Rate of Formation of Industrial Lubricant Additive Precursors from Maleic Anhydride and Polyisobutylene.
Rate of Formation of Industrial Lubricant Additive Precursors from Maleic Anhydride and Polyisobutylene.
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DOI：
10.1021/acs.oprd.2c00207
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发表时间：
2022-09-16
影响因子：
3.4
通讯作者：
Woodward, Simon
中科院分区：
文献类型：
--
作者：
Streets, Jessica;Proust, Nicolas;Parmar, Dixit;Walker, Gary;Licence, Peter;Woodward, Simon
研究了纯聚异丁烯（PIB）和马来酸酐（MAA）在150-180 °C下的Alder烯反应以制备工业上重要的润滑油添加剂前体聚异丁烯琥珀酸酐（PIBSA）。在[PIB]= 1.24 M（550 g mol-1级，>80%外链烯烃）和[MAA]= 1.75 M的厌氧条件下，外链PIB和MAA的转化遵循二级近似相等速率定律，两种组分的kobs高达5 × 10-5 M-1 s-1。外链烯烃衍生的初级产物PIBSA-I以相等的速率形成。exo-PIB中反应性较低的烯属质子也与MAA反应形成异构体PIBSA-II（kobs高达6 × 10-5 M-1 s-1）。部分exo-PIB转化为endo-PIB（含三取代烯烃）为一级反应（kobs = 1 × 10- 5s-1），而PIBSA-I被MAA二官能化为bis-PIBSA的反应非常缓慢。MAA和PIB衍生的活化参数ΔG（150 °C）34.3 ± 0.3 kcal mol-1支持一个协调的过程，PIBSA-I的活化参数表明一个晚期（类似产物）过渡态。
The Alder-ene reaction of neat polyisobutylene (PIB) and maleic anhydride (MAA) to produce the industrially important lubricant additive precursor polyisobutylene succinic anhydride (PIBSA) is studied at 150–180 °C. Under anaerobic conditions with [PIB] ∼ 1.24 M (550 g mol–1 grade, >80% exo alkene) and [MAA] ∼ 1.75 M, conversion of exo-PIB and MAA follows second-order near-equal rate laws with kobs up to 5 × 10–5 M–1 s–1 for both components. The exo-alkene-derived primary product PIBSA-I is formed at an equivalent rate. The less reactive olefinic protons of exo-PIB also react with MAA to form isomeric PIBSA-II (kobs up to 6 × 10–5 M–1 s–1). Some exo-PIB is converted to endo-PIB (containing trisubstituted alkene) in a first-order process (kobs ∼ 1 × 10–5 s–1), while PIBSA-I is difunctionalized by MAA to bis-PIBSAs very slowly. The MAA- and PIB-derived activation parameter ΔG‡(150 °C) 34.3 ± 0.3 kcal mol–1 supports a concerted process, with that of PIBSA-I suggesting a late (product-like) transition state.
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影响因子：
4.2
作者：
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通讯作者：
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影响因子：
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通讯作者：
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