A macromolecular hindered phenol antioxidant, polyhydroxylated polybutadiene containing thioether binding 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (PHPBT‐b‐TPH), was synthesized via a two‐step nucleophilic addition reaction using isophorone diisocyanate (IPDI) as linkage. First, the OH groups of PHPBT reacted with secondary NCO groups of IPDI to form the adduct PHPBT‐NCO, then the PHPBT‐b‐TPH was obtained by one phenolic OH of 2,2′‐thiobis(4‐methyl‐6‐tert‐butylphenol) (TPH) reacting with the PHPBT‐NCO. The PHPBT‐b‐TPH was characterized by Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance (¹H‐NMR), ¹³C‐NMR, and thermogravimetric analysis, and its antioxidant activity in natural rubber was studied by an accelerated aging test. Influences of reaction conditions on the two nucleophilic reactions between OH group and NCO group were investigated. In addition, catalytic mechanism for the reaction between PHPBT‐NCO and TPH was discussed. The results showed that the adduct PHPBT‐NCO could be obtained by using dibutyltin dilaurate (DBTDL) as catalyst, and the suitable temperature and DBTDL amount were 35°C and 3 wt %, respectively. However, triethylamine (TEA) was more efficient than DBTDL to catalyze the reaction between PHPBT‐NCO and TPH because of steric hindrance effect. In addition, it was found that the thermal stability and antioxidant activity of PHPBT‐b‐TPH were higher than those of the low molecular weight antioxidant TPH. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40942.

中文翻译：

---

异佛尔酮二异氰酸酯结合2,2'-硫代双（4-甲基-6-叔丁基苯酚）的多羟基化聚丁二烯的合成与表征

使用异佛尔酮二异氰酸酯通过两步亲核加成反应合成了一种高分子受阻酚抗氧化剂，多羟基化聚丁二烯，其中硫醚结合了2,2'-硫代双（4-甲基-6-叔丁基苯酚）（PHPBT-b-TPH）。 IPDI）作为链接。首先， PHPBT的OH基团与仲反应 NCO基团的IPDI，以形成加合物PHPBT-NCO，则PHPBT-B-TPH通过一种酚类得到 OH的2,2'-硫代双（4-甲基6-叔丁基苯酚（TPH）与PHPBT-NCO反应。PHPBT-b-TPH的特征在于傅立叶变换红外光谱，¹ H核磁共振（¹ H-NMR），¹³通过加速老化试验研究了13 C-NMR和热重分析及其在天然橡胶中的抗氧化活性。反应条件对OH基与的两个亲核反应的影响NCO组进行了调查。此外，还讨论了PHPBT-NCO与TPH之间反应的催化机理。结果表明，以二月桂酸二丁锡（DBTDL）为催化剂可以得到PHPBT-NCO加合物，适宜的温度为35℃，DBTDL的添加量为3 wt％。但是，由于空间位阻效应，三乙胺（TEA）比DBTDL更有效地催化PHPBT-NCO和TPH之间的反应。此外，还发现PHPBT-b-TPH的热稳定性和抗氧化活性高于低分子量抗氧化剂TPH。©2014 Wiley Periodicals，Inc. J. Appl。Polym。科学 2014，131，40942。