Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols.
Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols.
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DOI：
10.1021/acssuschemeng.0c04513
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发表时间：
2020-09-28
影响因子：
8.4
通讯作者：
Farmer TJ
中科院分区：
文献类型：
--
作者：
Little A;Pellis A;Comerford JW;Naranjo-Valles E;Hafezi N;Mascal M;Farmer TJ
呋喃二酸-己二酸共聚酯是一类新兴的生物可降解聚合物，具有取代聚己二酸丁二醇酯-对苯二甲酸丁二醇酯(PBAT)等化石衍生对苯二甲酸共聚酯的巨大潜力。呋喃二酸-己二酸酯聚酯几乎都是用传统的一次(1°)醇二醇合成的，而二次(2°)醇二醇单体到目前为止很大程度上被忽视了，尽管初步观察到使用甲基支化二醇会增加所得聚酯的玻璃化温度。2°酒精二醇的使用对材料强度、疏水性和酶水解率等其他性能的影响知之甚少，这些都是影响性能和寿命的关键参数。为了确定2°醇对呋喃二酸-己二酸酯共聚酯性能的影响，用1°和2°醇分别与己二酸二乙酯(DEA)和2，5-呋喃二酸二乙酯(FDEE)反应，制备了一系列聚合物。较长的酯交换时间和较大的二元醇过量(二醇/二酯摩尔比为2：1)被发现需要使用2°乙醇二醇来获得MWs>；20 kDa。所有来自2°二元醇的共聚酯都是完全无定形的，并且表现出比来自1°二元醇的线性等价物更高的玻璃化温度。与线性poly(1，4-butyleneadipate-co-1，4-butylenefurandioate)，甲基支化相比，poly(2，5-hexamethyleneadipate-co-2，5-hexamethylenefurandioate)(0：7：0.3呋喃二酸/己二酸)表现出更高的弹性系数(6 7.8vs19.1 Mpa)和更高的断裂伸长率(89.7vs44.5 mm)。与线性类似物相比，所有其他甲基支化共聚酯表现出较低的弹性系数，但保持较高的断裂伸长率。利用Humicola insolens角质酶进行的酶解研究表明，与使用1°酒精二醇合成的线性等价物相比，来自2°酒精二元醇的共聚酯的生物降解率显著降低，从而允许微调聚合物的稳定性。还发现，通过引入甲基支化，水接触角显示的疏水性通常也会增加，这显示了这些材料在涂料应用中的潜力。研究发现，二次醇中的甲基支化可以提高一类生物基共聚酯的玻璃化温度、疏水性和抗生物降解性，为微调材料性能提供了宝贵的工具。
Furandioate-adipate copolyesters are an emerging class of bio-based biodegradable polymers with great potential to replace fossil-derived terephthalic acid-based copolyesters such as poly(butylene adipate-co-terephthalate) (PBAT). Furandioate-adipate polyesters have almost exclusively been prepared with conventional primary (1°) alcohol diols, while secondary (2°) alcohol diol monomers have largely been overlooked until now, despite preliminary observations that using methyl-branched diols increases the Tg of the resultant polyesters. Little is known of what impact the use of 2° alcohol diols has on other properties such as material strength, hydrophobicity, and rate of enzymatic hydrolysis—all key parameters for performance and end-of-life. To ascertain the effects of using 2° diols on the properties of furandioate-adipate copolyesters, a series of polymers from diethyl adipate (DEA) and 2,5-furandicarboxylic acid diethyl ester (FDEE) using different 1° and 2° alcohol diols was prepared. Longer transesterification times and greater excesses of diol (diol/diester molar ratio of 2:1) were found to be necessary to achieve Mws > 20 kDa using 2° alcohol diols. All copolyesters from 2° diols were entirely amorphous and exhibited higher Tgs than their linear equivalents from 1° diols. Compared to linear poly(1,4-butyleneadipate-co-1,4-butylenefurandioate), methyl-branched, poly(2,5-hexamethyleneadipate-co-2,5-hexamethylenefurandioate) (0:7:0.3 furandioate/adipate ratio) displayed both higher modulus (67.8 vs 19.1 MPa) and higher extension at break (89.7 vs 44.5 mm). All other methyl-branched copolyesters displayed lower modulus but retained higher extension at break compared with their linear analogues. Enzymatic hydrolysis studies using Humicola insolens cutinase revealed that copolyesters from 2° alcohol diols have significantly decreased rates of biodegradation than their linear equivalents synthesized using 1° alcohol diols, allowing for fine-tuning of polymer stability. Hydrophobicity, as revealed by water contact angles, was also found to generally increase through the introduction of methyl branching, demonstrating potential for these materials in coatings applications. Methyl branching in secondary diols has been found to increase the Tg, hydrophobicity, and resistance to biodegradation relative to linear diols for a family of bio-based copolyesters, providing a valuable tool to fine-tune material performance.
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影响因子：
8.4
作者：
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