Low Number-average Molecular Weight Research Articles

Amphiphilic hot-melt pressure sensitive adhesives for transdermal administration made from low melt-processing temperature OSISO copolymers

Herein, an anionic polymerization method was employed to synthesize a series of amphiphilic poly(ethylene oxide-b-styrene-b-isoprene-b-styrene-b-ethylene oxide) penta-block copolymers (OSISO). Their molecular structure and properties were comprehensively characterized using GPC,1H-NMR, thermodynamic rheological testing and water contact angle test. Notably, the hydrophilic characteristics exhibited a proportional increase with the rise in poly(ethylene oxide) (PEO) content, ranging from 1.3 to 12.6 wt%. The polystyrene blocks with low number-average molecular weight (2000–3500) reduced the copolymer melt viscosity, surpassing a tenfold decrease than the control sample within the temperature range of 50–150 °C. Resultantly, this series of OSISO copolymers could be used to develop amphiphilic hot-melt pressure-sensitive adhesives (HMPSAs) by low temperature hot-melt processing method (<120 °C). HMPSAs loaded with 2 wt% of geniposide, prepared by an optimized composition formula of OSISO copolymers, tackifiers, and plasticizers (in a ratio of 5:5:2), displayed excellent in vitro drug release performance. Additionally, these adhesives presented impressive 180° peeling strength (0.05–0.14 kN/m) without residues left on the substrate in the 180° peeling tests. The incorporation of PEO block significantly enhanced both the adhesive properties and accumulative drug release. Geniposide showed a burst release behavior with a moderate accumulative drug release (15–30 wt%), attributed to the PEO phase without crystallization behavior of long PEO chains.

Branched copolymer surfactants impart thermoreversible gelation to LAPONITE® gels.

This investigation seeks to integrate LAPONITE® clay gels with thermoresponsive branched copolymer surfactants (BCSs) to develop advanced functional materials with temperature-induced sol-gel behaviour. It is known that a diverse range of molecules adsorb strongly to clays which may be used to control liberation of the species in healthcare applications, and as such the development of polymer/clay hybrid materials which can add function to the native clay behaviour are of great interest. BCS were synthesised with a structure that encompasses poly(ethylene glycol)methacrylate (PEGMA), ethylene glycol dimethacrylate (EGDMA), and dodecanethiol (DDT), conferring versatile and tuneable thermoresponsive attributes. Systematic modulation of the monomer : DDT/initiator ratio was used to facilitate the synthesis of BCS architectures spanning a range of molecular weights. Through application of small-amplitude oscillatory shear (SAOS) rheology and small-angle neutron scattering (SANS) in conjunction with controlled temperature variations, the sol-gel transition dynamics of these nanocomposite materials were elucidated. Complementary insights into the mechanisms underpinning this transition and temperature-induced alterations in the constituents are gleaned through the utilization of SANS techniques employing contrast-matching methodologies to mitigate clay and polymer scattering interference. It is found that heating systems from room- to body- temperature induces self-assembly of BCS in the bulk aqueous phase with concurrent structuration of clay in gel-forming samples with lower number average molecular weight (Mn). SANS study unpicks this phenomenon to find that gelation occurs with concurrent aggregation of BCS in the bulk, inducing clay-clay interactions only in lower Mn BCS systems with large nanoaggregates.

Influence of number average molecular weight on the properties of 3D printed precursor ceramics

A deliberately selected end-capping agent was introduced into the precursor to form a low number average molecular weight precursor and meet the need for liquid crystal display (LCD) 3D printing. The influence of number average molecular weight on the photocuring properties of precursor and the physical properties of pyrolysis samples were studied in detail for the first time. The results proved that a relatively low number average molecular weight precursors had low ceramic yields after pyrolysis. As the number average molecular weight of the precursor decreased, the photocuring ability of the precursor photosensitive resin increased. With the decrease in the number average molecular weight of the precursor in the precursor photosensitive resin, the ceramic yield of 3D printed PDCs decreased from 58.4% to 30.2%, and the linear shrinkage increased from 27.2% to 40.3%. The bending strength of the LCD 3D printed specimen reached 61.5 ± 3.7 MPa. The low cost of precursor synthesis and equipment in this study points the way for the preparation of precursor non-oxide ceramic composites and can be conducive to the development and application of LCD 3D printing precursor ceramics.

Bottom-up self-assembly of nanofibers in the surfactant mixture of CTAB and Pluronics

Bottom-up self-assembly of nanofibers in a chemical method is presented using the surfactant mixture of cetyltrimethylammonium bromide (CTAB) and Pluronics as the anisotropic micellar templates. Fully fluorinated perfluorooctanoic acids with highly hydrophobic C–F chains are imported for constructing exceptionally long nanofibers. Ag(I) provides robustness of the materials by the complexation with ethylene oxides in Pluronic copolymers. Fluorocarbons reside in the PPO (polypropylene oxide) blocks in Pluronic polymers and accordingly in reverse Pluronics, they are placed in the surrounding regions of nanofibers. During the segregation of water from hydrophobic cores, self-assembly is assumed to be driven by hydrophobic interactions among alkyl chains of CTAB, fluoroalkyl chains of perfluorooctanoic acids, and dehydrated methyl groups of PPO blocks in Pluronics. Nanofibers with relatively high aspect ratios were obtained when Pluronic copolymers with low number average molecular weights (Mn), such as L-31 (Mn ∼ 1100) and L-64 (Mn ∼ 2900), were used. Heterogeneous catalytic activities were monitored in the reduction reactions of 4-nitrophenol, and the nanorods prepared from Pluronic 31R1 show the best catalytic performances with a rate constant of 0.002 35 s−1. The roles of fluorine or C–F groups in perfluorooctanoic acids are believed to be the disruption of hydrogen bonding between water and polyethylene oxide groups, and the phase separation of nanofibers from the aqueous environment by the dehydration of hydrophobic cores.

Control of the temperature responsiveness of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) copolymer using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (poly(NIPAM-co-HEMA)) is a temperature-responsive copolymer that is expected to be applicable as an advanced functional polymeric material in various fields. In this study, a novel method was developed to control the responsive temperature of poly(NIPAM-co-HEMA) using an ultrasonic polymerization technique. Initially, the behavior of the reaction was investigated using NIPAM and HEMA monomers under ultrasonic irradiation. A high ultrasonic power was found to produce a high reaction rate and low number average molecular weight of the copolymer. The polydispersity of the synthesized copolymer was approximately 1.5 for all ultrasonic powers examined. In the early stage of the reaction, the molar fraction of NIPAM in the copolymer was lower than the initial molar fraction of the monomers. It was concluded that ultrasonic irradiation affected the initiation reaction and polymer degradation, but did not affect the propagation reaction. Furthermore, the effect of the ultrasonic irradiation conditions on the temperature responsiveness of the copolymer was investigated. The lower critical solution temperature (LCST) of the copolymer was found to increase with increasing ultrasonic irradiation time. In addition, in the early stages of the reaction, the measured values of the LCST were higher than the estimated values using copolymer composition. This can be attributed to some parts of the copolymer chain possessing a higher NIPAM fraction than the overall fraction due to different reactivities of the monomers and terminated radicals. This hypothesis was indirectly verified by the synthesis of a block copolymer from the PNIPAM homopolymer and HEMA monomer.

Several Shapes of Single Crystalline Gold Nanomaterials Prepared in the Surfactant Mixture of CTAB and Pluronics.

Twin structures in gold nanomaterials are destined because they reduce the severe strains in the misfit region of nanostructures. Defect-free single crystalline plasmonic nanomaterials gain interests these days as the integration of plasmonic materials or plasmons into electronic devices and circuits becomes more common. In this study, without subtle experimental adjustments, such as pH or halide additives, several shapes of single crystalline gold nanoparticles (NPs) are prepared in the surfactant mixture of cetyltrimethylammonium bromide (CTAB) and Pluronic triblock copolymers. The synthesized NPs are primarily composed of {100} planes with small numbers of particles possessing a [110] zone axis. Pluronic copolymers with low number average molecular weights (Mn), such as L-31 (Mn ≈ 1100) and L-64 (Mn ≈ 2900), prefer anisotropic nanorods with the aspect ratios of 4.3 and 3.0, respectively, while Pluronics with high Mn values, such as F-68 (Mn ≈ 8400) and F-108 (Mn ≈ 14 600), favor more concentric and isotropic cube-like NPs. Extended micelles are believed to form in Pluronics with low Mn values in which hydrophobic cores are merged with the increase of temperature, while the corona regions that are composed of long tails of PEO prevent the merge of hydrophobic cores, and the growth of the micelles is limited in Pluronic copolymers with high Mn values. The catalytic degradation reactions of methyl orange are conducted, and rather than isotropic particles, gold nanorods exhibit better catalytic performances. More hydrophilic environment and the steric alignment of rigid aromatic structures of methyl orange along the nanorods are thought to contribute to the catalytic activities. Overall, highly confined geometries of the appropriately swollen micellar templates of Pluronics and CTAB, which is not so hydrophobic as for the formation of contracted deswollen templates and for the inhibition of the growth of NPs, and which is not so hydrophilic as for the formation of coarse templates and for the formation of isotropic spheres with varying sizes, are believed as the main factor for the formation of single crystalline gold NPs.

Using Poloxamer® 407 as Building Block of Amphiphilic Poly(ether urethane)s: Effect of its Molecular Weight Distribution on Thermo-Sensitive Hydrogel Performances in the Perspective of Their Biomedical Application

Due to its hydroxyl terminal groups, Poloxamer® 407 (P407), a commercially available poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer can be used as macrodiol for the synthesis of high molecular weight amphiphilic poly(ether urethane)s (PEUs). This work was aimed at studying the effect of P407 purification by removing PEO-PPO diblock copolymer by-products on the chemical properties of PEU polymer and the physical properties of PEU hydrogels. Removal of PEO-PPO diblock copolymers (P407_P) was found to preserve the thermo-responsiveness of resulting hydrogels, although slightly lower gelation onset temperature (Tonset) was found for P407_P (15.3°C) vs. P407 (16.7°C) hydrogels (25% w/V) as assessed through temperature ramp test. P407 and P407_P were then reacted with 1,6-diisocyanatohexane and 1,4-cyclohexanedimethanol to synthesize two different PEUs, coded as CHP407 and CHP407_P, respectively. Lower Number Average Molecular Weight (Mn¯) and higher polydispersity Index (D) was measured for CHP407 (Mn¯: 34 kDa, D: 1.6) respect to CHP407_P (Mn¯: 40 kDa, D: 1.4) as a consequence of macrodiol purification. CHP407_P hydrogels formed bigger micelles (43.9 ± 4.1 nm vs. 28.7 ± 4 nm) while showed similar critical micellar temperatures (22.1°C vs. 21.6°C) respect to CHP407 formulations. Sol-to-gel transition of CHP407 and CHP407_P hydrogels was similar while CHP407_P gelation time at 37°C was longer as assessed by tube inverting test. The rheological analysis showed slightly lower Tonset for CHP407_P hydrogels (15% w/V), probably due to larger micelle size, promoting micellar assembly. However, CHP407_P hydrogels showed a significantly lower critical strain than CHP407 hydrogels, as assessed by strain sweep test, suggesting their higher brittleness due to a lower density of intermicellar bridge chains. Nano-scale hydrogel characterization by Low-Field Nuclear Magnetic Resonance spectroscopy supported previous findings, showing lower spin-spin relaxation time (i.e., 1,259 ms) for CHP407_P than for CHP407 hydrogels (i.e., 1,560 ms) at 37°C, which suggested the formation of a more tightly packed network for CHP407_P than CHP407 hydrogel. Finally, lower swelling capability and resistance against dissolution were measured for CHP407_P hydrogels. Overall, the here‐reported results suggested that the heterogeneous structure in the CHP407 hydrogel network caused by the presence of diblock copolymer-based macrodiols improved PEU hydrogel properties in light of their applicability in the biomedical field.

Vat photopolymerization of liquid, biodegradable PLGA-based oligomers as tissue scaffolds

Additive manufacturing (AM) of tissue scaffolds provides medical professionals and patients with personalized treatment options, which align with patients’ specific physiology and provide a more efficient and precise manufacturing process. Vat photopolymerization (VP) AM affords biocompatible, degradable, and high-resolution scaffolds capable of achieving specific pore sizes necessary for tissue regeneration. Earlier biodegradable, photoactive polymers for the VP platform usually require dissolution in a solvent or water, which often results in anisotropic shrinkage upon drying and inconsistencies in the final part geometry. This work describes a photoactive oligomeric precursor that eliminates the requirement for water or solvent during VP. Poly(lactide-co-glycolide) (PLGA) diacrylates with low number-average molecular weights (< 1400 g mol−1) provided liquid, viscous precursors. Upon crosslinking, the networks exhibited mechanical strength and low cytotoxicity, which are prerequisites for soft tissue scaffolds. Systematically varying the ratios of lactide to glycolide provided a range of degradation rates from 4 to 12 wks. Tailored degradation rates will enable use in different anatomical environments. Cytotoxicity and cell attachment studies revealed crosslinked films that promoted cell growth and proliferation. This manuscript describes an expanded polymer toolbox for AM of tissue scaffolds with precise resolution in the absence of solvents.

Insight on the influence of nano zinc oxide on the thermal, dynamic mechanical, and flow characteristics of Poly(lactic acid)– zinc oxide composites

Composites of Poly(lactic acid) (PLA) and spherical zinc oxide (ZnO) nanoparticles were prepared using melt processing followed by injection molding. The effect of nanosized ZnO on the molecular structure, thermal properties, dynamic mechanical properties, and flow characteristics of PLA composites were analyzed. Scanning electron microscopy images illustrated the formation of ZnO aggregates through PLA matrix. The molecular weight of PLA‐ZnO experienced a substantial decline by 55%, suggesting the presence of ZnO provoked degradation of PLA during composite preparation. Glass transition temperature of PLA‐ZnO decreased by 18% as compared with pure PLA, confirming the deleterious role of ZnO in PLA. The ZnO nanoparticles acted as a reactant and increased the thermal degradation rate. However, the incorporation of ZnO into PLA increased the crystallinity up to 20% and the storage modulus of composites in glassy state by 10%. The higher peak value of tan δ in composites suggested the more viscous behavior, which was further supported by lower number average molecular weight. The complex viscosity of composites exhibited a large Newtonian region over low shear rate, followed by shear thinning phenomenon. A significant decrease (96%) in complex viscosity was observed with the addition of ZnO into PLA. POLYM. ENG. SCI., 59:1242–1249 2019. © 2019 Society of Plastics Engineers

Copolycarbonates Based on a Bicyclic Diol Derived from Citric Acid and Flexible 1,4-Cyclohexanedimethanol: From Synthesis to Properties.

Octahydro-2,5-pentalenediol (OPD), is a compelling citric acid-based bicyclic diol with excellent rigidity and thermal stability. Herein, a series of copolycarbonates (co-PCs) were synthesized, starting from OPD, 1,4-cyclohexanedimethanol (CHDM), and diphenyl carbonate (DPC). All polycarbonates are amorphous with glass transition temperatures increased when increasing the content in OPD units. Dynamic mechanical analysis (DMA) revealed the sub Tg β-relaxations at low temperatures originating from the CHDM conformational transition, indicative of the possibility of impact-resistance. Morphological analysis of the fracture surfaces revealed the toughening mechanism under tensile was shear yielding of the matrix triggered by internal cavitation. The incorporation of OPD steadily increased the Young's modulus, from 482 to 757 MPa, with the OPD fraction increased from 0 to 30 mol %. As the OPD content further increased, a "ductile-to-brittle" transition occurred due to the low number-average molecular weight (Mn) and the low entangled strand density (high entanglement molecular weight).

Synthesis, characterization, and efficient electrohydrodynamic patterning with a high aspect ratio of a soluble oligomerpyrrole derivative

To efficiently manufacture high-aspect-ratio micro−/nanopatterns of conducting polymers (CPs) via electrohydrodynamic patterning (EHDP), a soluble oligomerpyrrole derivative was synthesized through the method of side-chain-induced solubilization. The oligomerpyrrole derivative shows a low number-average molecular weight (Mn) of 5674 due to the hindering effect of its bulky side chains and then exhibits excellent solubility, favorable film-forming ability and good thermal stability. It is found that because of the low viscosity and leaky dielectric property, a variety of high-aspect-ratio micro−/nanopatterns of the oligomerpyrrole derivative can be rapidly manufactured directly on a conductive substrate via changing the spacing of the air clearance of EHDP. This technique successfully provides a straightforward, economical and contactless way for patterning CP films into a series of high-aspect-ratio micro−/nanopatterns utilizing only a low-aspect-ratio mold.

Synthesis of poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) with low polydispersity using ultrasonic irradiation

Poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) having low polydispersity was synthesized in mixed solvent of ethanol and water using ultrasonic irradiation without any chemical polymerization initiator. The effects of the volume fraction of ethanol in the solvent, the molar ratio of two monomers, the monomer concentration and the ultrasonic power intensity on the time courses of the conversion to the polymer, the number average molecular weight, and the polydispersity of synthesized polymer were investigated in order to determine the optimal conditions to synthesize the copolymers with a narrow molecular weight distribution (i.e. low polydispersity). The optimum volume fraction of ethanol in the solvent was 60 vol% to synthesize the copolymers with a low polydispersity. A higher ultrasonic power intensity resulted in a faster polymerization rate and a lower number average molecular weight. The polydispersity was less than 1.5 for all ultrasonic power intensities up to 450 W/dm3 applied in this work. A higher monomer concentration gave a faster polymerization rate and a higher number average molecular weight. The polydispersity was less than 1.5 when the monomer concentration was lower than 0.4 mol/dm3. A higher molar ratio of N-isopropylacrylamide resulted in a higher polymerization rate and a lower number average molecular weight. The copolymers with polydispersity less than 1.5 can be obtained regardless of the molar ratio of N-isopropylacrylamide. The copolymers synthesized by the ultrasonic polymerization method had a high temperature responsibility.

Controlled Radical Polymerization of Styrene Mediated by Xanthene-9-thione and Its Derivatives

In our present work, a novel controlled radical polymerization system is developed based on xanthene-9-thione (XT). It was found that the radical polymerization of styrene (St) became controlled in the presence of a small amount of XT. At the early stage of the polymerization, the polymerization rate was relatively low and the as-formed polystyrene (PS) had low number-average molecular weight (Mn) and narrow polydispersity (Ð). After XT was consumed, the polymerization rate increased dramatically and the Mn of PS increased gradually with polymerization proceeding. When the polymerization of St was carried out with a proper molar ratio of initiator to XT and at an appropriate temperature, shortened slow polymerization stage and good control over Mn could be achieved. To further improve the regulating ability of XT, a series of substituent groups (-CF3, -CH(CH3)2, -N(CH3)2) were introduced onto the xanthene ring of XT, and the effects of these derivatives on the polymerization of St were investigated in detail. UV-Vis spectroscopy was carried out to monitor the concentration of XT during the polymerization and the chemical structure of the as-formed PS was fully characterized by 1HNMR and ESI-MS analysis. A possible mechanism involving the formation and evolution of the cross-termination products was proposed to interpret the observed polymerization behavior.

Atomic Force Microscopy Thermally-Assisted Microsampling with Atmospheric Pressure Temperature Ramped Thermal Desorption/Ionization-Mass Spectrometry Analysis.

The use of atomic force microscopy controlled nanothermal analysis probes for reproducible spatially resolved thermally assisted sampling of micrometer-sized areas (ca. 11 × 17 μm wide × 2.4 μm deep) from relatively low number-average molecular weight (Mn < 3000) polydisperse thin films of poly(2-vinylpyridine) (P2VP) is presented. Following sampling, the nanothermal analysis probes were moved up from the surface and the probe temperature ramped to liberate the sampled materials into the gas phase for atmospheric pressure chemical ionization and mass spectrometric analysis. The procedure and mechanism for material pickup, the sampling reproducibility and sampling size are discussed, and the oligomer distribution information available from slow temperature ramps versus ballistic temperature jumps is presented. For the Mn = 970 P2VP, the Mn and polydispersity index determined from the mass spectrometric data were in line with both the label values from the sample supplier and the value calculated from the simple infusion of a solution of polymer into the commercial atmospheric pressure chemical ionization source on this mass spectrometer. With a P2VP sample of higher Mn (Mn = 2070 and 2970), intact oligomers were still observed (as high as m/z 2793 corresponding to the 26-mer), but a significant abundance of thermolysis products were also observed. In addition, the capability for confident identification of the individual oligomers by slowly ramping the probe temperature and collecting data-dependent tandem mass spectra was also demonstrated. The material type limits to the current sampling and analysis approach as well as possible improvements in nanothermal analysis probe design to enable smaller area sampling and to enable controlled temperature ramps beyond the present upper limit of about 415 °C are also discussed.

Effect of molecular weight in diketopyrrolopyrrole-based polymers in transistor and photovoltaic applications

Uncovering the precise effect of the conjugated polymer chain length on the semiconducting properties in thin-film devices is confounded by the step-growth polymerization techniques typically used. Here, we use preparatory size exclusion chromatography to isolate fractions of two diketopyrrolopyrrole-thiophene based co-polymers with low molar-mass dispersity, ĐM, and number average molecular weights up to 180 kDa. We find that the charge carrier mobility can vary over three orders of magnitude in the range from 9 to 70 kDa, while a factor of 3–4 increase in photovoltaic performance was noted over the same range. The effect of ĐM was found to be most drastic when the largest chains were mixed with the shortest. The study of the thin-film morphology and crystallinity by GIWAXS give further insights into the origin of these effects. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016

Construction of an Immobilized Thermophilic Esterase on Epoxy Support for Poly(ε-caprolactone) Synthesis.

Developing an efficient immobilized enzyme is of great significance for improving the operational stability of enzymes in poly(ε-caprolactone) synthesis. In this paper, a thermophilic esterase AFEST from the archaeon Archaeoglobus fulgidus was successfully immobilized on the epoxy support Sepabeads EC-EP via covalent attachment, and the immobilized enzyme was then employed as a biocatalyst for poly(ε-caprolactone) synthesis. The enzyme loading and recovered activity of immobilized enzyme was measured to be 72 mg/g and 10.4 U/mg using p-nitrophenyl caprylate as the substrate at 80 °C, respectively. Through the optimization of reaction conditions (enzyme concentration, temperature, reaction time and medium), poly(ε-caprolactone) was obtained with 100% monomer conversion and low number-average molecular weight (Mn < 1300 g/mol). Further, the immobilized enzyme exhibited excellent reusability, with monomer conversion values exceeding 75% during 15 batch reactions. Finally, poly(ε-caprolactone) was enzymatically synthesized with an isolated yield of 75% and Mn value of 3005 g/mol in a gram-scale reaction.

In situ sonochemical synthesis of ZnO particles embedded in a thermoplastic matrix for biomedical applications.

Zinc oxide particles were synthesized and dispersed in situ in a polystyrene (PS) matrix using ultrasound. PS ultrasonic degradation was investigated at different polymer concentrations in organic solvent in contact with aqueous media prior to the particle synthesis. Decrease in weight-average molecular weight (Mw) was strongly dependent on polymer concentration in organic solvent and sonication time: degradation occurred less at higher polymer concentration, yet increased with longer times of more than 30min. The ZnO particles with a 800nm flower-like morphology were dispersed in the polystyrene matrix in situ; the composite presented both a lower average molecular weight (Mw) and lower number average molecular weight Mn when compared to pristine polystyrene, however thermal degradation temperature and Young's modulus were similar to the pristine polystyrene. The composite prepared in situ presented lower particle aggregation in comparison with ZnO commercially dispersed with ultrasound under the same conditions. Antibacterial activity of the ZnO/PS coating was tested against Escherichia coli (Gram-negative bacteria; DMS No. 10290) by evaluating bacterial growth inhibition after 20h on contact with the film surface. The results indicated that bacterial growth was inhibited in the medium in contact with the composite prepared in situ compared to the film of composite prepared by mixing and the pristine PS. This study showed the potential use of ZnO/PS composite prepared in situ as antibacterial coatings.

Hydrolytic degradation of linear 2-arm and branched 4-arm poly(dl-lactide)s: Effects of branching and terminal hydroxyl groups

“Linear” 2-arm and “Branched” 4-arm poly(dl-lactide) [i.e., poly(dl-lactic acid)s, or PDLLA] with relatively low number-average molecular weights (Mn) in the range 0.7–2.2 × 104 g mol−1 were synthesized using ring-opening polymerization of dl-lactide with the initiator of tin(II) 2-ethylhexanoate (i.e., stannous octoate) and the coinitiators of 1,3-propanediol and pentaerythritol. The hydrolytic degradation of 2- and 4-arm PDLLA was performed in phosphate-buffered solution at 97 °C for the period of time up to 10 h. The obtained results indicate that the molecular architecture (linear or branched) and the number of hydroxyl groups per unit mass of PDLLA alter the hydrolytic degradation mechanism, behavior, and rate. The hydrolytic degradation of 2-arm PDLLA and 4-arm PDLLA proceeds mainly via bulk and surface erosion mechanisms, respectively. However, 2-arm PDLLA acquired an additional surface erosion nature with decreasing molecular weight. The hydrolytic degradation rate monitored by Mn decrease was higher for 2-arm PDLLA than for 4-arm PDLLA and that of 2-arm PDLLA decreased with decreasing Mn. These findings can be explained by the strength of surface erosion nature. Another reason for lower k value of low-molecular-weight 2-arm PDLLA compared to that of higher-molecular-weight 2-arm PDLLA should be the suppressed segmental mobility of low-molecular-weight 2-arm PDLLA probably caused by the high density of hydrogen bonding formed during sample preparation.

Cationic polymerization of isoprene using zinc halides as co‐initiators: towards well‐defined oligo(isoprene)s under mild conditions

AbstractThe activity of ZnX2‐based initiating systems (X = Cl, Br, I) in the cationic polymerization of isoprene was studied. The highest activity was achieved when co‐initiator (ZnX2) was solubilized in a minimal amount of strongly coordinating solvent such as diethyl ether or acetone and when trichloroacetic acid was used as an initiator. It is shown that the polymerization rate increased in the series ZnI2 &lt; ZnCl2 &lt; ZnBr2. An increase of initiator concentration and temperature also led to an increase of the polymerization rate. The obtained polyisoprenes did not contain high‐molecular‐weight and insoluble fractions and were characterized by low number‐average molecular weight and relatively narrow molecular weight distribution. Unsaturation of polyisoprene decreased with an increase of monomer conversion and reaction temperature. The unsaturated part of the polyisoprene chain possessed predominantly 1,4‐trans microstructure with regular and inverse addition, whereas the 1,2‐ and 3,4‐isomers were present as minor components. It is shown that the synthesized low‐molecular‐weight polyisoprenes are effective plasticizers for rubber compounds in the manufacture of tyres. © 2012 Society of Chemical Industry

Controlled oligomerisation of isoprene-towards the synthesis of squalene analogues

Poly(isoprene) oligomers have been synthesised by the use of a range of controlled radical polymerisation techniques, including Catalytic Chain Transfer Polymerisation (CCTP), Reversible Addition Fragmentation Chain Transfer Polymerisation (RAFT), Atom Transfer Radical Polymerisation (ATRP) and Reverse Atom Transfer Radical Polymerisation (RATRP). The key molecular targets were (a) a low number average molecular weight equivalent to that of squalene and (b) a final backbone structure that contains a minimum of 75% of the 1,4 addition form of the isoprene monomer. These structural elements closely match those of the natural squalene which is the cosmetic/health care industry benchmark. CCTP and RAFT were successful in achieving the set targets via solution based polymerisation. The yields of oligomer from these techniques were approximately the same (∼42% from CCTP and ∼47% from RAFT), as were the Mns, (750 and 850 ± 220 g mol−1 respectively versus a GPC squalene target Mn of 570 g mol−1) and polydispersities (1.28 and 1.21 respectively versus a GPC squalene target of 1.02). The backbone structure of the materials produced by these techniques were shown to exceed the 75% 1,4 addition target. Therefore, both of these techniques have the potential to produce the target structures on a larger/commercial scale. However, the choice of initiator and/or RAFT agent was found to have a strong influence on the molecular weight obtained. The ATRP and RATRP techniques proved unable to demonstrate sufficient control over the polymerisation to produce the target oligomers under the reactions conditions applied whilst achieving acceptable yields (>40%).