Kinetics of Methyl Methacrylate Polymerization in the Presence of Initiating Systems “Peroxide + Zirconocene Dichloride” When the Methyl Methacrylate Adhesive is Cured

IF 3.8 3区工程技术 Q2 ENGINEERING, CHEMICAL Industrial & Engineering Chemistry Research Pub Date : 2024-06-26 DOI:10.1021/acs.iecr.4c01937

Konstantin A. Tereshchenko, Daria A. Shiyan, Andrey A. Osipov, Vera P. Bondarenko, Nikolai V. Ulitin*, Elina M. Sabitova, Anton V. Bekker, Yana L. Lyulinskaya, Nikolay A. Novikov, Natalia M. Nurullina, Svetlana N. Tuntseva, Tatyana L. Puchkova, Yaroslav O. Mezhuev, Kharlampii E. Kharlampidi and Sergey V. Kolesov,

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Abstract

A kinetic model of the curing of methyl methacrylate adhesive (including nanocomposite methyl methacrylate adhesive) in the presence of the initiating systems “aryl peroxide + zirconocene dichloride” and “aryl hydroperoxide + zirconocene dichloride” is made. Computational experiments have been carried out which demonstrate the relationship of the curing rate with the curing temperature in the range of 323–343 K and with the ratio of the initial concentration of zirconocene dichloride to the initial concentration of the initiator [Mc]₀/[I]₀ for the following initiators: benzoyl peroxide (PB), ethylbenzene hydroperoxide (HPEB), and ethylbenzene hydroperoxide adduct with cadmium 2-ethyl hexanoate [HPEB·Cd(EH)₂]. It is shown that in order to increase the curing rate of the adhesive, curing should be carried out at a higher temperature (343 K) and at a higher value of the ratio [Mc]₀/[I]₀ = 10 in the presence of the most rapidly decomposing initiator HPEB·Cd(EH)₂. To increase the weight-average molecular weight of poly(methyl methacrylate), the proportion of syndiotactic triads in its composition, and consequently, to improve the adhesion strength and heat resistance of the adhesive joint, the curing of the adhesive must be carried out at the reduced temperature (323 K) and the reduced ratio of the [Mc]₀/[I]₀ = 0.1 in the presence of the least rapidly decomposing initiator HPEB.

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甲基丙烯酸甲酯粘合剂固化时 "过氧化物+二氯化锆 "引发体系存在下的甲基丙烯酸甲酯聚合动力学

建立了在 "过氧化芳基+二氯化锆 "和 "过氧化氢芳基+二氯化锆 "引发体系存在下甲基丙烯酸甲酯粘合剂（包括纳米复合甲基丙烯酸甲酯粘合剂）固化的动力学模型。计算实验证明了在 323-343 K 范围内固化速率与固化温度的关系，以及二氯化锆初始浓度与以下引发剂初始浓度之比[Mc]0/[I]0：过氧化苯甲酰（PB）、过氧化乙苯（HPEB）和过氧化乙苯与 2-乙基己酸镉的加合物[HPEB-Cd(EH)2]。研究表明，为了提高粘合剂的固化率，应在较高的温度（343 K）和较高的[Mc]0/[I]0 = 10 的比值下，在分解速度最快的引发剂 HPEB-Cd(EH)2 的存在下进行固化。为了增加聚甲基丙烯酸甲酯的重量平均分子量和辛二酸三元组在其组成中的比例，从而提高粘合剂接头的粘合强度和耐热性，必须在较低的温度（323 K）和较低的[Mc]0/[I]0 = 0.1 的比率下，在分解速度最慢的引发剂 HPEB 的存在下固化粘合剂。

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来源期刊

Industrial & Engineering Chemistry Research 工程技术-工程：化工

CiteScore

7.40

自引率

7.10%

发文量

1467

审稿时长

2.8 months

期刊介绍： ndustrial & Engineering Chemistry, with variations in title and format, has been published since 1909 by the American Chemical Society. Industrial & Engineering Chemistry Research is a weekly publication that reports industrial and academic research in the broad fields of applied chemistry and chemical engineering with special focus on fundamentals, processes, and products.