Nucleation,Crystallization, and Thermal Fractionation of Poly (ε‐Caprolactone)‐Grafted‐Lignin: Effects of Grafted Chains Length and Lignin Content

Poly(ε‐caprolactone)‐grafted‐lignin (PCL‐g‐lignin) copolymers with 2 to 37 wt % lignin are employed to study the effect of lignin on the morphology, nucleation, and crystallization kinetics of PCL. Lignin displays a nucleating action on PCL chains originating an intersecting lamellar morphology. Lignin is an excellent nucleating agent for PCL at low contents (2–5 wt %) with nucleation efficiency values that are close to or >100%. This nucleating effect increases the crystallization and melting temperature of PCL under nonisothermal conditions and accelerates the overall isothermal crystallization rate of PCL. At lignin contents >18 wt %, antinucleation effects appear, that decrease crystallization and melting temperatures, reduce crystallinity degree, hinder annealing during thermal fractionation and significantly retard isothermal crystallization kinetics. The results can be explained by a competition between nucleating effects and intermolecular interactions caused by hydrogen bonding between PCL and lignin building blocks. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1736–1750     

Impact of the nature and shape of cellulosic nanoparticles on the isothermal crystallization kinetics of poly(ε-caprolactone)

Polycaprolactone (PCL)/cellulose nanocomposites were prepared by mixing PCL with surface modified sisal nanowhiskers (CNW) and microfibrillated cellulose (MFC) extracted from sisal fibers. The influence of cellulosic nanoparticles on the crystallization behavior of PCL was investigated by differential scanning calorimetry. Isothermal crystallization data were modeled with Avrami’s kinetics, Lauritzen–Hoffman secondary nucleation theory and equilibrium melting points were determined with the Hoffman–Weeks method. The cellulose nanoparticles, acting as nucleating agents, drastically accelerate the crystallization of PCL while depressing its equilibrium melting by 9–10 °C. The crystallization of MFC-nanocomposites is slightly faster than that of CNW-nanocomposites, in agreement with the slightly lower bulk activation energy for crystallization and nucleation parameter in the former. The results are discussed based on the differences of specific surface area and surface chemistry of nanoparticles, as well as the confinement phenomenon.     

Preparation of primary amine-based block copolymer vesicles by direct dissolution in water and subsequent stabilization by sol-gel chemistry

A new amphiphilic biocompatible diblock copolymer, poly(epsilon-caprolactone)-block-poly(2-aminoethyl methacrylate), PCL-b-PAMA, was synthesized in three steps by (i) ring-opening polymerization of epsilon-caprolactone, (ii) end-group modification by esterification, and (iii) atom transfer radical polymerization (ATRP) of 2-aminoethyl methacrylate hydrochloride (AMA) in its hydrochloride salt form. This copolymer forms block copolymer vesicles with the hydrophobic PCL block forming the vesicle membrane. Unusually, these vesicles are easily prepared by direct dissolution in water without using organic co-solvents, pH adjustment, or even stirring. These vesicles can be stabilized by aqueous sol-gel chemistry using tetramethyl orthosilicate (TMOS) as the silica precursor. It is well-known that cationic polymers can catalyze silica formation, but in this particular case, it seems that the TMOS precursor is solubilized within the hydrophobic PCL membrane. Thus, the neutral membrane actually directs silica formation, rather than the cationic PAMA chains. The final vesicle morphology and the silica content depend on the silicification conditions. Provided that the TMOS/AMA molar ratio does not exceed 10:1, silicification is solely confined within the PCL membrane. At higher ratios, silica nanoparticles (5-12 nm) are also observed on the outer surface of the silicified vesicles. However, these nanoparticles appear to be only weakly adsorbed, since they can be easily removed by dialysis. The mean hydrodynamic diameter of the silicified vesicles varies from 175 to 205 nm with solution pH due to (de)protonation of the externally expressed PAMA chains. Calcination of the silicified vesicles at 800 degrees C leads to the formation of hollow silica particles. 1H NMR, transmission electron microscopy (TEM), dynamic light scattering (DLS), aqueous electrophoresis, and thermogravimetric analysis (TGA) were employed to characterize the vesicles, both before and after silicification.     

Effect of acrylonitrile content of SAN on the bending morphology and its quantitative variation inside crystals of PCL/SAN blends confined in thin films

The effect of acrylonitrile content of SAN on the bending morphology of PCL/SAN blends was studied. The blends were prepared from solution with different compositions, and isothermally crystallized at a certain temperature. During crystallization at 45°C, the truncated lozenge-shaped morphology of the PCL crystals being modified to regular/inverted S- or C-shaped morphology for PCL/SAN blends with 9.5–25% AN in SAN. The bending curvature increases by lowering the crystallization temperature, and the growth rate of PCL decreases with SAN reflecting the miscible nature of the blends. For blends with 30% AN in SAN, mix morphologies with different crystal growth rates reflects the immiscible nature of the blends. Raman spectroscopy reveals at lower crystallization temperature, for miscible blends, a small amount of SAN is retained in the PCL crystal, with a regular increase in concentration from the midpoint to the edge of the crystal, whereas a homogeneous distribution of SAN is found in immiscible blends. Those distribution of SAN are completely absent at higher crystallization temperatures due to a higher crystallographic order of the PCL crystals.     

Fluorescence study of the solvation of fluorescent probes prodan and laurdan in poly(epsilon-caprolactone)-block-poly(ethylene oxide) vesicles in aqueous solutions with tetrahydrofurane

Steady-state and time-resolved fluorescence measurements were used to study the relaxation of the microenvironment of hydrophobic probes 6-propionyl-2-(dimethylamino)naphthalene (prodan) and 6-dodecanoyl-2-(dimethylamino)naphthalene (laurdan) in systems containing vesicles formed by the amphiphilic diblock copolymer poly(epsilon-caprolactone)-block-poly(ethylene oxide) (PCL-PEO) and water/tetrahydrofurane (THF) solvent mixtures. It was found that in case of prodan, both steady-state and time-resolved emission spectra were composed of two subspectra corresponding to the emission of prodan molecules located (i) in fairly rigid (effectively viscous) and hydrophobic domains of the vesicles close to the PCL/PEO interface and (ii) in a more polar and less viscous medium (in the bulk solution). The fraction of the emission from the more polar microenvironment increases with increasing content of THF in the system. Laurdan, in contrast to prodan, appeared to be solubilized preferentially in the hydrophobic domains up to 30 vol % of THF content, and its emission spectra changed only due to swelling of hydrophobic PCL domains by added THF. The study shows that the analysis of the time-resolved emission from a probe distributed in two media is, in principle, possible, but it is quite complex and appreciably less accurate, and the relaxation times are ill-defined averages of several processes. The bimodal or shoulder-containing time-resolved spectra have to be decomposed in pertinent time-resolved subspectra and treated separately. Another important result of the study is a piece of knowledge concerning the motion of the probe with respect to the vesicle. In the studied complex system, not only the relaxation of the solvent and reorganization of polymer segments around the fluorescent headgroup of the probe affect the emission but also a lateral motion of the probe with respect to the nanoparticle within the lifetime of the excited state contributes significantly to the relaxation and to the relatively slow time-resolved Stokes shift.     

Poly(butylene terephthalate)/poly(ε-caprolactone) blends: Influence of PCL molecular mass on PBT melting and crystallization behavior

The isothermal crystallization kinetics and melting behavior of poly(butylene terephthalate) (PBT) in binary blends with poly(ε-caprolactone) (PCL) was investigated as a function of PCL molecular mass by differential scanning calorimetry and optical microscopy. The components are miscible in the melt when oligomeric PCL (M_w = 1250) is blended with PBT, whereas only partial miscibility was found in mixtures with higher molecular mass (M_w = 10,000 and 50,000). The equilibrium melting point of PBT in the homopolymer and in blends with PCL was determined through a non-linear extrapolation of the T_m = f(T_c) curve. The PBT spherulitic growth rate and bulk crystallization rate were found to increase with respect to plain PBT in blends with PCL1250 and PCL10000, whereas addition of PCL50000 causes a reduction of PBT solidification rate. The crystallization induction times were determined by differential scanning calorimetry for all the mixtures through a blank subtraction procedure that allows precise estimation of the crystallization kinetics of fast crystallizing polymers. The results have been discussed on the basis of the Hoffman-Lauritzen crystallization theory and considerations on both the transport of chains towards the crystalline growth front and the energy barrier for the formation of critical nuclei in miscible and partially miscible PBT/PCL mixtures are widely debated.     

Investigations into the bending constant and edge energy of bilayers of salt-free catanionic vesicles

Using molecular dynamics simulation, we performed theoretical calculations on the curvature constant and edge energy of bilayers of salt-free, zero-charged, cationic and anionic (catanionic) surfactant vesicles composed of alkylammonium cations (C(m)(+)) and fatty acid anions (C(n)(-)). Both the minimum size and edge energy of vesicles were calculated to examine the relation between the length of the surfactant molecules and the mechanical properties of the catanionic bilayers. Our simulation results clearly demonstrate that, when the chain lengths of the cationic and anionic surfactants are equal, both the edge energy and the rigidity of the catanionic bilayers increase dramatically, changing from around 0.36 to 2.77 kBT·nm(-1) and around 0.86 to 6.51 kBT·nm(-1), respectively. For the smallest catanionic vesicles, the curvature is not uniform and the surfactant molecules adopt a multicurvature arrangement in the vesicle bilayers. We suspect that the multicurvature bending of bilayers of catanionic vesicles is a common phenomenon in rigid bilayer systems, which could aid understanding of ion transport through bilayer membranes.     

Confinement Effects on the Crystallization Kinetics and Self-Nucleation of Double Crystalline Poly(p-dioxanone)-b-poly(ϵ-caprolactone) Diblock Copolymers

The morphology, crystallization and self nucleation behavior of double crystalline diblock copolymers of poly(p-dioxanone) (PPDX) and poly(ϵ-caprolactone) (PCL) with different compositions have been studied by different techniques, including optical microscopy (OM), atomic force microscopy (AFM) and differential scanning calorimetry (DSC). The two blocks crystallize in a single coincident exotherm when cooled from the melt. The self-nucleation technique is able to separate into two exotherms the crystallization of each block. We have gathered evidences indicating that the PPDX block can nucleate the PCL block within the copolymers regardless of the composition. This effect is responsible for the lack of homogeneous nucleation or fractionated crystallization of the PCL block even when it constitutes a minor phase within the copolymer (25% or less). Nevertheless, we were able to show that decreasing amounts of PCL within the diblock copolymer still produces confinement effects that retard the crystallization kinetics of the PCL component and decrease the Avrami index. On the other hand evidence for confinement was also obtained for the PPDX block, since as its content is reduced within the copolymer, a depression in its self-nucleation and annealing temperatures were observed.     

Porous polyurethanes synthesized within high internal phase emulsions

PolyHIPE are highly porous, emulsion‐templated polymers typically synthesized via free‐radical polymerization within a water‐in‐oil (W/O) high internal phase emulsion (HIPE) whose dispersed, aqueous phase occupies more than 74% of the volume. The synthesis of a polyHIPE containing biodegradable polymers is not straightforward because the presence of both an organic phase and an aqueous phase within the HIPE limits the type of polymerization reactions that can be used. This article describes the synthesis of polyHIPE containing biodegradable poly(ε‐caprolactone) (PCL) groups through the step‐growth reaction of a diisocyanate with a flexible PCL triol to form a crosslinked polyurethane. The reaction of the diisocyanate with the water in the HIPE produced urea groups and large bubbles from the generation of CO₂. The polymer walls between these bubbles consisted of a porous, emulsion‐templated structure. Polymerization with an excess of diisocyanate produced a significant enhancement in the amounts of urea and CO₂. The reduction in the flexible PCL content and the enhancement in the rigid urea content produced an increase in wall modulus that was over 20‐fold. The ability to synthesize polyHIPE through such step‐growth reactions is an important advance in the adaptation of polyHIPE for such applications as tissue engineering. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5806–5814, 2009     

Two-dimensional Raman study of the submolecular, electric field-induced reorientation of a nematic liquid crystal

Two-dimensional Raman scattering is presented as a technique for the monitoring of electric field-induced, submolecular reorientation in liquid crystals. The motions of the flexible part and the rigid core of 4-pentyl-(4-cyanophenyl)cyclohexane (PCH5) are independently monitored in response to both step and oscillatory electric fields. Step voltage experiments show that the flexible group reorients before the rigid core. Also, oscillatory electric field experiments demonstrate that the flexible and rigid groups reorient asynchronously. In fact, at periodicities that are shorter than the bulk reorientation times, it is observed that the reorientation of the flexible part is amplified, while the motion of the rigid core is inhibited. The data suggest that the flexible group possesses a small, local dielectric anisotropy that can couple with the electric field to induce an independent, cooperative reorientation when the mobility of the rigid core is restricted.     

Blocky poly(ɛ‐caprolactone‐co‐butylene 2,5‐furandicarboxylate) copolyesters via enzymatic ring opening polymerization

Cyclic oligo(butylene 2,5‐furandicarboxylate) and ɛ‐caprolactone were copolymerized in bulk at 130–150 °C by enzymatic ring opening polymerization using CALB as catalyst. Copolyesters within a wide range of compositions were thus synthesized with weight‐average molecular weights between 20,000 and 50,000, the highest values being obtained for equimolar or nearly equimolar contents in the two components. The copolyesters consisted of a blocky distribution of the ɛ‐oxycaproate (CL) and butylene furanoate (BF) units that could be further randomized by heating treatment. The thermal stability of these copolyesters was comparable to those of the parent homopolyesters (PBF and PCL), and they all showed crystallinity in more or less degree depending on composition. Their melting and glass‐transition temperatures were ranging between those of PBF and PCL with values increasing almost linearly with the content in BF units. The ability of these copolyesters for crystallizing from the melt was evaluated by comparative isothermal crystallization and found to be favored by the presence of flexible ɛ‐oxycaproate blocks. These copolyesters are essentially insensitive to hydrolysis in neutral aqueous medium but they became noticeably degraded by lipases in an extend that increased with the content in CL units. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 290–299     

Poly(ε-caprolactone)-banded spherulites and interaction with MC3T3-E1 cells

We report that protein adsorption, cell attachment, and cell proliferation were enhanced on spherulites-roughened polymer surfaces. Banded spherulites with concentric alternating succession of ridges and valleys were observed on spin-coated thin films of poly(ε-caprolactone) (PCL) and two series of PCL binary homoblends composed of high- and low-molecular-weight components when they were isothermally crystallized at 25-52 °C. Their thermal properties, crystallization kinetics, and surface morphology were examined. The melting temperature (T(m)), crystallinity (χ(c)), crystallization rate, and spherulitic patterns showed strong dependence on the crystallization temperature (T(c)) and the blend composition. The surface roughness of the spherulites was higher when T(c) was higher; thus, the larger surface area formed in banded spherulites could adsorb more serum proteins from cell culture media. In vitro mouse preosteoblastic MC3T3-E1 cell attachment, proliferation, and nuclear localization were assessed on the hot-compressed flat disks and spherulites-roughened films of the high-molecular-weight PCL and one of its homoblends. The number of attached MC3T3-E1 cells and the proliferation rate were greater on the rougher surfaces than those on the flat ones. It is interesting to note that cell nuclei were preferentially, though not absolutely, located in or close to the valleys of the banded spherulites. The percentage of cell nuclei in the valleys was higher than 78% when the ridge height and adjacent ridge distance were ~350 and ~35 nm, respectively. This preference was weaker when the ridge height was lower or at a higher cell density. These results suggest that isothermal crystallization of semicrystalline polymers can be an effective thermal treatment method to achieve controllable surface roughness and pattern for regulating cell behaviors in tissue-engineering applications.     

高剪切速率对PCL/RGO附生结晶行为影响的原位研究

以聚己内酯(PCL)/还原氧化石墨烯(RGO)复合材料为研究对象, 利用同步辐射小角X射线散射(SAXS)和广角X射线衍射(WAXD)原位分析了75 s^?1的高速率剪切作用前后的附生晶体结构演变及其对本体晶体形成的影响. 研究结果表明, 在剪切后降温160 s后, PCL分子链开始在RGO表面附生, 形成表面结晶层, 同时形成部分PCL本体晶体; 在200~480 s的等温结晶阶段, 大量PCL本体片晶生成并形成规整的周期结构. 较高的剪切速率使体系的黏度降低, 因此在较高的剪切温度下PCL分子链更容易由伸直链转变为无规线团, 不利于PCL分子链在RGO表面形成表面结晶层. 在剪切速率为75 s^?1时, 70 ℃的剪切温度更有利于PCL分子链在RGO表面附生形成表面结晶层.     

The behavior of poly(ε -caprolactone) and poly(ethylene oxide)-b-poly(ε -caprolactone) grafted to a poly(glycerol adipate) backbone at the air/water interface

The behavior of crystallizable poly(ε-caprolactone) (PCL) and poly(ε-caprolactone)-b-poly(ethylene oxide) (PCL-b-PEO) is studied at the air/water interface prior and after grafting to an amorphous poly(glycerol adipate) (PGA) backbone (PGA-g-PCL, PGA-g-(PCL-b-PEO)). Langmuir isotherms are measured and the structure formation in the monolayers on the water surface is followed by Brewster angle microscopy (BAM) and in Langmuir–Blodgett films after a transfer to silicon substrates by atomic force microscopy (AFM). It is observed that PGA-g-PCL forms significantly smaller crystals on the water surface and has smaller crystallization rate compared to PCL homopolymers of identical molar masses as the grafted chains. In contrast to crystals formed by linear PCL, the crystals formed by grafted PCL in PGA-g-PCL do not melt (readsorb at the water surface) in an expansion cycle on the Langmuir trough. Additionally, increasing the subphase temperature at constant surface area significantly above the melting point of linear PCL in bulk results in the formation of a mesophase, and it does lead to the disappearance of crystals. The isotherms of PGA-g-(PCL-b-PEO) show a transition at the surface pressure of ～10 mN/m. This is related to the fact that PEO chains leave the water surface and submerge into the subphase and/or the crystallization of PCL chains. The monolayer collapse appears in an extended plateau region starting at π values of ～30 mN/m. AFM images of Langmuir–Blodgett films reveal that PCL chains in PGA-g-PCL and PGA-g-(PCL-b-PEO) form lamellar crystals with a disk-shape and interconnected platelets, respectively.     

Lamellar gels and spontaneous vesicles in catanionic surfactant mixtures

Caillé analysis of the small-angle X-ray line shape of the lamellar phase of 7:3 wt/wt cetyltrimethylammonium tosylate (CTAT)/sodium dodecylbenzene sulfonate (SDBS) bilayers shows that the bending elastic constant is kappa = (0.62 +/- 0.09)k(B)T. From this and previous results, the Gaussian curvature constant is kappa = (-0.9 +/- 0.2)k(B)T. For 13:7 wt/wt CTAT/SDBS bilayers, the measured bending elasticity decreases with increasing water dilution, in good agreement with predictions based on renormalization theory, giving kappa(o) = 0.28k(B)T. These results show that surfactant mixing is sufficient to make kappa approximately k(B)T, which promotes strong, Helfrich-type repulsion between bilayers that can dominate the van der Waals attraction. These are necessary conditions for spontaneous vesicles to be equilibrium structures. The measurements of the bending elasticity are confirmed by the transition of the lamellar phase of CTAT/SDBS from a turbid, viscoelastic gel to a translucent fluid as the water fraction is decreased below 40 wt %. Freeze-fracture electron microscopy shows that the gel is characterized by spherulite defects made possible by spontaneous bilayer curvature and low bending elasticity. This lamellar gel phase is common to a number of catanionic surfactant mixtures, suggesting that low bending elasticity and spontaneous curvature are typical of these mixtures that form spontaneous vesicles.     

聚己内酯和聚氧化乙烯共混体系中的两类片晶相间堆砌

对聚(ε-己内酯)(PCL)/聚氧化乙烯(PEO)共混物的相差显微镜、广角X-射线衍射(WAXD)、小角X-射线散射(SAXS)及示差扫描量热计(DSC)等的研究表明,只有当共混物中PCL(或PEO)的含量低于20％时,两组份是相容的.当PCL含量低于20％时,在共混物中形成了PEO片晶和PCL片晶相间堆砌的结晶形态,当PEO含量不超过20％时,PEO则完全以非晶形式混入PCL的非晶区,同时阻碍了PCL的结晶.可见在结晶过程中,相容的两组份对共混体系形态结构的影响却不尽相同.     

聚丙烯混杂复合体系的界面和力学性能

从刚性粒子增韧聚合物体系的界面层性质入手，研究了带有柔性分子链界面改性剂包覆的高岭土（Ｋａｏｌｉｎ）刚性粒子增韧的，短切玻纤（ＧＦ）增强的聚丙烯（ＰＰ）混杂复合体系的微观结构，结晶性质，ＰＰ／Ｋａｏｌｉｎ／ＧＦ混杂复合材料的加工流动性及力学性能．实验结果表明，所合成的界面改性剂对ＰＰ／Ｋａｏｌｉｎ复合材料有显著的增韧效果；加入少量的短切玻纤可以弥补因界面改性剂引入而引起的ＰＰ／Ｋａｏｌｉｎ复合材料强度和模量降低的缺点；经界面改性剂包覆的高岭土刚性粒子和短切玻纤同时加入ＰＰ，混杂复合后，ＰＰ复合材料的冲击韧性大幅度提高，材料的强度和模量不降低．这个结果不仅在较低的Ｋａｏｌｉｎ含量下，而且可在Ｋａｏｌｉｎ含量为５０％（ｗｔ％）的高填充量下也得以实现     

聚己内酯在聚己内酯/苯乙烯丙烯腈共聚物共混体系中的受限结晶

通过示差扫描量热 (DSC)、广角X 射线衍射 (WAXD)和小角X 射线散射 (SAXS)在不同尺度范围研究了聚己内酯 (PCL) 苯乙烯 丙烯腈共聚物 (SAN)共混体系中PCL的结晶行为 .由于该体系中SAN的玻璃化温度高于PCL的熔点 ,从而导致了PCL的结晶行为是一种受限结晶 .研究结果表明PCL的结晶行为从宏观 (DSC结果 )、介观 (SAXS结果 )到微观 (WAXD结果 )都受到了高玻璃化温度SAN的限制 .     

Crystallization kinetics and morphology of binary phenolic/poly(ϵ-caprolactone) blends

For the first time, quantitative analyses of the crystallization kinetics, surface free energy of chain folding, and morphology in phenolic/poly(ϵ-caprolactone) (PCL) binary blends have been studied. The spherulite growth rate and the overall crystallization rate depend on the crystallization temperature and PCL content in the blend. In addition, the crystallization and melting temperatures of the PCL phase decrease with an increase in the phenolic content. An Avrami analysis shows that the addition of phenolic to PCL results in a decrease in the overall crystallization rate of the PCL phase. The presence of an amorphous phenolic phase results in a reduction in the rate of the spherulite growth of PCL. The surface free energy of folding increases with increasing phenolic content, and the crystal thickness of a phenolic/PCL blend, according to small-angle X-ray scattering (SAXS), is greater than that of pure PCL because of the increase in the surface free energy of chain folding and the decrease in the degree of supercooling. The observed domain size of the crystalline/amorphous phase (5.9 nm) from SAXS is also consistent with that from solid-state NMR (3–20 nm). All these results indicate that the crystallization ability of PCL decreases with increasing phenolic content in the blends. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 117–128, 2004     

聚己内酯在有机/无机杂化体系中的受限结晶行为

通过Sol Gel技术合成了聚己内酯 (PCL) /二氧化硅 (SiO2 )杂化材料 ,并对杂化样品进行了DSC和WAXD测试 .实验结果表明杂化样品中PCL的结晶度随二氧化硅含量增加而减小 ,当样品中二氧化硅含量达到 60 %时 ,PCL为非晶态 ;含有PCL结晶的杂化样品中PCL熔融温度基本相同 ,但是比纯PCL的熔融温度低 .杂化样品中结晶PCL的结晶结构和微晶尺寸和纯PCL的一致 .这说明杂化材料中PCL的结晶行为和结晶度受到了限制 ,含PCL结晶的样品中PCL的结晶结构和微晶尺寸并没有受到影响 .