3,10-dimethyl-1,4,8,11-tetraoxacyclotetradecane-2,9-dione | 730984-85-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: 3,10-dimethyl-1,4,8,11-tetraoxacyclotetradecane-2,9-dione
• 英文别名: (3S,10S)-3,10-dimethyl-1,4,8,11-tetraoxacyclotetradecane-2,9-dione
• CAS: 730984-85-7
• 化学式: C₁₂H₂₀O₆
• 分子量: 260.287
• InChiKey: QKFHCPGNPRGVLT-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  L(-)-乳酸乙酯 在 硼烷四氢呋喃络合物 、 对甲苯磺酸 、 silver(l) oxide 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 19.0h， 生成 3,10-dimethyl-1,4,8,11-tetraoxacyclotetradecane-2,9-dione
  参考文献：
  名称：

  Isotactic Polymers with Alternating Lactic Acid and Oxetane Subunits from the Endoentropic Polymerization of a 14-Membered Ring

  摘要：

  A new isotactic, perfectly alternating polymer of (S)-lactic acid and oxetane was synthesized by the entropically driven ring-opening polymerization of a 14-membered cyclic diester (S,S-3) mediated by a zinc alkoxide catalyst. The polymer (S,S-PMOD) was characterized by NMR spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption ionization mass spectrometry. Under polymerization conditions the equilibrium concentration (0.17 +/- 0.05 M) of the monomer in toluene was essentially independent of temperature, and the average thermodynamic parameters for the ring-opening polymerization were found to be DeltaH(p)degrees = 0.2 +/- 0.7 kJ mol(-1) and DeltaS(p)degrees = +16 +/- 2 J mol(-1) K-1 (standard state [S,S-3] = 1.0 M). Theoretical calculations of the standard state enthalpy (DeltaH(p)degrees) for ring-opening polymerization of various oxocyclics, including S,S-3, were well-correlated with experimental values. Kinetic studies showed that the polymerization of S,S-3 was slower (k(p) = 0.82 +/- 0.04 M-1 s(-1) and k(dp) = 0.12 +/- 0.04 s(-1) at 25 degreesC) than that of lactide (k(p) = 2.2 M-1 s(-1)) using the same zinc alkoxide catalyst. Differential scanning calorimetry of S,S-PMOD showed a glass transition temperature of -30 degreesC for samples with molecular weights between 5 and 72 kg mol-1. In support of the potential utility of S,S-PMOD as a PLA plasticizer, the complete miscibility of the polymeric components was demonstrated by the observation of single T-g values for a series of blends of S,S-PMOD and atactic PLA.

  DOI：

  10.1021/ma049571s

文献信息

• Isotactic Polymers with Alternating Lactic Acid and Oxetane Subunits from the Endoentropic Polymerization of a 14-Membered Ring
  作者：Donghui Zhang、Jianyan Xu、Luis Alcazar-Roman、Loren Greenman、Christopher J. Cramer、Marc A. Hillmyer、William B. Tolman

  DOI：10.1021/ma049571s

  日期：2004.7.1

  A new isotactic, perfectly alternating polymer of (S)-lactic acid and oxetane was synthesized by the entropically driven ring-opening polymerization of a 14-membered cyclic diester (S,S-3) mediated by a zinc alkoxide catalyst. The polymer (S,S-PMOD) was characterized by NMR spectroscopy, size exclusion chromatography, and matrix-assisted laser desorption ionization mass spectrometry. Under polymerization conditions the equilibrium concentration (0.17 +/- 0.05 M) of the monomer in toluene was essentially independent of temperature, and the average thermodynamic parameters for the ring-opening polymerization were found to be DeltaH(p)degrees = 0.2 +/- 0.7 kJ mol(-1) and DeltaS(p)degrees = +16 +/- 2 J mol(-1) K-1 (standard state [S,S-3] = 1.0 M). Theoretical calculations of the standard state enthalpy (DeltaH(p)degrees) for ring-opening polymerization of various oxocyclics, including S,S-3, were well-correlated with experimental values. Kinetic studies showed that the polymerization of S,S-3 was slower (k(p) = 0.82 +/- 0.04 M-1 s(-1) and k(dp) = 0.12 +/- 0.04 s(-1) at 25 degreesC) than that of lactide (k(p) = 2.2 M-1 s(-1)) using the same zinc alkoxide catalyst. Differential scanning calorimetry of S,S-PMOD showed a glass transition temperature of -30 degreesC for samples with molecular weights between 5 and 72 kg mol-1. In support of the potential utility of S,S-PMOD as a PLA plasticizer, the complete miscibility of the polymeric components was demonstrated by the observation of single T-g values for a series of blends of S,S-PMOD and atactic PLA.