Probing the interface structure of block copolymer compatibilizers in semicrystalline polymer blends

The use of block copolymers to compatibilize immiscible plastics is an important strategy for upcycling municipal plastic wastes. Multiblock copolymers (MBCPs) have been proven to be more effective compatibilizers than di- and tri-block copolymers. Herein, we probe the interface structure of an effective multiblock copolymer compatibilizer and compare that with an ineffective triblock copolymer (TBCP). The interface activity of the compatibilizers is understood through a combination of small-angle neutron and x-ray scatterings (SANS and SAXS), by using deuterated homopolymer matrix and protonated compatibilizers. SANS analysis suggests that the MBCP forms a thicker interface layer (7–9 nm) than the TBCP (0–4 nm). In addition, SANS data seems to point to a stronger tendency for the MBCP to locate at the interface. Both factors contribute to its effectiveness at compatibilizing immiscible homopolymers.     

Morphology and thermal analysis of poly(ethylene-b-vinylacetate) copolymers

Summary Studies of crystallization kinetics and morphological analysis on three samples of poly(ethylene-b-vinylacetate) multiblock copolymers have been performed. The copolymers contain 28% by weight of vinylacetate and their macromolecules are builted up by different numbers of blocks, whose lengths are constant in all cases. An original method of staining puts into evidence the segregation of the polyethylenic blocks in crystalline domains, whose dimensions are less than 50 Å, in good agreement with the molecular characteristics. A structural model, involving fringed micellae for the rigid segments, is suggested and supported by values of the Avrami index, less than 2. The crystallization rates are also discussed as functions of the molecular weights of the samples.     

Effect of multiblock copolymers in polymer blends

The use of multiblock copolymers for the compatibilization of immiscible polymer blends is controversially discussed in the literature. Investigations have been carried out to estimate the effect of multiblock copolymers containing segments of a liquid crystalline polyester (LCP) and polysulfone (PSU) segments in blends of the based homopolymers. One goal was to determine whether multiblock copolymers provide an opportunity for compatibilizing PSU/LCP blends. By using PSU/LCP multiblock copolymers with different molecular weights of the blocks in the appropriate binary, solution-casted blends, it was shown that the interpenetration of the polysulfone phase of the block copolymer and the PSU matrix leads to an improved miscibility of the blend. This effect is retained in ternary blends of PSU, LCP, and the multiblock copolymer, assuming a certain critical molecular weight of the multiblock copolymer segments. In addition, some mechanical characteristics of PSU/LCP melt blends such as the E-modulus and fracture strength are improved by adding long-segmented multiblock copolymers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2293–2309, 1997     

Synthesis and properties of multiblock copolymers based on polydimethylsiloxane and piperazine-aromatic polyamides

Polydimethylsiloxane (PDMS)–polyamide multiblock copolymers were synthesized by three different methods, i.e., two-step low-temperature solution polycondensation, one-step solution polycondensation, and interfacial polycondensation. In the two-step method, α,ω-diacid chlorideterminated polyamide oligomers were prepared from trans-2,5-dimethylpiperazine (DMP) and terepthaloyl chloride (TPC) or isophthaloyl chloride (IPC) in chloroform in the presence of triethylamine, which in turn were subjected to reaction with α,ω-bis (3-aminopropyl) polydimethylsiloxane (PDMS–diamine) in the same solvent to from multiblock copolymers. In the one-step method, the reaction components, DMP, TPC (or IPC), and PDMS–diamine, were reacted altogether in chloroform in the presence of triethylamine. In the interfacial method, the reaction components were also reacted altogether in an aqueous sodium hydroxide–chloroform two-phase system. These polycondensations afforded the multiblock copolymers having inherent viscosities of 0.1–1.3 dL g^?1 in m-cresol. The PDMS–polyamide multiblock copolymers dissolved in formic acid and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and transparent, ductile, and elastomeric films were obtained by casting from the HFIP solutions. The films of the multiblock copolymers prepared by three different methods exhibited similar properties by means of thermal analysis and tensile measurements. In the multiblock copolymers, the tensile strength and modulus of the films decreased with increasing the PDMS content, whereas the elongation at break increased.     

Facile synthesis of multiblock copolymers composed of poly(tetramethylene oxide) and polystyrene using living free-radical polymerization macroinitiator

A facile synthetic strategy for well-defined multiblock copolymers utilizing ‘living’ free-radical polymerization macroinitiator has been presented. Polyurethane composed of alkoxyamine initiating units and poly(tetramethylene oxide) (PTMO) segments was prepared by polyaddition of tolylene 2,4-diisocyanate terminated PTMO with an alkoxyamine-based diol. Polymerization of styrene with the polyurethane macroinitiator was carried out under nitroxide-mediated free-radical polymerization (NMRP) condition. GPC, NMR, and IR data revealed that the polymerization was accurately controlled and well-defined polystyrene chains were inserted in the main chain of macroinitiator to give the poly(tetramethylene oxide)-b-polystyrene multiblock copolymers. The synthesized multiblock copolymers were characterized by tensile test, differential scanning calorimetry, and dynamic mechanical analysis. Mechanical properties of the multiblock copolymers can be tuned by the sufficient molecular weight control of PS chains. Soft segment of PTMO and hard segment of PS were apparently compatible due to the multiblock structure of low molecular weight segments and polar urethane groups.     

烯烃多嵌段共聚物的结构、合成及应用

烯烃多嵌段共聚物是一种新型的聚烯烃热塑性弹性体,主要通过催化乙烯和1-辛烯链穿梭聚合制备得到多嵌段含"软段"和"硬段"的聚合物,其独特结构和性能已经成为新材料的研究热点。本文概述了烯烃嵌段多共聚物的结构和制备合成,并指出了烯烃多嵌段共聚物性能和应用前景。     

LC multiblock copolymers containing polysulfone segments. I. Synthesis and morphology

Multiblock copolymers offer the possibility to combine the properties of different polymers. Thus, new materials with tailor-made unique properties are available by coupling of different suitable polymeric segments. The goal of the work discussed in this paper was to combine advantageous properties of liquid-crystalline polymers (LCP) with those of polysulfone (PSU). Therefore, liquid crystalline poly(ethylene terephthalate-co-1,4-oxybenzoates) were connected with PSU oligomers. Chemically homogeneous multiblock copolymers with high molecular weight were obtained by a melt transesterification procedure. It was demonstrated by wide angle x-ray scattering (WAXS), polarizing microscopy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC) that the properties of the multiblock copolymers (solid phase structure, phase behavior, morphology, glass transition, and melting behavior) can be balanced by the segment length of the incorporated blocks. The investigations clearly reveal the existence of a two-phase structure. However, a change of properties compared to the corresponding homopolymers refers to certain interactions between the phase due to the chemical connection of the LCP and PSU segments. © 1996 John Wiley & Sons, Inc.     

钪配合物催化丙烯与月桂烯的共聚合

研究了两种钪配合物(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2(记作钪配合物1,Me为甲基)和(C5Me4SiMe3)Sc(CH2SiMe3)2(THF)(记作钪配合物2,THF为四氢呋喃)催化丙烯与月桂烯共聚合的性能.结果表明:在室温及丙烯压力为0.6?MPa时,通过调控月桂烯的用量,采用钪配合物1和...     

New azo-chromophore-containing multiblock poly(butadiene)s synthesized by the combination of ring-opening metathesis polymerization and click chemistry

A combination of ring-opening metathesis polymerization (ROMP) and click chemistry approach was utilized for the first time in preparation of multiblock copolymers. The dibromo-functionalized telechelic poly(butadiene) (PBD) was synthesized firstly by ROMP of 1,5-cyclooctadiene in the presence of a symmetrical difunctional chain transfer agent and transformed into diazido-telechelic PBD, which was then reacted with a dialkynyl-containing azobenzene chromophore via click reaction, producing novel multiblock PBDs collected by azobenzene groups and newly formed triazole moieties. The monomer and polymer were characterized by IR, UV-vis, LC/MS, and NMR techniques. The produced multiblock copolymers have molecular weights within 13.3 and 57.8 kDa, and their polydispersity indices ranging from 1.98 to 2.38 by gel permeation chromatography measurement. The multiblock PBDs containing azo chromophores and triazole moieties with or without hydrogen-bonding interreaction with 4,4′-dihydroxybiphenyl molecule exhibited different photoisomerization efficiency from trans to cis as observation in UV-vis spectroscopy. The morphologies of multiblock PBDs were also investigated by atom force microscopy.     

The effect of short chain branching on local chain organisation in isotopically labelled blends of polyethylene

The complementary techniques of small angle neutron scattering (SANS) and infra-red spectroscopy have been used to determine features of molecular trajectory for isotopic blends incorporating linear polyethylene and copolymers containing butyl or hexyl branches. SANS data show both a more compact conformation for a copolymer guest molecule than for a linear guest and also a smaller molecular expansion with increasing molecular weight when both guest and host are copolymers. These blends also show the smallest proportion of [lcub ]110[rcub ] isolated guest stems, while wholly linear blends show the largest proportion, on the evidence of the infra-red CD₂ bending band profiles. Estimates are made of the sizes of ‘groups’ of adjacent stems, and these also show a corresponding dependence on the sample type, indicating a higher proportion of adjacent re-entry for copolymer blends than for linear blends.     

Hydrophilic-hydrophobic multiblock copolymers based on poly(arylene ether sulfone)s as novel proton exchange membranes - Part B

There has been growing evidence, both experimental and theoretical, that block copolymer systems with well-defined sulfonated regions may provide enhanced proton transport, especially at low relative humidity. We have recently demonstrated a novel way to make hydrocarbon hydrophobic-hydrophilic block copolymers. While the chemical structure and chemical compositions are very similar to random copolymers, the microstructure and the morphology are very different. The self-diffusion coefficients of water, as measured by Pulse Gradient Stimulated Echo (PGSE) NMR techniques, have indicated a significant improvement in water transport after reaching a particular block length. At that block length (10 kg/mol:10 kg/mol), the multiblocks display better proton conductivity under partially hydrated conditions than the random copolymers. The presence of increased free water content in the multiblocks with increasing block lengths was confirmed by states of water analysis. A significant change in the distribution of three types of water was also observed compared to the random copolymers. This paper will discuss the structure-property relationships of these multiblock copolymers for potential application as proton exchange membranes.     

Synthesis,characterization and properties of amphiphilic butadiene-oxyethylene multiblock copolymers

Butadiene-oxyethylene multiblock copolymers were synthesized via coupling reaction of telechelic α,ω-dihydroxypolybutadiene (PB) and poly(ethylene glycol) with tolylene-2,4-diisocyanate. The poly(oxyethylene) (PEO) content of the purified copolymer was determined by elemental analysis and the structural parameters were calculated from number-average molecular weights of the purified copolymer, determined by membrane osmometry, and those of the prepolymers, determined by vapor pressure osmometry. The total number of blocks varied from 60 to 100. Transmission electron microscopy showed the existence of multiphases in the copolymer. Wide angle X-ray diffraction indicated that the crystallinity increased from 0 to 50% with increasing weight ratio of PEO/PB. These multiblock copolymers exhibit excellent emulsifying properties, as compared to the multiblock copolymers or graft copolymer of oxyethylene and styrene. Only 0.1 g of polymer was needed to make 100 mL of a water/toluene (9:1, w/w) mixture form an emulsion completely. When the weight ratio of water/toluene was changed from 9:1 to 7:3 or the molecular weight of PEG from 6000 to 2000, the oil-in-water type emulsion was changed to water-in-oil type. The copolymers also showed a good phase transfer catalytic effect when applied to the Williamson reaction. Conversion of potassium phenolate into butyl phenolate reached over 95% when the multiblock copolymer containing 3 mmol of PEO was used for 1 g potassium phenolate, whereas no reaction occurred without using the multiblock copolymer at 90°C for 4 h.     

Synthesis of multiblock copolymers of poly(2‐vinylpyridine) and polyoxyethylene

Telechelic dihydroxy poly(2‐vinylpyridine) (THPVP) samples with different molecular weights were synthesized by using lithium α‐methylnaphthalene as an anionic initiator in mixed solvents of benzene and tetrahydrofuran (THF). Then multiblock copolymers of poly(2‐vinylpyridine) (P2VP) and polyoxyethylene (PEO) were obtained by condensing THPVP and PEO with dichloromethane in the presence of potassium hydroxide. The effects of reaction time, molecular weight of PEO and THPVP, and raw meal ratio PEO/THPVP (w/w) were investigated. The best conditions were found. The copolymers can be purified by water and toluene. The purified copolymers were characterized by infrared (IR) and ¹H nuclear magnetic resonance (¹H‐NMR). The PEO segment content was calculated from the integral curve of ¹H‐NMR spectra. The results showed that these multiblock copolymers were connected through oxymethylene. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1632–1636, 2003     

Morphology and thermomechanical properties of main-chain polybenzoxazine-block-polydimethylsiloxane multiblock copolymers

The main-chain polybenzoxazine-block-polydimethylsiloxane multiblock copolymers were synthesized via the Mannich polycondensation among 4,4′-dihydroxyldiphenylisopropane, 4,4′-diaminodiphenylmethane, aminopropyl-terminated polydimethylsiloxane and paraformaldehyde. The multiblock copolymers were characterized by means of Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and size exclusion chromatography (SEC). Atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) showed that the multiblock copolymers displayed microphase-separated morphology. Owing to the presence of the main-chain polybenzoxazine blocks, the multiblock copolymers are thermally-crosslinkable. The curing behavior of the multiblock copolymers was investigated according to the analysis of non-isothermal curing kinetics. The measurement of static contact angles showed that with the inclusion of polydimethylsiloxane blocks, the polybenzoxazine thermosets resulting from the multiblock copolymers displayed the improved surface hydrophobicity.     

The melt rheological behavior of AB,ABA, BAB,and (AB)n block copolymers with monodisperse aramide segments

The melt rheological behavior of segmented block copolymers with high melting diamide (A) hard segments (HS) and polyether (B) soft segments was studied. The block copolymers can be classified as B (monoblock), AB (diblock), ABA (triblock, diamide end segment), BAB (triblock, diamide mid‐segment) and ? (AB)_n? (multiblock) block copolymers. Varied were the number of HS in the chain, the HS concentration, the position of the HS (in the chain or at the end of the chain) and the molecular weight of the copolymers. The melt rheological behavior of the copolymers was studied with a plate–plate method. The materials B (monoblock), BAB (triblock, diamide mid‐segment), and ? (AB)_n? (multiblock) block copolymers had a rheological behavior of a linear polymer and the complex viscosity increased with molecular weight. Surprisingly, the diblock copolymers AB and the triblock copolymers ABA at low frequencies and near the melting temperature of the copolymers had the behavior of a gelled melt. The diamide segments at the chain end seemed to form aggregates, whereas the diamide mid‐segments did not. Also, time‐dependent rheology of diblock copolymer confirmed the network structure built up in the melt. The block copolymers with H‐bonding diamide end segments had a thixotropic behavior. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Hydrogels based on polyurethane–polyacrylic acid multiblock copolymers via macroiniferter technique

Polyurethane (PU)–polyacrylic acid (PAAc) multiblock copolymers have been prepared via a macroiniferter technique, and were tested for living mechanism, thermal, and water swell of the cast films. It was found that molecular weight of the PU–PAAc block copolymers linearly increased while molecular weight distribution decreased with conversion. As the PAAc content increases, water swell of the cast films and crystalline melting temperature (T_m) of PU decreased while glass transition temperature of PU increased.     

Biodegradable multiblock PEO/PLA thermoplastic elastomers: molecular design and properties

Given the need for highly flexible biodegradable polymers, a series of poly(ethylene oxide)/poly(l-lactic acid) (PEO/PLA) (PELA) multiblock poly(ether-ester-urethane)s, were synthesized and characterized. The first step of the synthesis consisted of the ring-opening polymerization of l-lactide, initiated by the hydroxyl terminal groups of the PEO chain, followed by the chain extension of these PLA-PEO-PLA triblocks, using hexamethylene diisocyanate (HDI). The trimers comprised PEO segments in the 1000-10,000 molecular weight range, with the length of each PLA block covering the 200-10,000 interval. DSC and X-ray analyses revealed that, depending on their composition, amorphous matrices, monophasic crystalline materials and copolymers comprising two crystalline phases, were generated. The multiblock copolymers synthesized exhibited superior mechanical properties, with ultimate tensile strength values around 30 MPa, Young's moduli as low as 14 MPa and elongation at break values well above 1000%. Because of their phase segregated morphology, most of these multiblock copolymers displayed remarkable mechanical properties also when fully hydrated, with typical UTS values around 9 MPa.     

Characterization of random and multiblock copolymers of highly sulfonated poly(arylene ether sulfone) for a proton‐exchange membrane

Random and multiblock copolymers of sulfonated poly(arylene ether sulfone) (SPAES) were synthesized and characterized to compare the differences in the properties of proton‐exchange membranes made with random and multiblock SPAES copolymers. Atomic force microscopy observations and small‐angle X‐ray scattering measurements suggested the presence of nanoscale, clusterlike structures in the multiblock SPAES copolymers but not in the random SPAES copolymers. Proton‐exchange membranes were prepared from random and multiblock copolymers with various ion‐exchange capacities (IECs). The water uptake, proton conductivity, and methanol permeability of the SPAES membranes depended on the IECs of the random and multiblock SPAES copolymers. At the same IEC, the multiblock SPAES copolymers exhibited higher performances with respect to proton conductivity and proton/methanol permeation selectivity than the random SPAES copolymers. The higher performances of the multiblock SPAES copolymers were thought to be due to their clusterlike structure, which was similar to the ionic cluster of a Nafion membrane. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Micromechanical simulation of molecular architecture and orientation effect on deformation and fracture of multiblock copolymers

Multiblock copolymers containing a large number of blocks have distinct microstructures and mechanical responses that are different from that of conventional diblock and triblock copolymers. A combined simulation method that utilized MesoDyn for morphologies and probabilistic lattice spring model (LSM) for mechanical properties was adopted in this work. Simulation results show that tensile strength increases dramatically with an increase in the number of blocks within “hard-soft” multiblock copolymers. This phenomenon can be described by the occurrence of bridging and looping chain conformations in experiment. One-dimensional lamellae were built to provide an ideal morphology for studying the influence of lamellar orientation on multiblock copolymer mechanical properties. During tensile tests different failure processes were observed with two kinds of interface strength that corresponded to a difference in chain structures (diblock, triblock or multiblock copolymers). These studies provide an efficient method for correlating the complex morphologies to the mechanical response of multiblock copolymers.     

Fatigue behaviour of multiblock thermoplastic elastomers. 2. Dynamic creep of poly(aliphatic/aromatic-ester) copolymers

The ‘dynamic creep’ behaviour of poly(aliphatic/aromatic-ester) (PED) multiblock copolymers has been evaluated by the hysteresis measurements method. The effect of the hard/soft segments concentration on the microphase separation in PED copolymers was determined by means of differential scanning calorimetry. The ‘dynamic creep’ of PED copolymers has been compared with poly(ether-ester) and segmented polyurethanes indicating on the good creep behaviour of PEDs compared to those materials. It was found that the hard segment content influences the creep behaviour of PED copolymers at ambient and elevated temperature indicating that stiffer materials are less susceptible to environmental conditions than polymers containing a high amount of the soft phase. PED copolymers compare very well with commercially available poly(ester-ethers) and show much lower creep compared to poly(ether-urethanes).