Perpendicular lamellae induced at the interface of neutral self-assembled monolayers in thin diblock copolymer films

We obtained perpendicular lamellar orientations in thin films of symmetric polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, on self-assembled monolayers (SAMs) of 3-(p-methoxyphenyl)propyltrichlorosilane (MPTS) prepared on silicon wafers. In contrast to completely parallel lamellae on silicon wafers having a native oxide layer, perpendicular lamellae at the MPTS interface with parallel lamellae at the air interface were directly observed by transmission electron microscopy (TEM) in cross-sectional view. The perpendicular lamellae at the MPTS interface were attributed to the non-preferential (neutral) MPTS-covered substrate to both PS and PMMA blocks. The neutrality of the SAMs of MPTS was confirmed by the similar interfacial tension values of the SAMs of MPTS with PS and PMMA, estimated by contact angle measurements.     

Crystal behavior of semicrystalline polystyrene‐block‐poly(l‐lactide) diblock copolymer in thin films with various structures

The crystal behavior of a semicrystalline polystyrene‐block‐poly(l ‐lactide) diblock copolymer in phase‐separated thin films with various thicknesses at different crystal temperatures has been investigated using atomic force microscopy and transmission electronic microscopy. Parallel and perpendicular lamellae could be obtained by annealing the thin films for different periods of time as reported previously (Chen et al., Macromolecules 40:6631 (2007)). At different temperatures, crystallization in thin films with parallel lamellar structure in the melt state gives dendrite crystals with orthorhombic structure, and the ordered structure in the melt is destroyed after crystallization. When crystallization occurs in thin films with perpendicular lamellar structure, crystal morphology and structure are greatly affected by the crystallization temperature (T_c). When T_c < T_g,ps, where T_g,ps is the glass transition temperature of a polystyrene block, crystallization is hardly confined within the lamellae. The morphology is preserved but the long period of the perpendicular lamellae is increased after crystallization. When T_c > T_g,ps, rod‐like crystals dominate the final morphology, and crystallinity destroys completely the structure in the melt.© 2012 Society of Chemical Industry     

Preparation and evaluation of double-hydrophilic diblock copolymer as viscosity reducers for heavy oil

In this work, a series of double-hydrophilic diblock copolymers of N-acryloylmorpholine (NAMO) and N,N-dialkylacrylamide are prepared as the additives for viscosity reduction, which could effectively interact with the asphaltenes and resins. The viscosity reduction effects of the types of N,N-dialkylacrylamide monomer (N,N-dimethyl acrylamide & N,N-diethyl acrylamide) and degree of polymerization (DP) of poly(N,N-dialkylacrylamide) block in copolymers on heavy oil are tested with heavy oils with different viscosities. These viscosity reducers can work with small dosages (>25 mg L⁻¹). The interfacial tension between oil and water is significantly weakened, and the aggregating structures of asphaltenes and resins are disassembled into smaller aggregates and covered with polymers with the addition of copolymers. The re-establishment of aggregates among polar components seems to be prevented, and the stability of the heavy oil/water emulsions is greatly enhanced as a result. All these results provide the prerequisites for water-soluble diblock copolymers working as viscosity reducers for various heavy oils.     

pH和磁场响应型嵌段共聚物基纳米复合材料的制备

采用自制链转移剂,通过可逆加成-断裂链转移聚合法制备p H和磁场响应型嵌段共聚物基纳米复合材料Y-054B。利用透射电子显微镜、扫描电子显微镜、傅里叶变换红外光谱仪等对其进行了表征。结果表明:Y-054B中的嵌段共聚物由疏水性且对p H敏感的甲基丙烯酸甲酯与丙烯酸共聚物嵌段和亲水性N-乙烯基吡咯烷酮均聚物嵌段组成;Y-054B在水溶液中可自组装生成纳米胶束,胶束平均粒径约70 nm,其中的自组装铁磁性成分平均粒径约8 nm,分散均匀,稳定性良好。     

Effect of the mold temperature on the electrical properties of carbon-black-loaded polystyrene/SB block copolymer blends

The electrical resistivities of a carbon-black-filled styrene–butadiene block copolymer (SB) and their blends with polystyrene were measured as a function of carbon content for specimens compression-molded at 200 and 250°C. The insulator–conductor point transition was greatly influenced by the mold temperature. This behavior associated to the scanning electronic microscopy investigations suggests the presence of some amount of the filler at the interface. A strong interaction between the filler and the polymer was also observed. The formation of bound rubber and a coherent rubber–filler gel depend on the molding conditions and the carbon black content in the composites. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 825–833, 1998     

苯乙烯-异戊二烯两嵌段对线型三嵌段聚合物性能的影响

苯乙烯-异戊二烯线型三嵌段（SIS）中加入一定量苯乙烯-异戊二烯两嵌段（SI）对于改进SIS热熔压敏胶性能有一定影响,主要考察不同分子量、嵌段比及含量的SI对线型SIS的力学性能、流动性能及制成热熔压敏胶的性能的影响,结果表明,线型三嵌段SIS中,掺入10％～30％（质量分数）的两嵌段SI,对产品的力学性能影响不明显,对产品的硬度、流动性能有一定影响;将掺有两嵌段SI的线型SIS制成热熔压敏胶后,产品的粘合性能较单纯使用线型SIS做热熔压敏胶有所改善。     

两亲嵌段共聚物的合成及其自组装研究进展

作者介绍了两亲嵌段共聚物的活性阴离子聚合、基团转移聚合、开环歧化聚合、活性阳离子聚合、活性／可控自由基聚合、缩聚法、嵌段共聚物化学改性法等合成方法,并对其自组装形成聚合物纳米胶束的制备方法、形成机理以及在药物控制释放领域的应用进行了综述,并对其未来发展趋势进行了展望。     

Oligomer and random copolymer layer in relation to enhancement of interfacial adhesion at polystyrene/poly(styrene‐co‐acrylonitrile) interface

This study examines the interfacial adhesion between poly(styrene) (PS) and poly(styrene‐co‐acrylonitrile) (SAN) interfaces reinforced with poly(styrene‐co‐vinyl phenol) (PS‐ran‐PSPh) random copolymers using an asymmetric double‐cantilever beam (ADCB) test. The effects of oligomer and copolymer composition on interfacial adhesion were investigated. The results showed that the interfacial adhesion of the PS/SAN interface was increased significantly after removing the residual oligomer from the SAN. The interfacial adhesion was also measured for five‐purified SAN materials in the range 17–31 wt%. The highest level of PS/SAN adhesion was observed for 17% AN (acrylonitrile) materials. In addition, the interfacial adhesion of a mixture of diblock and random copolymer was measured in order to investigate which is the most effective method. The results showed that mixture systems are more cost‐effective with higher adhesion, which is independent of temperature. Atomic force microscopy showed that a single craze ahead of the crack is a possible failure mode during PS/SAN interface fracture. Copyright © 2004 Society of Chemical Industry     

Influences of debonding rate and temperature on tack properties and peel behavior of polyacrylic block copolymer/tackifier system

The influences of debonding rate and temperature on the peel behavior of polyacrylic block copolymer/tackifier system were investigated. Poly(methyl methacrylate)-block-poly(n-butyl acrylate)-block-poly(methyl methacrylate) triblock copolymer (MAM) with hard block contents of 23 (MAM-23) and 16 wt.% (MAM-16) and a 1/1 blend with a diblock copolymer (MA) consisting of the same components (MAM-23/MA, total hard block content of 15 wt.%) were used as the base polymer. A special rosin ester was used as a tackifier at various contents in the block copolymer/tackifier system. The peeling process at the probe/adhesive interface during probe tack testing was observed using a high-speed microscope at 23 °C with debonding rate of 10 mm/s. Three different peeling mechanisms were observed. Type A, where peeling progressed linearly from the edge to the center of the probe without cavitation (MAM-23). Type B, where peeling progressed linearly from the edge to the center of the probe with cavitation (MAM-16). Type C, where cavitation occurred over the entire adhesive layer, and peeling initiation was delayed (MAM-23/MA). The peel behavior of MAM-23 changed from Type A to Type B with a decrease of the debonding rate (1 mm/s) or increase of the temperature (40 °C). In contrast, there was no change for MAM-16 and MAM-23/MA. Cavity formation in an adhesive layer restrains peeling; therefore, it is desirable for improvement of the adhesion strength. The tack properties increased with the tackifier content, and the formation of cavitation was less than that for the systems without the tackifier.     

Phase behavior and microstructural length scales of a diblock copolymer in the presence of a selective solvent

We employ self-consistent mean-field (SCMF) theory in studying the phase behavior as well as the microstructural domain sizes for a diblock copolymer in the presence of a selective solvent. First we examine the effects of solvent addition on the formation of fcc and bcc packed spheres. As has been found in experiments, the so-called “normal” spheres, i.e., formed by the minority blocks, tend to pack into the bcc array, while the “inverted” spheres formed by the majority blocks favor the fcc packing. Upon increasing the solvent selectivity and/or solvent amount, the formed inverted spheres tend to pack from bcc to fcc. This thermotropic transition of bcc → fcc upon increasing the solvent selectivity is induced by the fact that the intermicellar interactions vary from long-range to short-range via a combination of the solvent exclusion from the cores and an increase in the aggregation number. In analyzing the effects of solvent addition on the microstructural sizes, the SCMF results have successfully captured the crossover behavior of characteristic domain spacing from decreasing with added solvent to increasing by increasing the solvent selectivity. Further, the variation of the characteristic domain spacing when the systems transform to a more curved structure changes from a discontinuous decreasing behavior to even a discontinuous increasing behavior upon increasing the solvent selectivity and/or the formation of inverted structures.     

Adjustable temperature sensor with double thermoresponsiveness based on the aggregation property of binary diblock copolymers

This article presents a new and promising way to design a temperature sensor, which is based on the micellization or aggregation behavior of binary diblock copolymers of poly(ethylene glycol)‐b‐poly(N‐isopropylacrylamide) (PEG‐b‐PNIPAM) and poly(ethylene glycol)‐b‐poly(4‐vinylpyridine) (PEG‐b‐P(4‐VP)). The temperature sensor presents both a lower critical response temperature (LCRT) and an upper critical response temperature (UCRT), where the thermoreversible aggregating of PEG‐b‐P(4‐VP) and H₂SO₄ is used to control the LCRT, and the thermoreversible micellization of PEG‐b‐PNIPAM is used to control the UCRT. Furthermore, the LCRT can be altered by changing the H₂SO₄ concentration, and the UCRT can be adjusted by altering the PEG‐b‐PNIPAM concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3144–3148, 2006     

Thickness and composition dependence of the glass transition temperature in thin random copolymer films

Glass transition temperatures (T_g) of thin poly(styrene-co-methyl methacrylate) and poly(2-vinyl pyridine-co-styrene) films coated on a native oxide surface of Si wafer (100) were measured by ellipsometry. The thickness dependence of T_g can be properly fitted by previously suggested equation developed for homopolymers, based upon a continuous multi-layer model, although one component in thin random copolymer films demonstrates a slightly favorable interaction between a substrate and thin film, and another demonstrates a strongly favorable interaction. Surface and interface have a strong influence on T_g of thin film coated on substrate: the surface has the effect of reducing T_g, whereas the interface increases the T_g according to the degree of interaction between a substrate and thin film. This degree of interaction can be quantified as an interaction parameter (k), and is dependent on the composition of random copolymers. For the estimation of k values of thin random copolymer films, we proposed a parallel type additive function (1/k_ran=w₁/k₁+w₂/k₂) where w is a weight fraction of component.     

UP/PU嵌段共聚树脂/玻璃纤维界面粘结性的研究

合成了一种异氰酸酯嵌段共聚改性不饱和聚酯树脂(UP/PU),并以玻纤增强制备了复合材料(GFRP)。通过接触角、拉伸性能、弯曲性能测定和扫描电镜观察研究了UP/PU GFRP界面的粘结性能。结果表明:UP/PU树脂与玻璃表面的接触角为20°,对玻璃表面的润湿性较通用邻苯型UP好;GFRP拉伸强度1 050 MPa,弯曲强度1 220 MPa,较通用邻苯型UP的GFRP分别提高了145%和78%,说明UP/PU与玻纤的界面粘结性能较好。     

Effects of additives on the morphologies of thin titania films from self-assembly of a block copolymer

The effects of additives of poly(methyl methacrylate) (PMMA) and HAuCl₄ on the morphologies of hybrid titania films formed via co-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) copolymers, titania sol-gel precursor in a selective solvent were investigated. The results show that addition of PMMA or HAuCl₄ has an important influence on the morphologies of hybrid titania films. Addition of PMMA or HAuCl₄ can induce the morphology transition of the PS-b-PEO/titania sol-gel mixture from spherical micelles to vesicles. Therefore, the morphologies of the hybrid films formed on silicon substrate surfaces by spin-coating can be controlled by the addition of homopolymer (PMMA) or inorganic precursor (HAuCl₄) into the PS-b-PEO/titania sol-gel mixtures, allowing access to nanoparticles or nanoporous films. After removing the polymer matrix, nanoparticle aggregates or nanobowl-like structures are left behind on the substrate surfaces.     

Carboxybetaine,sulfobetaine, and cationic block copolymer coatings: A comparison of the surface properties and antibiofouling behavior

Two different zwitterionic block copolymers (BCs) and a cationic BC were synthesized from the same BC precursor, which consisted of a polystyrene (PS) block and a poly[N‐(3‐dimethylamino‐1‐propyl)acrylamide] block. The zwitterionic BCs contained the dimethylammonioacetate (carboxybetaine) and dimethylammoniopropyl sulfonate (sulfobetaine) groups. Thin films cast from these polymers were investigated for surface wettability, surface charge, and protein adsorption. Surface‐energy parameters calculated with advancing contact angle (θ_a) and receding contact angle (θ_r) of different probe liquids showed that it was θ_r and not θ_a that was representative of the polar/ionic groups in the near‐surface regions of the coatings. Electrophoretic mobility was used to characterize the influence of pH on the net surface charge. In aqueous dispersions, the carboxybetaine polymer showed an ampholyte behavior with an isoelectric point of 6, whereas the sulfobetaine polymer was found to be anionic at all pH values between 2 and 10. Protein adsorption on the carboxybetaine BC was relatively independent of the net charges on the protein or the polymer, but the negatively charged sulfobetaine polymer showed a higher adsorption of positively charged protein molecules. Regardless of the net protein charge, both zwitterionic coatings adsorbed less protein compared to the PS and poly(2,3,4,5,6‐pentafluorostyrene) controls. The sulfobetaine and cationic BCs adsorbed higher amounts of oppositely charged protein molecules than like‐charged protein molecules. However, the adsorption of oppositely charged protein was much higher on the cationic surface than on the sulfobetaine surface. The zwitterionic BCs, particularly the carboxybetaine polymer, from this article are expected to function as stable, low‐fouling surface modifiers in different biological environments. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

An in vitro focus on doxorubicin hydrochloride delivery of novel pH‐responsive poly(2‐succinyloxyethylmethacrylate) and poly[(N‐4‐vinylbenzyl),N,N‐diethylamine] diblock copolymers

Novel pH‐responsive poly(2‐succinyloxyethylmethacrylate)‐b‐poly[(N‐4‐vinylbenzyl),N,N‐diethylamine] [poly(SEMA‐b‐VEA)] diblock copolymers were synthesized via reversible addition fragmentation transfer (RAFT) polymerization to investigate their self‐assembly micellar behavior. The self‐assembly behaviors of synthesized diblock copolymers with distinct molecular weights (labeled (1) to) were confirmed by ¹H NMR spectroscopy, TEM and dynamic light scattering measurements. Doxorubicin hydrochloride (DOX) loading capacity was evaluated, and the in vitro cytotoxicity effect of DOX‐loaded diblock copolymer was also studied by assessing the survival rate of the breast cancer cell line MCF‐7 with 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. The results exhibited remarkable controlled release in the MTT assay. The DOX encapsulation efficiency was calculated to be 96.4%. The size and zeta potential of DOX‐loaded poly(SEMA‐b‐VEA) diblock copolymers were 204 nm and +5.7 mV at a pH of 7.4. DOX release values after 440 h at pH 7.4, 5.4 and 4 were 22.15%, 31.43% and 47.06%, respectively. The released values of DOX‐loaded poly(SEMA‐b‐VEA) and at pH 7.4 were 22.15%, 20.5% and 17.5%, respectively. Cell survival ratios were 18.9%, 23.16% and 16.92% after 72 h. Poly(SEMA‐b‐VEA) copolymers can be considered in nanomedicine applications due to their excellent pH‐responsive micellar behavior. © 2017 Society of Chemical Industry     

Effect of metal ions and pH values on the conformational transition of the copolymer chain in aqueous solutions

A novel salts‐ and pH‐responsive copolymer, poly(acrylic acid‐co‐ethyl 1‐(4‐chlorophenyl)‐5‐acrylamino‐1,2,3‐triazol‐4‐carboxylate), poly(AA‐co‐ECATC), was prepared by radical polymerization in methanol at room temperature with L ‐ascorbic acid (Vc) and peroxide hydrogen (H₂O₂) as initiators. The copolymer was characterized by Fourier Transform Infrared (FTIR) spectroscopy and Differential Scanning Calorimetry (DSC). The copolymer possessed excellent fluorescence properties. The effects of metal ions with different charges, radius and outer‐layer electron constructions and pH values on the conformation transition of copolymer chains were systematically investigated by the fluorescence intensity and the fluorescence anisotropy. It was found that fluorescence intensity and fluorescence anisotropy curves waved with the change of metal ions concentrations and pH values. Additionally, FTIR Subtraction spectroscopy was also carried out to confirm our results. The work provided a theory basis for the study of salts‐ and pH‐sensitive smart hydrogels, which were always used in the slow‐ or controlled‐release drugs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1714–1722, 2007     

Characterization of polystyrene‐b‐poly(ethylene oxide) diblock copolymer and investigation of its micellization behavior in water

The recent studies deal with a diblock copolymer, polystyrene–poly(ethylene oxide). Infrared spectroscopy, proton resonance spectroscopy (¹H‐NMR), and laser light scattering techniques have been used to characterize the polymer. It has been concluded that the sample investigated is diblock copolymer polystyrene–poly(ethylene oxide) having molecular mass 1.656 × 10⁴ g/mol and blocks ratio 1 : 2. The micellization behavior is explored through ¹H‐NMR, laser light scattering, light absorption, surface tension, and conductance and viscosity measurements. The results conclude that the critical micelles concentration of copolymer is 0.0951 g/dL at 25°C. It has been observed that the surface tension of solution decreases with the temperature and its impact is maxima in dilute concentration region. In addition, new methodologies have been introduced to get accurate critical micelles concentration and critical micelles temperature. © 2010 Wiley Periodicals, Inc., J Appl Polym Sci, 2010     

Toward efficient water/oil separation material: Effect of copolymer composition on pH‐responsive wettability and separation performance

Interest in functional soft matter with stimuli‐responsive wettability has increasingly intensified in recent years. From the chemical product engineering viewpoint, this study aims to fabricate reversible pH‐responsive polymeric surfaces with controllable wettability using [poly(2,2,3,4,4,4‐hexafluorobutyl methacrylate)‐block‐ poly(acrylic acid) (PHFBMA‐b‐PAA)] block copolymers. To attain this aim, three block copolymers with different PAA segment lengths were synthesized for the first time through Cu(0)‐mediated reversible‐deactivation radical polymerization and hydrolysis reaction. pH‐induced controllable wettability was achieved by spin‐coating the resulting block copolymers onto silicon wafers. Results showed that the pH‐responsive wetting behavior was introduced by incorporating the PAA block, and that the responsiveness of as‐fabricated surfaces was greatly influenced by PAA content. All three evolutions of water contact angle with pH shared a similar inflection point at pH 5.25. Furthermore, on the basis of the wetting properties and mechanism understanding, the application of copolymer coated meshes in layered water/oil separation was exploited. Given their superhydrophilicity and underwater superoleophobicity, PHFBMA₇₀‐b‐PAA₁₄₈ and PHFBMA₇₀‐b‐PAA₂₁₁ coated stainless steel meshes (SSMs) can efficiently separate water from different mixtures of organic solvent and water with high flux. However, considering long‐term use, the PHFBMA₇₀‐b‐PAA₁₄₈ coated SSM with good stability may be the best copolymer for water/oil separation. Therefore, a coordination of structure, composition, and functionality was necessary to enable practical applications of the functional materials. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1758–1771, 2016     

Photoinduced living cationic polymerization of tetrahydrofuran. I. Living nature of the system and its application to the diblock copolymer synthesis

The living nature of cationic polytetrahydrofuran (THF), photoinduced in the presence of diphenyliodonium hexafluorophosphate (initiator), was investigated. In the bulk polymerization of THF, the linear relationship between percent conversion and the number-average molecular weight of the resulting polymer strongly suggests the living nature of this polymer and this was confirmed by the monomer addition technique, that is, cationic poly(THF) is capable of initiating a newly added monomer. The loss of the living nature of the cationic poly(THF) in a polar solvent, dichloromethane, is explained in terms of the stabilization of the five-membered cyclic oxonium ion, a propagating species of cationic polymerization of THF, by ion-pair formation with a less nucleophilic counterion, hexafluorophosphate. Based on the living nature of cationic poly(THF), a diblock copolymer, composed of THF and N-2-(hydroxyethyl)ethyleneÍimine (HEEI) was synthesized by subsequent monomer addition method; however, it was found that the HEEI block of the compolymer has a nonlinear structure. The factors affecting the structure of the HEEI block are also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 611–618, 1998