Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared. When the film thickness exceeds another definite value (12.0 nm), the crystallization of PEO dominates the surface morphology. For films with thickness between these two values, microphase separation and crystallization can simultaneously occur.     

Crystallization and morphology of poly(ethylene oxide‐b‐lactide) crystalline–crystalline diblock copolymers

The crystallization behaviors and morphology of asymmetric crystalline–crystalline diblock copolymers poly(ethylene oxide‐lactide) (PEO‐b‐PLLA) were investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and microscopic techniques (polarized optical microscopy (POM) and atomic force microscopy (AFM)). Both blocks of PEO₅‐b‐PLLA₁₆ can be crystallized, which was confirmed by WAXD, while PEO block in PEO₅‐b‐PLLA₃₀ is difficult to crystallize because of the confinement induced by the high glass transition temperature and crystallization of PLLA block with the microphase separation of the block copolymer. Comparing with the crystallization and morphology of PLLA homopolymer and differences between the two copolymers, we studied the influence of PEO block and microphase separation on the crystallization and morphology of PLLA block. The boundary temperature (T_b) was observed, which distinguishes the crystallization into high‐ and low‐temperature ranges, the growth rate and morphology were quite different between the ranges. Crystalline morphologies including banded spherulite, dendritic crystal, and dense branching in PEO₅‐b‐PLLA₁₆ copolymer were formed. The typical morphology of dendritic crystals including two different sectors were observed in PEO₅‐b‐PLLA₃₀ copolymer, which can be explained by secondary nucleation, chain growth direction, and phase separation between the two blocks during the crystallization process. Lozenge‐shaped crystals of PLLA with screw dislocation were also observed employing AFM, but the crystalline morphology of PEO block was not observed using microscopy techniques because of its small size. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1400–1411, 2008     

聚乙烯基环己烷-聚乙烯-聚乙烯基环己烷三嵌段共聚物溶液的受限结晶研究

嵌段共聚物由于组分间的化学不相容性而发生微相分离,组装成各种有序的纳米结构,如球、圆柱、层及双连续结构等．半晶型嵌段共聚物由于引入了能结晶的组分,使体系中存在两种相互竞争的过程,即微相分离与结晶,所以能形成更为丰富的有序结构．聚乙烯基环己烷-聚乙烯-聚乙烯基环己烷[Poly(Vinylcyclohexane)-b-poly(ethylene)-b-poly(vinylcyclohexane),     

Synthesis,self‐assembly,drug‐release behavior,and cytotoxicity of triblock and pentablock copolymers composed of poly(ε‐caprolactone), poly(L‐lactide), and poly(ethylene glycol)

Biocompatible and biodegradable ABC and ABCBA triblock and pentablock copolymers composed of poly(ε‐caprolactone) (PCL), poly(L ‐lactide) (PLA), and poly(ethylene glycol) (PEO) with controlled molecular weights and low polydispersities were synthesized by a click conjugation between alkyne‐terminated PCL‐b‐PLA and azide‐terminated PEO. Their molecular structures, physicochemical and self‐assembly properties were thoroughly characterized by means of FT‐IR, ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, dynamic light scattering, and transmission electron microscopy. These copolymers formed microphase‐separated crystalline materials in solid state, where the crystallization of PCL block was greatly restricted by both PEO and PLA blocks. These copolymers self‐assembled into starlike and flowerlike micelles with a spherical morphology, and the micelles were stable over 27 days in aqueous solution at 37 °C. The doxorubicin (DOX) drug‐loaded nanoparticles showed a bigger size with a similar spherical morphology compared to blank nanoparticles, demonstrating a biphasic drug‐release profile in buffer solution and at 37 °C. Moreover, the DOX‐loaded nanoparticles fabricated from the pentablock copolymer sustained a longer drug‐release period (25 days) at pH 7.4 than those of the triblock copolymer. The blank nanoparticles showed good cell viability, whereas the DOX‐loaded nanoparticles killed fewer cells than free DOX, suggesting a controlled drug‐release effect. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Lithium‐Salt‐Containing High‐Molecular‐Weight Polystyrene‐block‐Polyethylene Oxide Block Copolymer Films

Ionic conductivity in relation to the morphology of lithium‐doped high‐molecular‐weight polystyrene‐block‐polyethylene oxide (PS‐b‐PEO) diblock copolymer films was investigated as solid‐state membranes for lithium‐ion batteries. The tendency of the polyethylene (PEO) block to crystallize was highly suppressed by increasing both the salt‐doping level and the temperature. The PEO crystallites completely vanished at a salt‐doping ratio of Li/EO>0.08, at which the PEO segments were hindered from entering the crystalline unit of the PEO chain. A kinetically trapped lamella morphology of PS‐b‐PEO was observed, due to PEO crystallization. The increase in the lamella spacing with increasing salt concentration was attributed to the conformation of the PEO chain rather than the volume contribution of the salt or the previously reported increase in the effective interaction parameter. Upon loading the salt, the PEO chains changed from a compact/highly folded conformation to an amorphous/expanded‐like conformation. The ionic conductivity was enhanced by amorphization of PEO and thereby the mobility of the PEO blocks increased upon increasing the salt‐doping level.     

Competition Between Interfacial Interaction and Microphase Separation in Crystallization of Filled Block Copolymers

Understanding the effect of repulsive interaction between blocks on crystallization in block copolymers is beneficial for the design and development of sophisticated nanostructures. Dynamic Monte Carlo simulations were performed to reveal the crystallization mechanism of block copolymers containing one‐dimensional nanofiller under different repulsive interaction strengths between crystallizable and noncrystallizable blocks. During crystallization, crystalline morphology is determined by the competition between segmental orientation perpendicular to microphase interfaces dominated by microphase separation and that along the direction of the long axis of the nanofiller controlled by interfacial interaction. As the repulsive interaction between different blocks is strengthened, the competition between microphase separation and interfacial interaction is intensified, eventually leading to an increase in crystallization rate and a degradation in crystalline morphology. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1516–1526     

Atomic force microscopy investigation of asymmetric diblock copolymer morphologies in thin films

Microphase separation and the resulting morphology of asymmetric diblock copolymers of poly(ε-caprolactone) (PCL) in thin films have been investigated by atomic force microscopy. Copolymers consisted of a short block of PCL (M_n∼2500-4500 g/mole) and a longer second block of poly(methyl methacrylate) (PMMA), poly(styrene) (PS) or poly(cyclohexene oxide) (PCHO). Tendency for microphase separation above the glass transition temperature of the second block (PMMA, PS or PCHO) resulted in a pitted morphology on the surface of the thin films. This tendency was strongest for PMMA and weakest for PCHO. The presence of up to 54% PMMA homopolymer in PCL-PMMA block copolymer did not prevent the formation of such pitted morphology on the surface. The effect of the chemical structure of the second block and the possible orientations of the block copolymer molecules in thin films are discussed.     

聚氧化乙烯-聚苯乙烯-聚氧化乙烯三嵌段共聚物的微相分离与结晶

本工作研究了多分散和单分散聚氧化乙烯-聚苯乙烯-聚氧化乙烯三嵌段共聚物(PEO-PS-PEO)的结晶行为,及这些试样按非晶型嵌段共聚物进行微相分离后再结晶的结晶特点.     

树枝状嵌段聚合物D-PCL-b-PS在不对称末端受限条件下的结晶行为

研究了树枝状嵌段聚合物聚(ε-b-己内酯)-b-聚苯乙烯(D-PCL-b-PS)的分子结构对PCL链段受限结晶行为的影响.首先,通过活性正离子开环聚合(ROP)合成了树枝状的嵌段聚合物D-PCL.在此基础上用原子转移自由基聚合(ATRP)的方法,合成了树枝状的嵌段聚合物D-PCL-b-PS,在结晶的PCL链段的两个末端...     

接枝共聚物聚苯乙烯－g－聚氧乙烯的微相分离形态研究

 本文利用透射电子显微镜技术，以两性接校共聚物聚苯乙烯－ｇ－聚氧乙烯为研究对象，研究了接枝共聚物的微相分离形态结构，发现聚苯乙烯－ｇ－聚氧乙烯能形成微相分离结构，微区的形状和尺寸与共聚物的组成和侧链长度有关．文中还讨论了嵌段共聚物和接枝共聚物在形成微相分离结构时的共性和个性．     

Crystallization of microphase-separated block copolymers with two crystallizing blocks

Statistical poly block copolymers of polyamide with polyethyleneoxide are investigated. The regularities governing the formation of their phase structure depending on the composition, temperature, and prehistory of the system are established. The character of crystallization of both blocks is shown to be due to their mutual solubility in the melt. Some peculiarities of microphase crystallization in PA/PEO block copolymers are revealed. It is found that, depending on the character of phase separation in the system, a PEO block may be crystallized either unimodally or in two well-separated temperature ranges.Dedicated to Prof. W. Pechhold on the occasion of his 60th birthday.     

Hydrogen bonding interactions,crystallization, and surface hydrophobicity in nanostructured epoxy/block copolymer blends

Hydrogen bonding interactions, phase behavior, crystallization, and surface hydrophobicity in nanostructured blend of bisphenol A‐type epoxy resin (ER), for example, diglycidyl ether of bisphenol A (DGEBA) and poly(ε‐caprolactone)‐block‐poly(dimethyl siloxane)‐block‐poly(ε‐caprolactone) (PCL–PDMS–PCL) triblock copolymer were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, transmission electron microscopy, small‐angle X‐ray scattering, and contact angle measurements. The PCL–PDMS–PCL triblock copolymer consisted of two epoxy‐miscible PCL blocks and an epoxy‐immiscible PDMS block. The cured ER/PCL–PDMS–PCL blends showed composition‐dependent nanostructures from spherical and worm‐like microdomains to lamellar morphology. FTIR study revealed the existence of hydrogen bonding interactions between the PCL blocks and the cured epoxy, which was responsible for their miscibility. The overall crystallization rate of the PCL blocks in the blend decreased remarkably with increasing ER content, whereas the melting point was slightly depressed in the blends. The surface hydrophobicity of the cured ER increased upon addition of the block copolymer, whereas the surface free energy (γ_s) values decreased with increasing block copolymer concentration. The hydrophilicity of the epoxy could be reduced through blending with the PCL–PDMS–PCL block copolymer that contained a hydrophobic PDMS block. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 790–800, 2010     

Thermal monitoring of morphology in triblock terpolymers with crystallizable blocks

The bulk morphology of poly(1,4‐butadiene)–block–polystyrene–block–poly (ethylene oxide) (PB‐b‐PS‐b‐PEO) and polyethylene–block–polystyrene–block–poly (ethylene oxide) (PE‐b‐PS‐b‐PEO) triblock terpolymers is analyzed under a thermal protocol. This allows the investigation of the morphology during the occurrence of thermal transitions, such as crystallization and melting, which is a neat way of studying the competition between microphase separation and crystallization for the morphology formation. Only one of the studied systems presented a morphological transition upon melting of the PEO and the PE blocks, attributed to the crystallization of the PE block in finite interconnected domains. All the other systems presented no morphological transitions during the thermal scan. The results prove that the crystallization only disrupt the microphases generated in the molten state under very specific circumstances for these block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3197–3206, 2007     

基于甲壳型液晶高分子的刚-柔型二嵌段共聚物的层状相:链伸展行为的研究

研究了一系列以聚己内酯(PCL)为柔性链段、甲壳型液晶高分子聚{2,5-二[(4-甲氧基苯基)氧羰基]苯乙烯}(PMPCS)为刚性链段的刚-柔型二嵌段共聚物(PCL-b-PMPCS)的微相分离结构.小角X射线散射(SAXS)和广角X射线衍射(WAXD)实验结果表明,当PMPCS为无定形态时,PCL-b-PMPCS的微相分离行为与柔-柔型二嵌段共聚物相似,其相形态主要取决于两段的体积分数.随温度升高,PMPCS链段采取伸展的棒状构象,形成六方柱状向列相(ΦHN),会诱导体系的微相分离结构出现"有序-有序"或"无序-有序"转变,使得在很宽的PMPCS体积分数(fPMPCS:40%~80%)内样品均呈现层状微相分离结构.我们对在200oC得到的层状相SAXS数据进行了一维相关函数分析,详细考察了层状相中PMPCS及PCL相区的厚度(LPMPCS、LPCL)与相应链段聚合度(NPMPCS、NPCL)的关系.对PMPCS相区,发现LPMPCS=0.2NPMPCS(nm).因棒状PMPCS链段与层的法线方向平行,该线性关系表明PCL-b-PMPCS的层状相为"单层近晶A相"结构,LPMPCS即为棒状PMPCS链段的长度,可通过控制PMPCS的聚合度予以精确控制.对PCL相区,则LPCL与NPCL近似有标度关系LPCL~NPCL0.85,说明处于熔融态的PCL链段受迫强烈伸展.进一步分析WAXD实验数据并计算每根PMPCS链段在层状相中的界面面积(S/X)可知,随NPMPS增大,PMPCS链段的液晶度从~20%增至~55%,S/X则从~2.4nm2增至~2.7 nm2.与此相应,PCL链段的伸展程度会略有降低,说明LPCL有较弱的NPMPCS依赖性.另一方面,LPCL与S/X的乘积与NPCL满足线性关系LPCL(S/X)=0.21NPCL(nm3),斜率即为PCL重复单元的体积.     

Preparation and characterization of V-shaped PS-b-PEO brushes anchored on planar gold substrate through the trithiocarbonate junction group

Trithiocarbonate group was introduced into the polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymers as the junction of the blocks through RAFT polymerization. Mixed PS and PEO brushes with a V-shape were prepared by anchoring the trithiocarbonate group on the planar gold substrate. The morphology of the V-shaped brushes was characterized by atomic force microscopy (AFM) and the surface composition responsive to solvent treatment was detected by X-ray photoelectron spectroscopy (XPS). Different morphologies were observed for the V-shaped PS-b-PEO brushes, depending on the chain structure and solvent treatment. The highly selective solvent for PEO, ethanol, can intensify or induce microphase separation of the V-shaped brushes, leading to vertical microphase separation. When the V-shaped brushes are treated with the co-solvent, THF, miscible morphology, lateral microphase separation, and vertical microphase separation are observed as the PS block length increases. After treatment with the non-selective poor solvent, cyclohexane, the V-shaped PS(106)-b-PEO(113) brush, exhibits a laterally microphase-separated morphology, but the V-shaped PS(52)-b-PEO(113) and PS(253)-b-PEO(113) brushes are vertically microphase-separated.     

Complexation and eutectic crystallization in poly(2-vinyl pyridine)-block-poly(ε-caprolactone) and pentadecylphenol mixtures

Crystallization behavior via hydrogen bonding interaction in amphiphilic block copolymer/surfactant mixtures consisting of poly(2-vinyl pyridine)-block-poly(ε-caprolactone) (P2VP-PCL) and 3-pentadecylphenol (PDP) were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The P2VP-PCL/PDP mixtures exhibit eutectic crystallization behavior; the eutectic composition is approximately at 70 wt.% PDP. Scanning probe microscopy (SPM) observation revealed the microphase structure in the P2VP-PCL/PDP mixtures and the unique eutectic morphology at the eutectic composition, which was further confirmed by small angle X-ray scattering (SAXS) results. To our knowledge, this is the first example of eutectic crystallization observed in amphiphilic block copolymer/surfactant systems. The FTIR study proved that there are competitive hydrogen bonding interactions between P2VP block/PDP and PCL block/PDP pairs in the P2VP-PCL/PDP mixtures. On the basis of the SPM results and FTIR study, a model describing the microstructure of the P2VP-PCL/PDP eutectic mixtures is proposed. The amorphous P2VP blocks are expelled from the ordered eutectic lamellae formed by the crystalline PCL blocks and PDP, which deviates remarkably from the existing structural model proposed by other authors for poly(vinyl pyridine)/PDP and poly(styrene-block-4-vinyl pyridine)/PDP mixtures.     

Crystallization and melting of poly(glycerol adipate)‐based graft copolymers with single and double crystallizable side chains

The crystallization and melting behavior of a series of poly(glycerol adipate) (PGA) based graft copolymers with either poly(ε‐caprolactone) (PCL), poly(ethylene oxide) (PEO), or PCL‐b‐PEO diblock copolymer side chains (i.e., PGA‐g‐PCL, PGA‐g‐PEO, and PGA‐g‐(PCL‐b‐PEO)) was studied using polarized light optical microscopy (POM), differential scanning calorimetry (DSC), small‐angle X‐ray scattering (SAXS), and wide‐angle X‐ray diffraction (WAXD). These results were compared with the behavior of the corresponding linear analogs (PEO, PCL, and PCL‐b‐PEO). POM revealed that spherulitic morphology was retained after grafting. However, spherulite radius as well as radial growth rate was significantly smaller in the graft copolymers. Evaluation of isothermal crystallization kinetics by means of the Avrami theory revealed that the nucleation density was much higher in the graft copolymers. The DSC results indicated that the degree of crystallinity decreased strongly upon grafting while the melting temperatures of PGA‐g‐PCL and PGA‐g‐PEO were found to be close to the values of neat PCL and PEO, respectively. This was attributed to the absence of specific thermodynamic interactions, and, additionally, to lamella thicknesses being similar to those of the homopolymers. The latter point was confirmed by SAXS measurements. In case of PCL‐b‐PEO diblock copolymers and PGA‐g‐(PCL‐b‐PEO) graft copolymers, the crystallization behavior and thus the resulting lamellar morphology is more complex, and a suitable model was developed based on a combination of DSC, WAXD, and SAXS data. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1581–1591     

聚四氢呋喃-聚甲基丙烯酸甲酯两嵌段共聚物的结晶行为

报导了系列聚四氢呋喃-聚甲基丙烯酸甲酯结晶-非晶(硬段型)两嵌段共聚物的结晶行为，结果表明，其微相分离和结晶规律与文献上唯一进行过系统研究的同类嵌段共聚物(PEO－b－PS)都有较大的差别；结晶段结晶能力的大小是制约这类体系微相分离和结晶规律的一个重要因素．     

聚己内酯和聚氧化乙烯共混体系中的两类片晶相间堆砌

对聚(ε-己内酯)(PCL)/聚氧化乙烯(PEO)共混物的相差显微镜、广角X-射线衍射(WAXD)、小角X-射线散射(SAXS)及示差扫描量热计(DSC)等的研究表明,只有当共混物中PCL(或PEO)的含量低于20％时,两组份是相容的.当PCL含量低于20％时,在共混物中形成了PEO片晶和PCL片晶相间堆砌的结晶形态,当PEO含量不超过20％时,PEO则完全以非晶形式混入PCL的非晶区,同时阻碍了PCL的结晶.可见在结晶过程中,相容的两组份对共混体系形态结构的影响却不尽相同.