Monte Carlo simulation of AB diblock copolymer between surface and substrate and comparison of experimental results

The morphologies of AB diblock copolymer film between the substrate and surface were investigated via Monte Carlo simulations on simple cubic lattices. The morphological dependence of the diblock copolymer thin film on the thickness, as well as the composition and interactive intensity has been mainly studied. With the increase of A‐segments fraction, various microdomain morphologies including regular parallel stripe‐like, mesh‐like, and normal lamella near the region of the surface were generated in this work. The morphology of thin films of asymmetric diblock copolymer was found to form cylinders in a bulk system when L_z was equal to 30. The morphologies of PS‐b‐PDMS diblock copolymer films have been studied via atomic force microscopy (AFM) and transition electron microscopy (TEM) measurements. The surface morphology of the PS‐b‐PDMS copolymer thin film shows a mesh‐like microphase separated structure, and PDMS continuous phase protruded on the PS dispersed phase. The surface composition of PS‐b‐PDMS copolymer thin films was measured by means of X‐ray photoelectron spectroscopy (XPS) and ATR‐IR. The comparison results show that the experimental observations are in good agreement with the simulation results. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1835–1845, 2006     

Synthesis and characterization of linear ABC triblock copolymer of ethylene oxide,methyl methacrylate,and styrene

A well‐defined linear ABC triblock copolymer of ethylene oxide (EO), methyl methacrylate (MMA), and styrene (St) was prepared by sequential living anionic and photo‐induced charge transfer polymerization (CTP) using p‐aminophenol as parent compound. In the first step, the diblock copolymer of PEO‐b‐PMMA with a protected aniline end group at PEO end was prepared by initiating of phenoxo‐anion the polymerization of EO and MMA successively, then the diblock copolymer of PEO‐b‐PMMA via deprotection of aniline at PEO end constituted a binary initiation system with benzophenone (BP) by charge transfer complex mechanism to initiate the polymerization of St under UV‐irradiation. The GPC and NMR measurements support that in copolymerization, either in the first or second step, neither homopolymer nor side reactions, such as chain transfer or chain termination, was found. The effect of the concentration of PEO_a‐b‐PMMA and St, and the polarity of solvent on the polymerization rate (R_p) of CTP is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 825–833, 1999     

Surface modification of polystyrene by blending substituted styrene copolymers

The surface modification of polystyrene (PS) by the blending of 4‐acetoxystyrene polymers and their corresponding hydrolysis products, 4‐hydroxystyrene polymers, was investigated on the basis of X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact‐angle measurements. According to XPS and AFM measurements, when polystyrene‐block‐poly(4‐acetoxystyrene) (PS‐b‐PAS) or polystyrene‐block‐poly(4‐hydroxystyrene) (PS‐b‐PHS) was incorporated into PS, the block copolymer was preferentially segregated at the highest surface region of the blend. This segregation increased to a plateau value when more than 5 wt % of either PS‐b‐PHS or PS‐b‐PAS was added. The contact angle of the modified PS by PS‐b‐PAS or PS‐b‐PHS was slightly lower than that of homopolystyrene, but no further decrease was observed with the blend ratio of the diblock copolymer increasing from 5 to 20 wt %. For a PS/PS‐b‐PHS blend, the surface atomic concentration ratio O/C increased linearly with the molecular weight of poly(4‐hydroxystyrene) blocks in diblock copolymer PS‐b‐PHS in the range of our study. The different structures of 4‐acetoxystyrene polymers and their hydrazinolyzed materials may affect the surface compositions of their blends with PS; among these polymers, PS‐b‐PHS and PS‐b‐PAS appeared to be most effective. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1046–1054, 2001     

Synthesis and Characterization of a Diblock Copolymer of Methyl Methacrylate and Vinyl Acetate by Successive Photo‐Induced Charge Transfer Polymerization Using Ethanolamine as the Parent Compound

Communication: A diblock copolymer consisting of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) with hydroxyl group at one end is prepared by successive charge transfer polymerization (CTP) under UV irradiation at room temperature using ethanolamine and benzophenone as a binary initiation system. The diblock copolymer PMMA‐b‐PVAc could be selectively hydrolyzed to the block copolymer of poly(methyl methacrylate) and poly(vinyl alcohol) (PVA) using sodium ethoxide as the catalyst. Both copolymers, PMMA‐b‐PVAc and PMMA‐b‐PVA, are characterized in detail by means of FTIR and ¹H NMR spectroscopy, and GPC. The effect of the solvent on CTP and the kinetics of CTP are discussed.     

Morphological change of a diblock copolymer film induced by selective doping of a photoactive chromophore

Tetrakis‐5,10,15,20‐(4‐carboxyphenyl)porphyrine (TCPP) was position‐selectively introduced into a diblock copolymer film of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a sea–island microphase structure. By immersing the PS‐b‐P4VP film into a solution of TCPP/methanol, TCPP was introduced into the island parts comprising P4VP phase. The morphology of the island parts depended on the immersion time and TCPP concentration. A schematic model for the morphological change caused by the phase‐selective introduction of TCPP was proposed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 368–375, 2007     

Synthesis of ABCD 4‐Miktoarm star‐shaped quarterpolymers by combination of the “click” chemistry with multiple polymerization mechanism

Well‐defined ABCD 4‐Miktoarm star‐shaped quarterpolymers of [poly(styrene)‐poly(tert‐butyl acrylate)‐poly(ethylene oxide)‐poly(isoprene)] [star(PS‐PtBA‐PEO‐PI)] were successfully synthesized by the combination of the “click” chemistry and multiple polymerization mechanism. First, the poly(styryl)lithium (PS^?Li⁺) and the poly(isoprene)lithium (PI^?Li⁺) were capped by ethoxyethyl glycidyl ether (EEGE) to form the PS and PI with both an active ω‐hydroxyl group and an ω′‐ethoxyethyl‐protected hydroxyl group, respectively. After these two hydroxyl groups were selectively modified to propargyl and 2‐bromoisobutyryl group for PS, the resulted PS was used as macroinitiator for ATRP of tBA monomer and the diblock copolymer PS‐b‐PtBA with a propargyl group at the junction point was achieved. Then, using the functionalized PI as macroinitiator for ROP of EO monomer and bromoethane as blocking agent, the diblock copolymer PI‐b‐PEO with a protected hydroxyl group at the conjunction point was synthesized. After the hydrolysis, the recovered hydroxyl group of PI‐b‐PEO was modified to bromoacetyl and then azide group successively. Finally, the “click” chemistry between them was proceeded smoothly. The obtained star‐shaped quarterpolymers and intermediates were characterized by ¹H NMR, FT‐IR, and SEC in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2154–2166, 2008     

Polymerization‐induced self‐assembly of block copolymer through dispersion RAFT polymerization in ionic liquid

Polymerization‐induced self‐assembly of block copolymer through dispersion RAFT polymerization has been demonstrated to be a valid method to prepare block copolymer nano‐objects. However, volatile solvents are generally involved in this preparation. Herein, the in situ synthesis of block copolymer nano‐objects of poly(ethylene glycol)‐block‐polystyrene (PEG‐b‐PS) in the ionic liquid of 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIN][PF₆]) through the macro‐RAFT agent mediated dispersion polymerization is investigated. It is found that the dispersion RAFT polymerization of styrene in the ionic liquid of [BMIN][PF₆] runs faster than that in the alcoholic solvent, and the dispersion RAFT polymerization in the ionic liquid affords good control over the molecular weight and the molecular weight distribution of the PEG‐b‐PS diblock copolymer. The morphology of the in situ synthesized PEG‐b‐PS diblock copolymer nano‐objects, e.g., nanospheres and vesicles, in the ionic liquid is dependent on the polymerization degree of the solvophobic block and the concentration of the fed monomer, which is somewhat similar to those in alcoholic solvent. It is anticipated that the dispersion RAFT polymerization in ionic liquid broads a new way to prepare block copolymer nano‐objects. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1517–1525     

Tuning microdomain spacing with light using ortho‐nitrobenzyl‐linked triblock copolymers

Using sequential RAFT polymerization, single monomer insertion, and “click” chemistry, a series of triblock copolymers, poly(ethylene oxide)‐b‐polystyrene‐b‐poly(ethylene oxide), PEO‐b‐PS‐b‐PEO, were synthesized, where one of the two junction points is a UV cleavable ortho‐nitrobenzyl (ONB). Ordered patterns of PEO‐b‐PS‐b‐PEO were produced by solvent vapor annealing. Upon exposure to ultraviolet (UV) light, the PEO‐b‐PS‐b‐PEO was converted into a mixture of a PEO homopolymer and a PS‐b‐PEO diblock copolymer. It was found that the microdomain spacing could be tuned by adjusting the UV exposure time, due to the change in the copolymer architecture and the swelling of the PEO microdomain by the PEO homopolymer produced. By selective area exposure of the PEO‐b‐PS‐b‐PEO thin films, the domain spacing was changed over selected locations across the film, generating patterns of different microdomain sizes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 355–361.     

Synthesis and characterization of amphiphilic diblock copolymer of polystyrene and polyvinyl alcohol using ethanolamine–benzophenone as photochemical binary initiation system

Amphiphilic diblock copolymers of polyvinyl alcohol (PVA) and polystyrene (PS), which are very difficult to prepare by common polymerization methods, have been obtained by initiation of the polymerization of styrene and vinyl acetate successively, followed by hydrolysis, using the ethanolamine–benzophenone (BP) charge-transfer complex (CTC). The effects of solvents, concentration of monomer, BP, ethanolamine, and PS prepolymer, with a reactive imino group (PS_a), on the photo-induced charge-transfer polymerization (CTP) of St and block copolymerization of VAc are discussed. The copolymer of PS-b-PVAc and the hydrolyzed product, PS-b-PVA, were characterized by FTIR, NMR, and GPC in detail. The effect of PS chain length on the crystallization of PVA was described. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 109–115, 1998     

Polymethylene‐b‐polystyrene diblock copolymer: Synthesis,property, and application

The design and synthesis of well‐defined polymethylene‐b‐polystyrene (PM‐b‐PS, M_n = 1.3 × 10⁴–3.0 × 10⁴ g/mol; M_w/M_n (GPC) = 1.08–1.18) diblock copolymers by the combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) was successfully achieved. The ¹H NMR spectrum and GPC traces of PM‐b‐PS indicated the successful extension of PS segment on the PM macroinitiator. The micellization behavior of such diblock copolymers in tetrahydrofuran were characterized by dynamic light scattering (DLS) and atomic force microscopy (AFM) techniques. The average aggregate sizes of PM‐b‐PS diblock copolymers with the same length of PM segment in tetrahydrofuran solution (1.0 mg mL^?1) increases from 104.2 nm to 167.7 nm when the molecular weight of PS segment increases. The spherical precipitated aggregates of PM‐b‐PS diblock copolymers with an average diameter of 600 nm were observed by AFM. Honeycomb porous films with the average diameter of 3.0 μm and 6.0 μm, respectively, were successfully fabricated using the solution of PM‐b‐PS diblock copolymers in carbon disulfide via the breath‐figure (BF) method under a static humid condition. The cross‐sections of low density polyethylene (LDPE)/polystyrene (PS)/PM‐b‐PS and LDPE/polycarbonate (PC)/PM‐b‐PS blends were observed by scanning electron microscope and reveal that the PM‐b‐PS diblock copolymers are effective compatilizers for LDPE/PS and LDPE/PC blends. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1894–1900, 2010     

Block copolymer containing poly(3‐hexylthiophene) and poly(4‐vinylpyridine): Synthesis and its interaction with CdSe quantum dots for hybrid organic applications

Poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer was synthesized by RAFT polymerization of 4‐vinyl pyridine using a trithiocarbonate‐terminated poly(3‐hexylthiophene) macro‐RAFT agent. The optoelectronic properties and the morphology of the block copolymer blends with CdSe quantum dots were investigated. UV‐vis and fluorescence experiments were performed to prove the charge transfer between CdSe and poly(3‐hexylthiophene)‐b‐poly(4‐vinylpyridine) diblock copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Radiation‐induced fabrication of polymer nanoporous materials from microphase‐separated structure of diblock copolymers as a template

Polymer nanoporous materials with periodic cylindrical holes were fabricated from microphase‐separated structure of diblock copolymers consisting of a radiation‐crosslinking polymer and a radiation‐degrading polymer through simultaneous crosslinking and degradation by γ‐irradiation. A polybutadiene‐block‐poly(methyl methacrylate) (PB‐b‐PMMA) diblock copolymer film that self‐assembles into hexagonally packed poly(methyl methacrylate) cylinders in polybutadiene matrix was irradiated with γ‐rays. Solubility test, IR spectroscopy, and TEM and SEM observations for this copolymer film in comparison with a polystyrene‐block‐poly(methyl methacrylate) diblock copolymer film revealed that poly(methyl methacrylate) domains were removed by γ‐irradiation and succeeding solvent washing to form cylindrical holes within polybutadiene matrix, which was rigidified by radiation crosslinking. Thus, it was demonstrated that nanoporous materials can be prepared by γ‐irradiation, maintaining the original structure of PB‐b‐PMMA diblock copolymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5916–5922, 2007     

In situ synthesis of ABA triblock copolymer nanoparticles by seeded RAFT polymerization: Effect of the chain length of the third a block on the triblock copolymer morphology

Synthesis of the ABA triblock copolymer nanoparticles of poly(N,N‐dimethylacrylamide)‐block‐polystyrene‐block‐poly(N,N‐dimethylacrylamide) (PDMA‐b‐PS‐b‐PDMA) by seeded RAFT polymerization is performed, and the effect of the introduced third poly(N,N‐dimethylacrylamide) (PDMA) block on the size and morphology of the PDMA‐b‐PS‐b‐PDMA triblock copolymer nanoparticles is investigated. This seeded RAFT polymerization affords the in situ synthesis of the PDMA‐b‐PS‐b‐PDMA core‐corona nanoparticles, in which the middle solvophobic PS block forms the compacted core, and the first solvophilic PDMA block and the introduced third PDMA block form the solvated complex corona. During the seeded RAFT polymerization, the introduced third PDMA block extends, and the molecular weight of the PDMA‐b‐PS‐b‐PDMA triblock copolymer linearly increases with the monomer conversion. It is found that, the size of the PS core in the PDMA‐b‐PS‐b‐PDMA triblock copolymer core‐corona nanoparticles is almost equal to that in the precursor of the poly(N,N‐dimethylacrylamide)‐block‐polystyrene diblock copolymer core‐corona nanoparticles and it keeps constant during the seeded RAFT polymerization, and whereas the introduction of the third PDMA block leads to a crowded complex corona on the PS core. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1777–1784     

The preparation of t‐butyl acrylate,methyl acrylate,and styrene block copolymers by atom transfer radical polymerization: Precursors to amphiphilic and hydrophilic block copolymers and conversion to complex nanostructured materials

Atom transfer radical polymerization conditions with copper(I) bromide/pentamethyldiethylenetriamine (CuBr/PMDETA) as the catalyst system were employed for the polymerization of tert‐butyl acrylate, methyl acrylate, and styrene to generate well‐defined homopolymers, diblock copolymers, and triblock copolymers. Temperature studies indicated that the polymerizations occurred smoothly in bulk at 50 °C. The kinetics of tert‐butyl acrylate polymerization under these conditions are reported. Well‐defined poly(tert‐butyl acrylate) (PtBA; polydispersity index = 1.14) and poly(methyl acrylate) (PMA; polydispersity index = 1.03) homopolymers were synthesized and then used as macroinitiators for the preparation of PtBA‐b‐PMA and PMA‐b‐PtBA diblock copolymers in bulk at 50 °C or in toluene at 60 or 90 °C. In toluene, the amount of CuBr/PMDETA relative to the macroinitiator was important; at least 1 equiv of CuBr/PMDETA was required for complete initiation. Typical block lengths were composed of 100–150 repeat units per segment. A triblock copolymer, composed of PtBA‐b‐PMA‐b‐PS (PS = polystyrene), was also synthesized with a well‐defined composition and a narrow molecular weight dispersity. The tert‐butyl esters of PtBA‐b‐PMA and PtBA‐b‐PMA‐b‐PS were selectively cleaved to form the amphiphilic block copolymers PAA‐b‐PMA [PAA = poly(acrylic acid)] and PAA‐b‐PMA‐b‐PS, respectively, via reaction with anhydrous trifluoroacetic acid in dichloromethane at room temperature for 3 h. Characterization data are reported from analyses by gel permeation chromatography; infrared, ¹H NMR, and ¹³C NMR spectroscopies; differential scanning calorimetry; and matrix‐assisted, laser desorption/ionization time‐of‐flight mass spectrometry. The assembly of the amphiphilic triblock copolymer PAA₉₀‐b‐PMA₈₀‐b‐PS₉₈ within an aqueous solution, followed by conversion into stable complex nanostructures via crosslinking reactions between the hydrophilic PAA chains comprising the peripheral layers, produced mixtures of spherical and cylindrical topologies. The visualization and size determination of the resulting nanostructures were performed by atomic force microscopy, which revealed very interesting segregation phenomena. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4805–4820, 2000     

Single‐step process to produce functionalized multiresponsive polymeric particles

Monodisperse functional multiresponsive particles were prepared by encapsulation of an amphiphilic diblock copolymer during the precipitation polymerization of polystyrene and divinylbenzene in one single step. The amphiphilic diblock copolymer employed throughout this study, polystyrene‐b‐poly (dimethylaminoethyl methacrylate) (PS‐b‐PDMAEMA) has been synthesized by ATRP in two consecutive polymerization steps. After encapsulation of the block copolymer within the microsphere, the surface modification of the particle occurs spontaneously upon exposure to water by surface segregation of the hydrophilic PDMAEMA block, thus without any additional post‐polymerization and/or chemical modification steps. The response of the functionalized particles both to pH and temperature was analyzed by potential zeta and DSC measurements. Upon dispersion of the particles in acidic media, the PDMAEMA block in its charged state is soluble and does not exhibit any change by heating. At higher pH values and temperatures above 35 °C (Low Critical Solubility Temperature of the PDMAEMA block) the hydrophilic segment collapses as detected by differential scanning calorimetry. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3523–3533, 2010     

Polymerization of n‐hexyl isocyanate with CpTiCl2(OR) (R = functional group or macromolecular chain): A route to ω‐functionalized and block copolymers and terpolymers of n‐hexyl isocyanate

Well‐defined ω‐cholesteryl poly(n‐hexyl isocyanate) (PHIC–Chol), as well as diblock copolymers of n‐hexyl isocyanate (HIC) with styrene, PS‐b‐PHIC [PS = polystyrene; PHIC = poly(n‐hexyl isocyanate)], and triblock terpolymers with styrene and isoprene, PS‐b‐PI‐b‐PHIC and PI‐b‐PS‐b‐PHIC (PI = polyisoprene), were synthesized with CpTiCl₂(OR) (R = cholesteryl group, PS, or PS‐b‐PI) complexes. The synthetic strategy involved the reaction of the precursor complex CpTiCl₃ with cholesterol or the suitable ω‐hydroxy homopolymer or block copolymer, followed by the polymerization of HIC. The ω‐hydroxy polymers were prepared by the anionic polymerization of the corresponding monomers and the reaction of the living chains with ethylene oxide. The reaction sequence was monitored by size exclusion chromatography, and the final products were characterized by size exclusion chromatography (light scattering and refractive‐index detectors), nuclear magnetic resonance spectroscopy, and, in the case of PHIC–Chol, differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6503–6514, 2005     

Probe diffusion in homogeneous diblock copolymers

Forced Rayleigh scattering was used to investigate the diffusion of a photoreactive dye molecule in two homogeneous poly(styrene-b-isoprene) (SI) diblock copolymers with overall molecular weights of approximately 2000. Although diffusion rates were intermediate to TTI transport in homopolymer polystyrene (PS) and polyisoprene (PI), system dynamics appear to be largely dictated in each case by the PI block. The size of the polymer jumping unit, on the other hand, is evaluated from a free-volume analysis of the data, and is found to be governed predominantly by the PS component of the copolymer. The mechanism for tracer diffusion in low-molecular-weight block copolymers appears analogous to transport in a high molecular weight SI diblock copolymer (M_n = 13,600) that has been solvated sufficiently in toluene to be microstructurally disordered. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1739–1746, 1998     

Thin films of PS/PS‐b‐pnipam and ps/pnipam polymer blends with tunable wettability

We developed thin films of blends of polystyrene (PS) with the thermoresponsive polymer poly(N‐isopropylacrylamide) (PNIPAM) (PS/PNIPAM) and its diblock copolymer polystyrene‐b‐poly(N‐isopropylacrylamide) (PS/PS‐b‐PNIPAM) in different blend ratios, and we study their surface morphology and thermoresponsive wetting behavior. The blends of PS/PNIPAM and PS/PS‐b‐PNIPAM are spin‐casted on flat silicon surfaces with various drying conditions. The surface morphology of the films depends on the blend ratio and the drying conditions. The PS/PS‐b‐PNIPAM films do not show an increase in their water contact angles with temperature, as it is expected by the presence of the PNIPAM block. All PS/PNIPAM films show an increase in the water contact angle above the lower critical solution temperature of PNIPAM, which depends on the ratio of PNIPAM in the blend and is insensitive to the drying conditions of the films. The difference between the wetting behavior of PS/PS‐b‐PNIPAM and PS/PNIPAM films is due to the arrangement of the PNIPAM chains in the film. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 670–679     

Behaviors of self‐assembled diblock copolymer with pendant photosensitive azobenzene segments

A novel monomer, ethyl 4‐[4‐(11‐methacryloyloxyundecyloxy)phenyl azobenzoyl‐oxyl] benzoate, containing a photoisomerizable N?N group was synthesized. The monomer was further diblock copolymerized with methyl methacrylate. Amphiphilic diblock copolymer poly(methyl methacrylate‐block‐ethyl 4‐[4‐(11‐methacryloyloxyundecyloxy)phenyl azobenzoyl‐oxyl] benzoate ( PMMA ‐ b ‐ PAzoMA ) was synthesized using atom transfer radical polymerization. The reverse micelles with spherical construction were obtained with 2 wt % of the diblock copolymer in a THF/H₂O mixture of 1:2. Under alternating UV and visible light illumination, reversible changes in micellar structure between sphere and rod‐like particles took place as a result of the reversible E‐Z photoisomerization of azobenzene segments in PMMA ‐ b ‐ PAzoMA . Microphase separation of the amphiphilic diblock copolymer in thin films was achieved through thermal and solvent aligning methods. The microphases of the annealed thin films were investigated using atom force microscopy topology and scanning electron microscopy analyses. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1142–1148, 2010     

Linear pentablock quintopolymers (l‐SIDMV) with five incompatible blocks: Polystyrene,polyisoprene‐1,4, poly(dimethylsiloxane), poly(tert‐butyl methacrylate), and poly(2‐vinylpyridine)

Three linear pentablock quintopolymers (l‐SIDMV), where S is polystyrene (PS), I polyisoprene‐1,4 (PI), D poly(dimethylsiloxane) (PDMS), M poly(tert‐butyl methacrylate) (PtBuM), and V poly(2‐vinylpyridine) (P2VP), were synthesized by anionic polymerization high vacuum techniques. The approach involves the following: (a) The synthesis of living triblock terpolymer PS‐b‐PI‐b‐PDMSLi and diblock copolymer P2VP‐b‐PtBuMK by sequential polymerizations of the corresponding monomers with sec‐BuLi and benzyl potassium, respectively; and (b) The selective linking of the living triblock terpolymer with the chlorosilane group of 2‐(chloromethylphenyl)ethyldimethylchlorosilane (CMPDMS), followed by linking of the living block copolymer with the remaining chloromethyl group of CMPDMS. Molecular characterization carried out by size exclusion chromatography, membrane osmometry, solution (in CDCl₃ or d₈‐toluene) and solid‐state ¹H‐NMR spectroscopy indicated a high degree of molecular and compositional homogeneity. Differential scanning calorimetry results on the precursors and final polymers were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3938–3946, 2008