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2018 Volume 36 Issue 7
2018, 36(7):
Abstract:
2018, 36(7): 799-804
doi: 10.1007/s10118-018-2136-5
Abstract:
We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer (rac-1), and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester (1s) and 4-isocyanobenzoyl-D-alanine decyl ester (1r), revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of 1s was higher than that of 1r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.
We report the polymerization of phenyl isocyanides with the chiral palladium(II) initiating system. The resulting polymers with optically active properties were obtained by polymerization of the racemic isocyanide monomer (rac-1), and enantiomerically unbalanced polymerization of the monomer was found, providing substantial evidence for the enantiomer-selective polymerization of rac-1 mediated through chiral catalyst. A comparison between the enantiomerically pure monomers, 4-isocyanobenzoyl-L-alanine decyl ester (1s) and 4-isocyanobenzoyl-D-alanine decyl ester (1r), revealed a drastic discrepancy in the reactivity ratio of their homopolymerizations. It turned out that the monomer reactivity ratio of 1s was higher than that of 1r with chiral ligands. The results clearly demonstrated the inclination for incorporation of the 1s enantiomer during the polymerization process and thus resulted in the enantiomer-selective polymerization in this system. The effects of the catalyst chirality on the optically active properties of polymerization were investigated, and it was concluded that the formation of higher-ordered conformation with a handed helicity might be attributed to the chiral induction of chiral palladium(II) catalyst. Moreover, the polymers obtained through the enantiomer-selective polymerization of the enantiomerically pure monomer were with a significant improvement of the optical activity if the chirality of the monomer and the catalyst matched with each other.
2018, 36(7): 805-810
doi: 10.1007/s10118-018-2140-9
Abstract:
In the " cycloketyl radical mediated living polymerization” (CMP) process, a cycloketyl compound, [9,9′]bixanthenyl-9,9′ diol (BIXAN) was ultilized as initiator and mediator. The cycloketyl (CK) radical was used as the dormant radical to achieve the increase of molecular weight. Herein, a series of cycloketyl thioketones were synthesised by Lawesson’s reagent by one step reaction with high yeild, and we found that, when a special cycloketyl thioketone compound, thioxanthene-9-thione (TXT), was added to a routine radical polymerization system, TXT could capture chain radical, and simultaneously formed an radical analogous to CK radical in structure, which could trigger the growth of polymer chains. This simple system was efficient to initiate the polymerization of methyl methacrylate (MMA) and in all cases the molecular weights increased with the increase of conversions. By the end-group analysis with 1H-NMR and MALDI-TOF MS, it was confirmed that the P-STXT radical was used to control the polymerization. The re-initiating reactions were achieved when PMMA was used as the macro-initiator.
In the " cycloketyl radical mediated living polymerization” (CMP) process, a cycloketyl compound, [9,9′]bixanthenyl-9,9′ diol (BIXAN) was ultilized as initiator and mediator. The cycloketyl (CK) radical was used as the dormant radical to achieve the increase of molecular weight. Herein, a series of cycloketyl thioketones were synthesised by Lawesson’s reagent by one step reaction with high yeild, and we found that, when a special cycloketyl thioketone compound, thioxanthene-9-thione (TXT), was added to a routine radical polymerization system, TXT could capture chain radical, and simultaneously formed an radical analogous to CK radical in structure, which could trigger the growth of polymer chains. This simple system was efficient to initiate the polymerization of methyl methacrylate (MMA) and in all cases the molecular weights increased with the increase of conversions. By the end-group analysis with 1H-NMR and MALDI-TOF MS, it was confirmed that the P-STXT radical was used to control the polymerization. The re-initiating reactions were achieved when PMMA was used as the macro-initiator.
2018, 36(7): 822-834
doi: 10.1007/s10118-018-2094-y
Abstract:
In this study a new series of magnetic and heat resistant nanocomposites were prepared based on a highly soluble poly(imide-ether) (PIE) reinforced with two different types of magnetic nanoparticles via a solution intercalation technique. New PIE with good solubility and desired molar mass containing bulky xanthene rings and amide groups in the side chains was synthesized via thermal cyclization of the poly(amic acid) precursor, obtained from the reaction of a new diamine derived from 9H-xanthene and 4,4′-oxydiphthalic dianhydride (ODPA). Improved solubility was attributed to the presence of xanthene group and flexible ether linkage in the polyimide backbones that reduce the chain-chain interaction and enhance solubility by penetrating solvent molecules into the polyimide chains. Fe3O4 nanoparticles (MNPs) which synthesized from chemical co-precipitation route were coated with silica (SiO2), sequentially with (3-aminopropyl)triethoxysilane and poly-melamine-terephthaldehyde (MNPs-PMT), and then separately dispersed in the poly(amic acid) solutions and thermally imidized to form PIE/Fe3O4 and PIE/MNPs-PMT nanocomposites. The nanostructures and properties of the resultant materials were investigated using FTIR spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The properties of the nanocomposites were strongly related to the dispersion and interaction between the nanoparticles and PIE matrix. The thermogravimetric analysis (TGA) results showed that the addition of MNPs-PMT nanoparticles resulted in a substantial increase in the thermal stability of the corresponding PIEN. The temperature at 10% weight loss (T10) was increased from 416 °C to 428 °C for PIEN containing 3 wt% MNPs-PMT as compared to neat PIE, as well the char yield enhanced. Furthermore, the MNPs-PMT nanoparticles had better dispersion in the polymer matrix due to the strong intermolecular hydrogen bond interactions between the NH and C＝N groups of surface-modified nanoparticles and the PIE matrix than the uncoated Fe3O4 nanoparticles, and exhibited a better intercalated morphology and improved thermal properties. Also, the PIEN nanocomposites under applied magnetic field exhibited the hysteretic loops of the superparamagnetic nature.
In this study a new series of magnetic and heat resistant nanocomposites were prepared based on a highly soluble poly(imide-ether) (PIE) reinforced with two different types of magnetic nanoparticles via a solution intercalation technique. New PIE with good solubility and desired molar mass containing bulky xanthene rings and amide groups in the side chains was synthesized via thermal cyclization of the poly(amic acid) precursor, obtained from the reaction of a new diamine derived from 9H-xanthene and 4,4′-oxydiphthalic dianhydride (ODPA). Improved solubility was attributed to the presence of xanthene group and flexible ether linkage in the polyimide backbones that reduce the chain-chain interaction and enhance solubility by penetrating solvent molecules into the polyimide chains. Fe3O4 nanoparticles (MNPs) which synthesized from chemical co-precipitation route were coated with silica (SiO2), sequentially with (3-aminopropyl)triethoxysilane and poly-melamine-terephthaldehyde (MNPs-PMT), and then separately dispersed in the poly(amic acid) solutions and thermally imidized to form PIE/Fe3O4 and PIE/MNPs-PMT nanocomposites. The nanostructures and properties of the resultant materials were investigated using FTIR spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The properties of the nanocomposites were strongly related to the dispersion and interaction between the nanoparticles and PIE matrix. The thermogravimetric analysis (TGA) results showed that the addition of MNPs-PMT nanoparticles resulted in a substantial increase in the thermal stability of the corresponding PIEN. The temperature at 10% weight loss (T10) was increased from 416 °C to 428 °C for PIEN containing 3 wt% MNPs-PMT as compared to neat PIE, as well the char yield enhanced. Furthermore, the MNPs-PMT nanoparticles had better dispersion in the polymer matrix due to the strong intermolecular hydrogen bond interactions between the NH and C＝N groups of surface-modified nanoparticles and the PIE matrix than the uncoated Fe3O4 nanoparticles, and exhibited a better intercalated morphology and improved thermal properties. Also, the PIEN nanocomposites under applied magnetic field exhibited the hysteretic loops of the superparamagnetic nature.
2018, 36(7): 835-847
doi: 10.1007/s10118-018-2101-3
Abstract:
Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer 1a with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiCl and NMP as a solvent through low-temperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including 1H-NMR and 13C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples of polyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol·L−1 HCl was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.
Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer 1a with different kinds of diacid chlorides (including oxalyl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, p-phenylene diacryloyl) in the presence of LiCl and NMP as a solvent through low-temperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy (including 1H-NMR and 13C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis (TGA), wide-angle X-ray diffraction analysis (WAXD) and scanning electron microscopy (SEM). Also, the corrosion inhibition behavior of selected examples of polyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol·L−1 HCl was studied using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency (P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer. The adsorption of these polymers was found to obey Langmuir adsorption isotherm.
2018, 36(7): 848-858
doi: 10.1007/s10118-018-2102-2
Abstract:
In this study, the maleic anhydride (MAH) and styrene (St) dual monomers grafted polypropylene (PP) and poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS), i.e. PP-g-(MAH-co-St) and SEBS-g-(MAH-co-St) are prepared as multi-phase compatibilizers and used to compatibilize the PA6/PS/PP/SEBS (70/10/10/10) model quaternary blends. Both PS and SEBS are encapsulated by the hard shell of PP-g-(MAH-co-St) in the dispersed domains (about 2 μm) of the PA6/PS/PP-g-(MAH-co-St)/SEBS (70/10/10/10) quaternary blend. In contrast, inside the dispersed domains (about 1 μm) of the PA6/PS/PP/SEBS-g-(MAH-co-St) (70/10/10/10) quaternary blend, the soft SEBS-g-(MAH-co-St) encapsulates both the hard PS and PP phases and separates them. With increasing the content of the compatibilizers equally, the morphology of the PA6/PS/(PP+PP-g-(MAH-co-St))/(SEBS+SEBS-g-(MAH-co-St)) (70/10/10/10) quaternary blends evolves from the soft (SEBS+SEBS-g-(MAH-co-St)) encapsulating PS and partially encapsulating PP (about 1 μm), then to PS exclusively encapsulated by the soft SEBS-g-(MAH-co-St) and then separated by PP-g-(MAH-co-St) inside the smaller domains (about 0.6 μm). This morphology evolution has been well predicted by spreading coefficients and explained by the reaction between the matrix PA6 and the compatibilizers. The quaternary blends compatibilized by more compatibilizers exhibit stronger hierarchical interfacial adhesions and smaller dispersed domain, which results in the further improved mechanical properties. Compared to the uncompatibilized blend, the blend with both 10 wt% PP-g-(MAH-co-St) and 10 wt% SEBS-g-(MAH-co-St) has the best mechanical properties with the stress at break, strain at break and impact failure energy improved significantly by 97%, 71% and 261%, respectively. There is a strong correlation between the structure and property in the blends.
In this study, the maleic anhydride (MAH) and styrene (St) dual monomers grafted polypropylene (PP) and poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS), i.e. PP-g-(MAH-co-St) and SEBS-g-(MAH-co-St) are prepared as multi-phase compatibilizers and used to compatibilize the PA6/PS/PP/SEBS (70/10/10/10) model quaternary blends. Both PS and SEBS are encapsulated by the hard shell of PP-g-(MAH-co-St) in the dispersed domains (about 2 μm) of the PA6/PS/PP-g-(MAH-co-St)/SEBS (70/10/10/10) quaternary blend. In contrast, inside the dispersed domains (about 1 μm) of the PA6/PS/PP/SEBS-g-(MAH-co-St) (70/10/10/10) quaternary blend, the soft SEBS-g-(MAH-co-St) encapsulates both the hard PS and PP phases and separates them. With increasing the content of the compatibilizers equally, the morphology of the PA6/PS/(PP+PP-g-(MAH-co-St))/(SEBS+SEBS-g-(MAH-co-St)) (70/10/10/10) quaternary blends evolves from the soft (SEBS+SEBS-g-(MAH-co-St)) encapsulating PS and partially encapsulating PP (about 1 μm), then to PS exclusively encapsulated by the soft SEBS-g-(MAH-co-St) and then separated by PP-g-(MAH-co-St) inside the smaller domains (about 0.6 μm). This morphology evolution has been well predicted by spreading coefficients and explained by the reaction between the matrix PA6 and the compatibilizers. The quaternary blends compatibilized by more compatibilizers exhibit stronger hierarchical interfacial adhesions and smaller dispersed domain, which results in the further improved mechanical properties. Compared to the uncompatibilized blend, the blend with both 10 wt% PP-g-(MAH-co-St) and 10 wt% SEBS-g-(MAH-co-St) has the best mechanical properties with the stress at break, strain at break and impact failure energy improved significantly by 97%, 71% and 261%, respectively. There is a strong correlation between the structure and property in the blends.
2018, 36(7): 859-865
doi: 10.1007/s10118-018-2103-1
Abstract:
In this work, the crystallization of immiscible polypropylene (PP)/polybutene-1 (PB) blends, in particular the effect of crystal morphology of PP (HTC, high Tm component) on the subsequent crystallization behavior of PB (LTC, low Tm component) was studied. Herein, we firstly indicated that PP/PB blends were not completely compatible but characterized as the LCST-like phase diagram above the melting temperature of PP. Crystallization of PP at different crystallization temperatures brought about different PP crystal morphologies and PB was segregated and confined at different locations. Much larger-sized domain of PB component appeared in PP spherulites resulting from the effects of non-negligible phase separation and the slower PP crystallization rate as PP crystallized at high temperature. As temperature continued to fall below Tm of PB, the fractionated and confined crystallization of PB occurred in the framework of PP spherulites, reflected by the decreased crystallization temperature (Tc) of PB and the formation of form I′ beside form II. Notably, if PP previously crystallized at high Tc, fractionated crystallization of PB became predominant and confined crystallization of PB became weak due to the much wider droplet-size distribution of PB domains.
In this work, the crystallization of immiscible polypropylene (PP)/polybutene-1 (PB) blends, in particular the effect of crystal morphology of PP (HTC, high Tm component) on the subsequent crystallization behavior of PB (LTC, low Tm component) was studied. Herein, we firstly indicated that PP/PB blends were not completely compatible but characterized as the LCST-like phase diagram above the melting temperature of PP. Crystallization of PP at different crystallization temperatures brought about different PP crystal morphologies and PB was segregated and confined at different locations. Much larger-sized domain of PB component appeared in PP spherulites resulting from the effects of non-negligible phase separation and the slower PP crystallization rate as PP crystallized at high temperature. As temperature continued to fall below Tm of PB, the fractionated and confined crystallization of PB occurred in the framework of PP spherulites, reflected by the decreased crystallization temperature (Tc) of PB and the formation of form I′ beside form II. Notably, if PP previously crystallized at high Tc, fractionated crystallization of PB became predominant and confined crystallization of PB became weak due to the much wider droplet-size distribution of PB domains.
2018, 36(7): 866-870
doi: 10.1007/s10118-018-2095-x
Abstract:
We successfully use a co-precipitation method to prepare inclusion complex between poly(butylene adipate) (PBA) chains (guest component) and urea molecules (host component). The PBA/urea inclusion complex is confirmed to adopt a hexagonal crystal modification with lattice parameters of a = 8.14 Å and c = 10.92 Å, and the interaction between PBA chains and urea is van der Waals force. The singly isolated PBA chains are suggested to take some gauche conformation, which is different from the all-trans conformation in β-form PBA. Furthermore, we employ the isolated PBA chains which are uniformly pre-established in a specific conformation in urea channels to regulate the crystal form of PBA for the first time. After removing the host urea molecules, the coalesced PBA chains are found to solely crystallize into α-form crystals at different coalescing temperatures. By comparing the FTIR spectra, it is found that PBA chains in inclusion complex plausibly contain some similar conformers as those in α-form crystal, which is suggested to be the intrinsic reason for the sole formation of α-form crystals. This research proves that inclusion complex can be used as a very effective method to regulate polymorphism of semi-crystalline polymers.
We successfully use a co-precipitation method to prepare inclusion complex between poly(butylene adipate) (PBA) chains (guest component) and urea molecules (host component). The PBA/urea inclusion complex is confirmed to adopt a hexagonal crystal modification with lattice parameters of a = 8.14 Å and c = 10.92 Å, and the interaction between PBA chains and urea is van der Waals force. The singly isolated PBA chains are suggested to take some gauche conformation, which is different from the all-trans conformation in β-form PBA. Furthermore, we employ the isolated PBA chains which are uniformly pre-established in a specific conformation in urea channels to regulate the crystal form of PBA for the first time. After removing the host urea molecules, the coalesced PBA chains are found to solely crystallize into α-form crystals at different coalescing temperatures. By comparing the FTIR spectra, it is found that PBA chains in inclusion complex plausibly contain some similar conformers as those in α-form crystal, which is suggested to be the intrinsic reason for the sole formation of α-form crystals. This research proves that inclusion complex can be used as a very effective method to regulate polymorphism of semi-crystalline polymers.
2018, 36(7): 871-879
doi: 10.1007/s10118-018-2098-7
Abstract:
Poly(lactic acid) (PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and DOPO-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), tensile testing, thermogravimetric analysis (TGA), limiting oxygen index (LOI), and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis (TGA) tests showed that the PLA, DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate (p-HRR). It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.
Poly(lactic acid) (PLA) composites with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and DOPO-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) were prepared via melting extrusion and injection molding. The crystallization, mechanical, and flame-retardant properties of PLA/DOPO and PLA/DOPO-POSS were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), tensile testing, thermogravimetric analysis (TGA), limiting oxygen index (LOI), and cone calorimeter test. The DSC results showed that the DOPO added could act as a plasticizer as reflected by lower glass transition temperature and inhibited crystallization of part of the PLA; the DOPO-POSS acted like a filler in the PLA matrix and slightly improved the crystallinity of the PLA matrix. The XRD and DSC analyses indicated that the PLA composites by cold molding injection were amorphous, and the PLA composites following a heat treatment in an oven at 120 °C for 30 min achieved crystallinity. All the PLA and its composites after heat treatment had improved mechanical properties. The thermogravimetric analysis (TGA) tests showed that the PLA, DOPO and DOPO-POSS decomposed separately in the PLA/DOPO and PLA/DOPO-POSS, respectively. The cone calorimeter tests offered clear evidence that addition of the DOPO-POSS resulted in an evident reduction of 25% for the peak of heat release rate (p-HRR). It was also confirmed that the crystalline flame-retardant PLA composites after heat treatment had better flame retardant properties than the amorphous PLA composites prepared by the cold molding.
2018, 36(7): 880-887
doi: 10.1007/s10118-018-2113-z
Abstract:
Polystyrene membranes with precisely controlled and vertically oriented pores are fabricated by a bidirectional freezing process. In this process, the influence of polymer in growth of diphenyl sulfone (DPS) crystals has been demonstrated by XRD and simulated by DFT based on the interaction between DPS crystal faces and polystyrene (PS). The influence of temperature gradient on membrane structures is also elucidated. Compared to the original membrane and modified traditional membranes, modified PS membranes with vertically oriented pores show large and stable fluxes in the processes of multiple oil and water separation.
Polystyrene membranes with precisely controlled and vertically oriented pores are fabricated by a bidirectional freezing process. In this process, the influence of polymer in growth of diphenyl sulfone (DPS) crystals has been demonstrated by XRD and simulated by DFT based on the interaction between DPS crystal faces and polystyrene (PS). The influence of temperature gradient on membrane structures is also elucidated. Compared to the original membrane and modified traditional membranes, modified PS membranes with vertically oriented pores show large and stable fluxes in the processes of multiple oil and water separation.
2018, 36(7): 888-896
doi: 10.1007/s10118-018-2106-y
Abstract:
ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self-consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lamella phase, two kinds of lamellae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.
ABCA tetrablock copolymers offer new opportunities for design of materials with novel structures. Using real-space self-consistent field theory and simulation, we systematically examined the self-assembly behavior of linear ABCA tetrablock copolymers in a 2D space. The simulation was carried out under conditions of symmetrical compositions and interactions. We focus on the influence of chain length ratio of block A and interactions between block A and other blocks B and C on the self-assembly behavior of the copolymer system. The simulation results show that most of the structures self-assembled by the ABCA tetrablock copolymers are centrosymmetric, such as diblock-like lamella phase, two kinds of lamellae with beads at interface, two kinds of hierarchical lamella phase, hexagonal honeycomb-like phase, lamella phase with mixed BC and hexagonal spheres with mixed BC. Furthermore, we find that a novel noncentrosymmetric Janus spheres can be obtained when the interaction between blocks B and C is strong, whereas a noncentrosymmetric lamella phase was obtained at weak interaction between blocks B and C. Phase diagrams for the ABCA tetrablock copolymers with different interaction strength between blocks B and C are constructed by comparing free energies of candidate ordered structures. In addition, studies on the metastable behavior of the system reveal that enthalpy plays an important role in the metastable behavior of the ABCA tetrablock copolymer system. Our work can provide useful guide for structure control of such kind of tetrablock copolymers in experiments.
