Recent advances in the solution self‐assembly of amphiphilic “rod‐coil” copolymers

Solution self‐assembly of amphiphilic “rod‐coil” copolymers, especially linear block copolymers and graft copolymers (also referred to as polymer brushes), has attracted considerable interest, as replacing one of the blocks of a coil‐coil copolymer with a rigid segment results in distinct self‐assembly features compared with those of the coil‐coil copolymer. The unique interplay between microphase separation of the rod and coil blocks with great geometric disparities can lead to the formation of unusual morphologies that are distinctly different from those known for coil‐coil copolymers. This review presents the recent achievements in the controlled self‐assembly of rod‐coil linear block copolymers and graft copolymers in solution, focusing on copolymer systems containing conjugated polymers, liquid crystalline polymers, polypeptides, and polyisocyanates as the rod segments. The discussions concentrate on the principle of controlling over the morphology of rod‐coil copolymer assemblies, as well as their distinctive optical and optoelectronic properties or biocompatibility and stimuli‐responsiveness, which afford the assemblies great potential as functional materials particularly for optical, optoelectronic and biological applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1459–1477     

Synthesis and self‐assembly in water of coil‐rod‐coil amphiphilic block copolymers with central π‐conjugated sequence

The purpose of this study is to correlate the nano‐organization in water of coil‐rod‐coil amphiphilic block copolymers constituted of a conjugated segment to their optoelectronic properties. The ABA block copolymer structures, easily achieved via coupling reactions, are based on conjugated rod of dihexylfluorene and 3,4‐ethylenedioxythiophene units linked to two flexible poly(ethylene oxide) or poly[(ethylene oxide)‐ran‐(propylene oxide)] chains. These well‐defined copolymers exhibited a range of specific morphologies in water, a good solvent of coil blocks and a bad solvent of the conjugated rod. Particularly, vesicles and micelles with spherical, cylindrical, or elongated shape were noticed. Correlations were attempted to be established between the weight percent of the conjugated sequence contained in the copolymers, the morphology of the nanostructures obtained by self‐assembly in solution and the resulting optical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4602–4616, 2008     

Photophysical properties of σ–π‐conjugated alternating oligothienylene–oligosilylene polymers

UV‐visible absorption and fluorescence properties of three series of σ–π‐conjugated polymers (copolymers of alternative oligothienylene and oligosilylene units) have been studied in dioxane solution. The energies of the absorption maximum, fluorescence maximum, and the 0–0 transition are found to be linearly dependent on the reciprocal of the number of thiophene rings in the repeating unit of the polymer chain, but almost independent of the silicon atom number. The σ–π‐conjugation in the polymers results in red shift in the absorption and fluorescence maxima, higher fluorescence quantum yields, and longer fluorescence lifetimes of the polymers, with respect to their corresponding analogous α‐oligothiophenes. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1873–1880, 1999     

One‐step synthesis of a thienylenepyridazinylenethienylene‐based coil‐rod‐coil copolymer with enhanced emission and improved fluorescence stability

A new coil‐rod‐coil copolymer is synthesized via Sonogashira coupling using one‐step methodology. The copolymer PEG‐OEPETPT‐PEG constitutes of poly(ethylene glycol) (PEG) as the coil block, and oligo[p‐(ethynylenephenyleneethynylene)‐alt‐(thienylenepyridazinylenethienylene)] (OEPETPT) as the rod segment. The conjugated polymer PEPETPT with the same conjugated building blocks is also synthesized for comparison. The structures of both polymers are confirmed by NMR, combined with other characterizations. PEG‐OEPETPT‐PEG has a 12 nm blue‐shift in the emission maximum compared with that of PEPETPT, and a higher quantum yield of fluorescence in THF. PEG‐OEPETPTE‐PEG tolerates up to 20% water content in H₂O/THF mixed solvent without significantly changing the emission wavelength and intensity, while the fluorescence of PEPETPT is dramatically quenched by a very small quantity of water. Further photophysical studies about these two polymers indicate that the introduction of PEG coils onto the conjugated block retards the water‐induced‐aggregation and therefore improves the fluorescence stability of PEG‐OEPETPT‐PEG. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Temperature‐dependent self‐assembly and rheological behavior of a thermoreversible pmma–PnBA–PMMA triblock copolymer gel

Self‐assembly and mechanical properties of triblock copolymers in a mid‐block selective solvent are of interest in many applications. Herein, we report physical assembly of an ABA triblock copolymer, [PMMA–Pn BA–PMMA] in two different mid‐block selective solvents, n‐butanol and 2‐ethyl‐1‐hexanol. Gel formation resulting from end‐block associations and the corresponding changes in mechanical properties have been investigated over a temperature range of ?80 °C to 60 °C, from near the solvent melting points to above the gelation temperature. Shear‐rheometry, thermal analysis, and small‐angle neutron scattering data reveal formation and transition of structure in these systems from a liquid state to a gel state to a percolated cluster network with decrease in temperature. The aggregated PMMA end‐blocks display a glass transition temperature. Our results provide new understanding into the structural changes of a self‐assembled triblock copolymer gel over a large length scale and wide temperature range. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 877–887     

Effects of donor unit and π‐bridge on photovoltaic properties of D–A copolymers based on benzo[1,2‐b:4,5‐c']‐dithiophene‐4,8‐dione acceptor unit

A series of donor‐π‐acceptor (D‐π‐A) conjugated copolymers ( PBDT‐AT, PDTS‐AT, PBDT‐TT , and PDTS‐TT ), based on benzo[1,2‐b:4,5‐c']dithiophene‐4,8‐dione (BDD) acceptor unit with benzodithiophene (BDT) or dithienosilole (DTS) as donor unit, alkylthiophene (AT) or thieno[3,2‐b]thiophene (TT) as conjugated π‐bridge, were designed and synthesized for application as donor materials in polymer solar cells (PSCs). Effects of the donor unit and π‐bridge on the optical and electrochemical properties, hole mobilities, and photovoltaic performance of the D‐π‐A copolymers were investigated. PSCs with the polymers as donor and PC₇₀BM as acceptor exhibit an initial power conversion efficiency (PCE) of 5.46% for PBDT‐AT , 2.62% for PDTS‐AT , 0.82% for PBDT‐TT , and 2.38% for PDTS‐TT . After methanol treatment, the PCE was increased up to 5.91%, 3.06%, 1.45%, and 2.45% for PBDT‐AT, PDTS‐AT, PBDT‐TT , and PDTS‐TT , respectively, with significantly increased FF. The effects of methanol treatment on the photovoltaic performance of the PSCs can be ascribed to the increased and balanced carrier transport and the formation of better nanoscaled interpenetrating network in the active layer. The results indicate that both donor unit and π‐bridge are crucial in designing a D‐π‐A copolymer for high‐performance photovoltaic materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1929–1940     

Temperature‐induced spontaneous sol–gel transitions of poly(D,L‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid‐co‐glycolic acid) triblock copolymers and their end‐capped derivatives in water

The spontaneous hydrogel formation of a sort of biocompatible and biodegradable amphiphilic block copolymer in water was observed, and the underlying gelling mechanism was assumed. A series of ABA‐type triblock copolymers [poly(D,L ‐lactic acid‐co‐glycolic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L ‐lactic acid‐co‐glycolic acid)] and different derivatives end‐capped by small alkyl groups were synthesized, and the aqueous phase behaviors of these samples were studied. The virgin triblock copolymers and most of the derivatives exhibited a temperature‐dependent reversible sol–gel transition in water. Both the poly(D,L ‐lactic acid‐co‐glycolic acid) length and end group were found to significantly tune the gel windows in the phase diagrams, but with different behaviors. The critical micelle concentrations were much lower than the associated critical gel concentrations, and an intact micellar structure remained after gelation. A combination of various measurement techniques confirmed that the sol–gel transition with an increase in the temperature was induced not simply via the self‐assembly of amphiphilic polymer chains but also via the further hydrophobic aggregation of micelles resulting in a micelle network due to a large‐scale self‐assembly. The coarsening of the micelle network was further suggested to account for the transition from a transparent gel to an opaque gel. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1122–1133, 2007     

Donor–acceptor conjugated copolymers incorporating tetrafluorobenzene as the π‐electron deficient unit

We present the synthesis and characterization of a new family of perfectly alternating conjugated polymers, obtained through different methodologies (Stille, Direct Arylation, and Horner–Wadsworth–Emmons polymerizations). The polymers comprise either 2,5‐dialkoxybenzene or benzodithiophene electron rich units, and 1,2,4,5‐tetrafluorobenzene as the electron‐deficient unit, eventually separated by a vinylene bridge, if suitable monomers and HWE polymerization procedures are used. As shown by NMR spectroscopy, the introduction of the fluorinated aromatic units brings complications in the polymer stereodefinition in the HWE polymerization, and regiodefinition in the case of the Direct Arylation. The polymers show moderate degrees of polymerization (up to 10 repeating alternating units in the backbone), which are however significant enough to unravel interesting properties such as energy HOMO–LUMO gaps and aggregation behavior in solution at room temperature. In depth calculations fully confirmed the aggregation tendency, highlighting the key role of the benzodithiophene as the donor component when in combination with the tetrafluorobenzene unit. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1601–1610     

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with n‐butyl acrylate: Design,synthesis, and characterization

A series of rod–coil diblock copolymers, consisting of poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} as a rigid segment and poly(n‐butyl acrylate) as a flexible part, were successfully prepared through two inverse procedures by atom transfer radical polymerization. The copolymers were characterized by ¹H NMR and gel permeation chromatography and had high molecular weights and relatively narrow polydispersities (polydispersity index < 1.20). All the block copolymers synthesized had two distinct glass‐transition temperatures according to differential scanning calorimetry. A polarizing optical microscopy investigation demonstrated the liquid crystallinity of the diblock copolymers. The self‐assembly behaviors in dilute solutions was studied by transmission electron microscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5935–5943, 2005     

ABA‐type liquid crystalline triblock copolymers via nitroxide‐mediated radical polymerization: Design,synthesis, and morphologies

We have designed and synthesized rod–coil–rod triblock copolymers of controlled molecular weight by two‐step nitroxide‐mediated radical polymerization, where the rod part consists of “mesogen‐jacketed liquid crystalline polymer” (MJLCP). The MJLCP segment examined in our studies is poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene} (MPCS) while the coil part is polyisoprene (PI). Characterization of the triblock copolymers by GPC, ¹H and ¹³C NMR spectroscopies, TGA, DSC confirmed that the triblock copolymers were comprised of microphase‐separated low T_g amorphous PI and high T_g PMPCS blocks. Analysis of POM and 1D, 2D‐WAXD demonstrated that the triblock copolymers formed nematic liquid crystal phase. Morphological studies using TEM indicated the sample formed lamellar structure. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5949–5956, 2007     

Palladium on carbon‐catalyzed direct C—H arylation polycondensation of 3,4‐ethylenedioxythiophene with various dibromoarenes

We have demonstrated a direct arylation polycondensation of 3,4‐ethylenedioxythiophene with 2,7‐dibromo‐9,9‐dioctylfluorene using palladium on carbon (Pd/C) as a catalyst. Pd/C is a low‐cost solid‐supported palladium catalyst, giving one of the effective catalytic systems for direct arylation. The Pd/C‐catalyzed direct arylation polycondensation with acetic acid/potassium carbonate in N,N‐dimethylacetamide furnished a high molecular weight π‐conjugated alternating copolymer of EDOT‐fluorene (M_n = 89,300, M_w/M_n = 3.27) in high yield. The polycondensation of EDOT with various dibromoarenes was also achieved, giving EDOT‐carbazole, EDOT‐dialylamine, and EDOT‐bithiophene polymers. Optical and electrochemical properties of the polymers were also discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 55, 1183–1188     

Ambipolar charge transport in a donor–acceptor–donor‐type conjugated block copolymer and its gate‐voltage‐controlled thin film transistor memory

We demonstrate a fully conjugated donor–acceptor–donor (D–A–D) triblock copolymer, PBDTT–PNDIBT–PBDTT, which contains PBDTT as the donor block and PNDIBT as the acceptor block. The polymer was synthesized by end‐capping each block with a reactive unit, followed by condensation copolymerization between the two blocks. The physical, optical, and electrochemical properties of the polymer were investigated by comparing those of donor‐ and acceptor‐homopolymers (i.e., PBDTT and PNDIBT), which are the oligomeric monomers, and their blends. On using the newly synthesized block copolymer, ambipolar charge transport behavior was observed in the corresponding thin‐film transistor, and the behavior was compared to that of blend film of donor‐ and acceptor‐homopolymers. Owing to the presence of donor and acceptor blocks in a single polymer chain, it was found that the triblock copolymer can store two‐level information; the ability to store this information is one of the most intriguing challenges in memory applications. In this study, we confirmed the potential of the triblock copolymer in achieving distinct two‐stage data storage by utilizing the ambipolar charge trapping phenomenon, which is expected in donor and acceptor containing random and block copolymers in a thin‐film transistor. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3223–3235     

Differences in self‐assembly features of thermoresponsive anionic triblock copolymers synthesized via one‐pot or two‐pot by atom transfer radical polymerization

The self‐assembly process in aqueous solutions of the methoxyl‐poly(ethylene glycol)‐block‐poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic sodium)‐block‐poly(N‐isopropyl acrylamide) (PNIPAAM) triblock copolymer, synthesized via two different atomic transfer radical polymerization methods, namely “one‐pot” (P3‐sample) and “two‐pot” (P2‐sample), was studied by various experimental techniques. The “one‐pot” procedure leads to a copolymer (P3) where the PNIPAAM block is contaminated with a minor quantity of 2‐acrylamido‐2‐methyl‐1‐propane sulfonate (AMPS) residuals and this sample does not form micelles over the considered temperature region, but unimers and temperature‐induced aggregates coexist in the presence of a small amount of salt. The P2 polymer forms micelles and intermicellar structures, but the former moieties disappear at high temperatures, whereas the latter species contract with increasing temperature. Small‐angle neutron scattering results revealed correlation peaks, both for P3 and P2, and no micelle formation for P3, but a pronounced upturn of the scattered intensity at low wavevector values at elevated temperatures for the P2 copolymer. The findings from this study clearly show that the spurious AMPS residuals have a drastic influence on the self‐assembly and micelle formation of the triblock copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 524–534     

Hydrolytic degradation of polyisobutylene and poly‐L‐lactide–based multiblock copolymers

The hydrolytic degradation of a series of poly‐L ‐lactide (PLLA)‐polyisobutylene (PIB) multiblock copolymers was studied in phosphate buffer solution (pH = 7.4) at 37 °C. The multiblock copolymers were synthesized by chain extension of PLLA‐b‐PIB‐b‐PLLA triblock copolymers, which were obtained by ring‐opening polymerization of L ‐lactide initiated by hydroxyallyl telechelic PIB. The degradation strongly depended on the PLLA segment length. At constant PIB segment length, the multiblock copolymer with the shortest PLLA segment length (DPn = 10), showed significant weight loss after 8 weeks, whereas weight loss for DPn = 36 was only observed after 24 weeks. The gel‐permeation chromatographic analysis showed a similar decrease in the number‐average molecular weight (M_n) with time further supporting the weight loss data. Dynamic mechanical analysis showed a decrease in ultimate stress and modulus with time. The crystallinity of multiblock copolymers changed significantly with degradation time as indicated from differential scanning calorimetric analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3767–3774, 2010     

Self‐assembly of star‐shaped polystyrene‐block‐polypeptide copolymers synthesized by the combination of atom transfer radical polymerization and ring‐opening living polymerization of α‐amino acid‐N‐carboxyanhydrides

The self‐assembling nature and phase‐transition behavior of a novel class of triarm, star‐shaped polymer–peptide block copolymers synthesized by the combination of atom transfer radical polymerization and living ring‐opening polymerization of α‐amino acid‐N‐carboxyanhydride are demonstrated. The two‐step synthesis strategy adopted here allows incorporating polypeptides into the usual synthetic polymers via an amido–amidate nickelacycle intermediate, which is used as the macroinitiator for the growth of poly(γ‐benzyl‐L ‐glutamate). The characterization data are reported from analyses using gel permeation chromatography and infrared, ¹H NMR, and ¹³C NMR spectroscopy. This synthetic scheme grants a facile way to prepare a wide range of polymer–peptide architectures with perfect microstructure control, preventing the formation of homopolypeptide contaminants. Studies regarding the supramolecular organization and phase‐transition behavior of this class of polymer‐block‐polypeptide copolymers have been accomplished with X‐ray diffraction, infrared spectroscopy, and thermal analyses. The conformational change of the peptide segment in the block copolymer has been investigated with variable‐temperature infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2774–2783, 2006     

Bis‐dendritic polyethylene prepared by ring‐opening metathesis polymerization in the presence of bis‐dendritic chain transfer agents

The synthesis of ABA triblock copolymers is described, in which the A blocks are poly(benzyl ether) dendrons and the B block is polycyclooctene or polyethylene. Bis‐dendritic cis‐olefins were synthesized and used as chain transfer agents in ring‐opening metathesis polymerization of cyclooctene in a process that inserts the dendrons at the polymer chain‐ends. Evaluation of the polymer products by spectroscopic, chromatographic, and titration methods supports their triblock structure. Hydrogenation of the unsaturated polycyclooctene B‐block of these ABA triblock copolymers provides the first reported synthesis of bisdendritic polyethylene. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5429–5439, 2005     

Insights into poly(3‐hexylthiophene)‐b‐poly(ethylene oxide) block copolymer: Synthesis and solvent‐induced structure formation in thin films

We report the synthesis, characterization, and solvent‐induced structure formation in thin films of an amphiphilic rod‐coil conjugated block copolymer, poly(3‐hexylthiophene)‐b‐poly(ethylene oxide). The diblock copolymers were prepared by a facile click reaction and their characterizations as well as thermal, crystalline, optical properties, and self‐assembly behavior have been investigated in detail. A series of morphologies including two‐phase separated nanostructure, nanofibrils, and their mixed morphology could be obtained depending on the selectivity of solvents to different blocks. Structural analyses demonstrate there is a subtle balance between microphase separation of copolymer and the π‐π stacking of the conjugated P3HT and such balance can be controlled by changing the solvents of different selectivity in solution and the length of P3HT block. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

High‐efficiency,electrophosphorescent polymers with porphyrin–platinum complexes in the conjugated backbone: Synthesis and device performance

A series of soluble, conjugated, electrophosphorescent copolymers with (meso‐tetraphenylporphyrinato‐κ⁴N)platinum(II) (PtTPP) complexes incorporated into the polymer main chain were synthesized through the copolymerization of narrow‐band‐gap monomeric porphyrin–platinum(II) complexes and wide‐band‐gap dialkyl‐substituted fluorene monomers by a modified Suzuki coupling reaction. The study of the photoluminescence decay indicated that poly[2,7‐(9,9‐dioctylfluorene)‐co‐2,12‐((meso‐tetraphenylporphyrinato‐κ⁴N)platinum(II))] (PFO–PtTPP) was a triplet emitter. The electroluminescence emission from the fluorene segment was completely quenched for copolymers with PtTPP contents as low as 0.5 mol %. The PFO–PtTPP copolymers emitted deep red light. The device based on the porphyrin–platinum(II) copolymer PFO–5PtTPP (with 5 mol % PtTPP in the copolymer) showed the highest external quantum efficiency of 1.95% with an emission peak at 684 nm in an indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polyvinylcarbazole (PVK)/70:30 (w/w) PFO–5PtTPP: 2‐(biphenyl‐4‐yl)‐5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole/Ba/Al device configuration. In comparison with the PFO–PtTPP copolymers synthesized via a postpolymerization metalation route, copolymerization from Pt metal complexes proved to be a more efficient synthetic route for high‐efficiency electrophosphorescent polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4174–4186, 2006     

Divinylsiloxane‐bisbenzocyclobutene‐based polymer modified with polystyrene–polybutadiene–polystyrene triblock copolymers

Divinylsiloxane‐bisbenzocyclobutene (DVS‐bisBCB) polymer has very low dielectric constant and dissipation factor, good thermal stability, and high chemical resistance. The fracture toughness of the thermoset polymer is moderate due to its high crosslink density. A thermoplastic elastomer, polystyrene–polybutadiene–polystyrene triblock copolymer, was incorporated into the matrix to enhance its toughness. The cured thermoset matrix showed different morphology when the elastomer was added to the B‐staged prepolymer or when the elastomer was B‐staged with the DVS‐bisBCB monomer. Small and uniformly distributed elastomer domains were detected by transmission electron micrographs (TEM) in the former case, but TEM did not detect a separate domain in the latter case. A high percentage of the polystyrene–polybutadiene–polystyrene triblock copolymer could be incorporated into the DVS‐bisBCB thermoset matrix by B‐staging the triblock copolymer with the BCB monomer. The elastomer increased the fracture toughness of DVS‐bisBCB polymer as indicated by enhanced elongation at break and increased K1c values obtained by the modified edge‐lift‐off test. Elastomer modified DVS‐bisBCB maintained excellent electrical properties, high T_g and good thermal stability, but showed higher coefficient of linear thermal expansion values. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1591–1599, 2006     

Synthesis and characterization of poly(DTC‐b‐PEG‐b‐DTC) triblock and poly(TMC‐b‐DTC‐b‐PEG‐b‐DTC‐b‐TMC) pentablock copolymers and kinetics of the polymerization

Dihydroxyl capped biodegradable poly(DTC‐b‐PEG‐b‐DTC) (BCB) triblock copolymer and poly(TMC‐b‐DTC‐b‐PEG‐b‐DTC‐b‐TMC) (ABCBA) pentablock copolymer have been synthesized by PEG and BCB copolymer as macroinitiator in the presence of yttrium tris(2,6‐di‐tert‐butyl‐4‐methylphenolate). The copolymers without random segments have been thoroughly characterized by ¹H, ¹³C‐NMR, SEC, and DSC. Molecular weights of the obtained copolymers are dependent on the amount of PEGs and coincide with the theoretical values. The exchange reaction of yttrium alkoxide and hydroxyl end group is essential for controlling the products' molecular weight. Their thermal behaviors are relevant to the chain lengths of PEG and PDTC segments. The Monte Carlo method has been developed to estimate the chain propagation constant and exchange reaction constant. In average, one exchange reaction will occur after approximately six monomer molecules insert into the growing chain. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1787–1796, 2005