A systematic study on the synthesis and characterization of di-block copolymers based on aliphatic polyesters such as poly(L-lactic acid) (PLLA) and poly(-caprolactone) (PCL), performed varying both the length of the blocks as well as the relative content of each block in the copolymers, is reported. The block-length and the molecular weight of each synthesized PCL-b-PLLA di-block copolymer were analyzed by nuclear magnetic resonance spectroscopy. The influence of the block length and of the amount of each block on the thermal properties and the morphology, was evaluated by differential scanning calorimetry and by small angle X-Ray scattering experiments. In particular, the correlation between the molecular weight of each block and its amorphous and/or crystalline structure was obtained, evidencing that the crystallization of the PLLA block was not influenced by the presence of PCL and depends mainly on its molecular weight but the crystallization of PCL is strongly interfered by the crystallization of PLLA. In particular PLLA blocks are amorphous for short lengths (≤ 672 g/mol, that means ≤ 9.3 LA repeat units) and start to crystallize for molecular weight ≥ 964 g/mol, that means ≥ 13.4 LA repeat units.

Asymmetric telechelic α-hydroxyl-ω-(carboxylic acid) poly(ε-caprolactone) (HA-PCL) and α-hydroxyl-ω-(carboxylic acid) poly(δ-valerolactone) (HA-PVL) were synthesized by ring-opening polymerization of ε-caprolactone (CL) and δ-valerolactone (VL), respectively. HA-PCL oligomers were obtained at 150 °C in 2 h using ammonium decamolybdate (NH4)8[Mo10O34] as catalyst and water as initiator. A control of the number-average molecular weight (measured by NMR) can be achieved in the range between 212 and 2198 Da, based on the initial monomer/initiator ratio. Number-average molecular weight (M n) shows a linear dependence with CL/H2O ratio in this range. The nature of hydroxyl and carboxylic acid end groups of HA-PCL and HA-PVL was studied by MALDI-TOF and 1H and 13C NMR. Changes in the chemical shifts observed in the NMR spectra as a function of molecular weight were explained in terms of hydrophobic interactions. Formation of macrocyclic species was studied by MALDI-TOF. It was found that macrocyclic species are favored at longer reaction times. Insertion of alcohols and polycondensation reactions occurring after complete monomer conversion were also studied. Alcohol insertion for this system depends on the nature of alcohol. Polycondensation reactions vary with reaction times and affect the polymer molecular weight in a nonlinear manner. Finally, the α-hydroxyl-ω-(sodium carboxylate) PCL salt (HC-PCL) was prepared from HA-PCL and characterized by FT-IR and solution and solid-state NMR. Important differences between CP-MAS and MAS spectra are observed and discussed in terms of morphology and polarization transfer.

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Twenty seven poly(ester−urethane−amide)s (PEUAs) were synthesized from the reaction of α,ω-telechelic poly(ε-caprolactone) diols, 1,6-hexamethylene diisocyanate, and three different diamide−diol chain extenders derived from ε-caprolactone and three aliphatic diamines with increasing length (n = 2, 4, and 6). The hard segment (HS) was designed to be crystalline and to introduce amide groups, more susceptible to hydrolysis than urethane or urea groups. Crystallization of the HS was achieved even at very low HS content, leading to a phase-separated material. Furthermore, HS crystallinity recovered from the material homogeneous melt on cooling. Thermal degradation was well above HS melting point, allowing for melt processing of these materials. HS melting point was affected by HS content, poly(ε-caprolactone) diol length, and chain extender length. The length scale of the phase-separated morphology lied in between 11 and 13 nm up to ∼60% HS content and decreased at higher HS content values. HS content was the main parameter affecting the mechanical properties. The prepared PEUAs degraded hydrolytically at very long times by surface erosion.

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Poly(L-lactide) (PLLA) oligo-esters with α-hydroxyl-ω-alkyl (alkyl = −CH 2 −[CH 2 −CH 2 ] n −CH 3 , where n = 1, 2, 4, 5, 6, 7, 8, 9, and 10) end groups were synthesized by ring-opening polymerization of L-lactide (L-LA) catalyzed by tin(II) 2ethylhexanoate Sn(Oct) 2 in the presence of aliphatic alcohols as initiators (HO−CH 2 −[CH 2 −CH 2 ] m −CH 3 , where m = 1, 2, 4, 5, 6, 7, 8, 9, and 10). High yields (∼ 62 to 71 %) and M n (NMR) in the range of 2120-2450 Da (PLLA) were obtained. Effects of alkyl end groups on thermal properties of the oligo-esters were analyzed by DSC, TGA and SAXS. Glass transition temperature (T g) gradually decreases with increase in the percent of −CH 2 −[CH 2 −CH 2 ] m −CH 3 end group, as results alkyl end group provides most flexibility to PLLA. An important effect of alkyl end group on a double cold crystallization (T c1 and T c2) was observed, and is directly related with the segregation phase between alkyl end group and PLLA. TGA analysis revealed that PLLA oligo-esters are more thermally stable with docosyl (−C 22 H 45) respect to the butyl (−C 4 H 9) end group, probably is due to steric hindrance of the end group (docosyl respect to butyl) toward intermolecular and intramolecular transesterification. SAXS analysis showed that alkyl end group as docosyl restricted the growth of lamellae thickness (D) due to steric hindrance. Characterization of hydroxyl and alkyl end groups in the PLLA oligo-esters was determined by MALDI-TOF, GPC, FT-IR and 1 H and 13 C NMR.

Lubricants have much importance in several industries, principally serving to reduce friction and wear in mechanical elements. In this study, the influence of Castor oil as bio-lubricant on the friction and wear performance of AISI 4140 steel was investigated. For that purpose, pin-on-disk friction tests were conducted according to ASTM G-99, by using pins of tungsten carbide (WC) as counterparts. The experiments were performed at two different temperatures. This work also presents the Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) and 1 H-NMR analyses for the chemical characterization of oils and a study of their degradation by oxidation. The analysis of the damage caused to steel due to friction was deepened by analyzing its microhardness and microstructure in the worn zone. As a reference, the same experiments were performed with a commercial oil. The friction behavior of 4140 steel/WC with Castor oil lubrication at the two temperatures was notably better than that obtained under the reference oil lubrication. The kinetic friction coefficient (µ k) was up to 76% lower. However, a slight increase in steel wear was observed under Castor oil lubrication. Despite this, these results suggest that Castor oil could be used as bio-lubricant in systems which are susceptible to levels of high friction.

Poly(ethylene‐b‐ε‐caprolactone) (PE‐b‐PCL) diblock copolymers were synthesized by ring‐opening polymerization (ROP) of ε‐caprolactone (CL) with α‐hydroxyl‐ω‐methyl polyethylene (PE‐OH) as a macroinitiator and ammonium decamolybdate (NH4)8[Mo10O34] as a catalyst. Polymerization was conducted in bulk (130–150°C) with high yield (87–97%). Block copolymers with different compositions were obtained and characterized by 1H and 13C NMR, MALDI‐TOF, SAXS, and DSC. End‐group analysis by NMR and MALDI‐TOF indicates the formation of α‐hydroxyl‐ω‐methyl PE‐b‐PCL. The PE‐b‐PCL degradation was studied using thermogravimetric analysis (TGA) and alkaline hydrolysis. The PCL block was hydrolyzed by NaOH (4M), without any effect on the PE segment. Copyright © 2009 John Wiley & Sons, Ltd.