力学性能可调、光学性能优异，可按需回收的聚烯烃→

新浪财经09-28

（来源：聚烯烃人）近日，上海交通大学唐山课题组报道了一种钯催化乙烯与双环环丁烯单体的交替共聚策略，成功合成了含有高密度双环机械响应单元的聚烯烃材料。该共聚物不仅具有可调控的力学性能和优异的光学透明度，还能通过力诱导环化反转实现化学回收，为高性能可持续聚烯烃材料的开发提供了新途径。相关论文以“Catalytic Alternating Copolymerization to Access ...

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mol/L时达到50%，表明形成了严格的交替序列共聚物。图2进一步通过动力学研究证实，分子量随时间增长而分散度保持较低，CB1插入率稳定在50%，排除了梯度或嵌段结构的可能性。图2. 乙烯与CB1的催化共聚。（A）不同催化剂对CB1插入率与聚合活性的影响；（B）温度对共聚行为的影响；（C）CB1浓度对其插入率与聚合活性的影响；（D）乙烯与CB1交替共聚的动力学曲线。通过核磁共振（图3B）、DSC和WAXD等表征手段，研究人员系统研究了不同CB1含量共聚物的结构与性能关系。随着CB1插入率从9.5%增至50%，共聚物从具有双熔融峰的部分结晶材料逐渐转变为以玻璃化转变为主的弱结晶或无定形材料（图3C–D）。拉伸测试表明（图3E），低CB1含量的聚-1-(9.5)表现出类弹性体行为，而接近交替序列的聚-1-(50)则显示出半结晶聚合典型的屈服和硬化行为，其强度和断裂伸长率均得到显著提升。图3. 共聚物的结构与性能。（A）链中环丁烷机械响应单元的分布示意图；（B）交替共聚物聚-1-(50)的核磁共振氢谱与碳谱；（C）DSC曲线；（D）广角X射线衍射谱；（E）应力-应变曲线与力学性能对比。进一步地，作者比较了不同双环结构单体（CB1、CB2和NBE）对共聚行为的影响（图4A–B）。CB1因其较高的环灵活性表现出更优的插入活性和交替倾向。 接近交替共聚物聚-1-(40)、聚-2-(41)和聚-3-(42)在光学性能上均表现优异，透光率超过79%，折射率约1.528，且聚-1-(40)还展现出优异的韧性和紫外稳定性（图4D–E），成功克服了传统COC材料的脆性问题。图4. 环结构对共聚行为与性能的影响。（A）乙烯与CB1/CB2/NBE的共聚反应；（B）单体浓度对插入率的影响；（C）聚-1-(40)、聚-2-(41)和聚-3-(42)的DSC曲线；（D）力学性能对比；（E）光学透光率与折射率。最引人注目的是，该交替共聚物中的双环环丁烷单元具有机械响应特性。通过球磨处理（图5A），聚-1-(50)可发生选择性环化开环反应，生成含双键的不饱和聚合物（图5B–D）。后续通过交叉复分解反应与生物基二元醇进行降解和再聚合，成功实现了材料的化学循环利用，获得具有更高结晶度和力学性能的再生聚酯材料（图5E）。图5. 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