Synthesis and Properties of Thermo-sensitive Amphiphilic Pluronic-b-poly((ε-caprolactone)-co-(6-(benzyl-oxycarbonylmethyl)-ε-caprolactone))
Received date: 2014-03-21
Online published: 2014-04-17
Supported by
Project supported by the National Natural Science Foundation of China (No. 21274039), the Shanghai Municipal Natural Science Foundation (No. 12ZR1427300) and the Leading Academic Discipline Project of Shanghai Education Committee, China (No. J50102).
In this paper, a series of amphiphilic block copolymers Pluronic-b-poly(ε-caprolactone-co-benzyl-oxycarbonyl-methyl-ε-caprolactone) (Pluronic-b-P(CL-co-BCL)) were synthesized successfully via ring-opening polymerization (ROP) of ε-caprolactone (CL) and 6-(benzyl-oxycarbonylmethyl)-ε-caprolactone (BCL) using stannous octoate as the catalyst (weight ratio: 0.5‰) and PEO99-b-PPO69-b-PEO99 (Pluronic F127) as macroinitiator. 1H NMR, GPC and FT-IR were employed to determine the structure, composition, molecular weight and molecular weight distribution. The result of 1H NMR showed the content of BCL in the copolymers was less than the theoretical value, which may be attributed to the low reactivity of BCL due to the steric hindrance of Bn substituent on the δ position of CL. The number-average molecular weight by GPC was different from the value calculated by 1H NMR, it may be attributed to the hydrodynamic volume of the copolymers being different from that of the poly(styrene) as the GPC calibration in THF. The thermal properties of the copolymers were evaluated by TGA, DSC and XRD. The results indicated that the stability and the crystallinity of the copolymers could be adjusted by the content of the BCL. Due to the BCL units in the copolymers reduced the regularity of the PCL chain and intensively disrupted its crystallinity and the steric hindrance effect of BCL trammeled the movement of the PCL chain, the melting point (Tm) of CL segment in copolymer shifted down and the glass transition temperature (Tg) of copolymer increased with the increase of the content of BCL respectively. Emulsion/solvent evaporation technique was employed to prepare the polymeric micelle solution. The formation, size and morphologies of the micelles in aqueous solution were studied by fluorescence spectroscopy, TEM and DLS, the results demonstrated that the micelles were spherical spheres with narrow distribution, the copolymer had low critical micelles concentration (CMC) and depended on the content of BCL in the copolymer. Moreover, DLS results showed that the Pluronic-b-P(CL-co-BCL) had a reversible thermosensitivity due to the introduction of BCL.
Du Zhengzhen , Zhang Jing , Zhang Yan , Lang Meidong . Synthesis and Properties of Thermo-sensitive Amphiphilic Pluronic-b-poly((ε-caprolactone)-co-(6-(benzyl-oxycarbonylmethyl)-ε-caprolactone))[J]. Acta Chimica Sinica, 2014 , 72(5) : 609 -614 . DOI: 10.6023/A14030211
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