Dilute solution properties of well-defined multiblock copolymers: poly(4,4′-isopropylidenediphenyl carbonate)-block-polystyrene

Light scattering, osmometric and viscometric studies were carried out with dilute solutions of well-defined poly(4,4′-isopropylidenediphenyl carbonate)-block-polystyrene multiblock copolymers, PC-b-PS, in non-selective and selective solvent systems. The influence of copolymer composition, numbers and lengths of blocks in the copolymer chain and type of solvent used on the dilute solution properties, conformation of the investigated multiblock copolymers and on some thermodynamic parameters are discussed. The intrinsic viscosity [η], the unperturbed dimension 〈R₀²〉/M and the second virial coefficient A₂ are larger in non-selective solvents than expected from the averaged values of the parent homopolymers. In benzene, a selective solvent for polystyrene, formation of micelles is possible.     

Micelle formation and polyisobutylene solubilization by polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene block copolymers

Thermodynamics of micellization and the structure of micelles formed by polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene block copolymers were studied. A molar mass influence on the aggregation number of micelles was found. The lower the molar mass, the higher the micelle aggregation number. The solubilization of polyisobutylene by micelles of these copolymers in methyl isobutyl ketone was also examined. The saturation concentrations of polyisobutylene solubilized by different block copolymers in methyl isobutyl ketone were determined by laser light scattering. The solubility curves found were linear and dependent on the molar mass of the polyisobutylene solubilized and the copolymer. The logarithm of the maximum amount of polyisobutylene solubilized by mass unity of the triblock copolymer varies linearly with the logarithm of the molar mass of the polyisobutylene. This variation is hardly dependent on the copolymer molar mass and strongly dependent on the type of block copolymer.     

Microstructure of poly[polytetrahydrofuran-block-poly(sebacoylchloride-alt-hexamethylenediamine)] and its role in blood compatibility

The microstructure of poly[polytetrahydrofuran-block-poly(sebacoyl chloride-alt-hexamethylenediamine)]s 1–4 , containing polytetrahydrofuran (PTHF) blocks of various molecular weights, and their blood compatibility were studied. These multiblock copolymers were prepared by interfacial polycondensation. The characterization of these copolymers was carried out by means of transmission electron microscopy (TEM), differential scanning calorimetry (DSC), dynamic mechanical measurements, wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and electron spectroscopy for chemical analysis (ESCA). The TEM observation revealed the formation of a spherulitic structure at the copolymer surfaces, which is closely related to the homopolymer, polyamide (PA) 610. The DSC and dynamic mechanical measurements indicate the presence of distinct phase separation between PTHF and PA 610 blocks, and of the PTHF block in the copolymer being partially crystallized. The WAXD and SAXS indicate the formation of microstructures composed of crystalline and amorphous phases in the copolymer. Moreover, ESCA measurements verify that the surface chemical composition of the copolymer is identical to their bulk composition. Blood compatibility of these copolymers was evaluated by estimating platelet adhesion on the copolymer surfaces. Platelet adhesion was found to be affected by the PA 610 crystallinity, including the size and distribution of the crystalline phase in the case of the copolymers in which the PTHF blocks are completely amorphous (M?_n = 980). On the contrary, platelet adhesion at the copolymers in which the PTHF blocks are partially crystallized (M?_n ≥ 1560) depends upon the crystallinity of both PA 610 and PTHF, including the balance of crystalline (PA 610 and PTHF) and amorphous (mainly PTHF) phases. This result suggests that the balance of the crystalline and amorphous phase distribution in the copolymer is the most determinative factor for suppressing platelet adhesion at the copolymer surface.     

Synthesis and properties of well-defined multiblock copolymers: poly(4,4′-isopropylidenediphenyl carbonate)-block-polystyrene

Well-defined poly(4,4′-isopropylidenediphenyl carbonate)-block-polystyrene multiblock copolymers, PC-b-PS, were prepared by condensation of PC prepolymers having chloroformyl end-groups with PS prepolymers having hydroxyl end-groups. Both prepolymers had narrow molecular weight distribution (PC prepolymer: M?_w/M?_n ≤ 1,31, PS prepolymer: M?_w/M?_n ≤ 1,03). The course of the polycondensation reaction depends on the molecular weight of the prepolymers used as substrates. After fractionation, the obtained multiblock copolymers are homogeneous in chemical composition and have a narrow molecular weight distribution. The mechanical properties of the copolymers depend on the weight fraction of the PS blocks. All copolymers exhibit two glass transition temperatures, close to those of the parent homopolymers.     

N‐Isopropylacrylamide/2‐Hydroxyethyl Methacrylate Star Diblock Copolymers: Synthesis and Thermoresponsive Behavior

Summary: Tri‐arm star diblock copolymers, poly(2‐hydroxyethyl methacrylate)‐block‐poly(N‐isopropylacrylamide) [P(HEMA‐b‐NIPAAm)] with PHEMA and PNIPAAm as separate inner and outer blocks were synthesized via a two‐step ATRP at room temperature. The formation, molecular weight and distribution of polymers were examined, and the kinetics of the reaction was monitored. The PDI of PHEMA was shown to be lower, indicating well‐controlled polymerization of trifunctional macro‐initiator and resultant star copolymers. The thermoresponsive behavior of diblock copolymer aqueous solution were studied by DSC, phase diagrams, temperature‐variable ¹H NMR, TEM and DLS. The results revealed that introducing a higher ratio of HEMA into copolymers could facilitate the formation of micelles and the occurrence of phase transition at lower temperatures. TEM images showed that I‐(HEMA₄₀‐NIPAAm₃₂₀)₃ solutions developed into core‐shell micelles with diameters of approximately 100 nm. I‐(HEMA₄₀‐NIPAAm₃₂₀)₃ was used as a representative example to elucidate the mechanism underlying temperature‐induced phase transition of copolymer solution. In this study we proposed a three‐stage transition process: (1) separately dispersed micelles state at ≈17–22 °C; (2) aggregation and fusion of micelles at ≈22–29 °C; (3) sol‐gel transition of PNIPAAm segments at ≈29–35 °C, and serious syneresis of shell layers.

Molecular architecture of Poly(HEMA‐b‐NIPAAm).     

Viscometric characterization of poly(oxyethylene)-block-poly(oxypropylene)-block-poly(oxyethylene) in aqueous solution

Viscometric measurements were carried out to characterize poly(oxyethylene)-block-poly-(oxypropy1ene)-block-poly(oxyethy1ene) (POE-POP-POE) in aqueous solution. The results were discussed in terms of a core-shell model of intramolecular phase separation which is based on (i) the selectivity of the solvent water, and (ii) the incompatibility of the POE and POP blocks. The interaction between the two blocks was analysed by vapour pressure osmometry and vapour sorption investigations. The results are:

• 1 The two homopolymer blocks (POE and POP) forming the triblock copolymer are incompatible with each other as vapour pressure osmometry and vapour sorption measurements using ethylbenzene as solvent have shown. This incompatibility of the blocks as well as the selectivity of the solvent water with respect to the different blocks causes the intramolecular (and intermolecular) phase separation of the copolymers in aqueous solution.
• 2 The viscometric data of the aqueous block copolymer solutions can be discussed in terms of the generally accepted core-shell model. This model for the structure of the self-organized molecules includes POP gel core (“melt”) surrounded by solvated POE shell. A quantitative analysis according to this simplified view shows that the hydrodynamic volume of the copolymer molecules is determined by the POE blocks. In the temperature range ? > 30°C, the influence of the POP block on the molecular dimensions is negligible, whereas at ? < 30°C the contributions of the POP and POE to the molecular volume are comparable.
• 3 Kuhn's statistical segment length of POE in the triblock molecules comprises about 4–5 monomeric units. The theta temperature of the triblock copolymer molecules is nearly identical to that of pure POE ((369 ± 3)K).

     

Solution Self‐Assembly of Poly(ferrocenylphenylphosphine)‐block‐polydimethylsiloxane: Formation of Spherical Micelles with an Organometallic Poly(ferrocenylphenylphosphine) Core

The novel organometallic‐inorganic diblock copolymer, poly(ferrocenylphenylphosphine)‐block‐polydimethylsiloxane (PFP‐b‐PDMS), with narrow molecular weight distribution has been synthesized by living anionic polymerization through sequential monomer addition. These block copolymers self‐assemble into “star‐like” spherical micelles in hexane with a dense organometallic PFP core surrounded by a swollen corona of the PDMS chains. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) were used to characterize these micellar aggregates. It was found that the block copolymer micelles have a relatively narrow core size distribution, but an overall broader distribution of hydrodynamic size in hexane. Significantly, the preparation method of the micelle solution was also found to have an influence on the size and size distribution of the resulting micellar structures.     

Crystallization in ABC Triblock Copolymers with Two Different Crystalline End Blocks: Influence of Confinement on Self‐Nucleation Behavior

The influence of different confinements active during crystallization within polybutadiene‐block‐polyisoprene‐block‐poly(ethylene oxide) (PB‐b‐PI‐b‐PEO) and the corresponding hydrogenated polyethylene‐block‐poly(ethylene‐alt‐propylene)‐block‐poly(ethylene oxide) (PE‐b‐PEP‐b‐PEO) triblock copolymers on the self‐nucleation behavior of the crystallizable PEO and PE blocks is investigated by means of differential scanning calorimetry (DSC). In triblock copolymers with PEO contents ≤ 20 wt.‐% crystallization of PEO is confined within small isolated microdomains (spheres or cylinders), and PEO crystallization takes place exclusively at high supercoolings. Self‐nucleation experiments reveal an anomalous behavior in comparison to the classical self‐nucleation behavior found in semicrystalline homopolymers. In these systems, domain II (exclusive self‐nucleation domain) vanishes, and self‐nucleation can only take place at lower temperatures in domain III_SA, when annealing is already active. The self‐nucleation behavior of the PE blocks is significantly different compared with that of the PEO blocks. Regardless of the low PE content (10–25 wt.‐%) in the investigated PE‐b‐PEP‐b‐PEO triblock copolymers a classical self‐nucleation behavior is observed, i.e., all three self‐nucleation domains, usually present in crystallizable homopolymers, can be located. This is a direct result of the small segmental interaction parameter of the PEP and PE segments in the melt. As a consequence, crystallization of PE occurs without confinement from a homogeneous mixture of PE and PEP segments.

Self‐nucleation regimes of a block copolymer showing confined crystallization by means of DSC.     

Theta-behaviour of poly(p-tert-butylstyrene)-block-poly(dimethylsiloxane)-block-poly(p-tert-butylstyrene)

The theta-behaviour of poly(p-tert-butylstyrene)-block-poly(dimethylsiloxane)-block-poly(p-tert-butylstyrene) ABA type triblock copolymers containing ca. 28% by weight tert-butylstyrene was studied in the selective solvents 1-nitropropane and 2-butanone using the phase separation method. The theta-temperatures in these solvents were found to be 157°C and 31°C, respectively. The intrinsic viscosities of the copolymers in 2-butanone (MEK) were obtained at different temperatures. The Mark-Houwink-Sakurada exponent α in MEK at 31°C is greater than 0,5, suggesting that the theta-behaviour of block copolymers is different from that of the homopolymers due to the presence of repulsive interactions between incompatible blocks.     

Self‐Assembly and Photoresponsivity Property of Amphiphilic ABA Triblock Copolymers Containing Azobenzene Moieties in Dilute Solution

The self‐assembly and photoresponsivity of amphiphilic azobenzene‐containing ABA triblock copolymers PA6C_m‐b‐PEG_n‐b‐PA6C_m synthesized by atom transfer radical polymerization (ATRP) were reported. Different self‐assembly morphologies formed by the gradual addition of water to the copolymer solutions in THF. The formation process and aggregate morphology were characterized by UV–Visible spectroscopy and transmission electron microscope (TEM). The triblock copolymers start to form aggregates at the critical water content (CWC). With the addition of water, the aggregates show different morphologies, such as spherical micelles, vesicles, network‐like aggregates, and colloidal spheres, which involves the transformation between primary and secondary aggregates and the association/disassociation of aggregates. Photoresponsive property and aggregation behavior of these copolymers in solution under UV–Visible light irradiation were also investigated.

     

Polymer Containing Multiple Secondary Structures—A Competition between Helical Induction and C-T Complexation

Though “foldamers” have greatly developed, molecules that fold beyond 2° structures are less common. The design and synthesis of triblock copolymers of the “A-B-A” type containing two types of helix formation blocks are presented. Two blocks (A and B) are chosen, with one comprised of L-polyproline as block “A” and the other block (B) comprised with three naphthalene diimide-derivatives separated by two proline residues. Block (B) is carefully designed to serve as a bifunctional initiator for the ring-opening polymerization of proline-N-carboxy anhydride as well as to encapsulate an electron-rich aromatic species by charge transfer complexation (C-T). As a result of (C-T) complexation with dialkoxy pyrene, the native helical structure of the middle block is transformed into a 1D columnar structure without affecting the 2° structure of the polyproline block. In this way, the initial helix₁-b-helix₂-b-helix₁ structure of the block copolymers is transformed into a helix₁-b-columnar-b-helix₁ structure. The C-T complexation and related structural changes of the block copolymers are characterized using UV-vis, fluorescence, and circular dichroism spectroscopy.     

Ternary ABC block copolymers based on one glassy and two crystallizable blocks: polystyrene-block-polyethylene-block-poly(ε-caprolactone)

The hydrogenation of polystyrene-block-polybutadiene-block-poly(ε-caprolactone) SBC triblock copolymers was performed in the presence of the Wilkinson catalyst RhCl(P(C₆H₅)₃)₃. Reaction conditions (hydrogen pressure, temperature and reaction time) were varied to ensure quantitative hydrogenation without detectable side reactions. Gel permeation chromatography showed no broadening of the molecular weight distribution during hydrogenation. The efficiency of the catalyst is markedly influenced by the molecular weight of the copolymer. Due to the presence of the polyethylene (PE) block, the resulting polymers exhibit a reduced solubility in comparison to the starting materials. Using differential scanning calorimetry (DSC), preliminary results about the crystallization and melting behavior of the PE-block were obtained. In the triblock copolymers, the PE-block showed a marked depression of the melting point and crystallinity when compared to pure hydrogenated polybutadiene of equivalent molecular weight and microstructure or to a comparable PE-block within a polyethylene-block-poly(ε-caprolactone) diblock copolymer. A fractionated crystallization process of the PCL-block was observed when the PCL component in the hydrogenated triblock copolymers was present as a minor phase.     

Triblock copolymer based thermoplastic elastomeric gels of a large service temperature range: preparation and characterization

Poly(methyl methacrylate)-block-polybutadiene-block-poly(methyl methacrylate) (MBM) triblock copolymers and their hydrogenated counterparts with poly(ethylene-co-1,2-butylene) midblock (MEBM) were swollen by an aliphatic oil of high boiling point which is a selective solvent for the central block. Thermoreversible gels are accordingly formed by both MBM and MEBM copolymers above a critical polymer content (Cr), which depends on the nature of the midblock and not on the copolymer molecular weight, at least in the investigated range. Cr has been found to be 5 wt.-% for an MBM block copolymer and 2 wt.-% for MEBM copolymers of various molecular weights. Gels of MEBM triblock copolymers exhibit interesting mechanical properties, such as high elongation at break (up to 870%) and high tensile strength (32 kPa). The most interesting feature of the MEBM gels is an upper service temperature as high as 170°C, thus more than 100°C higher than the value (47°C) reported for gels of an SEBS copolymer (S = polystyrene) of comparable molecular weight (100000) and composition (ca. 30 wt.-% hard block). The morphology of MEBM gels was studied by scanning electron microscopy (SEM) and found to be cocontinuous in case of a gel containing 20 wt.-% copolymer.     

ABC triblock polyampholytes containing a neutral hydrophobic block,a polyacid and a polybase

Well defined ABC triblock copolymers of polystyrene-block-poly(2-vinylpyridine)-block-poly(tert-butyl methacrylate) and polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) were synthesized by sequential living anionic polymerization in tetrahydrofuran. Triblock copolymers with narrow molecular weight distribution were obtained. Hydrolysis of the poly(tert-butyl methacrylate) block yields polystyrene-block-polyvinylpyridine-block-poly(methacrylic acid) which demonstrates pH-dependent solution properties. Interpolymer complexation of the polyvinylpyridine and poly(methacrylic acid) blocks in the micellar solution is studied in dependence of the pH in solution by potentiometric, conductometric and turbidimetric titration, and in bulk by FTIR spectroscopy.     

Spherical Compound Micelles with Lamellar Stripes Self‐Assembled from Star Liquid Crystalline Diblock Copolymers in Solution

Detailed investigations on the self‐assembly of amphiphilic star block copolymers composed of three‐arm poly(ethylene oxide) (PEO) and poly(methacrylate) (PMAAz) with an azobenzene side chain (denoted as 3PEO‐b‐PMAAz) into stable spherical aggregates with clear lamellar stripes in solution are demonstrated. Four block copolymers, 3PEO₁₂‐b‐PMA(Az)₃₃, 3PEO₂₂‐b‐PMA(Az)₃₁, 3PEO₂₂‐b‐PMA(Az)₆₂, and linear PEO₆₈‐b‐PMA(Az)₃₁, are synthesized. The liquid crystalline properties of the block copolymers are studied by differential scanning calorimetry, polarized optical microscopy techniques, and wide‐angle X‐ray diffraction. The morphologies of the compound micelles self‐assembled in tetrahydrofuran (THF)/water mixtures are observed by means of transmission electron microscopy and scanning electron microscopy. The size of the spherical micelles is influenced by the self‐assembly conditions and the lengths of two blocks. The well‐defined three‐arm architecture of the hydrophilic blocks is a key structural element to the formation of stable spherical compound micelles. The micelle surface integrity is affected by the lengths of PEO blocks. The lamellar stripes are clearly observed on these micelles. This work provides a promising strategy to prepare functional stable spherical compound micelles self‐assembled by amphiphilic block copolymers in solution.     

Synthesis and assembly of novel chitin derivatives having amphiphilic polyoxazoline block copolymer as a side chain

The first synthesis of chitin derivatives with well-defined block copolymer side chains, i. e., chitin-graft-[poly(2-methyl-2-oxazoline)-block-poly(2-phenyl-2-oxazoline)] ( 5 ), chitin-graft-[poly(2-methyl-2-oxazoline)-block-poly(2-butyl-2-oxazoline)] ( 6 ), and chitin-graft-[poly(2-methyl-2-oxazoline)-block-poly(2-tert-butyl-2-oxazoline)] ( 7 ), was achieved by the reaction of partially deacetylated chitin ( 1 ) with living polyoxazoline block copolymers 2 – 4 . The graft copolymers 5 – 7 are associated into micelles above the critical micelle concentration (CMC). CMCs of 5 (0.01–0.02 wt.-%) are smaller than those (0.32–0.50 wt.-%) of ω-hydroxyl-terminated poly(2-phenyl-2-oxazoline)-block-poly(2-methyl-2-oxazoline) ( 2 -OH), which is a model block copolymer of the side chain segment of 5 . The self-aggregates of 5 – 7 are capable of forming a complex with hydrophobic low molecular weight substances such as pyrene and magnesium 1-anilinonaphthalene-8-sulfonate (ANS). Cryo-transmission electron microscopy showed that the graft copolymer 5 forms globular particles (diameter: 40 nm) and larger cylindrical aggregates (diameter: 40 nm, length: 80–200 nm). The average radius of gyration of the particles of 5 from the SANS analysis is 36 nm.     

Characterization of the thermo- and pH-responsive assembly of triblock copolymers based on poly(ethylene glycol) and functionalized poly(ε-caprolactone)

A series of novel triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(ε-caprolactone)-bearing benzyl carboxylate on the α-carbon of ε-caprolatone were synthesized through ring opening polymerization of α-benzyl carboxylate-ε-caprolactone by dihydroxylated PEG. The debenzylation of the synthesized copolymer, i.e., poly(α-benzyl carboxylate-ε-caprolactone)-b-PEG-b-poly(α-benzyl-carboxylate-ε-caprolactone) (PBCL-b-PEG-b-PBCL), in the presence of hydrogen gas using different levels of catalyst, was carried out to achieve copolymers with various degrees of free α-carboxyl to α-benzyl-ε-carboxylate groups on the hydrophobic block. Incomplete reduction of PBCL led to the formation of poly(α-carboxyl-co-benzyl caboxylate-ε-caprolactone) PCBCL in the lateral blocks at 27%, 50% and 75% carboxyl group substitution. The molecular weight and polydispersity of the resultant copolymers were estimated by ¹H NMR and MALDI-TOF. Synthesized triblock copolymers formed stable micelles at low concentrations (critical micellar concentrations (CMC) of 0.34–12.5 μg ml⁻¹). Polymers containing carboxyl groups in their structure showed a pH-dependent increase in CMC. As the pH was raised from 4.0 to 9.0, CMC increased from 0.76 to 1.06 μg ml⁻¹, for 27% debenzylated polymer, and from 1.30 to 2.20 μg ml⁻¹, for 50% debenzylated polymers. In contrast, the CMC in polymers without carboxyl group was independent of pH (0.55 μg ml⁻¹). Different changes in micellar size as a function of temperature was observed depending on the degree of debenzylation on the PCBCL block: polymers with 27% degree of debenzylation illustrated a rise in micelle size from ∼38 to 55 nm as the temperature increased above 29 °C, while polymers with 50% debenzylation showed a decrease in micelle size, from ∼52 to 38 nm, with increase in temperature. A similar trend was observed at pH 4.5, 7.0 and 9.0 for polymers containing carboxyl groups on their hydrophobic block. The temperature for the onset of size change and/or the extent of aggregate size change was found to be dependent on the pH of the medium and the polymer concentration. The results point to a potential for the formation of thermo- and pH-responsive micelles from triblock copolymers of PEG and carboxyl substituted caprolactone. The results also imply a potential for the 27% debenzylated PCBCL-b-PEG-b-PCBCL copolymers to form a biodegradable thermoreversible gel with a transition temperature a few degrees below 37 °C.     

Synthesis and permeation behavior of membranes from segmented multiblock copolymers containing poly(ethylene oxide) and poly(β-benzyl L-aspartate) blocks

Novel segmented multiblock copolymers ( 7 ) were synthesized by linking poly(ethylene oxide) (PEO) blocks with poly(β-benzyl L -aspartate)(PBLA) blocks via urethane and urea bonds, which were formed by the reaction of 4,4′-methylenediphenyl isocyanate ( 5 ) with the terminal hydroxyl groups of α-hydro-ω-hydroxypoly(oxyethylene) ( 4 ) and the terminal amino groups of poly(β-benzyl L -aspartate)-block-iminohexamethyleneimino-block-poly(β-benzyl L -aspartate) ( 3 ) [prepared from 1,6-hexanediamine ( 1 ) and β-benzyl L -aspartate N-carboxy anhydride ( 2 )], respectively. Membranes with various water contents were obtained from these copolymers by changing the lengths of the PEO and PBLA segments. The study of the permeation of 1-phenyl-1,2-ethanediol, vitamin B₁₂ and myoglobin through the membranes showed a high dependency of the permeability on the molecular weight of the solutes.     

Folate‐Conjugated Poly(N‐(2‐hydroxypropyl) methacrylamide)‐block‐Poly(benzyl methacrylate): Synthesis,Self‐Assembly,and Drug Release

Well‐defined amphiphilic diblock copolymers of poly(N‐(2‐hydroxypropyl)methacrylamide)‐block‐poly(benzyl methacrylate) (PHPMA‐b‐PBnMA) are synthesized using reversible addition–fragmentation chain transfer polymerization. The terminal dithiobenzoate groups are converted into carboxylic acids. The copolymers self‐assemble into micelles with a PBnMA core and PHPMA shell. Their mean size is <30 nm, and can be regulated by the length of the hydrophilic chain. The compatibility between the hydrophobic segment and the drug doxorubicin (DOX) affords more interaction of the cores with DOX. Fluorescence spectra are used to determine the critical micelle concentration of the folate‐conjugated amphiphilic block copolymer. Dynamic light scattering measurements reveal the stability of the micelles with or without DOX. Drug release experiments show that the DOX‐loaded micelles are stable under simulated circulation conditions and the DOX can be quickly released under acidic endosome pH.     

Block copolymers with bipyridine containing segments: Synthesis and self-organization by Cu(I) complexation

The synthesis and properties of segmented ABA triblock and (AB)_n multiblock copolymer systems with 6,6′-disubstituted 2,2′-bipyridine (bpy) building blocks B and poly(oxytetramethylene) soft segments A are described. The access to the disubstituted bipyridines in large scale quantities was achieved by modification of conventional synthetic routes. In the presence of copper(I) ions these polymers formed mononuclear [Cu(I)(bpy)₂] complexes in solution through self-assembly. The complexed copolymers were microphase separated systems in bulk with nano to mesoscopic superstructures consisting of copper-bpy complex aggregates in a polyether matrix. The thermal, mechanical and elastomer properties of the block copolymers varied with composition.