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A Thermodynamic Roadmap for the Grafting-through Polymerization of PDMS11MA
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-08-24 , DOI: 10.1021/acsmacrolett.0c00350 Michael R Martinez 1 , Yidan Cong 2 , Sergei S Sheiko 2 , Krzysztof Matyjaszewski 1
ACS Macro Letters ( IF 5.1 ) Pub Date : 2020-08-24 , DOI: 10.1021/acsmacrolett.0c00350 Michael R Martinez 1 , Yidan Cong 2 , Sergei S Sheiko 2 , Krzysztof Matyjaszewski 1
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Grafting-through atom transfer radical polymerization (ATRP) was used to polymerize a sterically hindered poly(dimethylsiloxane) methacrylate (PDMS11MA, Mn = 1000) macromonomer to high conversion as a function of temperature, solvent, initial monomer concentration, and pressure. Higher polymerization yields were obtained when polymerizations were conducted at (i) lower temperature (T), (ii) in a poor solvent for the side chain, (iii) higher initial monomer concentration ([M]0), and (iv) higher pressure by mitigating the contribution of the equilibrium monomer concentration ([M]eq). The enthalpy of polymerization (ΔHp) and entropy of polymerization (ΔSp) were more negative in poor solvents. Polymerizations at ambient pressure required higher [M]0, use of a poor solvent, and lower temperatures to reach higher conversion with good control, whereas high pressure ATRP (HP-ATRP) displayed better control under dilute conditions. Grafting-through polymerization at high P and higher [M]0 was less controlled, plausibly due to limited solubility and mobility of the copper catalyst in the highly viscous medium.
中文翻译：
PDMS11MA 接枝聚合的热力学路线图
接枝原子转移自由基聚合 (ATRP) 用于将位阻聚 (二甲基硅氧烷) 甲基丙烯酸酯 (PDMS 11 MA, M n = 1000) 大单体聚合成随温度、溶剂、初始单体浓度和压力变化的高转化率. 当聚合在 (i) 较低温度 ( T )、(ii) 在侧链不良溶剂中、(iii) 较高初始单体浓度 ([M] 0 ) 和 (iv) 较高通过减轻平衡单体浓度 ([M] eq ) 的贡献来施加压力。聚合焓 (Δ H p ) 和聚合熵 (ΔS p ) 在不良溶剂中更负。环境压力下的聚合需要更高的 [M] 0、使用不良溶剂和更低的温度以达到更高的转化率和良好的控制，而高压 ATRP (HP-ATRP) 在稀释条件下表现出更好的控制。在高P和更高 [M] 0下的接枝聚合受到的控制较少，这可能是由于铜催化剂在高粘度介质中的溶解度和流动性有限。
更新日期：2020-09-15
中文翻译：
PDMS11MA 接枝聚合的热力学路线图
接枝原子转移自由基聚合 (ATRP) 用于将位阻聚 (二甲基硅氧烷) 甲基丙烯酸酯 (PDMS 11 MA, M n = 1000) 大单体聚合成随温度、溶剂、初始单体浓度和压力变化的高转化率. 当聚合在 (i) 较低温度 ( T )、(ii) 在侧链不良溶剂中、(iii) 较高初始单体浓度 ([M] 0 ) 和 (iv) 较高通过减轻平衡单体浓度 ([M] eq ) 的贡献来施加压力。聚合焓 (Δ H p ) 和聚合熵 (ΔS p ) 在不良溶剂中更负。环境压力下的聚合需要更高的 [M] 0、使用不良溶剂和更低的温度以达到更高的转化率和良好的控制，而高压 ATRP (HP-ATRP) 在稀释条件下表现出更好的控制。在高P和更高 [M] 0下的接枝聚合受到的控制较少，这可能是由于铜催化剂在高粘度介质中的溶解度和流动性有限。
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