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甲基支化对基于生物基仲二醇的呋喃二甲酸-己二酸共聚酯的性能和表现的影响。

Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols.

作者信息

Little Alastair, Pellis Alessandro, Comerford James W, Naranjo-Valles Edwin, Hafezi Nema, Mascal Mark, Farmer Thomas J

机构信息

Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.

Department of Agrobiotechnology, Institute of Environmental Biotechnology, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz Straβe 20, Tulln an der Donau 3430, Austria.

出版信息

ACS Sustain Chem Eng. 2020 Sep 28;8(38):14471-14483. doi: 10.1021/acssuschemeng.0c04513. Epub 2020 Sep 4.

Abstract

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--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 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 s > 20 kDa using 2° alcohol diols. All copolyesters from 2° diols were entirely amorphous and exhibited higher s than their linear equivalents from 1° diols. Compared to linear poly(1,4-butyleneadipate--1,4-butylenefurandioate), methyl-branched, poly(2,5-hexamethyleneadipate--2,5-hexamethylenefurandioate) (0:7:0.3 furandioate/adipate ratio) displayed both higher modulus (67.8 19.1 MPa) and higher extension at break (89.7 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 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.

摘要

呋喃二甲酸 - 己二酸共聚酯是一类新兴的生物基可生物降解聚合物,具有巨大潜力来替代化石衍生的对苯二甲酸基共聚酯,如聚(己二酸丁二醇酯 - 对苯二甲酸丁二醇酯)(PBAT)。呋喃二甲酸 - 己二酸聚酯几乎完全是用传统的伯(1°)醇二醇制备的,而仲(2°)醇二醇单体到目前为止在很大程度上被忽视了,尽管初步观察表明使用甲基支化二醇会提高所得聚酯的 。关于使用仲醇二醇对其他性能如材料强度、疏水性和酶促水解速率(所有这些都是性能和使用寿命结束的关键参数)有什么影响知之甚少。为了确定使用仲二醇对呋喃二甲酸 - 己二酸共聚酯性能的影响,制备了一系列由己二酸二乙酯(DEA)和2,5 - 呋喃二甲酸二乙酯(FDEE)与不同的伯醇和仲醇二醇组成的聚合物。发现使用仲醇二醇时需要更长的酯交换时间和更大过量的二醇(二醇/二酯摩尔比为2:1)才能达到 s > 20 kDa。所有由仲二醇制成的共聚酯完全是无定形的,并且比由伯醇二醇制成的线性等效物表现出更高的 s。与线性聚(1,4 - 丁二醇己二酸酯 - 1,4 - 丁二醇呋喃二甲酸酯)相比,甲基支化的聚(2,5 - 己二醇己二酸酯 - 2,5 - 己二醇呋喃二甲酸酯)(呋喃二甲酸/己二酸比例为0:7:0.3)显示出更高的模量(67.8 19.1 MPa)和更高的断裂伸长率(89.7 44.5 mm)。所有其他甲基支化共聚酯与它们的线性类似物相比模量较低,但保留了更高的断裂伸长率。使用角质酶进行的酶促水解研究表明,由仲醇二醇制成的共聚酯的生物降解速率比使用伯醇二醇合成的线性等效物显著降低,这使得聚合物稳定性可以进行微调。通过水接触角揭示的疏水性也发现通常会通过引入甲基支化而增加,这表明这些材料在涂料应用中的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8d51/7525809/c73c39bf8d0c/sc0c04513_0011.jpg

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