Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(ω-hydroxyfatty acid)s and their ester derivatives
Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(ω-hydroxyfatty acid)s and their ester derivatives
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DOI：
10.1039/c3py01261a
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发表时间：
2014-04
影响因子：
4.6
通讯作者：
J. Jose;Ghazaleh Pourfallah;Devon Merkley;Shaojun Li;L. Bouzidi;A. Leão;S. Narine
中科院分区：
文献类型：
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作者：
J. Jose;Ghazaleh Pourfallah;Devon Merkley;Shaojun Li;L. Bouzidi;A. Leão;S. Narine
以单不饱和脂肪酸和醇为原料，通过臭氧化-还原/交叉复分解反应合成了一系列ω-羟基脂肪酸单体及其甲酯衍生物(ω-ω-OHFA)。将这些单体熔融缩聚，得到热塑性聚(ω-羟基脂肪酸)S[-(CH2)n-COO-]x，具有中等(n=8)和长(n=17)重复单体单元。ω-OHFAs和Me-ω-OHFAs均以较好的产率(≥80%)和纯度(≥97%)得到，经核磁共振氢谱、傅立叶变换红外光谱(FT-IR)、电喷雾质谱(ESI-MS)和高效液相色谱(HPL C)分析证实。凝胶渗透色谱仪测定了聚(ω-羟基脂肪酸)S(P(ω-OHFA)S)和聚(ω-羟基脂肪酸酯)S(P(Me-ω-OHFA)S)的平均分子尺寸和分布随有机金属钛(IV)异丙醇盐[Ti(OIPR)4]缩聚催化剂用量、反应时间和温度的变化。聚合工艺的优化为P(ω-OHFA)S和P(Me-ω-OHFA)S提供了高端应用所需的MN和PDI值。长链(n=12)和中链(n=8)Me-ω-OHFA通过熔融缩聚反应合成了不同摩尔组成的无规共聚酯(ω-羟基十三酸/ω-羟基壬酸)共聚酯(Mn=11000~18500gmoL−1)。
The synthesis of a series of ω-hydroxyfatty acid (ω-OHFA) monomers and their methyl ester derivatives (Me-ω-OHFA) from mono-unsaturated fatty acids and alcohols via ozonolysis-reduction/cross-metathesis reactions is described. Melt polycondensation of the monomers yielded thermoplastic poly(ω-hydroxyfatty acid)s [–(CH2)n–COO–]x with medium (n = 8 and 12) and long (n = 17) repeating monomer units. The ω-OHFAs and Me-ω-OHFAs were all obtained in good yield (≥80%) and purity (≥97%) as established by 1H NMR, Fourier Transform infra-red spectroscopy (FT-IR), mass spectroscopy (ESI-MS) and high performance liquid chromatography (HPLC) analyses. The average molecular size (Mn) and distribution (PDI) of the poly(ω-hydroxyfatty acid)s (P(ω-OHFA)s) and poly(ω-hydroxyfatty ester)s (P(Me-ω-OHFA)s) as determined by GPC varied with organo-metallic Ti(IV) isopropoxide [Ti(OiPr)4] polycondensation catalyst amount, reaction time and temperature. An optimization of the polymerization process provided P(ω-OHFA)s and P(Me-ω-OHFA)s with Mn and PDI values desirable for high end applications. Co-polymerization of the long chain (n = 12) and medium chain (n = 8) Me-ω-OHFAs by melt polycondensation yielded poly(ω-hydroxy tridecanoate/ω-hydroxy nonanoate) random co-polyesters (Mn = 11 000–18 500 g mol−1) with varying molar compositions.