Narrow Molecular Weight Distribution Research Articles

A cost‐effective strategy for the synthesis of polystyrene‐polyisobutylene‐polystyrene triblock copolymer (SIBS) based on dicumyl chloride/TiCl4/Ti(OiPr)4 initiating system

AbstractA cost‐effective strategy has been developed for the synthesis of polystyrene‐polyisobutylene‐polystyrene (PS‐PIB‐PS) triblock copolymer (SIBS) with relative narrow molecular weight distribution (MWD) via the addition of Ti(OiPr)4. First, the controlled polymerization of styrene (St) was achieved by using TMPCl/TiCl4/Ti(OiPr)4 initiating system from −80 to −50°C in a cost‐effective solvent mixture n‐Hexane/CH2Cl2 (v/v = 6/4). The –OiPr group was present in the form TiCl3(OiPr) for TiCl4/Ti(OiPr)4 ratio more than 3/1 and moderated the lifetime of the growing PS cation. Subsequently, Ti(OiPr)4 was added to the living charge of PIB initiated by initiator 1,4‐dicumyl chloride (DCC), followed by the addition of styrene monomer. The success of this developed synthesis methodology was confirmed by comparing the findings from GPC (Gel permeation chromatography) traces with and without the addition of Ti(OiPr)4. SIBS with nearly 30% weight content of PS (SIBS30) was successfully obtained with an optimally narrow MWD of 1.49 at −80°C by employing the TiCl4/Ti(OiPr)4 ratio of 6/1. Interestingly, SIBS30 with a very narrow PDI of 1.22 could be successfully synthetized at an elevated temperature of −60°C.

Ring-opening polymerization of cyclic esters mediated by zinc complexes coordinated with benzotriazo-based imino-phenoxy ligands

A series of zinc complexes coordinated with benzotriazo-based imino-phenoxy ligands (ZnII(BTPIP)) has been developed for the mediation of ring-opening polymerization (ROP) of ε−caprolactone (ε−CL) and L−lactide (L−LA). In the presence of ZnII(BTPIP), the polymerization generated the PCL with the molecular weights in the range of 9600–17700 g mol−1 and narrow dispersity (Ð) around 1.08 to 1.33 as well as the PLA showing a molecular weight as 12300–14400 g mol−1 with narrow molecular weight distribution (Ð < 1.11). Furthermore, the living characters of the linearly increased molecular weight with monomer conversion and the synthesis of the tri-block copolymer of PEG-b-PCL-b-PLA were achieved. The substituent effect of ZnII(BTPIP) in the ROPs of ε−CL and L−LA was rationalized by the DFT calculations based on the coordination-insertion mechanism.

Lactate and glucose responsive boronic acid-substituted amphiphilic block copolymer nanoparticles of high aspect ratio

The establishment of conditions for formation of higher order morphologies (e.g. rods and worms) is important, as such nanoparticles are more efficient than spheres in drug delivery. Glucose-binding of core–shell nanoparticles comprising of boronic acid (BA) moieties occurs under basic conditions at above the pKa of the BA (pH 8.7). The resulting increased solubility of the core-forming BA-containing block is utilised in the delivery of therapeutics to diabetics. In contrast, the binding of the key anaerobic metabolite lactate to the BA moiety of amphiphilic block copolymers is unreported, despite occurring at lower physiological neutral pH 7.4. Herein, for the first time, high aspect ratio nanoparticles are observed for (unprotected) BA-substituted amphiphilic block copolymers in water, achieved by incorporating a non-stimuli responsive hydrophobic (tert-butylacrylamide) block. Amphiphilic diblock (Mn = 24,100 and 27,700 gmol−1) and triblock copolymers (Mn = 21,500 and 25,200 gmol−1) with relatively narrow molecular weight distributions (ᴆ = 1.31–1.48) were prepared by reversible addition-fragmentation chain transfer (RAFT) solution polymerizations. Aggregates formed upon dialysis with lactate at pH 7.4 were generally similar to those formed upon self-assembly with glucose at pH 8.7. Spherical nanoparticles for poly(N,N-dimethylacrylamide, DMA)28-b-(3-(acrylamidophenyl)boronic acid, 3-BAPhA)84-TTC (trithiocarbonate) decreased in size from Dh = 259 nm to mostly 100–150 nm upon ionization of BA-moieties with lactate, base, and glucose. Poly(DMA)96-b-(3-BAPhA)62 gave ∼ 500 nm long worms and lamellae under basic conditions, which transitioned to irregular spheres and rods upon addition of glucose. Self-assembly for triblock copolymers with BA-binding gave worms and fused spherical micelle rod-like structures.

Phosphine-functionalized amidinate ligated rare-earth metal complexes for highly 3,4-selective living polymerization of 1,3-conjugated dienes.

A series of rare-earth metal bis(alkyl) complexes have been prepared via protonolysis reactions of tris(aminobenzyl) complexes (Ln(CH2C6H4N(Me)2-o)3) with phosphine-functionalized amidinated ligands (DippNCN(CH2)nPPh2, n = 2 (L1-H) and n = 3 (L2-H)). The X-ray diffraction of P2-Sc (DippNCN(CH2)3PPh2Sc(CH2C6H4N(Me)2-o)2) showed the un-coordination of the diphenylphosphine group due to the inherent saturation of the central metal ion. In conjunction with [Ph3C][B(C6F5)4], all the rare-earth metal complexes showed a high catalytic activity for the polymerization of 1,3-conjugated dienes (isoprene, β-myrcene and β-farnesene), affording highly 3,4-regular polymers (up to 100% 3,4-) with high molecular weight and narrow molecular weight distribution. After the abstraction of the alkyl moiety -CH2C6H4N(Me)2-o of P1-Sc by [Ph3C][B(C6F5)4], the species with the coordination of the diphenylphosphine group to the central metal probably formed, as shown in the 31P NMR spectra and DFT calculation results, and it might serve as the true active species in the 3,4-selective polymerization of 1,3-conjugated dienes.

Synthesis of ROS-responsive poly(thioacetal)s with narrow molecular weight distributions via lactone ring-opening polymerization

Poly(thioacetal)s with narrow molecular weight distributions were synthesized via lactone ring-opening polymerization. They showed ROS-responsive degradability according to their electronic structures.

Enzyme and pH dual responsive linear-dendritic block copolymer micelles based on a phenylalanyl-lysine motif and peripherally ketal-functionalized dendron as potential drug carriers.

Stimuli-responsive linear-dendritic block copolymers (LDBCs) have attracted significant research attention as novel drug carriers. We report here three generations of new enzyme and pH dual responsive linear-dendritic block copolymers (LDBCs) with a phenylalanyl-lysine (Phe-Lys) dipeptide linking hydrophilic linear poly(N-vinylpyrrolidone) (PNVP) and a hydrophobic peripherally ketal-functionalized dendron derived from 2,2'-bis(hydroxymethyl)propionic acid (bis-MPA). The LDBCs are synthesized via a combination of interchange of xanthates/reversible addition-fragmentation chain transfer (MADIX/RAFT) polymerization of N-vinylpyrrolidone (NVP) and "chain-first" strategy. Their structures are confirmed by 1H NMR spectra. The gel permeation chromatograph (GPC) analysis revealed that the LDBCs have a narrow molecular weight distribution (PDI ≤ 1.25). The amphiphilic LDBCs can self-assemble into spherical nanomicelles in aqueous solution. The presence of enzyme or/and the change of pH cause disassembly of micelles to release encapsulated cargos. The release rates of the guest molecules are faster in buffer solution at pH 5.0 than those upon the addition of the activating enzyme and can be fine-tuned by changing the generation of bis-MPA dendrons. The combination of enzyme and pH dual stimuli results in significantly accelerated and more complete release of the loaded hydrophobic guests. The cell viability assay confirmed the favorable biocompatibility until the LDBC micelle concentration reached 800 μg mL-1. These results indicate that the LDBCs can be considered as a good candidate for targeting drug delivery.

Living ring-opening polymerization of β-butyrolactone initiated by mononuclear zirconium compounds containing sterically hindered N,O-chelate and anionic dimethylamide ligands.

The ring-opening polymerization of β-lactones into polyhydroxyalkanoates (PHA), biodegradable polymers with high molecular weight and narrow polydispersity, is of significant interest. The mononuclear zirconium compound containing sterically hindered N,O-chelate and anionic dimethylamide ligands was used as an initiator for the polymerization of β-butyrolactone (BBL), resulting in polyhydroxylbutyrate (PHB) with a number-average molecular weight of 12 000 g mol-1. Kinetic studies demonstrate a first-order dependence on β-butyrolactone (BBL) concentration at room temperature, accompanied by narrow molecular weight distributions (ca. 1.03-1.07), indicating a well-controlled living polymerization.

Study of the radical polymerization mechanism and its application in the preparation of high-performance PMMA by reactive extrusion.

In this study, the mechanism of radical polymerization was further explored by pre-dissolving different polymers and studying the kinetics of the bulk polymerization of methyl methacrylate (MMA) under shear-free conditions. Based on the analysis of the conversion and absolute molecular weight, it was found that, contrary to the shearing effect, the inert polymer with viscosity was the key factor to preventing the mutual termination of radical active species and reducing the termination rate constant k t. Therefore, pre-dissolving the polymer could increase the polymerization rate and molecular weight of the system simultaneously, making the polymerization system enter the automatic acceleration zone faster and greatly reducing the generation of small molecular weight polymers, leading to a narrower molecular weight distribution. When the system entered the auto-acceleration zone, k t decreased rapidly and greatly and entered the second steady-state polymerization stage. Then, with the increase in the polymerization conversion, the molecular weight gradually increased, while the polymerization rate gradually decreased. In shear-free bulk polymerization systems, k t can be minimized and radical lifetimes maximized, but the polymerization system is at best a long-lived polymerization rather than a living polymerization. On this basis, by using MMA to pre-dissolve ultrahigh molecular weight PMMA and core-shell particles (CSR), the mechanical properties and heat resistance of the PMMA with pre-dissolved polymer obtained by reactive extrusion polymerization were better than for pure PMMA obtained under the same conditions. Compared with pure PMMA, the flexural strength and impact strength of PMMA with pre-dissolved CSR were up to 166.2% and 230.5%. With the same quality of CSR, the same two mechanical properties of the samples obtained by the blending method were just improved by 29.0% and 20.4%. This was closely related to the distribution of CSR in the pre-dissolved PMMA-CSR matrix with a distribution of spherical single particles 200-300 nm in diameter, which enabled PMMA-CSR to exhibit a high degree of transparency. This one-step process for realizing PMMA polymerization and high performance shows extremely high industrial application prospects.

Reductive Amination of Dialdehyde Cellulose: Access to Renewable Thermoplastics.

The reductive amination of dialdehyde cellulose (DAC) with 2-picoline borane was investigated for its applicability in the generation of bioderived thermoplastics. Five primary amines, both aliphatic and aromatic, were introduced to the cellulose backbone. The influences of the side chains on the course of the reaction were examined by various analytical techniques with microcrystalline cellulose as a model compound. The obtained insights were transferred to a 39%-oxidized softwood kraft pulp to study the thermal properties of thereby generated high-molecular-weight thermoplastics. The number-average molecular weights (Mn) of the diamine celluloses, ranging from 60 to 82 kD, were investigated by gel permeation chromatography. The diamine celluloses exhibited glass transition temperatures (Tg) from 71 to 112 °C and were stable at high temperatures. Diamine cellulose generated from aniline and DAC showed the highest conversion, the highest Tg (112 °C), and a narrow molecular weight distribution (D̵ of 1.30).

Precision Synthesis of Polypeptides via Living Anionic Ring-Opening Polymerization of N-Carboxyanhydrides by Tri-thiourea Catalysts.

The chemistry of α-amino acid N-carboxyanhydrides (NCAs) has a history of over 100 years, but precise and efficient ring-opening polymerization methods for NCAs remain highly needed to facilitate the studies of polypeptides─that is, mimics of natural proteins─in various disciplines. Moreover, the universally accepted NCA polymerization mechanisms are largely limited to the "amine" and the "activated monomer" mechanisms, and the anionic ring-opening polymerization of NCAs has so far not been invoked. Herein, we show an unprecedented anion-binding catalytic system combining tripodal tri-thiourea with sodium thiophenolate that enables the fast and selective anionic ring-opening polymerization of NCAs. This method leads to the precision construction of various polypeptides with living polymerization behavior and is evidenced by narrow molecular weight distributions (Mw/Mn < 1.2), chain extension experiments, and minimal "activated monomer" pathway. Calculations and experimental results elucidate a living anionic polymerization mechanism, and high selectivities for monomer propagation relative to other deleterious side reactions, such as the "activated monomer" pathway, are attributed to the enhanced stabilization of the propagating carbamate anion, which is enforced by an intramolecular hydrogen bond within the tri-thiourea structure.

End functionalization of polyisoprene and polymyrcene obtained by anionic polymerization via one-pot ring-opening mono-addition of epoxides

End-functionalization of polyisoprene and polymyrcene were successfully synthesized using anionic polymerization in THF. A number of epoxides, propylene oxide (PO), butylene oxide (BO), allyl glycidyl ether (AGE), 1,2-epoxy-5-hexene (EH) and N,N-dibenzyl amino glycidol (DBAG), were utilised as terminating agents for the induction of hydroxyl functional group in the final products. Polymers were fully hydrogenated following epoxide termination. The functional polymers were characterized by 1H and 13C NMR showing high levels of regioselective termination, SEC showing good control over molecular weight to polymers with narrow molecular weight distributions, MALDI-ToF MS confirming very high levels of functionalisation and thermal analysis (TGA & DSC).

Photoresponsive thiourea and urea catalysts for ring‐opening polymerization of L‐lactide

AbstractStimulus responsive catalysts have received increasing attention. Photoresponsive catalytic polymerization is particularly attractive because the noninvasive and versatile nature of light. Most photoresponsive ROP catalytic systems exhibit low activities, allowing ROP to be completed within several hours to 10 h. In this contribution, a series of (thio)ureas bearing dithienylcyclopentene optical molecular switch moiety are designed, synthesized, and characterized. The photoresponsive effects in (thio)urea/alkoxide mediated ROP of L‐lactide are investigated. These catalysts allow the ROP reactions of L‐lactide to be completed within a few minutes to 1 h and the resulting polyesters have narrow molecular weight distributions. The dithienylcyclopentene moiety allows photoisomerization to be completed within 1 min. The catalytic activity of the ROP catalyst can be altered by the photoisomerization of the dithienyl cyclopentene moiety by exposure to ultraviolet or visible light, respectively.

Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals

AbstractWe report a novel method to synthesize degradable poly(vinyl ether)s with cleavable thioacetal bonds periodically arranged in the main chains using controlled cationic copolymerization of vinyl ethers with a 7‐membered cyclic thioacetal (7‐CTA) via degenerative chain transfer (DT) to the internal thioacetal bonds. The thioacetal bonds, which are introduced into the main chain by cationic ring‐opening copolymerization of7‐CTAwith vinyl ethers, serve as in‐chain dormant species to allow homogeneous propagation of vinyl ethers for all internal segments to afford copolymers with controlled overall and segmental molecular weights. The obtained polymers can be degraded into low‐ and controlled‐molecular‐weight polymers with narrow molecular weight distributions via hydrolysis. Various vinyl ethers with hydrophobic, hydrophilic, and functional pendants are available. Finally, one‐pot synthesis of multiblock copolymers and their degradation into diblock copolymers are also achieved.

Synthesis and Degradation of Vinyl Polymers with Evenly Distributed Thioacetal Bonds in Main Chains: Cationic DT Copolymerization of Vinyl Ethers and Cyclic Thioacetals.

We report a novel method to synthesize degradable poly(vinyl ether)s with cleavable thioacetal bonds periodically arranged in the main chains using controlled cationic copolymerization of vinyl ethers with a 7-membered cyclic thioacetal (7-CTA) via degenerative chain transfer (DT) to the internal thioacetal bonds. The thioacetal bonds, which are introduced into the main chain by cationic ring-opening copolymerization of 7-CTA with vinyl ethers, serve as in-chain dormant species to allow homogeneous propagation of vinyl ethers for all internal segments to afford copolymers with controlled overall and segmental molecular weights. The obtained polymers can be degraded into low- and controlled-molecular-weight polymers with narrow molecular weight distributions via hydrolysis. Various vinyl ethers with hydrophobic, hydrophilic, and functional pendants are available. Finally, one-pot synthesis of multiblock copolymers and their degradation into diblock copolymers are also achieved.

How we can improve ARGET ATRP in an aqueous system: Honey as an unusual solution for polymerization of (meth)acrylates

Aqueous solutions of various types of honey as a source of reducing sugars – glucose and fructose, were used to accelerate or control activators regeneration by electron transfer atom transfer radical polymerization (ARGET ATRP) in a homogeneous or heterogeneous environment. The aqueous or alcoholic-aqueous solution was applied for the polymerization of hydrophilic methacrylates i.e. 2-(dimethylamino)ethyl methacrylate (DMAEMA), glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA), while the polymerization of a hydrophobic monomer – n-butyl acrylate (nBA) was conducted in miniemulsion under ion-pair and interfacial catalysis. The polymerization of DMAEMA in a honey solution accelerated the polymerization rate up to 30-fold with a significant improvement in the control over the structure of the product, namely, the polymers were characterized by narrow molecular weight distribution (Mw/Mn = 1.33), and initiation efficiency up to 98 %. Controlled polymerization of nBA was conducted in a honey-contained miniemulsion. Honey-based miniemulsion was successfully checked for the synthesis of both linear and branched polymers. The use of chemical reducing agents found in commercially available food products for polymerization is an economic concept that eliminates the need for high purity laboratory reagents, moreover, food products are widely available and therefore much cheaper. The proposed concept has great potential for industrial applications.

Photoassisted Radical Depolymerization.

Controlled radical polymerization techniques enable the synthesis of polymers with predetermined molecular weights, narrow molecular weight distributions, and controlled architectures. Moreover, these polymerization approaches have been routinely shown to result in retained end-group functionality that can be reactivated to continue polymerization. However, reactivation of these end groups under conditions that instead promote depropagation is a viable route to initiate depolymerization and potentially enable closed-loop recycling from polymer to monomer. In this report, we investigate light as a trigger for thermal depolymerization of polymers prepared by reversible-addition-fragmentation chain-transfer (RAFT) polymerization. We study the role of irradiation wavelength by targeting the n → π* and π → π* electronic transitions of the thiocarbonylthio end-groups of RAFT-generated polymers to enhance depolymerization via terminal bond homolysis. Specifically, we explore depolymerization of polymers with trithiocarbonate, dithiocarbamate, and p-substituted dithiobenzoate end groups with the purpose of increasing depolymerization efficiency with light. As the wavelength decreases from the visible range to the UV range, the rate of depolymerization is dramatically increased. This method of photoassisted depolymerization allows up to 87% depolymerization efficiency within 1 h, results that may further the advancement of recyclable materials and life-cycle circularity.

Sulfur-Free Radical RAFT Polymerization of Methacrylates in Homogeneous Solution: Design of exo-Olefin Chain-Transfer Agents (R-CH2 C(=CH2 )Z).

In this work, the development of exo-olefin compounds (R-CH2 C(=CH2 )Z) as chain-transfer agents for the sulfur-free reversible addition-fragmentation chain transfer (RAFT) radical polymerization of methacrylates in homogeneous solution is described. A series of exo-olefin compounds with a methyl methacrylate (MMA) dimer structure as the R group and a substituted α-methylstyrene unit as the -CH2 C(=CH2 )Z (Z: Ph-Y) group were synthesized and used for the radical polymerization of MMA in toluene and PhC(CF3 )2 OH. These compounds underwent transfer of the CH2 C(=CH2 )Z group via addition-fragmentation of the propagating methacryloyl radical. More electron-donating (Y) substituents, such as methoxy and dimethylamino groups, produced polymers with narrower molecular weight distributions. A continuous monomer addition method further improved molecular weight control and enabled the synthesis of colorless, sulfur-free, multiblock copolymers of methacrylates in homogeneous solutions.

Sulfur‐Free Radical RAFT Polymerization of Methacrylates in Homogeneous Solution: Design of exo‐Olefin Chain‐Transfer Agents (R−CH2C(=CH2)Z)

AbstractIn this work, the development of exo‐olefin compounds (R−CH2C(=CH2)Z) as chain‐transfer agents for the sulfur‐free reversible addition‐fragmentation chain transfer (RAFT) radical polymerization of methacrylates in homogeneous solution is described. A series of exo‐olefin compounds with a methyl methacrylate (MMA) dimer structure as the R group and a substituted α‐methylstyrene unit as the −CH2C(=CH2)Z (Z: Ph−Y) group were synthesized and used for the radical polymerization of MMA in toluene and PhC(CF3)2OH. These compounds underwent transfer of the CH2C(=CH2)Z group via addition‐fragmentation of the propagating methacryloyl radical. More electron‐donating (Y) substituents, such as methoxy and dimethylamino groups, produced polymers with narrower molecular weight distributions. A continuous monomer addition method further improved molecular weight control and enabled the synthesis of colorless, sulfur‐free, multiblock copolymers of methacrylates in homogeneous solutions.

Simple and safe liquid seal approach to oxygen-tolerant ATRP

Trace oxygen is fatal to the conventional reversible deactivation radical polymerization (RDRP), so it is necessary to eliminate the influence of oxygen through some strict deoxygenation operations or by adding external components (post-treatment required). Here, we report the effective barrier of oxygen dissolution in an open system built by a liquid seal. Two different liquid seal materials, liquid paraffin and lithium grease, are used in this work. Lithium grease materials can stably isolate oxygen at a high stirring speed (450 rpm) to intensify the heat and mass transfer processes during the reaction. An effective atom transfer radical polymerization (ATRP) could be assisted by simply adding liquid seal materials with a thickness of 5 mm, providing polymers with high conversion (≥90 %), controlled molecular weight, narrow molecular weight distribution (Mw/Mn ≤ 1.15) and high end-group fidelity. With this liquid seal strategy, dozens of grams of the polymer were obtained, which is expected to have potential industrial applications under ambient atmosphere and conditions.

Unusual Effect of α-olefins as Chain Transfer Agents in Ethylene Polymerization over the Catalyst with Nonsymmetrical Bis(imino)pyridine Complex of Fe(II) and Modified Methylalumoxane (MMAO) Cocatalyst.

Ethylene polymerization with bis(imino)pyridlyiron precatalysts generally produces linear polyethylene (PE) even with the presence of α-olefins because α-olefins are not incorporated into polymeric products. Interestingly, α-olefins, such as hexene-1 or butene-1, have been found to act as effective chain transfer agents in the ethylene polymerization promoted by nonsymmetrical bis(imino)pyridyliron complexes with modified methylalumoxane (MMAO), resulting in higher catalytic activities with higher amounts of polymers with lower molecular weights, and, more importantly, narrower molecular weight distributions of the resultant polyethylenes (PE). This phenomenon confirms the assistance of α-olefins in the chain-termination reaction of iron-initiated polymerization and regeneration of the active species for further polymerization. Besides higher activities of the catalytic system, the formation of linear PE with trans-vinylene terminal groups and lower molecular weights are explained. The observation will provide a new pathway for enhancing catalytic activity and improving the quality of polyethylenes obtained by regulation of molecular weights and molecular weight distribution.