通过（甲基）丙烯酸的酯化合成具有低聚（乙二醇）和（或）低聚（丙二醇）嵌段的两亲性（甲基）丙烯酸酯,Journal of Applied Polymer Science

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通过（甲基）丙烯酸的酯化合成具有低聚（乙二醇）和（或）低聚（丙二醇）嵌段的两亲性（甲基）丙烯酸酯
Journal of Applied Polymer Science ( IF 2.7 ) Pub Date : 2021-05-15 , DOI: 10.1002/app.50982
Dmitry V. Orekhov ₁ , Oleg A. Kazantsev ₁ , Sergey V. Orekhov ₁ , Alexey P. Sivokhin ₁ , Denis M. Kamorin _{1,

2} , Alexander S. Simagin _{1,

2} , Maria V. Savinova ₁ , Evgeniya A. Bolshakova ₁ , Michail S. Korotaev ₁

Affiliation

热响应性基于 PEG（PEG 代表聚乙二醇）的聚合物因其低毒性、良好的生物相容性和生物降解性而在医学上的应用是独一无二的，但通常使用疏水性和毒性更大的共聚单体来调节较低的临界溶解温度 (LCST)。克服这个问题和微调 LCST 的一种方便的方法是使用烷氧基低聚（乙二醇）或烷氧基低聚（丙二醇）（甲基）丙烯酸酯作为起始共聚单体。在这里，我们报告了以高产率简单且经济地合成甲氧基低聚（丙二醇）（甲基）丙烯酸酯和甲氧基低聚（丙二醇）-嵌段低聚（乙二醇）（甲基）丙烯酸酯基大分子单体的条件。 80%–98。7%）通过（甲基）丙烯酸与含有低聚（乙二醇）（OEG）和/或低聚（丙二醇）（OPG）嵌段的烷氧基低聚（亚烷基二醇）进行酸催化酯化。对甲苯磺酸 (pTSA)，烷基 (C₁₂ –C ₁₄ )苯磺酸 (ABSA) 和 H ₂ SO ₄被用作催化剂。已经表明 pTSA 和 ABSA 在催化活性方面几乎相同并且优于硫酸。发现关于催化剂的反应级数在所有情况下都接近于 1。已经表明，该反应实际上对 OEG 和 OPG 嵌段的长度以及末端烷基的结构不敏感，而与甲基丙烯酸 (MAA) 相比，丙烯酸 (AA) 的酯化进行得更快相同条件下的一种。确定了温度对醇平衡转化率的影响，发现在 60-120°C 的温度范围内，AA 的酯化为 89%-93%，MAA 的为 61%-86%。通过引入共沸剂（甲苯）进一步提高转化率，

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Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.

更新日期：2021-07-02

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