CN115109226A - 一种聚氨酯弹性体及其制备和应用 - Google Patents
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Abstract
本发明涉及一种聚氨酯弹性体及其制备和应用,如结构式I所示。本发明聚氨酯弹性体材料其表现出较低解离温度,高效的自愈合性及优异的再加工性能,在电子领域具有广泛的应用。
Description
技术领域
本发明属于功能性聚合物材料领域,特别涉及一种聚氨酯弹性体及其制备和应用。
背景技术
聚氨酯(PU)弹性体是一种结构可调性强、力学性能优异、应用范围广的聚合物材料,其常被用于构筑电子皮肤、能量转换器件和医疗植入设备等等。根据化学结构的不同,聚氨酯弹性体可细分为热塑性弹性体和热固性弹性体,这两类材料的结构和性能均有较大的差异。热塑性PU弹性体由于其线性结构,易于加工和回收,但其耐溶剂性和模量通常较低,蠕变变形大,机械强度低,热稳定性差。和热塑性PU相比,热固性PU弹性体由于自身三维交联结构,其力学和热性能都有明显改善。然而,传统热固性弹性体由于具有永久***联网络,难以再加工和回收利用,造成了严重的资源浪费和环境污染。
发明内容
本发明所要解决的技术问题是提供一种聚氨酯弹性体及其制备和应用。
本发明的一种如结构式I所示的聚氨酯弹性体,
其中波浪线表示基团的连接位置;
其中m的范围值麻烦限定;m为≥1的整数;
n的范围值麻烦限定;n为≥1的整数;
x的范围值麻烦限定。x为≥1的整数。
本发明的一种聚氨酯弹性体的制备方法,包括:
(1)在保护气体下,将聚酯或聚醚二元醇和溶剂混合,然后加入异佛尔酮二异氰酸酯IPDI和催化剂,反应,得到二异氰酸酯端封的预聚体;
(2)将双酚类化合物和溶剂混合,然后滴加到步骤(1)的异氰酸酯端封的预聚体中,反应,再加入甘油继续反应,得到聚氨酯弹性体。
上述制备方法的优选方式如下:
所述步骤(1)中保护气体为氮气;所述聚酯或聚醚二元醇的平均分子量为400-10000g/mol;所述聚酯或聚醚二元醇为聚四氢呋喃二醇;所述溶剂为四氢呋喃;催化剂为二月桂酸二丁基锡。
所述步骤(1)中聚酯或聚醚二元醇、异佛尔酮二异氰酸酯IPDI摩尔比为1:2.1~1:12;催化剂的用量比为所有原料(聚酯或聚醚二元醇、异佛尔酮二异氰酸酯IPDI、双酚类化合物和甘油)总质量分数的0.1%~0.5%。
所述步骤(1)具体为:将聚酯或聚醚二元醇为80-120℃条件下抽真空加热除水0.5-4h,去除真空,在保护气体氛围下,待温度降至25-70℃,加入溶剂、异佛尔酮二异氰酸酯IPDI和催化剂,保护气体氛围下,25-70℃反应0.5-2h。
所述步骤(2)中双酚类化合物为六氟双酚A或双酚A;溶剂为四氢呋喃。
所述步骤(2)中双酚类化合物、异氰酸酯端封的预聚体、甘油的摩尔比为0.5:1.25:0.5~5:5.75:0.5。
所述步骤(2)中将双酚类化合物和溶剂混合,然后滴加到步骤(1)的异氰酸酯端封的预聚体中,25-70℃反应0.5-5h,再加入甘油,25~70℃继续反应4-24h。
本发明的一种基于所述聚氨酯弹性体薄膜。
进一步地,将聚氨酯弹性体倒入模具后,在30~80℃条件下放置12-36h,最后在40-80℃真空条件下24-60h,得到聚氨酯弹性体薄膜。
本发明的一种复合导体,所述复合导体含所述聚氨酯弹性体。
进一步地,所述复合导体包括导电介质和覆盖在导电介质表面的保护层;其中导电介质为镓铟锡共融合金;保护层为所述聚氨酯弹性体。
本发明的一种摩擦纳米发电机,所述摩擦纳米发电机含所述聚氨酯弹性体。
进一步地,所述摩擦纳米发电机依次包括:聚二甲基硅氧烷PDMS层、所述聚氨酯弹性体层、导电金属板(如铜板)。
本发明的一种所述聚氨酯弹性体在电子领域中的应用,如可穿戴电子设备等。
有益效果
本发明公开了一种新型的FPPU弹性体,其表现出较低解离温度,高效的自愈合性及优异的再加工性能。以FPPU为弹性基底,制备了具有可再加工和自清洁的性能的摩擦电纳米发电机(TENG)。该装置能作为可穿戴设备的自供电源,可将外界的机械运动转化为电能。同时也利用FPPU弹性体构筑了可拉伸的自愈合复合导体,以探索其在柔性电子领域的应用。
另外,本发明还利用双酚A(BPA)代替双酚AF(BPAF)合成了无氟聚酚氨酯弹性体(APPU),探索了由不同取代基的双酚类化合物制备PUs的可行性,***地研究了氟原子对弹性体整体性能的影响。具体来说,强吸电子能力的三氟甲基是构成弹性体的关键,它可显著降低酚氨基甲酸酯键的解离温度,赋予FPPU较高的自愈合效率和显著的再加工性能。与APPU相比,FPPU弹性体还表现出更高的自清洁效率和更低的介电常数,这也将有利于其在电子领域的应用。
附图说明
图1为聚酚氨酯弹性体(FPPU及APPU)的合成示意图;其中(a)为聚酚氨酯弹性体结构;(b)为分子示意图及相关性能;
图2为(a)相同加热时间(5min),采用-NCO/C6H6比值在不同温度下衡量酚氨酯键解离度。(b)根据Arrhenius方程拟合松弛时间,由斜率确定弹性体的活化能;
图3为FPPU和APPU弹性体的自修复和后处理性能;(a)FPPU和(b)APPU的应力-应变曲线;(c)FPPU和APPU弹性体在30、50和70℃下愈合1小时后的自愈合效率;(d)自愈合过程分子示意图,比例尺=1.0cm;(e)弹性体在75℃和90℃,5MPa压力下处理30min后的碎片照片;重塑试样FPPU(f)和APPU(g)的应力-应变曲线;(h)不同加工周期下拉伸强度恢复;
图4为FPPU和APPU的原始及重塑试样的FTIR光谱;
图5为简易的电子电路和复合导体的原理图(a)以及导体的切割愈合拉伸实验(b);
图6为(a)“三明治”结构的TENG;(b)TENG的工作机理;(c)基于FPPU及APPU的重塑前后TENG的电输出性能;(d)FPPU(上)和APPU(下)接触角图(e)由接触角得到的表面能;(f)基于FPPU和APPU的TENG的自清洁性能。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
一、原料来源:
双酚A(BPA)和六氟双酚A(BPAF)均购于(上海)泰坦科技有限公司;聚四氢呋喃二醇(PTMG-1000,Mn=1000g/mol)购于阿拉丁试剂(上海)有限公司,使用前110℃真空干燥2h;
异佛尔酮二异氰酸酯(IPDI)购于万华化工(山东);四氢呋喃超干溶剂(THF,99.9%)购于百灵威(上海)科技公司;甘油(Glycerol,98%)购于阿拉丁试剂(上海)有限公司;二月桂酸二丁基锡(DBTDL,95%)购于上海麦克林生化科技有限公司。所有试剂使用前未做进一步处理。
二、测试标准和方法
采用电子万能材料试验机表征了材料的力学性能和自愈合性能。
拉伸强度测试方法如下:选择电子万能材料试验机的单轴拉伸模式对同一样条进行五次测试,结果取平均值,拉伸速率为50mm min-1。
愈合效率测试:将材料裁成矩形(0.5mm(T)×5mm(W)×15mm(L)),而后完全切断后拼在一起,不施加外力将其放置在特定条件下愈合。利用试样的愈合前后的拉伸强度表征材料的愈合效率。
实施例1
聚氨酯弹性体FPPU的合成
首先将聚四氢呋喃二醇(PTMG-1000,4.000g,4.000mmol)加入到50ml反应瓶中,油浴锅温度控制在110℃,抽真空加热除水2h。然后,去除真空,插上氮气球保持N2氛围。待温度降到60℃,加入8ml超干溶剂四氢呋喃(THF),将异佛尔酮二异氰酸酯(IPDI,2.334g,10.500mmol)缓慢滴加到反应瓶中,加入催化剂二月桂酸二丁基锡(DBTDL),在60℃氮气氛围中反应2h。
将六氟双酚A(BPAF,1.345g,4.000mmol)溶于5ml超干试剂四氢呋喃(THF)中,滴加到二异氰酸酯端封的预聚体(Prepolymer)溶液中,60℃反应1h。将甘油(0.147g,1.600mmol)继续添加到上述反应溶液中,温度维持在60℃。4h后,将整个混合溶液全部倒入四氟模具后转移到烘箱中,在40℃、60℃条件下分别放置12h,最后在80℃真空条件下维持24h以获取FPPU薄膜。
实施例2
具体制备同实施例1,区别仅仅在于将实施例1中的BPAF替换成双酚A(BPA,0.913g,4.000mmol)合成APPU薄膜。
对实施例1的FPPU和实施例2的APPU进行性能表征:
(1)酚氨酯键的动态特性研究
基于变温傅立叶变换红外光谱和应力松弛试验,从热力学和动力学的角度分别验证了氟化基团的引入可以有效地调节酚氨基甲酸酯键的动态性能。酚氨酯键属于解离型的动态共价键,不同的酚氨基甲酸酯键的动态性质可由其初始解离温度确定,该温度对应于酚酯键解离出游离的-NCO基团(2270cm-1)时的初始温度。如图2a所示,两种弹性体在50℃下受热5min后,酚氨酯键未发生解离,红外光谱中未检测到游离-NCO基团的吸收峰;其在60℃受热5min,FPPU中在2270ccm-1处出现较弱的吸收峰。而APPU中对应于游离-NCO的初始解离温度则为70℃。和APPU相比,FPPU的初始解离温度明显较低,这是因为三氟甲基强吸电子作用增强了酚氨酯键的动态特性。因此,和APPU相比较,FPPU中由于中酚氨酯键的解离和缔合所因其的网络重排温度将越低。另外,在60-130℃范围内,随着温度的升高,酚氨酯键的解离速率和程度均逐渐增加。然而,当温度高于130℃时,随着温度增加,游离的-NCO数量在逐渐减少,初步推断高温下解离出的-NCO被热空气中的水分消耗。此外,还从动力学的角度研究了基于不同电子效应的酚氨酯键的PU-CANs网络重排速率。在30℃,和APPU(τ*=25s)相比,FPPU的特征松弛时间(τ*=18s)略有缩短。随着温度升高,两种弹性体的τ*均不断减少,并且相同条件下FPPU的τ*始终小于APPU的τ*。如图2b所示,FPPU弹性体的Ea(48.8kJ mol-1)略低于APPU弹性体的Ea(53.9kJ mol-1),这表明APPU比FPPU的网络更稳定。换句话说由于氟化基团的电子效应,FPPU中酚氨酯键的动态特性得到了改善。
(2)FPPU的自愈合和可重塑性能
FPPU和APPU在室温下的原始拉伸强度分别为11.42±0.36MPa和11.10±0.92MPa,如图3a和3b所示。为了比较它们的自愈性,用剃须刀刀片将0.5×5×20mm3的矩形样条切割成两个部分。将两断裂部位轻触10s后,放置在不同条件下让其愈合。
如图3c和表1所示,FPPU弹性体在30℃处理1h后的自愈合率(~65%)高于APPU在相同温度下的自愈合率(~31%),这表明含氟基团强吸电子作用能够改善酚氨酯键的动态性能。此外,升温能够显著提高两种弹性体的自愈合效率,这是因为高温条件下,分子链的迁移率更快,同时酚氨酯键的解离速率和解离程度也相应地提高。FPPU在50℃和70℃下1h的自愈合率分别达到~85%和~98%,高于同样条件下APPU的自愈合率(~71%和~96%)。对FPPU及APPU而言,由于弹性体网络中含有大量的酚氨酯键和氢键,这些断裂试样能够很好地相互接触并通过动态键的交换而愈合。
如图3d所示,生动地解释了酚氨酯键高温解离交换的动力学性质及其低温稳定性。为了进一步评价FPPU可加工和回收性能,将制备的弹性体切成小块,在5MPa的压力和温度75℃的条件下进行热压30min,将上述处理后的样品在50℃受热平衡24h,以确保酚氨酯键的完全重组和交换(图3e)。此外,APPU在不同热压温度(90℃)下也经过了相同的处理。通过对重塑前后的试样进行了评估,得到如图4所示的FTIR光谱。原始和重塑后的两种光谱几乎是一致,证实了FPPU和APPU的化学结构均没有发生变化。重塑样品的单轴拉伸试验表明(图3f和3g),再加工后的FPPU可以保持原始试样的大部分力学性能,其抗拉强度恢复超过95%,与原始抗拉强度相当,而相同条件下APPU的抗拉强度恢复达到90%(图3h)。
表1不同条件下FPPU和APPU的自愈效率
实施例3
可拉伸及自愈合的复合导体:
FPPU由于优异的自愈合效率和断裂伸长率,因此可将其制备成具有可拉伸性和自愈性的复合导体。如图5a所示。镓铟锡共融合金作为导电介质,FPPU弹性体覆盖其外部充当保护层。上述设备与3V的电池和发光二极管(LED)连接成一个完整的电路。如图5b(I)所示,LED正常发光,当含有液态金属的复合导体被分成两部分时,LED熄灭(II)。将断裂的导体放在70℃的烘箱中30min,接入电路后,LED再次亮起(III),并且愈合后导体可被拉伸为原始长度的4倍。这表明FPPU具有良好的热自愈性和力学性能,在柔性电子领域展现出良好的应用前景。
实施例4
可重塑及自清洁的摩擦纳米发电机
“三明治”结构的TENG(如6a和6b所示),其结构和具体组成如下:单电极模式TENG的结构包括自清洁、可再处理和自愈合的摩擦正极材料(FPPU或APPU)、摩擦负极材料(聚二甲基硅氧烷(PDMS)和导电电极层(铜片)。并测试其电输出性能。如图6c和表2结果表明基于FPPU的TENG的开路电压、短路电流、短路电荷量比基于APPU的TENG的开路电压(VOC)、短路电流、短路电荷量分别高了45V、1.1μA、16nC。此外,将FPPU弹性基底分割并切割成小块,然后在75℃及5MPa下,热压30min,重塑后的样品在50℃热平衡24h,将其组装成TENG。测试结果发现重塑后FPPU的TENG的开路电压输出效率高达93.2%。重塑TENG相应的短路电流和短路电荷量的输出效率分别达到93.6%和93.0%。
表2基于FPPU和APPU弹性基底的可重塑TENG的输出性能
Sample | O<sub>V</sub> | R<sub>V</sub> | O-E(%) | O<sub>A</sub> | R<sub>A</sub> | O-E(%) | O<sub>Q</sub> | R<sub>Q</sub> | O-E(%) |
TENG-FPPU | 103V | 96V | 93.2 | 4.7μA | 4.4μA | 93.6 | 43nC | 40nC | 93.0 |
TENG-APPU | 58V | 53V | 91.4 | 3.6μA | 3.5μA | 97.2 | 27nC | 22nC | 81.5 |
Notes:O代表原始的,R代表重塑后的,V代表开路电压,A代表短路电流,Q代表短路电荷量,O-E(%)代表电输出效率.
其次,通过计算自清洁效率来表征TENG防污能力。FPPU由于具有更高的疏水性和更低的表面能,由其制成的TENG将被赋予较好的自清洁性能,从图6d和6e所示,FPPU的水接触角明显高于APPU,因此,相应的表面能是较低的。将FPPU基底置于粉尘污染的环境中10h,用一定量的水(100mL min-1)将两基底分别冲洗30min,用热风枪烘干备用。将经过上述处理的FPPU或APPU薄膜重新组装成完整的TENG。如图6f和表3所示,由FPPU制备的TENG自清洁效率为~92.2%,明显高于用APPU制备的TENG的自清洁效率(~74.1%)。
表3基于FPPU和APPU弹性体基板的自清洗TENG输出效率
Sample | O<sub>V</sub> | S-C<sub>V</sub> | O-E(%) |
TENG-FPPU | 103V | 95V | 92.2 |
TENG-APPU | 58V | 43V | 74.1 |
Notes:O代表原始的,S-C代表自清洁后的,V代表开路电压,O-E(%)=代表电输出效率。
Claims (10)
2.一种聚氨酯弹性体的制备方法,包括:
(1)在保护气体下,将聚酯或聚醚二元醇和溶剂混合,然后加入异佛尔酮二异氰酸酯IPDI和催化剂,反应,得到二异氰酸酯端封的预聚体;
(2)将双酚类化合物和溶剂混合,然后滴加到步骤(1)的异氰酸酯端封的预聚体中,反应,再加入甘油继续反应,得到聚氨酯弹性体。
3.根据权利要求2所述制备方法,其特征在于,所述步骤(1)中保护气体为氮气;所述聚酯或聚醚二元醇的平均分子量为400-10000g/mol;所述聚酯或聚醚二元醇为聚四氢呋喃二醇;所述溶剂为四氢呋喃;催化剂为二月桂酸二丁基锡。
4.根据权利要求2所述制备方法,其特征在于,所述步骤(1)中聚酯或聚醚二元醇、异佛尔酮二异氰酸酯IPDI摩尔比为1:2.1~1:12;催化剂的用量比为所有原料总质量分数的0.1%~0.5%。
5.根据权利要求2所述制备方法,其特征在于,所述步骤(1)具体为:将聚酯或聚醚二元醇为80-120℃条件下抽真空加热除水0.5-4h,去除真空,在保护气体氛围下,待温度降至25-70℃,加入溶剂、异佛尔酮二异氰酸酯IPDI和催化剂,保护气体氛围下,25-70℃下反应0.5-2h。
6.根据权利要求2所述制备方法,其特征在于,所述步骤(2)中双酚类化合物为六氟双酚A或双酚A;溶剂为四氢呋喃;所述步骤(2)中双酚类化合物、异氰酸酯端封的预聚体、甘油的摩尔比为0.5:1.25:0.5~5:5.75:0.5。
7.根据权利要求2所述制备方法,其特征在于,所述步骤(2)中将双酚类化合物和溶剂混合,然后滴加到步骤(1)的异氰酸酯端封的预聚体中,25-70℃反应0.5-5h,再加入甘油,25-70℃继续反应4-24h。
8.一种复合导体,其特征在于,所述复合导体含权利要求1所述聚氨酯弹性体。
9.一种摩擦纳米发电机,其特征在于,所述摩擦纳米发电机含权利要求1所述聚氨酯弹性体。
10.一种权利要求1所述聚氨酯弹性体在电子领域中的应用。
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