当前位置：
X-MOL 学术
›
Polym. Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
A sulfur copolymer with a pyrrole compound for the crosslinking of unsaturated elastomers
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-08-30 , DOI: 10.1039/d4py00706a Simone Naddeo 1 , Vincenzina Barbera 1 , Maurizio Galimberti 1
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-08-30 , DOI: 10.1039/d4py00706a Simone Naddeo 1 , Vincenzina Barbera 1 , Maurizio Galimberti 1
Affiliation
|
Effective applications must be found for sulfur, a widely available and inexpensive element. Over the last decade, copolymers with unsaturated comonomers have been prepared via so-called inverse vulcanization. In this work, a sulfur copolymer with a circular and biosourced di-pyrrole compound was obtained for the first time and was used as the sole crosslinking agent of an unsaturated elastomer. Pyrrole compounds (PyCs) were synthesized via the Paal–Knorr reaction of 2,5-hexanedione (HD) and hexamethylenediamine (HMD) or ethylenediamine (EDM). The PyCs were obtained without using solvents or catalysts in high yield and with water as the only co-product. Poly(S-co-HMDP) and poly(S-co-EDP) copolymers were prepared under the typical conditions of inverse vulcanization. Throughout the entire synthetic pathway, the overall yield was up to 92% and the atom efficiency was up to 73%. The E-factor evaluated for organic compounds was almost null. The sulfur weight content in the copolymers ranged from 40% to 80% and the average number of sulfur atoms in the sequences ranged from 3 to 17. The copolymers were found to be amorphous with a glass transition temperature ranging from −2 to 38 °C, increasing with the content of the pyrrole ring. The number average molecular weight was found to be in the range from 1500 to 9000 g mol−1. The molecular weight distribution was pretty narrow, with values lower than 2. NMR investigation suggested that the β position of the pyrrole ring reacted with sulfur atoms. A poly(S-co-HMDP) copolymer with an average sequence of 3 sulfur atoms was used as the sole crosslinking agent in a composite based on an unsaturated elastomer such as poly(styrene-co-butadiene) from anionic polymerization. More efficient crosslinking was obtained by promoting the ionic reaction of sulfur with elastomer chains by using 1,5-diazabicyclo(5.4.0)undec-7-ene. These results pave the way for the synthesis of a wide variety of sulfur copolymers with comonomers containing pyrrole rings for the sustainable crosslinking of elastomers, avoiding the use of oil-based accelerators.
中文翻译：
用于不饱和弹性体交联的含吡咯化合物的硫共聚物
硫是一种广泛使用且廉价的元素，必须找到有效的应用。在过去的十年中，具有不饱和共聚单体的共聚物是通过所谓的逆硫化制备的。在这项工作中，首次获得了具有环状生物源二吡咯化合物的硫共聚物，并将其用作不饱和弹性体的唯一交联剂。吡咯化合物（PyCs）是通过2,5-己二酮（HD）和己二胺（HMD）或乙二胺（EDM）的Paal-Knorr反应合成的。 PyCs 无需使用溶剂或催化剂即可高产率获得，且水作为唯一的副产物。聚(S- co -HMDP)和聚(S- co -EDP)共聚物是在典型的反硫化条件下制备的。整个合成路径中，总收率高达92%，原子效率高达73%。有机化合物的E因子评估几乎为零。共聚物中的硫重量含量为 40% 至 80%，序列中硫原子的平均数量为 3 至 17。发现共聚物是无定形的，玻璃化转变温度为 -2 至 38 °C ，随着吡咯环含量的增加而增加。发现数均分子量在1500至9000g mol -1的范围内。分子量分布很窄，数值低于2。NMR研究表明吡咯环的β位与硫原子发生反应。 平均序列为3个硫原子的聚(S- co -HMDP)共聚物被用作基于不饱和弹性体例如阴离子聚合的聚(苯乙烯-丁二烯)的复合材料中的唯一交联剂。通过使用1,5-二氮杂双环(5.4.0)十一碳-7-烯促进硫与弹性体链的离子反应，获得更有效的交联。这些结果为合成各种含吡咯环共聚单体的硫共聚物铺平了道路，从而实现弹性体的可持续交联，避免使用油基促进剂。
更新日期：2024-08-30
中文翻译：
用于不饱和弹性体交联的含吡咯化合物的硫共聚物
硫是一种广泛使用且廉价的元素，必须找到有效的应用。在过去的十年中，具有不饱和共聚单体的共聚物是通过所谓的逆硫化制备的。在这项工作中，首次获得了具有环状生物源二吡咯化合物的硫共聚物，并将其用作不饱和弹性体的唯一交联剂。吡咯化合物（PyCs）是通过2,5-己二酮（HD）和己二胺（HMD）或乙二胺（EDM）的Paal-Knorr反应合成的。 PyCs 无需使用溶剂或催化剂即可高产率获得，且水作为唯一的副产物。聚(S- co -HMDP)和聚(S- co -EDP)共聚物是在典型的反硫化条件下制备的。整个合成路径中，总收率高达92%，原子效率高达73%。有机化合物的E因子评估几乎为零。共聚物中的硫重量含量为 40% 至 80%，序列中硫原子的平均数量为 3 至 17。发现共聚物是无定形的，玻璃化转变温度为 -2 至 38 °C ，随着吡咯环含量的增加而增加。发现数均分子量在1500至9000g mol -1的范围内。分子量分布很窄，数值低于2。NMR研究表明吡咯环的β位与硫原子发生反应。 平均序列为3个硫原子的聚(S- co -HMDP)共聚物被用作基于不饱和弹性体例如阴离子聚合的聚(苯乙烯-丁二烯)的复合材料中的唯一交联剂。通过使用1,5-二氮杂双环(5.4.0)十一碳-7-烯促进硫与弹性体链的离子反应，获得更有效的交联。这些结果为合成各种含吡咯环共聚单体的硫共聚物铺平了道路，从而实现弹性体的可持续交联，避免使用油基促进剂。
京公网安备 11010802027423号