CN110698635B - 一种具有可循环利用与自修复功能的高韧性和高力学强度的聚氨酯弹性体及其制备方法 - Google Patents
一种具有可循环利用与自修复功能的高韧性和高力学强度的聚氨酯弹性体及其制备方法 Download PDFInfo
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- CN110698635B CN110698635B CN201911034060.4A CN201911034060A CN110698635B CN 110698635 B CN110698635 B CN 110698635B CN 201911034060 A CN201911034060 A CN 201911034060A CN 110698635 B CN110698635 B CN 110698635B
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Abstract
一种具有可循环利用与自修复功能的高韧性和高力学强度的聚氨酯弹性体及其制备方法，属于聚氨酯弹性体制备技术领域。本发明通过分子拓扑学设计，构建具有结晶增强部分和弹性部分多相分离结构的多嵌段聚氨酯，并将动态超分子作用力引入体系以充当耗散能量的牺牲键，以提高弹性体的强度和韧性并赋予材料修复能力。所制备的材料具有弹性高、延展性好、韧性出色、断裂强度高、热稳定性高等优点，可以极大满足人们对高性能弹性体的要求。在具体指标上，材料的断裂强度>40MPa，撕裂能史无前例地达到了>100kJ m‑2；最为重要的是，该弹性体材料具有良好的修复和可循环利用能力，损伤的弹性体在特定温度下加热一段时间后即可完全修复。
Description
技术领域
本发明属于聚氨酯弹性体制备技术领域，具体涉及一种具有可循环利用与自修复功能的高韧性和高力学强度的聚氨酯弹性体及其制备方法。
背景技术
以聚氨酯弹性体为代表的弹性体材料，因具有良好的弹性和延展性，可被用于制备轮胎、生物医药材料等高附加值的产品，在工农业中可被大量地使用(Angew.Chem.Int.Ed.2013,52,9422–9441)。通常来说，为保证弹性体制品具有良好的橡胶弹性和力学强度，大多数被使用的弹性体制品具有一个比较稳定的网络结构。因而，弹性体制品一般呈现热固性，不具备后续加工和处理的能力。当弹性体制品发生损伤后通常只能进行报废或焚烧处理。这不仅会造成了极大的资源浪费，也会造成严重的环境污染。制备具有抗撕裂能力(高韧性)的聚氨酯弹性体，同时赋予弹性体以自修复和可循环利用能力，不仅可以显著提高弹性体制品的安全性、稳定性并延长材料的服役寿命，也对“资源节约型和环境友好型社会建设”和“人类永续发展”具有十分重要的现实意义。
通常来说，具有自修复功能的聚合物材料皆是使用在聚合物链段之间引入动态可逆的超分子作用力的方法来进行构筑(ACS Nano 2017,11,7134-7141)。但是，动态超分子作用力的引入，必然导致材料网络稳定性的下降，因而自修复聚合物材料的力学强度和橡胶弹性通常较低。传统的掺杂纳米粒子、引入共价交联点等增强弹性体力学强度的方式，又极易导致材料修复和循环利用能力的丧失(ACS Nano 2017,11, 7134–7141，Science2018,359,72–76)。因此制备兼具优秀力学强度、高韧性和自修复、可循环利用能力的弹性体极具挑战。
发明内容
本发明的目的是通过分子拓扑结构设计，使用聚合物链段形成的结晶成分充当物理交联位点，使用动态可逆的分子间作用力充当耗散能量的牺牲键，解决聚合物材料难以协同修复能力和力学强度的问题，在一个弹性体网络里集成高强度、高韧性、高延展性、高弹性、修复和可循环利用等性能或功能。
本发明所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其步骤如下：
(1)预聚体的合成：将充当增强成分的结晶性双羟基或双氨基封端的聚合物A 和充当弹性成分的双羟基或双氨基封端的聚合物B溶于干燥的溶剂(四氢呋喃、氯仿、二氯甲烷、N-甲基吡咯烷酮、二甲基亚砜等)中，后加入双异氰酸酯封端的化合物C，在30～120℃下反应0.5～48h。其中，化合物C的摩尔量是聚合物A与聚合物 B摩尔量之和的2倍；
(2)引入增韧位点：将相当于聚合物A和聚合物B摩尔用量之和的0.0～1.0 倍的双羟基或双氨基封端的增韧剂D加入到步骤(1)得到的反应体系中反应0.5～72 h。
(3)聚合物扩链：将相当于聚合物A和聚合物B摩尔用量之和的1.0～0.0倍的双羟基或双氨基封端的扩链剂E加入步骤(2)得到的反应体系中反应0.5～72h；增韧剂D和扩链剂E的摩尔量之和与聚合物A和聚合物B的摩尔量之和相等；
(4)成型：若增韧剂D能与金属离子配位，则将可与增韧剂D产生配位键的无机盐加入到反应体系中，于20～60℃下反应0.1～12h；后铸膜或在聚合物的劣溶剂中置换溶剂以除去溶剂，并视具体情况对脱去溶剂的聚合物进行挤出、热压等工艺使材料成型，得到具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体。
本发明步骤(1)所述的充当增强成分的结晶的聚合物A包括羟基或氨基封端的聚己内酯、聚丙交酯、聚乙烯、聚乙二醇等聚合物的一种或多种；充当弹性成分的聚合物B包括羟基或氨基封端的聚二甲基硅氧烷、聚四氢呋喃、聚异戊二烯、聚环氧丙烷等聚合物的一种或多种；双异氰酸酯封端的化合物C包括1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷二异氰酸酯、1,5-奈二异氰酸酯、1,4-环已烷二异氰酸酯、二环己甲烷4,4'-二异氰酸酯、邻苯二甲基二异氰酸酯等化合物的一种或多种。
本发明步骤(1)所述的聚合物A的添加摩尔量占聚合物A和聚合物B摩尔量之和的10～90％；
本发明步骤(2)所述的双羟基或双氨基封端的增韧剂D包括5,6-二氨基-1,10- 邻菲罗啉、2,2’-联吡啶-4,4’-二甲醇、乙二胺等化合物的一种或多种；
本发明步骤(3)所述的双羟基或双氨基封端的扩链剂E包括乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇和一缩二乙二醇，1,4-丁二胺，1,6-己二胺等化合物的一种或几种；
本发明步骤(4)所述的无机盐包括氯化锌、高氯酸锌、硫酸锌、氯化铁、氯化亚铁、醋酸锌等的一种或多种；无机盐的添加摩尔量是增韧剂D摩尔量的0.0～1.0 倍。
本发明步骤(4)所述的劣溶剂包括乙醚、石油醚、正己烷、正戊烷等溶剂的一种或多种。
聚合物制备完成后，使用铸膜或溶剂置换等工艺成型，使用万能材料试验机表征材料的延展性、韧性、强度、杨氏模量等机械性质，使用流变仪在剪切模式下表征材料的粘弹性。将破损的材料在结晶熔融温度以上加热验证材料的修复能力，通过热压、挤出和溶液重铸的方法对破损的材料进行循环利用，并使用万能材料试验机验证循环利用效率。
本发明通过分子拓扑学设计，构建具有结晶增强部分和弹性部分多相分离结构的多嵌段聚氨酯，并将动态超分子作用力引入体系以充当耗散能量的牺牲键，以提高弹性体的强度和韧性并赋予材料修复能力。所制备的材料具有弹性高、延展性好、韧性出色、断裂强度高、热稳定性高等优点，可以极大满足人们对高性能弹性体的要求。在具体指标上，材料的断裂强度>40MPa，撕裂能史无前例地达到了>100kJ m-2；最为重要的是，该弹性体材料具有良好的修复和可循环利用能力，损伤的弹性体在特定温度下加热一段时间后即可完全修复；可通过溶剂重铸或热压等工艺将报废的材料完全回收。该发明可以在极大程度上满足人们对高性能弹性体材料的需求，对“资源节约型社会”建设具有重要意义。
附图说明
图1：a)初始(曲线1)、在100℃修复后(曲线2)和循环利用后(曲线3)的高韧性聚(二甲基硅氧烷/乙二醇)氨酯弹性体的应力应变曲线，和b)对材料循环利用过程的数码相片。对应实施例1；
图2：完全切断的高韧性聚(异戊二烯/乙二醇)氨酯弹性体薄膜的数码相片(i)、高韧性聚(异戊二烯/乙二醇)氨酯弹性体薄膜在100℃下修复3h后的数码相片(ii)、修复后的高韧性聚(异戊二烯/乙二醇)氨酯弹性体薄膜提拉2 500g砝码验证修复能力的数码相片(iii)。对应实施例2；
图3：聚(二甲基硅氧烷/乙烯)氨酯薄膜的高韧性测试曲线；将宽度为5mm的聚(二甲基硅氧烷/乙烯)氨酯薄膜的一侧切出一个2.5mm的切口(图a)。该受损的薄膜在逐渐拉伸到原长的1.5倍(图b)，3.0倍(图c)，6.0倍(图d)，9.0倍(图e) 和10.5倍(图f)的长度后，切口都不向材料内部扩展，证明了材料良好的抗撕裂能力(韧性)。对应实施例3；
图4：聚(环氧丙烷/二甲基硅氧烷/己内酯)氨酯弹性体被切成毫米尺寸碎片的数码相片(i)、在120℃下使用4MPa的压力热压10min实现材料重塑后的数码相片(ii)，证明材料具有良好的循环利用能力。对应实施例4。
具体实施方式
以下通过一些实施例来进一步阐明本发明的具体实施和结果，而不是要用这些实施例来限制本发明。
实施例1：以氢键和配位键充当牺牲键和修复驱动力的高韧性聚(二甲基硅氧烷/乙二醇)氨酯。
1)将充当弹性成分的双羟基封端的聚二甲基硅氧烷(Mn～5 600，5.6g，1.0mmol)和充当增强成分的结晶性双羟基封端的聚乙二醇(Mn～300，7.0g，2.0mmol)溶于除水的四氢呋喃，与2.0摩尔当量的异佛尔酮二异氰酸酯(1.32g,6.0mmol)在50℃下反应48h，制备预聚物；
2)将0.40倍摩尔当量的5,6-二氨基-1,10-邻菲罗啉(0.25g,1.2mmol)加入步骤1)得到的反应体系，继续于50℃下反应48h；
3)将0.6倍摩尔当量的1,4-丁二醇(0.16g,1.8mmol)加入步骤2)得到的反应体系，继续在60℃下反应24h；
4)向步骤3)得到的反应体系中加入0.4mmol的FeCl3于60℃下反应6h交联聚合物，后将聚合物溶液在玻璃板上铸膜，待溶剂挥发完全，即完成高韧性聚氨酯的制备。
图1给出的应力应变曲线(图a)对应本实施例，该聚氨酯具有良好的机械强度、修复和重塑能力。其断裂强度高达43MPa，断裂伸长率>15mmmm-1(图a，曲线1)。损伤的材料在100℃下加热10h即可完全修复其机械损伤(图a，曲线2)。损伤后的材料可以重新溶于四氢呋喃溶液，重新铸膜后，材料的力学强度可完全恢复(图a，曲线3和图b)。
实施例2：以氢键和配位键充当牺牲键和修复驱动力的高韧性聚(异戊二烯/乙二醇) 氨酯。
1)将充当弹性成分的双羟基封端的聚异戊二烯(Mn～2 000,2.0g,1.0mmol)和充当增强成分的结晶性的双羟基封端的聚乙二醇(Mn～3 500,10.5g,3.0mmol)溶于除水的N-甲基吡咯烷酮中，与2倍摩尔当量的二环己甲烷4,4'-二异氰酸酯(2.0g,8.0 mmol)在100℃下反应0.5h，制备预聚物；
2)将0.50倍摩尔当量的5,6-二氨基-1,10-邻菲罗啉(0.42g，2.0mmol)入步骤1)得到的反应体系，继续在100℃下反应16h；
3)将0.50倍摩尔当量的1,4-丁二醇(0.18g，2.0mmol)加入步骤2)得到的反应体系，继续在100℃下反应24h；
4)向步骤3)反应体系中加入1.5mmol的FeCl3于50℃下反应12h交联聚合物，后将聚合物溶液在玻璃板上铸膜，待溶剂挥发完全，即完成高韧性聚氨酯的制备。
构筑的聚氨酯具有良好的透明性，具有良好的修复能力。图2给出的修复流程对应本实施例，将厚度为0.5mm、宽度为5.0mm的材料完全切开(图2i)；后在100℃加热3h，伤口即可完全消失(图2ii)，并可承载24.5N的拉力(图2iii)。
实施例3：以氢键充当增韧和修复驱动力的聚(二甲基硅氧烷/乙烯)氨酯。
1)将充当弹性成分的双羟基封端的聚二甲基硅氧烷(Mn～1 500,1.5g,1.0mmol)和充当增强成分的结晶性双羟基封端的聚乙烯(Mn～7 000,7.0g,1.0mmol)溶于除水的氯仿中，与2倍摩尔当量的1,6-己二异氰酸酯(0.67g,4.0mmol)在55℃下反应6 h，制备预聚物；
2)将1.0倍摩尔当量的乙二胺(0.12g,2.0mmol)入步骤1)得到的反应体系，继续反应8h。
3)将聚合物溶液在玻璃板上铸膜，待溶剂挥发完全，即完成高韧性聚氨酯的制备。
此实施例中，所制备的聚氨酯弹性体具有很好的力学强度，和超高的抗撕裂能力(韧性)。图3对应本实施例，将一个宽度为5mm的薄膜的一侧引入一个2.5mm 的切口，破损的薄膜可以耐受～8.5mm mm-1的形变，并且材料上引入的切口，在材料被拉伸的过程中不向内部延伸。经测定其断裂能(Fracture energy)高达131kJ m-2。
实施例4：以氢键或充当牺牲键和修复驱动力的聚(环氧丙烷/二甲基硅氧烷/己内酯) 氨酯。
1)将充当弹性成分的双羟基封端的聚环氧丙烷(Mn～2 000,1.0g,0.5mmol)及聚二甲基硅氧烷(Mn～1 500,0.75g,0.5mmol)和充当增强成分的结晶性双羟基封端的聚己内酯(Mn～4 000,8.0g,2.0mmol)溶于除水的四氢呋喃中，与2.0摩尔当量的 1,3-苯二异氰酸酯(0.96g,6.0mmol)在50℃下反应12h，制备预聚物；
2)将0.50倍摩尔当量的乙二胺(0.09g,1.5mmol)入步骤1)得到的反应体系，继续在100℃下反应8h；
3)将0.50倍摩尔当量的1,4-丁二醇(0.14g，1.5mmol)加入步骤2)得到的反应体系，继续在100℃下反应24h；
4)将步骤3)反应体系浓缩后倾倒在大量的正己烷中，收集沉淀，后在125℃下，在双螺杆挤出机中加工成型，即完成材料的制备。
此实施例中，构筑的弹性体具有良好的透明性，良好的抗撕裂能力和重塑能力。图4对应本实施例，将切成毫米尺寸的碎片在120℃下，使用4MPa压力热压10min，即可实现材料的重塑，重塑后的材料的机械性能与初始材料基本相同。
实施例5：以氢键和配位键充当增韧成分和修复驱动力的聚(环氧丙烷/二甲基硅氧烷 /己内酯/乙烯)氨酯。
1)将充当弹性成分的双羟基封端的聚环氧丙烷(Mn～2 000,1.0g,0.5mmol)及聚二甲基硅氧烷(Mn～1 500,0.75g,0.5mmol)和充当增强成分的结晶性双羟基封端的聚己内酯(Mn～4 000,4.0g,1.0mmol)及聚乙烯(Mn～2 000,2.0g,1.0mmol)溶于10mL除水的四氢呋喃中，与二倍摩尔当量的二环己甲烷4,4'-二异氰酸酯(1.57g, 6.0mmol)在50℃下反应12h，制备预聚物；
2)将0.15倍摩尔当量的乙二胺(0.10g，0.45mmol)和0.15摩尔当量的2,2’- 联吡啶-4,4’-二甲醇(0.09g，0.45mmol)加入到步骤1)得到的反应体系，继续在50 ℃下反应48h；
3)将0.7倍摩尔当量的丁二醇(0.19g，2.1mmol)加入至步骤2)得到的反应体系，继续在50℃下反应12h；
4)向步骤3)得到的反应体系中加入0.3mmol的ZnCl2，30℃搅拌反应3h后，在玻璃板上铸膜。
此实施例中，构筑的聚氨酯弹性体具有良好的透明性，良好的抗撕裂能力，可被重塑和修复，其断裂强度为46MPa，断裂伸长率为15mm mm-1，断裂能达到151kJ m-2。
Claims (7)
1.一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其步骤如下：
（1）预聚体的合成：将充当增强成分的结晶性双羟基或双氨基封端的聚合物A和充当弹性成分的双羟基或双氨基封端的聚合物B溶于干燥的溶剂中，后加入双异氰酸酯封端的化合物C，在30~120 ºC下反应0.5~48 h；其中，化合物C的摩尔量是聚合物A与聚合物B摩尔量之和的2倍；
（2）引入增韧位点：将相当于聚合物A和聚合物B摩尔用量之和0.3~ 1.0倍的双羟基或双氨基封端的增韧剂D加入到步骤（1）得到的反应体系中反应0.5~72 h；增韧剂D为5,6-二氨基-1,10-邻菲罗啉或2,2’-联吡啶-4,4’-二甲醇中的一种或一种以上；
（3）聚合物扩链：将相当于聚合物A和聚合物B 摩尔用量之和的1.0~ 0.7倍的双羟基或双氨基封端的扩链剂E加入步骤（2）得到的反应体系中反应0.5~ 72 h；增韧剂D和扩链剂E的摩尔量之和与聚合物A和聚合物B的摩尔量之和相等；
（4）成型：将可与增韧剂D产生配位键的无机盐加入到反应体系中，于20~60 ºC下反应0.1~12 h；后铸膜或在聚合物的劣溶剂中置换溶剂以除去溶剂、成型后得到具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体。
2.如权利要求1所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其特征在于：步骤（1）所述的聚合物A为羟基或氨基封端的聚己内酯、聚丙交酯、聚乙烯、聚乙二醇中一种或多种；聚合物B为羟基或氨基封端的聚二甲基硅氧烷、聚异戊二烯、聚环氧丙烷中的一种或多种；化合物C为1,6-己二异氰酸酯、异佛尔酮二异氰酸酯、二苯甲烷二异氰酸酯、1,5-萘二异氰酸酯、1,4-环己烷二异氰酸酯、二环己甲烷4,4'-二异氰酸酯、邻苯二甲基二异氰酸酯中的一种或多种；聚合物A的添加摩尔量占聚合物A和聚合物B摩尔量之和的10~90 %。
3.如权利要求1所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其特征在于：步骤（1）中所述的溶剂为四氢呋喃、氯仿、二氯甲烷、N-甲基吡咯烷酮或二甲基亚砜。
4.如权利要求1所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其特征在于：步骤（3）所述的扩链剂E为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、一缩二乙二醇、1,4-丁二胺、1,6-己二胺中的一种或几种。
5. 如权利要求1所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其特征在于：步骤（4）所述的无机盐为氯化锌、高氯酸锌、硫酸锌、氯化铁、氯化亚铁、醋酸锌中的一种或多种；无机盐的添加摩尔量是增韧剂D摩尔量的0.0 ~1.0倍，但不为0。
6.如权利要求1所述的一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体的制备方法，其特征在于：步骤（4）所述的劣溶剂为乙醚、石油醚、正己烷、正戊烷中的一种或多种。
7.一种具有可循环利用与自修复功能的高韧性和高力学强度聚氨酯弹性体，其特征在于：是由权利要求1~6任何一项所述的方法制备得到。
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