Tert-butyl Methacrylate Research Articles

Multivariate analysis of 13C NMR spectra of methacrylate copolymers and homopolymer blends

13C NMR spectra of copolymers of methyl methacrylate and tert-butyl methacrylate with various chemical compositions, the homopolymers of the two methacrylates, and blends of the homopolymers with various blend ratios were subjected to principal component analysis. The first and second principal components correlated chemical composition and the randomness of comonomer sequence, respectively. Chemical composition of the copolymers was determined with high accuracy and precision by the partial least-squares regression without assignment of individual resonance peaks.

Alignment of Tellurium Nanorods via a Magnetization−Alignment− Demagnetization (“MAD”) Process Assisted by an External Magnetic Field

Tellurium (Te) nanorods have been successfully aligned on a solid substrate via a magnetization-alignment-demagnetization ("MAD") process in the presence of an external magnetic field. Te nanorods carrying a poly(tert-butyl methacrylate) shell were first converted into magnetic nanocylinders by assembling magnetite nanoparticles on their surface via a hydrophobic interaction in THF. We demonstrate that, below a critical concentration of the nanoparticles, this assembly process is able to quantitatively tune the magnetite nanoparticles' density on the nanorods in terms of their stoichiometric ratio. Due to the polymer and surfactant on their surface, the formed magnetic nanocylinders are soluble in THF and aligned when dried on a solid substrate in the presence of an external magnetic field. The demagnetization of the prealigned nanocylinders was achieved via an acid-etching process, leaving Te nanorods in an aligned state. This MAD process can be extended as a general procedure for other nonmagnetic 1-D nanostructures. Additionally, the nonetched magnetic nanocylinders can be potentially applied in field of magnetorheology.

Multicompartment Core Micelles of Triblock Terpolymers in Organic Media

The formation of multicompartment micelles featuring a “spheres on sphere” core morphology in acetone as a selective solvent is presented. The polymers investigated are ABC triblock terpolymers, polybutadiene-b-poly(2-vinyl pyridine)-b-poly(tert-butyl methacrylate) (BVT), which were synthesized via living sequential anionic polymerization in THF. Two polymers with different block lengths of the methacrylate moiety were studied with respect to the formation of multicompartmental aggregates. The micelles were analyzed by static and dynamic light scattering as well as by transmission electron microscopy. Cross-linking of the polybutadiene compartment could be accomplished via two different methods, “cold vulcanization” and with photopolymerization after the addition of a multifunctional acrylate. In both cases, the multicompartmental character of the micellar core is fully preserved, and the micelles could be transformed into core-stabilized nanoparticles. The successful cross-linking of the polybutadiene core is indicated by 1H NMR and by the transfer of the aggregates into nonselective solvents such as THF or dioxane.

Thermal degradation of a heteroarm starlike polymer with fullerene C60 core

The mechanism of thermal degradation of a 12-arm starlike polymer with fullerene C60 core and equal number of polystyrene and poly(tert-butyl methacrylate) arms was studied by thermal desorption mass spectrometry. Thermal characteristics of the heteroarm stars were compared with those of six-arm starlike fullerene-containing polystyrenes and linear poly(tert-butyl methacrylate).

Undulated Multicompartment Cylinders by the Controlled and Directed Stacking of Polymer Micelles with a Compartmentalized Corona

Like a bamboo rod: Long, bamboo-like undulated cylinders with distinct branch points and end groups (see picture) were obtained by the stacking of block terpolymer micelles that contain a fluorinated polybutadiene core and a compartmentalized corona of poly(4-tert-butoxystyrene) and poly(tert-butyl methacrylate). Stacking of the polymer micelles, which can be reversed, occurred when the solvent was changed from dioxane to ethanol.

Combination of “living” nitroxide-mediated and photoiniferter-induced “grafting from” free-radical polymerizations: From branched copolymers to unimolecular micelles and microgels

We report on solution properties of lightly grafted copolymers composed of polystyrene (PS) backbone (degree of polymerization of PS backbone, N b = 95 ) and variable length of poly( tert-butyl methacrylate) P( tBuMA) side chains (degree of polymerization of side chains, N sc = 14 – 222 ) at fixed number of grafting sites n = 11 and polydispersity index ( M w / M n ) ranging from 1.05 to 2.63. Synthesis of these graft copolymers is based on a novel synthetic route [Gromadzki D, Makuška R, Netopilík M, Holler P, Lokaj J, Janata M, et al. Eur Polym J 2008;44:59–71] involving two independent controlled/“living” polymerization mechanisms, namely nitroxide-mediated radical polymerization (NMP) for the synthesis of the backbone and photoinduced “grafting from” iniferter process for building of P( tBuMA) branches. The viscosity-related contraction factors g ′ < 1 confirmed high degree of branching of the studied graft copolymers. Dilute solutions of graft copolymers in non-selective solvent (THF), examined by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS) and viscometry, revealed a transition from comb-like conformation through wormlike-star to a microgel architecture under increasing number of monomeric units in side chains. These data were further supported by the structure factors R η / R h and R g / R h obtained by independent measurements and extrapolated to infinite dilution. Persistence lengths of the samples exhibiting comb-like topology were larger compared to linear polystyrene backbone and P( tBuMA) side chains in THF suggesting stiffening of the main chain with increasing size of the attached side chains. Unimolecular micelles were detected by DLS and SAXS in solvent selective for grafts, tert-amyl alcohol.

PH-Responsive Supramolecular Self-Assembly of Well-Defined Zwitterionic ABC Miktoarm Star Terpolymers

We report the first example of the synthesis and pH-responsive supramolecular self-assembly of double hydrophilic ABC miktoarm star terpolymers. Well-defined ABC miktoarm star terpolymers consisting of poly(ethylene glycol), poly(tert-butyl methacrylate), and poly(2-(diethylamino)ethyl methacrylate) arms [PEG(-b-PtBMA)-b-PDEA] were synthesized via the combination of consecutive click reactions and atom transfer radical polymerization (ATRP), starting from a trifunctional core molecule, 1-azido-3-chloro-2-propanol (ACP). The click reaction of monoalkynyl-terminated PEG with an excess of ACP afforded difunctional PEG bearing a chlorine and a secondary hydroxyl moiety at the chain end, PEG113(-Cl)-OH (1). After azidation with NaN3, PEG-based macroinitiator PEG113(-N3)-Br (3) was prepared by the esterification of PEG113(-N3)-OH (2) with 2-bromoisobutyryl bromide and then employed in the ATRP of tert-butyl methacrylate (tBMA). The obtained PEG(-N3)-b-PtBMA copolymers (4) possessed an azido moiety at the diblock junction point. The preparation of PEG(-b-PtBMA)-b-PDEA miktoarm star terpolymers was then achieved via the click reaction of 4 with an excess of monoalkynyl-terminated PDEA. The obtained miktoarm star terpolymers were successfully converted into PEG(-b-PMAA)-b-PDEA, where PMAA is poly(methacrylic acid). In aqueous solution, PEG(-b-PMAA)-b-PDEA zwitterionic ABC miktoarm star terpolymers can self-assemble into three types of micellar aggregates by simply adjusting solution pH at room temperature. Above pH 8, PDEA-core micelles stabilized by PEG/ionized PMAA hybrid coronas were formed due to the insolubility of PDEA block. In the range of pH 5-7, micelles possessing polyion complex cores formed as a result of charge compensation between partially ionized PMAA and partially protonated PDEA sequences. At pH<4, hydrogen bonding interactions between fully protonated PMAA and PEG led to the formation of another type of micellar aggregates possessing hydrogen-bonded complex cores stabilized by protonated PDEA coronas. The fully reversible pH-responsive formation of three types of aggregates were characterized by 1H NMR, dynamic and static laser light scattering (LLS), and transmission electron microscopy (TEM).

Controllable Formation of Nanorods through Electrostatic-Assisted Assembly of Star Poly(methacrylic acid) Induced by Surfactants

Star poly(methacrylic acid) (Star-(PMAA)6) was prepared by hydrolysis of star poly(tert-butyl methacrylate) (Star-(PtBMA)6). The self-assembly behaviors of Star-(PMAA)6 induced by surfactant hexadecyl pyridinium chloride (HDPC) were investigated. It is of great interest that rodlike aggregates with different lengths and diameters could be obtained from the complexation of Star-(PMAA)6 and HDPC by adjusting the length of the polymer arm and the ratio of [HDPC]/[carboxyl group] in the system. The self-assembly mechanisms for the formation of rodlike aggregates were discussed.

Structured and Gradient Polymer Brushes from Biphenylthiol Self-Assembled Monolayers by Self-Initiated Photografting and Photopolymerization (SIPGP)

The self-initiated photografting and photopolymerization (SIPGP) of styrene, methyl methacrylate, and tert-butyl methacrylate on structured self-assembled monolayers (SAMs) of electron beam cross-linked omega-functionalized biphenylthiols SAMs on gold was investigated. Polymer brushes with defined thickness can be prepared on crosslinked benzyl-, phenyl-, hydroxyl-, and amino-functionalized SAMs, whereas non-cross-linked SAM regions desorb from the surface during the SIPGP process. By the preparation of brush gradients on different functionalized SAMs, it was demonstrated that the resulting polymer brush layer thickness is determined by the locally applied electron beam dosage. Defined micro-nanostructured polymer brush patterns can be prepared down to a size of 50 nm. Finally, it was shown that polymer brushes obtained by the SIPGP process have a branched architecture.

Chain-Length-Dependent Termination in n-Butyl Methacrylate and tert-Butyl Methacrylate Bulk Homopolymerizations Studied via SP-PLP-ESR

The chain-length dependence of the termination rate coefficient, kt, of bulk homopolymerizations of n-butyl methacrylate (n-BMA) and tert-butyl methacrylate (t-BMA) at ambient pressure and temperatures between −30 and 60 °C has been studied via the single pulse−pulsed laser polymerization−electron spin resonance (SP-PLP-ESR) technique. The decay of radical concentration, cR, after laser SP initiation is monitored with a high time resolution of microseconds by ESR spectroscopy. Radical chain length, i, increases linearly with time t after applying the laser pulse. The experimental kti,i values refer to rate coefficients for termination of two radicals of identical chain length i. The variation of kti,i with chain length is adequately represented via the composite model proposed by Smith et al., in which two power-law expressions, kti,i ∝ i−α, are contained with the exponents αs and αl referring to short-chain and long-chain radicals, respectively. The transition between the two regimes occurs at the crosso...

Wettability of Methacrylate Copolymer Films Deposited on Anodically Oxidized and Roughened Aluminium Surfaces

The wetting behavior of water on methacrylate copolymer films was studied on anodically oxidized and micro-roughened aluminium surfaces and also on smooth model surfaces. The copolymerization of tert-butyl methacrylate with a methacrylate containing a fluoroorganic side chain led to a considerable decrease of the surface free energy, but not to a superhydrophobic behavior of polymer-coated, micro-roughened aluminium surfaces. However, copolymers containing both hydrophobic and hydrophilic sequences are able to form superhydrophobic films. X-ray photoelectron spectroscopy showed that an enrichment of the interface between the solid phase and the air by fluorine-containing polymer components was the reason for the strong decrease of the surface free energy. The hydrophilic segments of the copolymers improved the ability to wet the highly polar aluminium surface and to form films of higher density.

Amphiphilic block copolymers bearing strong push–pull azo chromophores: Synthesis, micelle formation and photoinduced shape deformation

In this work, a series of amphiphilic diblock copolymers bearing strong push–pull type azo chromophores was synthesized through post-polymerization azo-coupling reaction scheme. The copolymers (P(CNAZOm-b-MAAn)), composed of 2-(N-ethyl-N-(4-(4′-cyanophenylazo)-phenyl)amino)ethyl methacrylate (CNAZO) and methacrylic acid (MAA) blocks, were obtained through four-step reactions. Firstly, precursor diblock copolymers (P(EMAm-b-tBMAn)) were obtained through sequential two-stage ATRP reactions of 2-(N-ethyl-N-phenylamino)ethyl methacrylate (EMA) and tert-butyl methacrylate (tBMA). Then, 4-amino-4′-cyanoazobenzene chromophores were introduced by azo-coupling reaction of P(EMAm-b-tBMAn) with diazonium salt of 4-aminobenzonitrile. Finally, P(CNAZOm-b-MAAn) was obtained through selective hydrolysis of the tert-butyl ester linkages in the tBMA blocks. Three block copolymers with the same CNAZO block length (m=100) and different MAA block lengths (n=5, 13, 23) were prepared by this method. The polymer and copolymers prepared in the process were characterized by GPC, 1H NMR, UV–vis, DSC and TGA measurements. Results show that P(CNAZOm-b-MAAn) forms spherical micellar aggregates by gradually increasing the water content in THF/H2O mixtures. The diameters of the spherical aggregates are related to the composition of the block copolymers and the water-adding rate. The block copolymer with larger molecular weight of the hydrophilic MAA block forms the aggregates with the smaller average size. The increase of the water-adding rate also shows an effect to reduce the diameters. Upon irradiation with a linearly polarized Ar+ laser beam, the spherical aggregates can be elongated in the light polarization direction. The deformation degree shows an almost linear dependence on the light irradiation time in the testing period. The deformed aggregates can recover the original spherical shape after thermal annealing at a temperature above Tg of the block copolymer.

Tuning Micellization and Dissociation Transitions of Thermo- and pH-Sensitive Poly(ethylene oxide)-b-poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid) in Aqueous Solution by Combining Temperature and pH Triggers

We report in this article on the active control of multiple micellization and dissociation transitions of thermo- and pH-sensitive water-soluble block copolymers, poly(ethylene oxide)-b-poly(methoxydi(ethylene glycol) methacrylate-co-methacrylic acid) (PEO-b-P(DEGMMA-co-MAA)), in aqueous solutions by combining temperature and pH triggers. Two block copolymers and one random copolymer P(DEGMMA-co-MAA) were prepared by atom transfer radical polymerization of a mixture of methoxydi(ethylene glycol) methacrylate (DEGMMA) and tert-butyl methacrylate (t-BMA) with a molar ratio of 100: 13 from a PEO macroinitiator and a small molecule initiator, respectively, and subsequent removal of t-butyl group. PDEGMMA is a thermosensitive water-soluble polymer exhibiting a lower critical solution temperature in water at 25 °C. The cloud point of P(DEGMMA-co-MAA) in water can be readily tuned from 24 to 60 °C by changing the solution pH. The block copolymers dissolved molecularly in cold aqueous buffer solutions with a pH o...

&lt;em&gt;Vibrio fischeri&lt;/em&gt; and &lt;em&gt;Escherichia coli&lt;/em&gt; adhesion tendencies towards photolithographically modified nanosmooth poly (&lt;em&gt;tert&lt;/em&gt;-butyl methacrylate) polymer surfaces

This study reports the adhesion behavior of two bacterial species, Vibrio fischeri and Escherichia coli, to the photoresistant poly(tert-butyl methacrylate) (P(tBMA)) polymer surface. The data has demonstrated that ultraviolet irradiation of P(tBMA) was able to provide control over bacterial adhesion tendencies. Following photolithography, several of the surface characteristics of P(tBMA) were found to be altered. Atomic force microscopy analysis indicated that photolithographically modified P(tBMA) (henceforth termed 'modified polymer') appeared as a 'nanosmooth' surface with an average surface roughness of 1.6 nm. Although confocal laser scanning microscopy and scanning electron microscopy analysis clearly demonstrated that V. fischeri and E. coli presented largely different patterns of attachment in order to adhere to the same surfaces, both species exhibited a greater adhesion propensity towards the 'nanosmooth' surface. The adhesion of both species to the modified polymer surface appeared to be facilitated by an elevated production of extracellular polymeric substances when in contact with the substrate.

Integral Geometry Analysis of Fluorescence Micrographs for Quantitative Relative Comparison of Protein Adsorption onto Polymer Surfaces

Most methods developed to study protein binding to distinct surfaces can only determine the average amount of adsorbed protein or merely provide (qualitative) information on its spatial distribution. Both these features can be characterized rigorously by integral geometry analysis of fluorescence micrographs. This approach is introduced here to compare the relative protein adsorption onto various polymer surfaces: polystyrene (PS), poly(methyl methacrylate) (PMMA), poly( n-butyl methacrylate) (PnBMA), poly( tert-butyl methacrylate) (PtBMA), and PS(PETA) and cross-linked poly(ethylene oxide) (PEO*(PETA)), admixed with pentaerythritol triacrylate (PETA). The polymeric surfaces were incubated for 15 min in phosphate-buffered saline (pH 7.4) containing 125 mug/mL fluorescently labeled lectins, either lentil lectin (LcH) or concanavalin A (ConA). Fluorescence images were recorded at identical conditions (physiological buffer, same exposure time, magnification, gain). For each image, taken a few times for each polymer, the distribution and average value of the normalized intensity were determined. The results show that the binding of LcH to PS(PETA), PtBMA, PS, PnBMA, PMMA, and PEO*(PETA) can be expressed by the ratio of the following values (mean +/- 95% confidence interval): 0.356 +/- 0.022, 0.298 +/- 0.030, 0.241 +/- 0.014, 0.083 +/- 0.008, 0.039 +/- 0.008, and 0.010 +/- 0.006, respectively. In turn, the relative adsorption of ConA is described by the values 0.252 +/- 0.016, 0.217 +/- 0.014, 0.222 +/- 0.016, 0.046 +/- 0.006, 0.116 +/- 0.008, and 0.006 +/- 0.002, respectively. Low dispersions of fluorescence intensity around average values indicate homogeneous distribution of adsorbed proteins. The introduced approach enables a fast and easy way not only to quantify the relative amount of bound proteins but also to characterize quantitatively the organization of their surface distribution, as demonstrated for patchlike protein adsorption onto the polymer blend surface.

Joint Theoretical Experimental Investigation of the Electron Spin Resonance Spectra of Nitroxyl Radicals: Application to Intermediates in in Situ Nitroxide Mediated Polymerization (in Situ NMP) of Vinyl Monomers

Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-phenyl- N- tert-butylnitrone and AIBN, (b) N- tert-butyl-alpha-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.

Controlled crosslinking of polybutadiene containing block terpolymer bulk structures: A facile way towards complex and functional nanostructures

The controlled crosslinking of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (SBT) block terpolymers in their microphase-segregated bulk state is investigated. Two different methods, cold vulcanization and free radical crosslinking as well as its optimized procedure, the thiol–polyene method, are applied for crosslinking the lamellar polybutadiene microdomains within the lamella–lamella (ll) morphology of SBT bulk structures. It was found that the microphase-separated structures of the block terpolymers react very sensitively towards the addition of swelling solvents and crosslinking agents. The changes in the microphase-segregated morphologies are followed at all stages with transmission electron microscopy to give an in-depth view of the nanoscopic transformations. These partially unexpected changes in the morphologies make a careful adjustment and optimization of the reaction conditions necessary. For cold vulcanization, i.e. the reaction of double bonds with sulphur monochloride, several swelling solvents and concentrations of crosslinking agents are explored. In the case of free radical crosslinking, it is found that an increase of the radical initiator concentration above 5wt% does not lead to an increase of insoluble material as radical chain cleavages occur as side reactions, thus limiting the amount of the desired gel fraction. However, the addition of a trifunctional thiol can further increase the desired network formation. By means of this procedure and a subsequent homogenization, it is possible to create novel disc-like Janus particles. Dynamic light scattering and scanning force microscopy are used to highlight the flat nanoparticle structure and to demonstrate the influence of the crosslinker on the formed structures.

Staleya guttiformis attachment on poly( tert-butylmethacrylate) polymeric surfaces

The attachment behaviour of Staleya guttiformis DSM 11458 T on poly( tert-butyl methacrylate) (P( tBMA)) polymeric surfaces has been studied. The electrostatic charge of the S. guttiformis cell surface (measured as zeta potential via microelectrophoresis) was −43.18 mV. S. guttiformis cells appeared weakly hydrophilic as the water contact angle measured on lawns of bacterial cells was found to be 55 ± 4.9°. It was found that while attaching on P( tBMA) surfaces, S. guttiformis cells produced extracellular polymeric substances (EPS) as observed from atomic force microscopy (AFM) and scanning electron microscopy (SEM) analysis. The AFM high resolution imaging revealed the nano-topography of the ‘free’ (the EPS that is produced by the bacterial cells, but no longer directly attached to the cells) EPS associated on the cell surface and also found on P( tBMA) surface. The ‘free’ EPS exhibited granular structure with lateral dimensions of 30–50 nm and a vertical nano-roughness of 7–10 nm. Another type of the EPS secreted by S. guttiformis cells appeared as a hydogel substance, presumably polysaccharide that formed a biopolymer network that facilitated bacterial attachment.

Facile synthesis of diphenylethylene end-functional polyisobutylene and its applications for the synthesis of block copolymers containing poly(methacrylate)s

The convenient synthesis of methoxy-free 1,1-diphenylethylene end-functionalized polyisobutylene (PIB–DPE) has been accomplished by capping living PIB with 1,4-bis(1-phenylethenyl)benzene, followed by hydride transfer reaction with tributylsilane. The proposed method eliminates the need for methylation of the capped living PIB in which large excess of dimethylzinc must be used, resulting in a large amount of inorganic salt contamination. The obtained PIB–DPE was quantitatively lithiated with 1.5-fold excess n-butyllithium in tetrahydrofuran (THF) at room temperature. The methine proton at the chain end remained intact during the lithiation procedure. The resulting macroanion efficiently initiated the polymerization of alkyl methacrylates. Poly(methyl methacrylate) (PMMA)-b-PIB-b-PMMA, poly(2-hydroxyethyl methacrylate) (PHEMA)-b-PIB-b-PHEMA and poly(tert-butyl methacrylate) (PtBMA)-b-PIB-b-PtBMA have been prepared with high blocking efficiency by the proposed methodology. Complete hydrolysis of PtBMA-b-PIB-b-PtBMA into poly(methacrylic acid) (PMAA)-b-PIB-b-PMAA was realized in THF/1,4-dioxane, as confirmed by FTIR, 1H NMR, and DSC analyses.

Comb copolymers of polystyrene-poly( tert-butyl (meth)acrylate) prepared by combination of nitroxide mediated polymerization and photoinduced iniferter technique

Comb copolymers consisting of polystyrene backbone and poly( tert-butyl (meth)acrylate) side chains were synthesized by combination of nitroxide (TEMPO)-mediated polymerization (NMP) and photoinduced grafting from macro-iniferters. First, poly(chloromethylstyrene), PCMS, with the degree of polymerization DP n ¯ ≈ 200 and two random poly(styrene- co-chloromethylstyrene) copolymers, P(S- co-CMS), with similar DP n ¯ ≈ 75 but different content (8 and 14 mol%) of CMS units, were synthesized by NMP. In the second step the CMS units both in the homopolymer and the copolymers were converted to N, N-diethyldithiocarbamyl groups (DC) yielding photosensitive multifunctional macro-iniferters. Finally, tert-butyl methacrylate tBuMA was grafted from the synthesized polymer backbones by iniferter technique under UV-irradiation yielding copolymers polystyrene- graft-poly( tert-butyl methacrylate) PS- g-P( tBuMA). Grafting initiated by the macro-iniferters containing ∼6–11 DC initiating sites per macromolecule proceeded by pseudo-living polymerization mechanism, i.e., the number-average molecular weight increased with conversion and the SEC traces were unimodal. In contrast, photo-polymerization initiated by highly functionalized polystyrene backbone was poorly controlled. Hydrolysis of loosely grafted copolymers PS- g-P( tBuMA) afforded amphiphilic copolymers polystyrene- graft-poly(methacrylic acid). Molecular parameters of the synthesized graft copolymers in dilute THF solutions were determined by scattering (DLS, SLS, SAXS) and viscometric measurements.