Tertiary Amine Methacrylates (TAMAs), such as 2-(N,N-diethylamino)ethyl methacrylate (DEAEMA) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA), and PEGylated (macro)monomers, such as 2-ethoxyethyl methacrylate (EEMA₁) and poly(ethylene glycol) methyl ether methacrylates with 9 and 23 units (PEGMA₉ and PEGMA₂₃, respectively), are two families of monomers frequently used in the synthesis of stimuli-responsive and biocompatible materials. They, along with methyl (MMA) and butyl (BMA) methacrylate, were used to synthesize a minilibrary of copolymers, namely poly(DEAEMA-co-EEMA₁), poly(DEAEMA-co-PEGMA₂₃), poly(DMAEMA-co-PEGMA₉), poly(DMAEMA-co-PEGMA₂₃), poly(DEAEMA-co-MMA), and poly(BMA-co-PEGMA₉). The rate of copolymerization increased as the length of the PEG-side chain is decreased, and was higher for DEAEMA compared to DMAEMA systems. The estimated values of the reactivity ratios are: r_DEAEMA = 0.61 ± 0.06 and r_EEMA1 = 0.92 ± 0.09, r_DEAEMA = 0.71 ± 0.15 and r_PEGMA23 = 1.05 ± 0.21, r_DMAEMA = 0.83 ± 0.01 and r_PEGMA9 = 1.08 ± 0.02, r_DMAEMA = 0.52 ± 0.09 and r_PEGMA23 = 0.76 ± 0.14, and r_BMA = 0.55 ± 0.13 and r_PEGMA9 = 0.38 ± 0.09; p-dioxane at 70 °C: r_DEAEMA = 0.91 ± 0.12 and r_PEGMA9 = 0.75 ± 0.09; and tetrahydrofuran at 66 °C: r_DEAEMA = 0.96 ± 0.13 and r_PEGMA9 = 0.81 ± 0.11. While there was no difference in relative reactivity between the two amine-functional monomers when copolymerized with PEGylated methacrylates, the increased relative activity of the TAMAs compared to BMA is attributed to the formation of a cyclic intermediate. Additionally, as the PEG side-chain length is extended, the reactivity ratios for the amino monomers decreased. Finally, although a higher content of DEAEMA is incorporated in the copolymer for the poly(DEAEMA-co-MMA) when a more polar solvent is used, no differences were observed in the Mayo–Lewis plots for the poly(DEAEMA-co-PEGMA₂₃) using p-dioxane, tetrahydrofuran and ethanol.

中文翻译：

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单体结构和溶剂对叔胺与聚甲基丙烯酸酯自由基共聚反应的影响

叔胺甲基丙烯酸酯 (TAMA)，例如 2-( N , N-二乙氨基) 乙基甲基丙烯酸酯 (DEAEMA) 和 2-( N , N-二甲氨基) 甲基丙烯酸乙酯 (DMAEMA)，以及聚乙二醇化（大分子）单体，例如 2-甲基丙烯酸乙氧基乙酯 (EEMA ₁ ) 和具有 9 个和 23 个单元的聚（乙二醇）甲基醚甲基丙烯酸酯（分别为PEGMA ₉和 PEGMA ₂₃）是常用于合成刺激响应和生物相容性材料的两大类单体。它们与甲基丙烯酸甲酯 (MMA) 和丁酯 (BMA) 一起用于合成共聚物的小型库，即聚 (DEAEMA- co -EEMA ₁ )、聚 (DEAEMA-co -PEGMA ₂₃ )、聚(DMAEMA- co -PEGMA ₉ )、聚(DMAEMA- co -PEGMA ₂₃ )、聚(DEAEMA- co -MMA)和聚( BMA- co -PEGMA ₉ )。共聚速率随着 PEG 侧链长度的减少而增加，并且与 DMAEMA 系统相比，DEAEMA 的共聚速率更高。反应性比的估计值为：r _DEAEMA = 0.61 ± 0.06 和r _EEMA1 = 0.92 ± 0.09，r _DEAEMA = 0.71 ± 0.15 和r _PEGMA23 = 1.05 ± 0.21，r _DMAEMA = _0.013和 ±r _PEGMA9 = 1.08 ± 0.02，r _DMAEMA = 0.52 ± 0.09 和r _PEGMA23 = 0.76 ± 0.14，和r _BMA = 0.55 ± 0.13 和r _PEGMA9 = 0.38 ± 0.09；p-二恶烷在 70 °C：r _DEAEMA = 0.91 ± 0.12 和r _PEGMA9 = 0.75 ± 0.09；和四氢呋喃在 66 °C：r _DEAEMA = 0.96 ± 0.13 和r _PEGMA9= 0.81 ± 0.11。虽然当与聚乙二醇化甲基丙烯酸酯共聚时，两种胺官能单体之间的相对反应性没有差异，但与 BMA 相比，TAMA 的相对活性增加归因于环状中间体的形成。此外，随着 PEG 侧链长度的延长，氨基单体的反应性比率降低。最后，虽然DEAEMA较高含量在共聚物的聚（DEAEMA-并入共当使用更极性的溶剂-MMA），分别在梅奥路易斯地块为聚没有观察到差异（DEAEMA-共-PEGMA ₂₃ ) 使用对二恶烷、四氢呋喃和乙醇。