚乳液降至40℃,逐滴加入含有7g十八烷的甲苯溶液,搅拌1h,降温出料,倒入模具中,于40℃下真空干燥48h脱除水与溶剂得到丙烯酸改性聚氨酯的相变储能材料。
经DSC测试,其复合材料的相变焓数据达到了89J/g,而经TGA分析,最大热失重分解速率峰在415℃。
Claims (6)
1.一种用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,所述固-固相变储能材料,是以丙烯酸酯类单体共聚水性聚氨酯为固-固相变储能材料的载体,制备步骤如下所示:
(1)将大分子二元醇、二羟甲基丙酸扩链剂、小分子二元醇、含双键小分子单元醇分别真空除水,并加入二异氰酸酯和催化剂,反应得到双键封端的聚氨酯预聚体,过程中粘度过大时加入溶剂,降至室温加入碱中和与去离子水乳化,得到含双键的聚氨酯分散液;所述大分子二元醇为聚乙二醇、聚丙二醇、聚四亚甲基醚二醇、聚己内酯二醇、聚己二酸丁二醇酯二醇、聚碳酸酯二醇中的一种;小分子二元醇为乙二醇、丙二醇、一缩二乙二醇、1,4-丁二醇、己二醇、异戊二醇、新戊二醇中的一种;所述含双键小分子单元醇为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯中的一种;
(2)室温下,向含有双键的聚氨酯分散液中加入一部分丙烯酸酯类单体,搅拌均匀,再加入引发剂溶液以及另一部分丙烯酸酯类单体,升至一定温度进行自由基共聚反应,反应后得到丙烯酸改性聚氨酯乳液;
(3)在丙烯酸改性聚氨酯乳液中逐滴加入相变材料,升温至30~50 ℃,搅拌一段时间,置于真空烘箱干燥,得到固-固相变储能材料;相变材料为十六烷、十八烷、十二醇或十四醇;所述相变材料用量为相变储能材料总量的20 %~64.5%。
2.根据权利要求1所述用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,步骤(1)中所述的二异氰酸酯为异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯中的一种;
所述催化剂为二月桂酸二丁基锡、辛酸亚锡、异辛酸锡中的一种;
所述溶剂为丙酮、甲苯、乙酸乙酯、N,N-二甲基甲酰胺、二甲苯中的一种。
3.根据权利要求1所述用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,所述碱为三乙胺、三乙醇胺、N,N-二甲基乙醇胺、乙醇胺、N,N-二异丙基乙胺中的一种或多种;
所述去离子水乳化的乳化温度为0~30℃,乳化时间为30~60分钟;含双键的聚氨酯分散液固含量为10~30%。
4.根据权利要求1所述用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,步骤(1)中所述反应温度为50~70 ℃,反应时间为2~6 h。
5.根据权利要求1所述用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,步骤(2)中所述丙烯酸酯类单体为甲基丙烯酸甲酯和甲基丙烯酸丁酯,或丙烯酸甲酯和丙烯酸丁酯;所述引发剂为偶氮二异丁腈。
6.据权利要求1所述用于室温热能储存的固-固相变储能材料的制备方法,其特征在于,步骤(2)中所述丙烯酸酯类单体与含双键小分子单元醇质量比为(2:1~5:1);所述自由基共聚反应温度为60~80 ℃,反应时间为3~5 h,引发剂质量为丙烯酸酯类单体总质量的0.1 %~0.8 %。
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