Synthesis of poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene triblock copolymers by two-step atom transfer radical polymerization

The synthesis of ABC triblock copolymer poly(ethylene oxide)-block-poly(methyl methacrylate)-block-polystyrene (PEO-b-PMMA-b-PS) via atom transfer radical polymerization (ATRP) is reported. First, a PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide, which was subsequently used in the preparation of halo-terminated poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymers under ATRP conditions. Then PEO-b-PMMA-b-PS triblock copolymer was synthesized by ATRP of styrene using PEO-b-PMMA as a macroinitiator. The structures and molecular characteristics of the PEO-b-PMMA-b-PS triblock copolymers were studied by FT-IR, GPC and ¹H NMR.     

Epoxy resin containing poly(ethylene oxide)-block-poly(?-caprolactone) diblock copolymer: Effect of curing agents on nanostructures

An amphiphilic diblock copolymer, poly(ethylene oxide)-block-poly(?-caprolactone) (PEO-b-PCL) was synthesized via the ring-opening polymerization of ?-caprolactone in the presence of a hydroxyl-terminated poly(ethylene oxide) monomethyl ether. The diblock copolymer was incorporated into epoxy thermosets. It is found that the formation of nanostructures of thermosetting blends is quite dependent on the uses of aromatic amine hardeners. For 4,4′-methylenebis(2-chloroaniline) (MOCA)-cured thermosetting system, the homogeneous morphology was obtained at the compositions investigated. Nonetheless, the nanostructured thermosets were obtained when the blends were cured with 4,4′-diaminodiphenylsulfone (DDS). The differential scanning calorimetry (DSC) showed that the nanostructured thermosets did not displayed any crystallinity although the subchains of the diblock copolymer are crystalline. The nanostructures were evidenced by means of atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The dependence of morphological structures on the types of aromatic amines for epoxy and PEO-b-PCL thermosetting blends were interpreted on the basis of the difference in hydrogen bonding interactions resulting from the structure of curing agents. Considering the complete miscibility of the subchains (viz. PEO and PCL) with the precursors of epoxy resin before curing, it is judged that the formation of the nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation, which is in marked contrast to the mechanism of self-assembly, i.e., micelle structures of block copolymers are formed prior to curing, followed by fixing these nanostructures via curing.     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Thermosets with core-shell nanodomain by incorporation of core crosslinked star polymer into epoxy resin

Core crosslinked star (CCS) polymers, which have crosslinked poly (divinyl benzene-co-styrene) [P(DVB-St)] core and multiple arms of polystyrene-b-poly(ethylene oxide) diblock copolymer (PEO-b-PS) [denoted as PEO-b-PS/P(DVB-St) CCS], were synthesized via atom transfer radical polymerization(ATRP). PEO-b-PS/P(DVB-St) CCS polymer was spherical with average diameters of scores of nanometers from transmission electron microscopy (TEM) and dynamic light scattering (DLS), and blended with diglycidyl ether of bisphenol (DGEBA) and 4,4′-diamino diphenyl methane (DDM) in tetrahydrofuran (THF). With 5 or 10 wt% PEO-b-PS/P(DVB-St) CCS polymer, spherical core-shell nanodomains with average diameters of 29 or 32 nm were observed from atomic force microscopy (AFM), which were randomly distributed in the resultant thermosets. Considering the difference in miscibility of the epoxy with P(DVB-St) and PEO-b-PS after and before curing reaction, a reaction-induced microphase separation (RIMPS) mechanism was proposed to account for the formation of the core-shell nanodomains in the thermosets. During curing, the RIMPS of PS subchain occurred but was confined by P(DVB-St) core, resulting in formation of thermoplastic PS shell around the crosslinked core. Such core-shell nanodomain could be easily etched away by THF, whereas the control thermosets containing PEO/P(DVB-St) CCS polymer could not be etched by THF. The glass transition temperatures (T_gs) of the epoxy thermosets containing PEO-b-PS/P(DVB-St) CCS polymer were significantly improved compared with pure epoxy thermosets.     

Synthesis of nonionic flocculants by gamma irradiation of mixtures of polyacrylamide and poly(ethylene oxide)

The synthesis of polyacrylamide (PAM) graft poly(ethylene oxide) (PEO) has been investigated and the reaction conditions were varied by gamma irradiation to optimize polystyrene latex flocculation by the copolymers. The effects of the gamma ray dosage, the PEO chain length, the ratio of PEO to PAM, and the crosslinking degree of copolymer were studied. The most effective flocculant was obtained by exposing a mixture of 1.2 wt % PAM (M_w = 5 × 10⁶) and 0.94 wt % PEO (M_w = 5000) to 816 krad of gamma radiation. The resulting copolymer contained 24 wt % PEO. Crosslinking to give insoluble gels was an undesirable side reaction increased with γ-ray dose and decreased with PEO addition. The most effective flocculants contained more than 15 wt % PEO with little crosslinking. The grafting behavior of triblock copolymer, poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (E_mP_nE_m, where m and n are oxyethylene and oxypropylene unit, respectively), onto PAM by gamma radiation was also studied; grafting occurred but effective flocculants were not obtained. © 1994 John Wiley & Sons, Inc.     

A biodegradable triblock copolymer poly(ethylene glycol)-b-poly(l-lactide)-b-poly(l-lysine): Synthesis,self-assembly,and RGD peptide modification

A novel biodegradable triblock copolymer poly(ethylene glycol)-b-poly(l-lactide)-b-poly(l-lysine) (PEG–PLA–PLL) was synthesized by acidolysis of poly(ethylene glycol)-b-poly(l-lactide)-b-poly(ɛ-benzyloxycarbonyl-l-lysine) (PEG–PLA–PZLL) obtained by the ring-opening polymerization (ROP) of ɛ-benzyloxycarbonyl-l-lysine N-carboxyanhydride (ZLys NCA) with amino-terminated PEG–PLA–NH₂ as a macroinitiator, and the pendant amino groups of the lysine residues were modified with a peptide known to modulate cellular functions, Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) in the presence of 1,1′-carbonyldiimidazole (CDI). The structures of PEG–PLA–PLL/RGD and its precursors were confirmed by ¹H NMR, FT-IR, amino acid analysis and XPS analysis. The cell adhesion and cell spread on the PEG–PLA–PLL/RGD film were enhanced compared to those on pure PLA film. Therefore, the novel RGD-grafted triblock copolymer is promising for cell or tissue engineering applications. Both copolymers PEG–PLA–PZLL and PEG–PLA–PLL showed an amphiphilic nature and could self-assemble into micelles of homogeneous spherical morphology. The micelles were determined by fluorescence technique, dynamic light scattering (DLS), and field emission scanning electron microscopy (ESEM) and could be expected to find application in drug and gene delivery systems.     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Morphology and mechanical properties of nanostructured blends of epoxy resin with poly(?-caprolactone)-block-poly(butadiene-co-acrylonitrile)-block-poly(?-caprolactone) triblock copolymer

Poly(?-caprolactone)-block-poly(butadiene-co-acrylonitrile)-block-poly(?-caprolactone) triblock copolymer was synthesized via the ring-opening polymerization of ?-caprolactone with dihydroxyl-terminated butadiene-co-acrylonitrile random copolymer. The amphiphilic block copolymer was used to toughen epoxy thermosets via the formation of nanostructures. The morphology of the thermosets was investigated by means of atomic force microscopy, transmission electronic microscopy and small-angle X-ray scattering. It was judged that the formation of the nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation. The thermal and mechanical properties of the nanostructured thermosets were compared to those of the ternary blends composed of epoxy, poly(butadiene-co-acrylonitrile) and poly(?-caprolactone) with the identical content of the modifiers. It is noted that at the same composition the nanostructured thermosets displayed higher glass transition temperatures (T_gs) than the ternary blends, which was evidenced by dynamic mechanical analysis. The fracture toughness of the thermosets was evaluated in terms of the measurement of critical stress field intensity factor (K_1C). It is noted that at the identical composition the nanostructured blends significantly displayed higher fracture toughness than the ternary blends. In addition, the K_1C of the nanostructured thermosets attained the maximum with the content of the modifier less than their counterpart of ternary blending.     

Nanostructured unsaturated polyester modified with poly[(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)] triblock copolymer

Miscibility, crystallization and morphology of unsaturated polyester (UP) matrices, nanostructured with a poly[(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)] (PEO-b-PPO-b-PEO) block copolymer (BCP) from 0 to 50 wt% has been investigated. Additionally, the role of each block on miscibility and morphology of cured mixtures was studied. Behaviours of non-reactive mixtures of UP thermosetting precursor with two BCPs composed of similar and strong immiscible central PPO block were compared. It was found that one BCP had PEO blocks with not enough molecular weight to compatibilize the PPO block with the UP thermosetting precursor at room temperature. Transmitted light intensity study of mixtures indicated that during curing at 35 °C no macrophase separation took place, contrary to the systems cured at temperatures equal or higher than 60 °C. Curing mixtures at 35 °C produced nanostructured matrices with almost unchanged transparency. Phase separation and miscibility of BCP with UP matrix were measured by means of DSC and DMA. AFM analysis showed worm-like morphology with diameters from 10 to 20 nm and length that evolved from 50 nm to 1 μm with increase of BCP content.     

Vesicle formation of polystyrene-block-poly (ethylene oxide) block copolymers induced by supercritical CO2 treatment

A novel route for a preparation of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer vesicles induced by supercritical carbon dioxide (scCO₂) is demonstrated. When PS-b-PEO block copolymer solutions in tetrahydrofuran (THF) are treated with scCO₂ at 70 °C for different times, PS-b-PEO copolymers first assemble into aggregated spheres; then aggregated spheres change into large compound micelles and finally evolve into vesicles. The possible formation mechanism of the vesicles is discussed.     

Miscibility with positive deviation in Tg-composition relationship in blends of poly(2-vinyl pyridine)-block-poly(ethylene oxide) and poly(p-vinyl phenol)

Phase behavior and miscibility with positive deviation from linear T_g-composition relationship in a copolymer/homopolymer blend system, poly(2-vinyl pyridine)-block-poly(ethylene oxide) (P2VP-b-PEO)/poly(p-vinyl phenol) (PVPh), were investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR) and solid-state ¹³C nuclear magnetic resonance (¹³C NMR), optical microscopy (OM), and scanning electron microscopy (SEM). Optical and electron microscopy results as well as NMR proton spin-lattice relaxation times in laboratory frame () all confirmed the miscibility as judged by the T_g criterion using DSC. In comparison to the literature result on a homopolymer/homopolymer blend of P2VP/PVPh, fitting with the Kwei equation on the T_g-composition relationship for the block-copolymer/homopolymer blend of P2VP-b-PEO/PVPh blend system yielded a smaller q value (q = 120) for P2VP-b-PEO/PVPh than that for P2VP/PVPh blend (q = 160). The FT-IR and ¹³C NMR results revealed hydrogen-bonding interactions between the pendant pyridine group of P2VP-b-PEO and phenol unit in PVPh, which is responsible for the noted positive deviation of the T_g-composition relationship. Comparison of the shifts of hydroxyl IR absorbance band, reflecting the average strength of H-bonding, indicates a decreasing order of P2VP/PVPh > P2VP-b-PEO/PVPh > PEO/PVPh blends. The PEO block in the copolymer segment tends to defray the interaction strength in the P2VP-b-PEO/PVPh blends because of relative weaker interaction between PEO and PVPh than that between P2VP and PVPh pairs. A comparative ternary (P2VP/PEO)/PVPh blend was also studied as the controlling experiments for comparison to the P2VP-b-PEO/PVPh blend. The thermal behavior and interaction strength in (P2VP/PEO)/PVPh ternary blends are discussed with those in the P2VP-b-PEO/PVPh copolymer/homopolymer blend.     

Role of intermolecular interaction between hydrophobic blocks in block-selected inclusion complexation of amphiphilic poly(ethylene oxide)-poly[(R)-3-hydroxybutyrate]-poly(ethylene oxide) triblock copolymers with cyclodextrins

The influence of hydrophobic interaction between poly[(R)-3-hydroxybutyrate] blocks on block-selected inclusion complexation between amphiphilic poly(ethylene oxide)-poly[(R)-3-hydroxybutyrate]-poly(ethylene oxide)) (PEO-PHB-PEO) triblock copolymers and α-cyclodextrin (α-CD) or γ-cyclodextrin (γ-CD) was studied by X-ray diffraction, differential scanning calorimetry (DSC), FTIR and ¹H NMR. Due to the stronger hydrophobic interaction at higher temperature, the amphiphilic triblock copolymer tends to aggregate to form tighter core-shell sphere with PHB block in the core and PEO in the corona. Therefore, the CD threaded onto PEO blocks cannot further slide onto the PHB block, which resulted in a highly block-selected inclusion complex formation. Moreover, the DSC results indicated that the triblock copolymer coalesced from its ICs with hot water showed an increase in microphase separation compared with the as-synthesized triblock copolymer, which further supports our hypothesis that CD only selectively includes PEO blocks of the triblock copolymer at higher temperature.     

Dissipative particle dynamics study on the multicompartment micelles self-assembled from the mixture of diblock copolymer poly(ethyl ethylene)-block-poly(ethylene oxide) and homopolymer poly(propylene oxide) in aqueous solution

Dissipative particle dynamics (DPD) method is applied to model the self-assembly of diblock copolymer poly(ethyl ethylene)-block-poly(ethylene oxide) (PEE-b-PEO) and homopolymer poly(propylene oxide) (PPO) in aqueous solution. In this study, several segments are coarse-grained into a single simulation bead based on the experimental density. For the self-assembly of pure diblock copolymer PEE-b-PEO in dilute solution, the DPD simulation results are in good agreement with experimental data of micelle morphologies and sizes. The chain lengths of the block copolymers and the volume ratios between PPO and PEE-b-PEO are varied to find the conditions of forming multicompartment micelles. The micelles with core-shell-corona structure and the micelles with two compartments are both formed from the mixture of PEE-b-PEO and PPO in aqueous solution.     

Isothermal crystallization kinetics of poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymer with two crystallizing blocks

The isothermal crystallization kinetics and morphology of poly(ethylene terephthalate)-poly(ethylene oxide) (PET30-PEO6) segmented copolymer, and poly(ethylene terephthalate) (PET) and poly(ethylene oxide) (PEO) homopolymers have been studied by means of differential scanning calorimetry (DSC) and a transmission electron microscope (TEM). It is found that the nucleation mechanism and growth dimension of PEO in the copolymer are different from that in the homopolymer, which is attributed to the effect of the crystallizability of PET-blocks. Furthermore, the crystallization rate of PEO-blocks in the copolymer is slower than that in the homopolymer because the PET-blocks phase is always partially solidified at the temperatures when PEO-blocks begin to crystallize. In contrast, the isothermal crystallization rate of PET-blocks in the copolymer is faster than that in the homopolymer because the lower glass transition temperature of the PEO-blocks (soft blocks) increases the mobility of the PET-blocks in the copolymer.     

Formation of nanostructures in thermosets containing block copolymers: From self-assembly to reaction-induced microphase separation mechanism

In this work, we investigated the effect of formation mechanisms of nanophases on the morphologies and thermomechanical properties of the nanostructured thermosets containing block copolymers. Toward this end, the nanostructured thermosets involving epoxy and block copolymers were prepared via self-assembly and reaction-induced microphase separation approaches, respectively. Two structurally similar triblock copolymers, poly(ε-caprolactone)-block-poly(butadiene-co-styrene)-block-poly(ε-caprolactone) (PCL-b-PBS-b-PCL) and poly(ε-caprolactone)-block-poly(ethylene-co-ethylethylene-co-styrene)-block-poly(ε-caprolactone) (PCL-b-PEEES-b-PCL) were synthesized via the ring-opening polymerization of ε-caprolactone (CL) with α,ω-dihydroxyl-terminated poly(butadiene-co-styrene) (HO-PBS-OH) and α,ω-dihydroxyl-terminated poly(ethylene-co-ethylethylene-co-styrene) (i.e., HO-PEEES-OH) as the macromolecular initiators, respectively; the latter was obtained via the hydrogenation reduction of the former. Both the triblock copolymers had the same architecture, the identical composition and close molecular weights. In spite of the structural resemblance of both the triblock copolymers, the formation mechanisms of the nanophases in the thermosets were quite different. It was found that the formation of nanophases in the thermosets containing PCL-b-PBS-b-PCL followed a reaction-induced microphase separation mechanism whereas that in the thermosets containing PCL-b-PEEES-b-PCL was in a self-assembly manner. The different formation mechanisms of nanophases resulted in the quite different morphologies, glass transition temperatures (T_g's) and fracture toughness of the nanostructured thermosets.     

Synthesis and characterization of poly(ethylene glycol)-b-poly(l-histidine)-b-poly(l-lactide) with pH-sensitivity

In this paper, amphiphilic biodegradable methoxy-poly(ethylene glycol)-poly(l-histidine)-poly(l-lactide) (mPEG–PH–PLLA) triblock copolymers with pH sensitivity were synthesized. The properties of mPEG–PH–PLLA triblock copolymers were investigated by GPC, ¹H NMR, DSC, TGA, XRD and polarized optical microscopy. The results showed that the thermal properties of the triblock copolymers varied with the chain length of PH blocks. The glass transition temperatures (Tg) of the triblock copolymers increased with increasing poly(l-histidine) chain length. The morphologies of PLLA crystals changed from spherulite to dendritic crystal. Moreover, the crystallization rate of triblock copolymers was faster than that of PLLA homopolymer. The pH sensitivity of the self-assembled mPEG–PH–PLLA nanoparticles was investigated. The mean diameter and morphology of the nanoparticles were characterized by DLS, AFM and TEM. The results showed that the mean diameter of mPEG₄₅–PH₃₀–PLLA₈₂ nanoparticles in pH = 5.0 was smaller than that in pH = 7.4.     

Synthesis of (ABCB)n type ternary amphiphilic multiblock copolymer via poly(ethylene oxide) macro-chain transfer agent

A novel (ABCB)_n type ternary amphiphilic multiblock copolymer was synthesized by stepwise insertion of monomers into the trithiocarbonate-embedded poly(ethylene oxide) (PEO) macro-chain transfer agent (PEO-CTA)_n. (PEO-CTA)_n was synthesized first by coupling of α,ω-dihydroxyl PEO with dicarboxylic trithiocarbonate, then styrene (St) and t-butyl acrylate (^tBA) were inserted into the (PEO-CTA)_n successively to yield (PEO-b-PS)_n and (PEO-b-PS-b-P^tBA-b-PS)_n, respectively. After hydrolysis of the (PEO-b-PS-b-P^tBA-b-PS)_n, the final product (PEO-b-PS-b-PAA-b-PS)_n was obtained.     

Synthesis and characterization of copolymers with the same proportions of polystyrene and poly(ethylene oxide) compositions but different connection sequence by the efficient Williamson reaction

The AB type diblock PS‐b‐PEO and ABA type triblock PS‐b‐PEO‐b‐PS copolymers containing the same proportions of polystyrene (PS) and poly(ethylene oxide) (PEO) but different connection sequence were synthesized and investigated. Using the sequential living anionic polymerization and ring‐opening polymerization mechanisms, diblock PS‐b‐PEO copolymers with one hydroxyl group at the PEO end were obtained. Then, using the classic and efficient Williamson reaction (realized in a ‘click’ style), triblock PS‐b‐PEO‐b‐PS copolymers were achieved by a coupling reaction between hydroxyl groups at the PEO end of PS‐b‐PEO. The PS‐b‐PEO and PS‐b‐PEO‐b‐PS copolymers were well characterized by ¹H NMR spectra and SEC measurements. The critical micelle concentration (CMC) and thermal behaviors were also investigated by steady‐state fluorescence spectra and DSC, respectively. The results showed that, because the PEO segment in triblock PS‐b‐PEO‐b‐PS was more restricted than that in diblock PS‐b‐PEO copolymer, the former PS‐b‐PEO‐b‐PS copolymer always gave higher CMC values and lower crystallization temperature (T_c), melting temperature (T_m) and degree of crystallinity (X_c) parameters. © 2015 Society of Chemical Industry     

Self-assembly and crystallization behavior of a double-crystalline polyethylene-block-poly(ethylene oxide) diblock copolymer

The self-assembly and crystallization behavior of a well-defined low molecular weight polyethylene-block-poly(ethylene oxide) (PE-b-PEO) diblock copolymer was studied. The number-average degrees of polymerization for the PE and PEO blocks were 29 and 20, respectively. The molecular weight distribution was 1.04 as determined by size-exclusion chromatography. The PE-b-PEO sample exhibited two melting points at 28.7 and 97.4 °C for the PEO and the PE crystals, respectively. The crystallization of the PE blocks was unconfined, while the crystallization of the PEO blocks was confined between pre-existing PE crystalline lamellae, as demonstrated by simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) studies. In the fully crystalline state, both PE and PEO blocks formed extended-chain crystals with PE chains tilted ∼22° from the lamellar normal and PEO chains parallel to the lamellar normal, as evidenced by two-dimensional WAXD study of shear-oriented samples. Regardless of hydrogen bonding among hydroxyl chain ends in the PEO blocks, interdigitated, single-crystalline layer morphology was observed for both PE and PEO crystals. The partial crystalline morphology, where the PE crystallizes and the PEO is amorphous, had the same overall d-spacing as the fully crystalline morphology. A double-amorphous PEO layer sandwiched between neighboring PE crystalline layers was deduced based on a chain conformation study using Fourier transform infrared. The confined crystallization kinetics for PEO blocks was investigated by differential scanning calorimetry, which could be explained by a heterogeneous nucleation mechanism. The slower crystallization rate in the PEO-block than the same molecular weight homopolymer was attributed to the effects of nanoconfinement and PEO chains tethered to the PE crystals.