Synthesis Of Well-defined Block Copolymers Research Articles

Simple and Rapid Access toward AB, BAB and ABAB Block Copolyesters from One-Pot Monomer Mixtures Using an Indium Catalyst.

The synthesis of well-defined block copolymers from one-pot monomer mixtures is particularly challenging when monomers are from the same class and show similar reactivity. Herein, an indium-based catalyst that shows comparable rates in the ring-opening homopolymerization of β-butyrolactone (β-BL) and ε-decalactone (ε-DL), demonstrates monomer-selective behavior in one-pot copolymerizations of β-BL and ε-DL. This provides simple and rapid access to well-defined di-, tri-, or tetra-block copolyesters from monomer mixtures. The sequence-controlled nature of these polymers was confirmed by kinetic analysis, 13C{1H} NMR spectroscopy, DSC, and TGA measurements.

Sequentially bridging anionic addition and ring-opening polymerization by cooperative organocatalysis: well-defined block copolymers from methacrylates and cyclic esters

Facile synthesis of well-defined block copolymers from “one-pot” sequential copolymerization of (meth)acrylates and cyclic esters were achieved by the optimalt-BuP4/(thio)ureas cooperative catalyst.

Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization

The synthesis of well-defined block copolymers from a mixture of monomers without additional actions (“one-pot/one-step”) is an ideal and industrially valuable method. In addition, the presence of controlled alternating sequences in one or both blocks increases the structural diversity of polymeric materials, but, at the same time, the synthetic difficulty. Here we show that the “one-pot/one-step” ring-opening terpolymerization of a mixture of three monomers (N-sulfonyl aziridines; cyclic anhydrides and epoxides), with tert-butylimino-tris(dimethylamino)phosphorene (t-BuP1) as a catalyst, results in perfect diblock dialternating terpolymers having a sharp junction between the two blocks, with highly-controllable molecular weights and narrow molecular weight distributions (Ð < 1.08). The organocatalyst switches between two distinct polymerization cycles without any external stimulus, showing high monomer selectivity and kinetic control. The proposed mechanism is based on NMR, in-situ FTIR, SEC, MALDI-ToF, reactivity ratios, and kinetics studies.

Polyphosphonate-Based Macromolecular RAFT-CTA Enables the Synthesis of Well-Defined Block Copolymers Using Vinyl Monomers.

Reversible addition-fragmentation chain transfer (RAFT) polymerization has become a straightforward approach to block copolymers using a wide variety of functional vinyl monomers. Polyphosphoester (PPE) macroinitiators from ring-opening polymerization (ROP) of their corresponding cyclic phosphoesters have been previously prepared for atom transfer radical polymerization; however, to date, these biodegradable macroinitiators for RAFT polymerization have not been reported. Herein, a macromolecular RAFT-chain transfer agent (CTA) based on poly(ethyl ethylene phosphonate) was prepared by the organocatalytic ROP of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using 2-cyano-5-hydroxypentan-2-yl dodecyl trithiocarbonate as the initiator and 1,8-diazabycyclo[5.4.0]undec-7-ene as the catalyst. Precise macro-CTAs of degrees of polymerization (DPn) from 34 to 70 with Đ ≤ 1.10 were prepared and used in the dioxane solution RAFT polymerization of acrylamide, acrylates, methacrylates, and 2-vinylpyridine to yield a library of well-defined block copolymers. Additionally, the PPE-based macro RAFT-CTA was used as a nonionic surfactant in a typical aqueous emulsion polymerization of styrene to produce well-defined nanoparticles with the hydrophilic PPEs on their surface as the stabilizing agent. This general protocol allowed the combination of polyphosphoesters with RAFT polymerization.

Branching Regulation in Olefin Polymerization via Lewis Acid Triggered Isomerization of Monomers.

We present a new strategy to regulate branching in chain-walking olefin polymerization by triggering a rapid isomerization of 1-alkene monomers into internal olefins by adding a Lewis acid. Polymerization of internal alkenes proceeds via chain-walking to give polymers with much higher branching than 1-alkene analogues. The utility of this approach is exemplified by synthesis of well-defined block copolymers with distinct branching characteristics per block by addition of Lewis acid midway through a reaction. We propose a novel mechanism whereby Lewis acid undergoes a counterion swap with the complex which favors isomerization as well as forming adducts with ancillary ligands, freeing coordination sites for internal alkene coordination polymerization.

Precise Synthesis of Ultra-High-Molecular-Weight Fluoropolymers Enabled by Chain-Transfer-Agent Differentiation under Visible-Light Irradiation.

Ultra-high-molecular-weight (UHMW) polymers display outstanding properties and hold potential for wide applications. However, their precise synthesis remains challenging. Herein, we developed a novel reversible-deactivation radical polymerization based on the strong and selective fluorine-fluorine interaction, allowing chain-transfer agents to spontaneously differentiate into two groups that take charge of the chain growth and reversible deactivation of the growing chains, respectively. This method enables dramatically improved livingness of propagation, providing UHMW polymers with a surprisingly narrow molecular weight distribution (Đ≈1.1) from a variety of fluorinated (meth)acrylates and acrylamide at quantitative conversions under visible-light irradiation. In situ chain-end extensions from UHMW polymers facilitated the synthesis of well-defined block copolymers, revealing the excellent chain-end fidelity achieved by this method.

Living Coordination Polymerization of a Six-Five Bicyclic Lactone to Produce Completely Recyclable Polyester.

The development of chemically recyclable polymers promises a closed-loop approach towards a circular plastic economy but still faces challenges in structure/property diversity and depolymerization selectivity. Here we report the first successful coordination ring-opening polymerization of 4,5-trans-cyclohexyl-fused γ-butyrolactone (M1) with lanthanide catalysts at room temperature, producing P(M1) with Mn up to 89 kg mol-1 , high thermal stability, and a linear or cyclic topology. The same catalyst also catalyses selective depolymerization of P(M1) back to M1 exclusively at 120 °C. This coordination polymerization is also living, enabling the synthesis of well-defined block copolymer.

Synthesis and characterization of well-defined ligand-terminated block copolymer brushes for multifunctional biointerfaces

Abstract Polymer brush-functionalized surfaces promise to provide access to absolute control over the biointerface functionality. To enable in this context systematic studies of cell attachment and proliferation, we investigated the synthesis of well-defined block copolymer brushes of poly(acrylamide) (PAAm), poly(oligo(ethylene glycol)methylether methacrylate) (POEGMA) and poly(acrylic acid) (PAA) by surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequently the introduction of exposed ligands for cell adhesion. Detailed X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, time of flight secondary ion mass spectrometry (ToF-SIMS) and ellipsometry measurements unraveled the progress and the livingness of the homo- and copolymerization of the three monomers. In particular, the correlation of the temporal evolution of the ellipsometric thickness with the decrease in bromine content pointed to a progressive loss of active chain ends, which limits the attainable maximum brush thickness. Non-fouling brushes of POEGMA and PAAm exhibited long term stability and full functionality in cell medium for more than 1 month. Block copolymer brushes with defined thickness comprising a non-fouling POEGMA or PAAm block and a short terminal PAA block were functionalized with a peptide containing the arginine-glycine-aspartic acid (RGD) sequence. Cell attachment assays with fibroblasts revealed facilitated cell adhesion on RGD modified block copolymer brushes. The specific signaling was further confirmed with inhibited cell adhesion on arginine-alanine-aspartic acid (RAD) functionalized brushes (negative control). Hence on the basis of the unraveled synthesis behavior of block copolymer brushes and side chain modification a versatile strategy to fabricate biologically inert surfaces that facilitate integrin-specific cell adhesion has been developed.

Facile anionic synthesis of well-defined block copolymers with pendent triphenylamine and ethynylpyridine for nonvolatile memory device applications with high performances

The sequential block copolymerization of 4,4′-vinylphenyl-N,N-bis(4-tert-butylphenyl)benzenamine (A) with 2-(2-(4-vinylphenyl)ethynyl)pyridine (B) was simply carried out using only potassium naphthalenide (K-Naph) as an initiator without any additives in tetrahydrofuran (THF) at −78 °C. The well-defined functional block copolymers containing A block as an electron donor and B block as a weak electron acceptor had predictable molecular weights (Mn = 8,800–14,500 g/mol) and narrow molecular weight distributions (Mw/Mn = 1.09–1.10). The bicontinuous microphase-separated film morphology of the precisely synthesized poly(B-b-A-b-B) (PBAB) with 0.71 of fpoly(A), formed by thermal annealing at 230 °C for 9 h, was expected to be a potential active layer for nonvolatile memory device applications. Indium tin oxide (ITO)/PBAB/aluminum (Al) memory devices with an 8 × 8 cross-bar array structure exhibited nonvolatile resistive switching characteristics. The memory devices showed reliable memory performance in terms of ON/OFF ratios of ∼104, endurance cycles and retention time, and statistical data with regard to cumulative probability of the switching currents and threshold voltage distribution. Filamentary conduction mechanism was proposed to explain the switching of PBAB-based memory devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2625-2632

Droplet synthesis of well-defined block copolymers using solvent-resistant microfluidic device

Well-defined diblock copolymers were synthesized via an exothermic RAFT route by a droplet microfluidic process using a solvent-resistant and thermally stable fluoropolymer microreactor fabricated by a non-lithographic embedded template method. The resulting polymers were compared to products obtained from continuous flow capillary reactor and conventional bulk synthesis. The droplet based microreactor demonstrated superior molecular weight distribution control by synthesizing a higher molecular weight product with higher conversion and narrow polydispersity in a much shorter reaction time. The high quality of the as-synthesized block copolymer PMMA-b-PS led to a generation of micelles with a narrow size distribution that could be used as a template for well-ordered mesoporous silica with regular frameworks and high surface areas.

No matter the order of monomer addition for the synthesis of well-defined block copolymers by sequential group transfer polymerization using N-heterocyclic carbenes as catalysts

Unsaturated N-heterocyclic carbenes (NHCs) such as 1,3-bis(di-isopropyl)imidazol-2-ylidene (1) and 1,3-bis(di-tert-butyl)imidazol-2-ylidene (2) are shown to catalyze the sequential group transfer polymerization (GTP) of (meth)acrylic monomers. A variety of block copolymers including not only alkyl methacrylate but also alkyl acrylate monomer units as well as blocks deriving from N,N-dimethylacrylamide and methacrylonitrile were thus obtained at room temperature, using 1-methoxy-2-methyl-1-trimethylsiloxypropene (MTS) as initiator in THF as solvent. Block copolymerizations could be achieved, starting indifferently from the GTP of the acrylic monomer to that of the methacrylic one or vice versa, that is, regardless of the order of addition of the two monomers, in contrast to most examples of block copolymer synthesis by “controlled/living” sequential polymerization. It is postulated that these NHC-catalyzed GTPs of (meth)acrylics proceed via a single step concerted-like associative mechanism, involving the formation of thermodynamically unstable intermediates or transition states, likely hypervalent siliconates, with no detectable anionic enolates formed.

High‐Speed Living Polymerization of Polar Vinyl Monomers by Self‐Healing Silylium Catalysts

This contribution describes the development and demonstration of the ambient-temperature, high-speed living polymerization of polar vinyl monomers (M) with a low silylium catalyst loading (≤ 0.05 mol % relative to M). The catalyst is generated in situ by protonation of a trialkylsilyl ketene acetal ((R)SKA) initiator (I) with a strong Brønsted acid. The living character of the polymerization system has been demonstrated by several key lines of evidence, including the observed linear growth of the chain length as a function of monomer conversion at a given [M]/[I] ratio, near-precise polymer number-average molecular weight (M(n), controlled by the [M]/[I] ratio) with narrow molecular weight distributions (MWD), absence of an induction period and chain-termination reactions (as revealed by kinetics), readily achievable chain extension, and the successful synthesis of well-defined block copolymers. Fundamental steps of activation, initiation, propagation, and catalyst "self-repair" involved in this living polymerization system have been elucidated, chiefly featuring a propagation "catalysis" cycle consisting of a rate-limiting C--C bond formation step and fast release of the silylium catalyst to the incoming monomer. Effects of acid activator, catalyst and monomer structure, and reaction temperature on polymerization characteristics have also been examined. Among the three strong acids incorporating a weakly coordinating borate or a chiral disulfonimide anion, the oxonium acid [H(Et(2)O)(2)](+)[B(C(6)F(5))(4)](-) is the most effective activator, which spontaneously delivers the most active R(3)Si(+), reaching a high catalyst turn-over frequency (TOF) of 6.0×10(3) h(-1) for methyl methacrylate polymerization by Me(3)Si(+) or an exceptionally high TOF of 2.4×10(5) h(-1) for n-butyl acrylate polymerization by iBu(3)Si(+), in addition to its high (>90 %) to quantitative efficiencies and a high degree of control over M(n) and MWD (1.07-1.12). An intriguing catalyst "self-repair" feature has also been demonstrated for the current living polymerization system.

Synthesis and MALDI-TOF-MS of PS-PMA and PMA-PS block copolymers

The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique.

Synthesis of well-defined block copolymers and star-branched polymers by using terminal 1,3-butadiene functionalized polymers as reactive building blocks

Terminal 1,3-buadiene (Bd) functional polymers are stoichiometrically reacted with living anionic polymers in a monoaddition manner in THF at −78 °C, but neither polymerization nor oligomerization occurs under the conditions. By utilizing this reactive but non-polymerizable character of the Bd function toward living anionic polymers, a variety of block copolymers and regular and asymmetric star-branched polymers were successfully synthesized. In these syntheses, the terminal Bd functionalized polymers work effectively as reactive building blocks, namely polymeric efficient linking agents, to construct such architectural polymers. Since all the polymer segments used for the syntheses were derived from living anionic polymers and the linking reactions quantitatively proceeded, the architectural polymers herein synthesized were well-defined in structure and were precisely controlled in chain length. A new protocol based on iterative approach by repeating a two reaction sequence involving linking reaction and re-introduction of Bd group was proposed and developed to successively synthesize asymmetric star-branched polymers up to a 6-arm ABCDEF type. The terminal Bd functionalized polymers were readily and quantitatively converted to anhydride or diepoxide functionalized polymers by Diels–Alder or oxidation reactions. Because of their high reactive termini, the resulting polymers are also usable as reactive building blocks to synthesize the core-functionalized star-branched polymers with carboxylic acids or hydroxyl groups. The reactions between terminal anhydride and amine functionalized polymers were carried out in bulk at 180 °C to examine the synthetic possibility of star-branched polymers under such conditions.

Facile Synthesis of Well-Defined Block Copolymers Containing Regioregular Poly(3-hexyl thiophene) via Anionic Macroinitiation Method and Their Self-Assembly Behavior

P3HT-P2VP block copolymers were synthesized using anionic macroinitiation of a vinyl end-functionalized P3HT. With different block ratio of P2VP to P3HT, the block copolymers exhibit sphere, cylinder, lamellae, and nanofiber nanostructures.

RAFT and click chemistry: A versatile approach to well-defined block copolymers

The combination of reversible chain transfer chemistry with highly orthogonal [2 + 3] cycloadditions ('click chemistry') allows for the synthesis of well-defined block copolymers of monomers with extremely disparate reactivities.

Synthesis of well-defined block copolymers containing poly(N-isopropylacrylamide) segment by anionic block copolymerization of N-methoxymethyl-N-isopropylacrylamide

Anionic polymerization of N-methoxymethyl-N-isopropylacrylamide (1) was carried out with diphenylmethyllithium,-potassium and-cesium in the presence of diethylzinc in THF at-78°C for 1-3 h. The resulting poly(1)s possessed the predicted molecular weights based on the molar ratios between monomer and initiators and the narrow molecular weight distributions (M w/M n = 1.1). The methoxymethyl protecting groups were completely hydrolyzed to afford a poly(N-isopropylacrylamide) (poly(NIPAM)), having well-defined chain structures by treatment with aqueous HCl in 1,4-dioxane at room temperature for 12 h. Stereoregularity of the resulting poly(NIPAM) was strongly affected by the counterions of anionic initiator. From the 1H-NMR measurement, the racemo dyad of poly(NIPAM) obtained with diphenylmethyllithium, -potassium and -cesium in the presence of Et2Zn was found to be 75, 50 and 30%, respectively. The sequential copolymerization of styrene or isoprene with 1 and the subsequent deprotection quantitatively gave well-defined block copolymers containing poly(NIPAM) segments. The copolymers had the predicted molecular weights, compositions and the narrow molecular weight distributions, and showed the typical amphiphilic character with regard to solubility.

Synthesis of well-defined block copolymers of n-hexyl isocyanate with isoprene by living anionic polymerization

n-Hexyl isocyanate (HIC) was polymerized at different reaction temperatures and times, using alkali metal naphthalenide, via anionic polymerization in THF. To prevent the formation of trimers, the polymerization of HIC was also performed utilizing sodium tetraphenylborate (NaBPh 4) as a common ion salt. As the reaction temperature decreases, yield of the polymer increases due to stabilization of the active amidate anion at low temperature. In the absence of the additive, a quantitative yield was obtained at −98 °C. However, after most of the monomer was polymerized, further reaction led to trimerization. This was prevented in the presence of NaBPh 4 effectively and the living polymerization was performed successfully at −98 °C. The reaction rate retarded with increasing concentration of NaBPh 4, the optimum concentration of NaBPh 4 was 10 times the concentration of the initiator for the living polymerization of HIC. The living system led to the polymers of molecular weight (MW) as high as 50,000 g/mol. The observed MW was well in agreement with the calculated one. At the higher reaction temperature, −78 °C, the quantitative yield was obtained at 2 min of the reaction time, however the living character was not observed at longer reaction time. The study indicated that the amidate anion was stabilized using NaBPh 4 having bulky contact ion pair. The block copolymer of HIC with isoprene, poly(HIC- b-isoprene- b-HIC), was synthesized with help of the living character of polyisoprene and NaBPh 4. The morphology and composition of the block copolymers were investigated using TEM and 1H NMR, respectively.

Synthesis of well-defined block copolymers tethered to polysilsesquioxane nanoparticles and their nanoscale morphology on surfaces.

Synthesis of well-defined block copolymers tethered to polysilsesquioxane nanoparticles and their nanoscale morphology on surfaces.

Living Anionic Polymerization of Phosphorus-Bridged [1]Ferrocenophanes: Synthesis and Characterization of Well-Defined Poly(ferrocenylphosphine) Homopolymers and Block Copolymers

The living anionic ring-opening polymerization (ROP) of the phosphorus-bridged [1]ferrocenophane (η-C5H4)2FePPh initiated by n-BuLi in THF at 25 °C has allowed the preparation of well-defined poly(ferrocenylphenylphosphines) [(η-C5H4)2FePPh]n 5, with molecular weight control, narrow polydispersities, and controlled end-group structures. Reaction of polymers 5 with sulfur allowed the synthesis of the analogous poly(ferrocenylphenylphosphine sulfides) [(η-C5H4)2FeP(S)Ph]n 6. Analysis of the high-molecular-weight polymers 5 and 6 (where n = 100) by DSC showed glass-transition temperatures of 126 and 206 °C, respectively. The absence of melt transitions and the featureless WAXS profiles indicated that the materials are amorphous. The living nature of the ROP also permitted the synthesis of well-defined block copolymers, poly(ferrocenylphenylphosphine)-b-poly(dimethylsiloxane) (PFP-b-PDMS), PFP11-b-PDMS81 (7a) and PFP50-b-PDMS141 (7b), and poly(ferrocenylphenylphosphine)-b-poly(ferrocenyldimethylsilane) PFP11-b-PFS11 (8). Analysis of the block copolymer 7b by DSC showed the presence of individual thermal transitions for each block which indicated that they were incompatible. Metal coordination studies on copolymer 7b showed that this material coordinates PdCl2, to yield the insoluble copolymer 11, as well as Fe(CO)4, which resulted in the formation of 12 which remained soluble in hexane.