Block copolymers with liquid crystalline segments

This paper describes the synthesis and characterization of polystyrene-block-poly(2,2'-dimethyl-4,4'-biphenylene phenylterephthalate)-block-polystyrene and of poly(ethylene glycol)-black-poly(2,2'-dimethyl-4,4'-biphenylene phenylterephthalate)-block-poly (ethylene glycol) block copolymers. The ABA-triblock copolymers were synthesized by condensation reaction of telechelic poly(2,2'-dimethyl-4,4'-biphenylene phenylterephthalate) with ω-hydroxy polystyrene and ω-hydroxy poly(ethylene glycol) methyl ether of different molecular weights prepared by anionic polymerization. Some aspects of the liquid crystalline behavior and the phase transitions with respect to the block copolymer composition will be discussed.     

Ion conductivity studies of blends of poly(methyl methacrylate)-g-poly(ethylene glycol) and poly(ethylene glycol) complexed with LiCF3 SO3

Polymer electrolytes which are adhesive, transparent, and stable to atmospheric moisture have been prepared by blending poly(methyl methacrylate)-g-poly(ethylene glycol) with poly(ethylene glycol)/LiCF₃ SO₃ complexes. The maximum ionic conductivities at room temperature were measured to be in the range of 10⁻⁴ to 10⁻⁵ s cm⁻¹. The clarity of the sample was improved as the graft degree increased for all the samples studied. The graft degree of poly(methyl methacrylate)-g-poly(ethylene glycol) was found to be important for the compatibility between the poly(methyl methacrylate) segments in poly(methyl methacrylate)-g-poly(ethylene glycol) and the added poly(ethylene glycol), and consequently, for the ion conductivity of the polymer electrolyte. These properties make them promising candidates for polymer electrolytes in electrochromic devices. © 1996 John Wiley & Sons, Inc.     

Preparation of polyethylene block copolymers by a combination of postmetallocene catalysis of ethylene polymerization and atom transfer radical polymerization

The synthesis of block copolymers consisting of a polyethylene segment and either a poly(meth)acrylate or polystyrene segment was accomplished through the combination of postmetallocene-mediated ethylene polymerization and subsequent atom transfer radical polymerization. A vinyl-terminated polyethylene (number-average molecular weight = 1800, weight-average molecular weight/number-average molecular weight =1.70) was synthesized by the polymerization of ethylene with a phenoxyimine zirconium complex as a catalyst activated with methylalumoxane (MAO). This polyethylene was efficiently converted into an atom transfer radical polymerization macroinitiator by the addition of α-bromoisobutyric acid to the vinyl chain end, and the polyethylene macroinitiator was used for the atom transfer radical polymerization of n-butyl acrylate, methyl methacrylate, or styrene; this resulted in defined polyethylene-b-poly(n-butyl acrylate), polyethylene-b-poly(methyl methacrylate), and polyethylene-b-polystyrene block copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 496–504, 2004     

Preparation of stable gold nanoparticles by using diblock copolymer mixture as encapsulating agent

Gold nanoparticles by using the mixture of polystyrene-block-poly(2-vinyl pyridine)/poly(2-vinyl pyridine)-block-poly(ethylene oxide) (PS-b-P2VP/P2VP-b-PEO) block copolymers as encapsulating agent was prepared. The prepared nanoparticles were characterized by transmission electron microscopy, UV-Vis spectroscopy and contact angle. It is demonstrated that the obtained gold nanoparticles are covered with mixed block copolymer shells. The hydrophilic property of the nanoparticles can be varied by the change of the dispersion medium. The obtained gold nanoparticles with mixed block copolymer shells are stable in organic solvents (such as tetrahydrofuran and toluene) and water.     

Novel synthesis of biodegradable poly(lactide-co-ethylene glycol) block copolymers

Biodegradable and amphiphilic diblock copolymers [polylactide-block-poly(ethylene glycol)] and triblock copolymers [polylactide-block-poly(ethylene glycol)-block-polylactide] were synthesized by the anionic ring-opening polymerization of lactides in the presence of poly(ethylene glycol) methyl ether or poly(ethylene glycol) and potassium hexamethyldisilazide as a catalyst. The polymerization in toluene at room temperature was very fast, yielding copolymers of controlled molecular weights and tailored molecular architectures. The chemical structure of the copolymers was investigated with ¹H and ¹³C NMR. The formation of block copolymers was confirmed by ¹³C NMR and differential scanning calorimetry investigations. The monomodal profile of the molecular weight distribution by gel permeation chromatography provided further evidence of block copolymer formation as well as the absence of cyclic species. Additional confirmation of the block copolymers was obtained by the substitution of 2-butanol for poly(ethylene glycol); butyl groups were clearly identified by ¹H NMR as polymer chain end groups. The effects of the copolymer composition and lactide stereochemistry on the copolymer properties were examined. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2235–2245, 2007     

Closed-Loop Phase Behavior and Baroplasticity of deuterated Polystyrene-block-Poly(n-pentyl methacrylate) Copolymer investigated by SANS and FTIR Spectroscopy

The closed-loop phase behavior of deuterated polystyrene-block-poly(n-pentyl methacrylate) copolymer (dPS-PnPMA) was investigated by small-angle neutron scattering (SANS) and temperature-dependent Fourier transform infrared (FT-IR) spectroscopy. The effect of hydrostatic pressure on the transition temperatures was studied by using SANS. We found that dPS-PnPMA has large pressure coefficients of transition temperatures (dT/dP = ±725 °C/kbar). Since this block copolymer exhibited excellent baroplastic property, it was easily molded into a desirable shape at a relatively low temperature under medium pressure. On the other hand, commercially available polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene copolymers were not molded at the same processing condition. Finally, we investigated the driving force inducing the closed-loop phase behavior by using temperature-dependent FT-IR.     

Synthesis of carbosilane block copolymers by means of a living anionic polymerization of 1,1-diethylsilacyclobutane

Block polymerization of 1,1-diethylsilacyclobutane with styrene derivatives and methacrylate derivatives was investigated. Sequential addition of styrene to a living poly(1,1-diethylsilabutane), which was prepared from phenyllithium and 1,1-diethylsilacyclobutane in THF–hexane at −48°C, gave poly(1,1-diethylsilabutane)-b-polystyrene. Similarly, addition of 4-(tert-butyldimethylsiloxy)styrene to the living poly(1,1-diethylsilabutane) provided poly(1,1-diethylsilabutane)-b-poly(4-(tert-butyldimethylsiloxy)styrene). Poly(1,1-diethylsilabutane)-b-poly(methyl methacrylate) was obtained by treatment of living poly(1,1-diethylsilabutane) with 1,1-diphenylethylene followed by an addition of methyl methacrylate. Poly(1,1-diethylsilabutane)-b-poly(2-(tert-butyldimethylsiloxy)ethyl methacrylate) was also synthesized by adding 2-(tert-butyldimethylsiloxy)ethyl methacrylate to the living poly(1,1-diethylsilabutane) which was end-capped with 1,1-diphenylethylene in the presence of lithium chloride. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2699–2706, 1998     

Meticulous Doxorubicin Release from pH-Responsive Nanoparticles Entrapped within an Injectable Thermoresponsive Depot

The dual stimuli-controlled release of doxorubicin from gel-embedded nanoparticles is reported. Non-cytotoxic polymer nanoparticles are formed from poly(ethylene glycol)-b-poly(benzyl glutamate) that, uniquely, contain a central ester link. This connection renders the nanoparticles pH-responsive, enabling extensive doxorubicin release in acidic solutions (pH 6.5), but not in solutions of physiological pH (pH 7.4). Doxorubicin-loaded nanoparticles were found to be stable for at least 31 days and lethal against the three breast cancer cell lines tested. Furthermore, doxorubicin-loaded nanoparticles could be incorporated within a thermoresponsive poly(2-hydroxypropyl methacrylate) gel depot, which forms immediately upon injection of poly(2-hydroxypropyl methacrylate) in dimethyl sulfoxide solution into aqueous solution. The combination of the poly(2-hydroxypropyl methacrylate) gel and poly(ethylene glycol)-b-poly(benzyl glutamate) nanoparticles yields an injectable doxorubicin delivery system that facilities near-complete drug release when maintained at elevated temperatures (37 °C) in acidic solution (pH 6.5). In contrast, negligible payload release occurs when the material is stored at room temperature in non-acidic solution (pH 7.4). The system has great potential as a vehicle for the prolonged, site-specific release of chemotherapeutics.     

Nanoparticle directed domain orientation in thin films of asymmetric block copolymers

We investigated the thin film morphology of two different asymmetric block copolymers (BCP), polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) and poly(n-pentyl methacrylate)-block-poly(methyl methacrylate) (PPMA-b-PMMA), loaded with pre-synthesized iron oxide nanoparticles (NP). The chemical composition of the BCP constituents determines the strength of the interaction between polymer chains and nanoparticles. In the case of NP/PS-b-P4VP system, the nanoparticles interact preferentially with the P4VP block and hence localize selectively in the P4VP cylindrical microdomains. However, for the NP/PPMA-b-PMMA system, the nanoparticles have no significant preference for the copolymer blocks and segregate at the polymer/substrate interface. Interestingly, this changes the effective substrate surface energy and hence leads to a remarkable change in domain orientation from parallel to perpendicular with respect to the substrate. These results clearly demonstrate the importance of both enthalpic and entropic factors which determine spatial distribution of NP in BCP films and influence domain orientation.     

Polymer Blend for Electrolyte and Electrode Coatings

Summary: The thermal and morphological properties of PEO/copolyether electrolyte and carbon black composite have been studied. A copolyether poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) was used at 20 wt.-% in relation to PEO in order the improve the carbon black dispersion through interaction with the amino end capped function. The polymer matrix presented semicrystalline structure and the addition of LiClO₄ and carbon black decreases significantly the crystallinity of the system. Sub-micrometric dispersion of carbon black was observed. The conductivity results as a function of temperature exhibited a typical VTF behaviour for the electrolyte. Almost constant conductivities of 2 × 10⁻⁴ S · cm⁻¹ were observed for the composite with 5 wt.-% of carbon black, in the range of temperature between 35 and 95 °C, which indicates a significantly contribution of electronic conduction.     

Morphology and photoluminescence study of titania nanoparticles

Titania nanoparticles are prepared by sol–gel chemistry with a poly(ethylene oxide) methyl ether methacrylate-block-poly(dimethylsiloxane)-block-poly(ethylene oxide) methyl ether methacrylate triblock copolymer acting as the templating agent. The sol–gel components—hydrochloric acid, titanium tetraisopropoxide, and triblock copolymer—are varied to investigate their effect on the resulting titania morphology. An increased titania precursor or polymer content yields smaller primary titania structures. Microbeam grazing incidence small-angle X-ray scattering measurements, which are analyzed with a unified fit model, reveal information about the titania structure sizes. These small structures could not be observed via the used microscopy techniques. The interplay among the sol–gel components via our triblock copolymer results in different sized titania nanoparticles with higher packing densities. Smaller sized titania particles, (∼13–20 nm in diameter) in the range of exciton diffusion length, are formed by 2% by weight polymer and show good crystallinity with less surface defects and high oxygen vacancies.     

Surface patterns of block copolymers in thin layers after vapor treatment

A systematic study of formation of surface patterns in block copolymer thin layers after their exposure to solvent vapors was performed. The studied effect involves layers of thickness approximately equal to the ordering size of polymers - about 45 nm. Experiments were performed on three styrene - methacrylate derivative block copolymers, synthesized by living anionic polymerization: poly(4-octylstyrene)-block-poly(butyl methacrylate), poly(4-fluorostyrene)-block-poly(butyl methacrylate) and poly(p-octylstyrene)-block-poly(methyl methacrylate). The polymers were exposed to vapors of chloroform, 1,4-dioxane, hexane, acetone and tetrahydrofuran.     

Semi‐micro reversed‐phase liquid chromatography for the separation of alkyl benzenes and proteins exploiting methacrylate‐ and polystyrene‐based monolithic columns

Monolithic columns were synthesized inside 1.02 mm internal diameter fused‐silica lined stainless‐steel tubing. Styrene and butyl, hexyl, lauryl, and glycidyl methacrylates were the functional monomers. Ethylene glycol dimethacrylate and divinylbenzene were the crosslinkers. The glycidyl methacrylate polymer was modified with gold nanoparticles and dodecanethiol (C₁₂). The separation of alkylbenzenes was investigated by isocratic elution in 60:40 v/v acetonitrile/water. The columns based on polystyrene‐co‐divinylbenzene and poly(glycidyl methacrylate)‐co‐ethylene glycol dimethacrylate modified with dodecanethiol did not provide any separation of alkyl benzenes. The poly(hexyl methacrylate)‐co‐ethylene glycol dimethacrylate and poly(lauryl methacrylate)‐co‐ethylene glycol dimethacrylate columns separated the alkyl benzenes with plate heights between 30 and 60 μm (50 μL min^?1 and 60°C). Similar efficiency was achieved in the poly(butyl methacrylate)‐co‐ethylene glycol dimethacrylate column, but only at 10 μL min^?1 (0.22 mm s^?1). Backpressures varied from 0.38 MPa in the hexyl methacrylate to 13.4 MPa in lauryl methacrylate columns (50 μL min^?1 and 60°C). Separation of proteins was achieved in all columns with different efficiencies. At 100 μL min^?1 and 60°C, the lauryl methacrylate columns provided the best separation, but their low permeability prevented high flow rates. Flow rates up to 500 μL min^?1 were possible in the styrene, butyl and hexyl methacrylate columns.     

A new way to the “knitting pattern” via blending of ABC triblock copolymers

The “knitting pattern” morphology was obtained via blending of two polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock copolymers. This demonstrates that blending of block copolymers is a useful way to design periodic superstructures by taking advantage of the self-assembling nature of microphase separated block copolymers.     

Synthesis of Amphiphilic ABCBA-Type Pentablock Copolymer from Consecutive ATRPs and Self-Assembly in Aqueous Solution

Summary: A novel amphiphilic ABCBA-type pentablock copolymer with properties that are sensitive to temperature and pH, poly(2-dimethylaminoethyl methacrylate)-block-poly(2,2,2-trifluoroethyl methacrylate)-block-poly(ε-caprolactone)-block-poly(2,2,2- trifluoroethyl methacrylate)-block-poly(2-dimethylaminoethyl methacrylate) (PDMAEMA- b-PTFEMA-b-PCL-b-PTFEMA-b-PDMAEMA), was synthesized via consecutive atom transfer radical polymerizations (ATRPs). The copolymers obtained were characterized by gel permeation chromatography (GPC) and ¹H nuclear magnetic resonance (NMR) spectroscopy, respectively. The aggregation behaviors of the pentablock copolymers in aqueous solution with different pH (pH = 4.0, 7.0 and 8.5) were studied. Transmission electron microscopic images revealed that spherical micelles from self-assembly of the pentablock copolymer were prevalent in all cases. The mean diameters of these micelles increased from 34, 46, to 119 nm when the pH of the aqueous solution decreased from 8.5, 7.0, to 4.0, respectively.     

Synthesis of rod-coil block copolymers via end-functionalized poly(p-phenylene)s

This paper describes a new way to synthesize rod-coil block copolymers consisting of poly(p-phenylene) (PPP) as rigid rod and either polystyrene (PS) or poly(ethylene oxide) (PEO) as flexible coil. The Suzuki-coupling of the AB-type monomer 4-bromo-2,5-diheptylbenzeneboronic acid (1) under strictly proton-free conditions leads to the control of PPP endgroups and hence allows the synthesis of a variety of differently end-functionalized poly(p-phenylene)s. The poly(2,5-diheptyl-p-phenylene)-block-polystyrene (7) is then prepared via condensation via condensation of anionically polymerized living polystyrene ( 6 ) with α-(4-formylphenyl)-ω-phenyl-poly(2,5diheptyl-p-phenylene) ( 4 ). Toluenesulfonic acid catalyzed condensation of α-methyl-ω-amino-poly(oxyethylene) ( 8 ) with PPP 4 yields poly(2,5-diheptyl-p-phenylene)-block-poly(ethylene oxide) ( 9 ).     

Effects of poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer on the spinodal decomposition of corresponding homopolymer blends

Effects of adding a small amount of poly(methyl methacrylate)-block-poly(vinyl acetate) (PMMA-b-PVAc) to poly(methyl methacrylate)/poly(vinyl acetate) (PMMA/PVAc) blends with a lower critical solution temperature (LCST) phase diagram on the kinetics of late-stage spinodal decomposition (SD) were investigated by time-resolved light scattering at 160°C. It is found that the coarsening process of the structure was slowed down or accelerated upon addition of PMMA-b-PVAc depending on the composition of the block copolymer and the blend. The effect of the block copolymer on the domain size were interpreted as compatibilizing and incompatibilizing effects of the block copolymer on PMMA/PVAc blends based on the evaluation of changes in the stability limits of PMMA/PVAc with the addition of block copolymer using random phase approximation (RPA).     

Poly(methyl methacrylate) dispersions in decane stabilized by a diblock copolymer

In a dispersion polymerization, the monomer is miscible with the reaction medium, while the resulting polymer is insoluble under the same conditions. The macroscopic precipitation of the polymer is prevented by a steric stabilizer. Methyl methacrylate was polymerized in decane in presence of polystyrene-block-poly(ethylene-co-propylene) and spherical dispersion particles of poly(methyl methacrylate) (PMMA) were obtained. The static light scattering yielded molar masses of particles in the range 4 × 10⁷ to 7 × 10⁹ g mol⁻¹. Dynamic light scattering provided the hydrodynamic radii from 60 to 190 nm and also information on the non-uniformity of the particles. The relations between the characteristics of the dispersion particles (concentration of components, particle mass and dimensions, molar mass of PMMA chains, surface density of stabilizing chains, etc.) were looked for. The kinetics of polymerization seems to be only little affected by the colloidal character of the system.     

Nickel-Impregnated Silica Nanoparticle Synthesis and Their Evaluation for Biocatalyst Immobilization

In the present investigation, impact of nickel-impregnated silica paramagnetic particles (NSP) as biocatalyst immobilization matrices was investigated. These nanoparticles were synthesized by sol–gel route using a nonionic surfactant block co polymer [poly (ethylene glycol)-block-poly-(propylene glycol)-block-poly (ethylene glycol)]. Diastase enzyme was immobilized on these particles (enzyme-impregnated NSP) as model enzyme and characterized using Fourier-transform infrared spectroscopy and X-ray crystallography. Analysis of enzyme-binding nature with these nanoparticles at different physiological conditions revealed that binding pattern and activity profile varied with the pH of the reaction mixture. The immobilized enzyme was further characterized for its biocatalytic activity with respect to kinetic properties such as Km and Vmax and compared with free enzyme. Paramagnetic nanoparticle-immobilized enzyme showed more affinity for substrate compared to free one. The nature of silica and nickel varied from amorphous to crystalline nature and vice versa upon immobilization of enzyme. To the best of our knowledge, this is the first report of its kind for change of nature from one form to other under normal temperatures upon diastase interaction with NSP.     

Formation of block copolymer micelles in solutions of a linear homopolymer in a good solvent

The existence of micelles of polystyrene-block-poly(ethylene/propene) in solutions of polystyrene in toluene was investigated. Toluene is a good solvent of both copolymer blocks whereas polystyrene and poly(ethylene/propene) are immiscible polymers. The presence of homopolystyrene at high enough concentration can induce the micellization of polystyrene-block-poly(ethylene/propene) in solution of a good solvent such as toluene. The thermodynamics of this new micelle system at a given polystyrene concentration was studied. Light scattering measurements were carried out in order to determine the critical micelle temperature (CMT) of different micellar solutions. Standard Gibbs energy, enthalpy and entropy of micellization were estimated from CMT and concentration data. The numerical values found were less negative than those found for micelle systems consisting in a block copolymer dissolved in a single selective solvent.