Glycerol Ketals as Building Blocks for a New Class of Biobased (Meth)acrylate Polymers
Glycerol Ketals as Building Blocks for a New Class of Biobased (Meth)acrylate Polymers
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DOI：
10.1021/acssuschemeng.1c02931
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发表时间：
2021-08
影响因子：
8.4
通讯作者：
Shailja Goyal;Fang-Yi Lin;Michael J. Forrester;William Henrichsen;Grace Murphy;Liyang Shen;Tung-ping Wang;Eric W. Cochran
中科院分区：
文献类型：
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作者：
Shailja Goyal;Fang-Yi Lin;Michael J. Forrester;William Henrichsen;Grace Murphy;Liyang Shen;Tung-ping Wang;Eric W. Cochran
在这里，我们提出了一种使用甘油缩酮作为性能差异化平台来开发下一代生物（甲基）丙烯酸酯的方法。粗甘油（一种生物柴油副产品）和源自生物质增值的酮是这些聚合物材料的组成部分。由于人们对碳足迹和石油资源枯竭的认识不断增强，生物基材料的研究和商业化正在蓬勃发展。生物柴油和生物聚合物是未来几年改善世界可持续能源和材料需求的主要关键。通过甘油和各种酮反应合成的甘油缩酮（甲基）丙烯酸酯单体包含 65-74 wt% 的生物来源含量。我们研究中使用的不同酮（丙酮、环戊酮和丁酮）的甘油缩酮是（甲基）丙烯酸酯聚合物主链上的侧基。我们研究了各种侧链缩酮基团对这些聚合物的热性能和流变性能的影响。甲基丙烯酸酯聚合物具有较高的玻璃化转变温度 (Tg) (8–40 °C)，而丙烯酸酯衍生物的玻璃化转变温度 (Tg) 低得多，在 -11 至 2 °C 之间。这些聚合物上的侧链基团为我们提供了一个强大的旋钮来调节硬嵌段聚合物和粘合剂等各种应用的热性能（例如 Tg）和流变性能（例如模量和缠结行为）。
Here, we present an approach for developing the next generation of bio(meth)acrylates using glycerol ketals as a platform for property differentiation. Crude glycerol, a biodiesel byproduct, and ketones, derived from biomass valorization, are the building blocks for these polymeric materials. Biobased materials are witnessing a prominent boom in research and commercialization due to increased awareness about the carbon footprint and depletion of petroleum resources. Biodiesel and biopolymers are major linchpins to improve sustainable energy and material needs of the world in the coming years. Glycerol ketal (meth)acrylate monomers synthesized by the reaction of glycerol and various ketones consist of 65–74 wt % bioderived content. Glycerol ketals from different ketones used in our study (acetone, cyclopentanone, and butanone) are the pendant groups on the (meth)acrylate polymer backbone. We studied the effect of various pendant side chain ketal groups on the thermal and rheological properties of these polymers. The methacrylate polymers had a higher glass transition temperature (Tg) (8–40 °C), whereas the acrylate derivatives had a much lowerTgbetween −11 and 2 °C. The side chain group on these polymers offers us a robust knob to tune the thermal properties (e.g.,Tg) and rheological properties (e.g., modulus and entanglement behavior) for varied applications such as hard block polymers and adhesives.