Preparation and characterization of fluorine-containing acrylate copolymers by Co γ-ray radiation co-polymerization

A series of fluorine-containing acrylate copolymers were prepared by ⁶⁰Co γ-ray radiation co-polymerization in a mixed acrylate system, including butyl acrylate, acrylic acid, acrylonitrile, N-hydroxymethyl acrylamide and perfluoroalkylethyl methacrylate (FMA). The yield of the copolymers reached 96% when they were radiated for 34 h with the radiation dose of 1 kGy/h. Moreover, the surface structure and properties of the copolymers were determined by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and contact angle (CA) analysis. And the glass-transition temperature was measured by dynamic mechanical thermal analysis (DMTA). It was found that the fluoropolymer was of large water static contact angle and fluorine was enriched at the polymer-air interface. The relationship between the copolymer composition, annealed temperature and static contact angle was also discussed in detail. Furthermore, when the FMA content reached 3%, the cotton treated with our products exhibited better oil repellency.     

Synthesis and properties of poly(aryl ether benzimidazole) copolymers for high-temperature fuel cell membranes

A series of poly(aryl ether benzimidazole) copolymers bearing different aryl ether linkage contents were synthesized by condensation polymerization in polyphosphoric acid (PPA) by varying the feed ratio of 4,4′-dicarboxydiphenyl ether (DCPE) to terephthalic acid (TA). As the ether unit content in the copolymer increased, the solubility of the copolymer in PPA and N,N′-dimethylacetamide/LiCl improved. For example 3–7 wt.% DMAc solution containing 2 wt.% of LiCl could be prepared from the copolymers. XRD studies revealed that the incorporation of flexible aryl ether linkages increased the chain d-spacings of the polymer backbones and decreased the crystallinity of the copolymers. Still, these copolymers having ether linkages showed reasonably good thermal/mechanical stability and high proton conductivity. For example, the copolymer with 30 mol% ether linkage had a tensile strength of 43 MPa (at 26 °C and 40% relative humidity) at an acid doping level of 7.5 mol H₃PO₄ and a proton conductivity of 0.098 S cm⁻¹ (at 180 °C and 0% relative humidity) at an acid doping level of 6.6 mol H₃PO₄.     

Breadth of glass transition temperature in styrene/acrylic acid block,random, and gradient copolymers: Unusual sequence distribution effects

Block, random, and gradient copolymers of styrene (S) and acrylic acid (AA) are synthesized by conventional or controlled radical polymerization, and their glass transition temperature (T_g) behaviors are compared. The location and breadth of the T_gs are determined using derivatives of differential scanning calorimetry heating curves. Each S/AA random copolymer exhibits one narrow T_g, consistent with a single phase of limited compositional nanoheterogeneity. Block copolymers exhibit two narrow T_gs originating from nanophase separation into ordered domains with nearly pure S or nearly pure AA repeat units. Each gradient copolymer exhibits a T_g response with a ～50–56 °C breadth that extends beyond the upper T_g of the block copolymers. For copolymers of similar composition, the maximum value in the gradient copolymer T_g response is consistent with that of a random copolymer, which has an enhanced T_g relative to poly(acrylic acid) due to more effective hydrogen bonding when AA units are separated along the chain backbone by S units. These results indicate that gradient copolymers with ordered nanostructures can be rationally designed, which exhibit broad glass transitions that extend to higher temperature than the T_gs observed with block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2842–2849, 2007     

Morphology of polystyrene-block-poly(styrene-co-acrylonitrile) and polystyrene-block-poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) diblock copolymers prepared by nitroxide-mediated radical polymerization and “click” chemistry

Well-defined polystyrene-block-poly(styrene-co-acrylonitrile) PS-block-P(S-co-AN) and poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) PS-block-P(S-co-AN-co-5VT) block copolymers with various content of acrylonitrile units in the statistical block were synthesized by nitroxide mediated radical polymerization (NMRP) and post-functionalized using efficient “click” chemistry process. In the second step, acrylonitrile units were successfully modified using 1,3-dipolar cycloaddition (“click” chemistry) type polymer analogue reaction. The original pristine diblock copolymers can be molecularly dissolved in THF and dioxane while the “tetrazolated” versions aggregate to clusters as determined by dynamic light scattering (DLS). Small-angle X-ray scattering (SAXS) and Transmission Electron Microscopy (TEM) revealed ordered lamellar morphology with interlamellar spacing d = 60 nm increasing to d = 80 nm for “tetrazolated” diblock copolymers. The morphological features of diblock copolymer thin layers observed by Atomic Force Microscopy (AFM) depend on the tunable content of both acrylonitrile and 5-vinyltetrazole units and on the quality (polarity) of the solvents used.     

Supramolecular structures from self-assembled poly(γ-benzyl-l-glutamate)-polydimethylsiloxane-poly(γ-benzyl-l-glutamate) triblock copolypeptides in thin films

We describe the self-assembly of A-B-A triblock copolymers in thin films composed of a soft polydimethylsiloxane (PDMS) central block (B) and two polypeptidic (A) blocks, poly(γ-benzyl)-l-glutamate (PBLG). The PBLG segment exhibits depending on the chain length two distinct secondary conformations either a β-sheet or a α-helical conformation. The direct relationship between the surface morphology and the secondary conformation of the polypeptide segment has been evidenced by atomic force microscopy. For chain lengths below 20 U the polypeptide segments adopt preferentially a β-sheet secondary structure and the triblock copolymer self-assembled in fibers. Moreover, the fiber diameters increased with the chain length of the triblock copolymer. For chain lengths above 20, the α-helical structure is stabilized and a lamellar morphology is formed driven by rod-rod interactions in spite of the very asymmetric composition of the triblock copolymer. However, decreasing the film thickness from 25 to 8 nm, i.e., below the L/2 and due to the preferential attraction of the polypeptide block for the hydrophilic substrate employed, instead of a lamellar morphology a rod-like morphology could be found. Thus, the use of hybrid block copolymer containing polypeptides with particular secondary structures offers novel alternatives to control the self-assembly in thin films compared to traditional amorphous block copolymers.     

Studies on the photophysical characteristics of poly(carboxylic acid)s bound protoporphyrin IX and metal complexes of protoporphyrin IX

The copolymers of methacrylic acid with protoporphyrin IX (PPIX) and the metal complexes, zinc protoporphyrin IX and magnesium protoporphyrin IX were synthesised and characterised. Corresponding acrylic acid copolymers were also synthesised. The steady state absorption and fluorescence spectral properties of the macromolecular bound fluorophores PPIX, Zn-PPIX and Mg-PPIX were investigated. Poly(methacrylic acid) bound protoporphyrin IX, zinc protoporphyrin IX and magnesium protoporphyrin IX show an increase in the fluorescence intensity and lifetime with increase in the pH in the range 2-8 with a marked transition around pH 6.0-7.0. The fluorophore concentration in the dilute solution of the copolymers is micromolar and the fluorophore to the carboxylic acid monomer ratios in the copolymer is around 10⁻³. The molecular weight of the copolymers is 100 ± 10 kD. The fluorescence decay curves of all the fluorophore bound polymers follow biexponential decay fit independent of pH. Poly(MAA-co-PPIX) and poly(MAA-co-MgPPIX) undergo well marked pH induced structural transitions in the pH range of 6.0-7.0 whereas poly(MAA-co-ZnPPIX) undergoes pH induced structural transitions in the pH range of 4.0. In the case of polyacrylic acid copolymers the changes observed in the steady state and time resolved fluorescence studies are less marked. The distinct hydrophobic and hydrophilic environments experienced by the fluorophore bound to PMMA are attributed to the dynamics of the macromolecules in dilute aqueous solutions manifested by the α-methyl group present in the copolymer. The studies carried out using the fluorophores in the time windows from 2 ns to 12 ns indicate evolving trends in the dynamic coiling and reverse coiling of poly methacrylic acid chain.     

Enhancement of mechanical properties of triblock copolymers by random copolymer middle blocks

Symmetric styrene-b-styrene-co-butadiene-b-styrene (S-SB-S) tri-block copolymers with varying middle and outer block composition have been studied. We report our findings based on a systematic variation of the effective interaction parameter (χ) by adjusting the composition of the random copolymer in the middle block and of the outer blocks (in terms of PS-chain length) which allows us to explore the χ-parameter space with regard to molecular architecture more thoroughly than in SBS triblock copolymers. A variation in the S/B middle block composition or in the PS outer block content leads to a change in phase behaviour and morphology simultaneously accompanied by significant changes in mechanical properties, varying from elastomeric to thermoplastic property profile. Despite high PS contents of 55-75 wt.% these S-SB-S triblock copolymers reveal high strain at break values between 650% and 350% which is in striking contrast to the conventional SBS triblock copolymers where only about 10% strain at break have been reported to be achieved with similar PS-content (∼75 wt.%).     

Crosslinking and characterization of commercially available poly(VDF-co-HFP) copolymers with 2,4,4-trimethyl-1,6-hexanediamine

Fluorinated copolymers are well known for their large range of applications. These applications can be improved by grafting or crosslinking of several agents. The mechanism of crosslinking of hexamethylene diamine and 2,4,4-trimethyl-1,6-hexanediamine is well known and occurs in four different steps. To elaborate a film of commercially available poly(VDF-co-HFP) copolymer crosslinked by 2,4,4-trimethyl-1,6-hexanediamine, a step of press cure under air is necessary. Temperature, time and pressure were optimised by regarding the solubility of the press cured films, the mechanical properties, the swelling rate in methyl ethyl ketone, and the degradation of the films. The best temperature, time and pressure for press cure were 150 °C, from 15 to 30 min, and 20 bars, respectively. Other properties of crosslinked poly(VDF-co-HFP) copolymers containing 10 mol.% and 20 mol.% of HFP were characterized. First, all films were insoluble in concentrated HCl. Secondly, swelling rates of different amounts of diamine crosslinked copolymers were measured in ethylene carbonate/dimethyl carbonate and in methyl ethyl ketone; it was proved that the higher the molar percentage of diamine, the higher the crosslinking density, so the lower the swelling rate. Concerning thermal properties, glass transition temperature mainly increased when the amount of diamine increased. Thermal stability measurements showed a higher decomposition temperature when the percentage of diamine was very low (5 mol.%). Finally, mechanical properties were measured by dynamic mechanical analysis; the storage tensile modulus (E′) of a diamine crosslinked Kynar^® copolymer versus temperature exhibited a high drop because Kynar^® was a highly amorphous copolymer. Moreover, the higher the amount of diamine, the higher the rubbery modulus.     

Novel electrospun poly(ε-caprolactone)-based bicomponent nanofibers possessing surface enriched in tertiary amino groups

For the first time preparation of electrospun poly(ε-caprolactone) (PCL) based nanofibers possessing surface enriched in tertiary amino groups is shown. For that purpose the pair PCL and poly(ε-caprolactone)-b-poly[(2-dimethylamino)ethyl methacrylate] (PCL-b-PDMAEMA) diblock copolymers was used. PCL-b-PDMAEMA copolymers were synthesized using a combination of ring-opening polymerization and atom transfer radical polymerization (ATRP). Nanofibers with mean diameters ranging from 400 to 800 nm were obtained. Their morphology was evaluated by scanning electron (SEM) and atomic force microscopy (AFM). It was found that the morphology of the fibers depended on the weight ratio between the partners and the length of the PDMAEMA-block in the copolymers. The enrichment of the fiber surface in tertiary amino groups was studied by X-ray photoelectron spectroscopy (XPS). Increasing the copolymer content and the length of the PDMAEMA-block led to increase of the amount of tertiary amino groups on the fiber surface. The AFM analyses of the mechanical properties of the fiber surface showed that increasing the copolymer content led to decrease of the surface stiffness. The increase of the copolymer content led also to decrease of the melting temperature and the crystallinity degree in respect to PCL from the (co)polymer as determined by differential scanning calorimetry.     

Synthesis and properties of poly(ether ether ketone)-block-sulfonated polybutadiene copolymers for PEM applications

A novel series of sulfonated block copolymers were successfully synthesized by the condensation of modified poly(ether ether ketone) (PEEK) and polybutadiene (PB), followed by the selective post-sulfonation of PB blocks using acetyl sulfate as the sulfonating reagent. The sulfonic acid groups were only attached onto PB segments due to the high reactivity of double bonds to sulfonating reagent. The degree of sulfonation was controlled by changing the feed ratio of sulfonating reagent to block copolymer. PEEK-b-sPB could be easily cast into flexible and transparent membranes. The obtained membranes exhibited good thermal stability and satisfied mechanical properties. Tensile test showed the incorporation of sulfonate groups into PB blocks resulted in an increase in tensile strength and a decrease in elongation at break. TEM images revealed the existence of ionic spherical domains with the average sizes of 50-100 nm. Some of these small domains further aggregated to form large hydrophilic regions. The proton conductivity values were measured in the range of 10⁻² S/cm in water and increased with increasing IEC and temperature.     

Toughness Properties of Lightly Crosslinked Epoxies Using Block Copolymers

Summary: In this work is discussed an alternative approach to the toughening of epoxy networks by the addition of acrylic block copolymers, composed of rigid and rubbery blocks. Once the reaction is completed, the initial self-assembly of block copolymers in epoxy thermoset precursors produces rubbery domains: depending on the block copolymer structure and composition, these domains are of the micrometer or the nanometer size. Nanostructures are obtained when the rigid block is a random copolymer of methylmethacrylate and N,N-dimethylacrylamide. The rubbery domains prevent rapid crack propagation and the highest toughness is obtained with filament-like microparticles or wormlike micelles.     

Synthesis and phase separation of amine-functional temperature responsive copolymers based on poly(N-isopropylacrylamide)

Free radical copolymerizations of N-isopropyl acrylamide (NIPAM) and cationic N-(3-aminopropyl) methacrylamide hydrochloride (APMH) were investigated to prepare amine-functional temperature responsive copolymers. The reactivity ratios for NIPAM and APMH were evaluated in media of different ionic strength (r_NIPAM = 0.7 and r_APMH = 0.7-1.2). Phase separation behavior of the random copolymers with only 5 mol% of the APMH was found to be suppressed in pure water at temperatures up to 45 °C due to electrostatic repulsion among the cationic amine groups randomly distributed along the copolymer chain. Alternate sequential addition of PNIPAM/APMH mixtures and pure NIPAM was used to provide increased control of the location of APMH units along the chain. Consequently (close to) homo-PNIPAM block(s) were formed as evidenced by its characteristic phase transition at 33 °C. The influences of the monomer feeding time and feeding interval time to the APMH distribution were investigated to prepare copolymers with thermo-induced phase separation under physiologically relevant temperature and to determine the extent of conjugation to poly(ethylene oxide).     

Novel copolyesters based on poly(alkylene dicarboxylate)s: 1. Thermal behavior and biodegradation of aliphatic-aromatic random copolymers

In order to improve the thermal and mechanical properties of the poly(butylene 1,12-dodecanedioate), some novel aliphatic-aromatic random copolyesters have been prepared by starting from 1,4-butanediol and different molar ratio of 1,12-dodecanedioc acid and terephthalic acid. The samples were characterized by ¹H NMR and the molecular structure was correlated with the crystalline phase present, the level of crystallinity, the glass transition temperature, the mechanical behavior, and the biodegradability. In particular, the copolymer containing the 70 mol% of PBT repeating units notably improves the thermal and mechanical properties of the poly(butylene 1,12-dodecanedioate) towards those of PBT and maintains a very high thermal stability, but loses the biodegradability of the poly(alkylene dicarboxylate). Therefore, for this class of aliphatic-aromatic copolymers the chemical composition must be carefully chosen to reach a compromise between good thermal and mechanical performances and biodegradability, according to the necessity.     

Preparation and sorption studies of polyester microsphere copolymers containing β-Cyclodextrin

Polyester copolymer sorbent materials that incorporate β-Cyclodextrin (β-CD) were prepared using water-in-oil (w/o) micro-emulsion conditions at variable β-CD: cross linker mole ratios; where the cross linker units were sebacoyl chloride (SCl) and terephthaloyl chloride (TCl). The copolymers were characterized using TGA, nitrogen adsorption, and NMR/IR spectroscopy. The dye-based sorption properties of the copolymers with p-nitrophenol (PNP) in aqueous solution were evaluated at pH 4.6 and 295 K using UV-Vis spectrophotometry. The uptake of PNP varied from 0.221 to 0.352 mmol/g, according to the nature of the cross linker and the copolymer mole ratio. The sorption capacity of SCl-based copolymers exceed that for TCl-based copolymers, and correlate with the relative swelling properties and hydrated surface areas of the sorbent frameworks. ¹H NMR spectroscopy of copolymers with low levels of linker content (i.e. SCl or TCl) indicate dual sorption sites for PNP (i.e. β-CD inclusion sites and non-inclusion (interstitial) linker domains). The existence of dual sorption sites is similarly concluded for copolymers containing higher levels of cross linker. Inclusion complexes are firstly formed between PNP and the β-CD inclusion sites of the copolymer; thereafter, PNP is adsorbed onto the linker domains of the copolymer sorbent framework.     

Poly(ethylene oxide)-poly(styrene oxide)-poly(ethylene oxide) copolymers: Micellization, drug solubilization, and gelling features

Two new poly(ethylene oxide)-poly(styrene oxide) triblock copolymers (PEO-PSO-PEO) with optimized block lengths selected on the basis of previous studies were synthesized with the aim of achieving a maximal solubilization ability and a suitable sustained release, while keeping very low material expense and excellent aqueous copolymer solubility. The self-assembling and gelling properties of these copolymers were characterized by means of light scattering, fluorescence spectroscopy, transmission electron microscopy, and rheometry. Both copolymers formed spherical micelles (12-14 nm) at very low concentrations. At larger concentration (>25 wt%), copolymer solutions showed a rich phase behavior, with the appearance of two types of rheologically active (more viscous) fluids and of physical gels depending on solution temperature and concentration. The copolymer behaved notably different despite their relatively similar block lengths. The ability of the polymeric micellar solutions to solubilize the antifungal drug griseofulvin was evaluated and compared to that reported for other structurally-related block copolymers. Drug solubilization values up to 55 mg g⁻¹ were achieved, which are greater than those obtained by previously analyzed poly(ethylene oxide)-poly(styrene oxide), poly(ethylene oxide)-poly(butylene oxide), and poly(ethylene oxide)-poly(propylene oxide) block copolymers. The results indicate that the selected SO/EO ratio and copolymer block lengths were optimal for simultaneously achieving low critical micelle concentrations (cmc) values and large drug encapsulation ability. The amount of drug released from the polymeric micelles was larger at pH 7.4 than at acidic conditions, although still sustained over 1 day.     

Radiation-induced graft polymerization of acrylic acid onto fluorinated polymers. II. Graft copolymer–metal complexes obtained by radiation grafting onto poly(tetrafluoroethylene-ethylene) copolymer

A study has been made on the graft copolymers obtained by radiation-induced grafting of acrylic acid onto poly(tetrafluoroethylene-ethylene) (ET) films. The conversion of the graft copolymer into metal acrylate copolymer complex was carried out by treatment with different metal salts. Such a prepared graft copolymer–metal complex was confirmed by different methods: IR, UV spectrometry, degree of coloration, and x-ray fluorescence. Some selected properties of the graft copolymer–metal complexes such as electrical conductivity, swelling behavior, and mechanical properties were investigated. The influence of metal complexes in the graft copolymers was determined and compared with the grafted films. The possibility of the practical uses for such prepared graft copolymer–metal complexes was discussed and determined. It was assumed that such materials may be of great interest in the field of semiconducting materials in addition to their applicability as cation-exchange membranes. © 1993 John Wiley & Sons, Inc.     

Formation of polymer–colloid complexes of aluminoxane particles with poly(acrylic acid) and its copolymers with acrylamide

Formation of polymer–colloid complexes formed by positively charged aluminoxane particles with a size of ~4.6 nm, which constitute the main part of the dispersed phase in aluminum polyhydroxychloride sols with poly(acrylic acid) and acrylic acid copolymers with acrylamide, is studied. Conditions of preparing water-soluble polymer–colloid complexes are determined. It is shown that water-soluble polycomplexes are obtained through the interaction of aluminoxane particles with acrylic acid–acrylamide copolymers containing no more than 0.8 mol% acrylic acid units. In the polymer–colloid complex, aluminoxane particles are uniformly distributed over polyelectrolyte macromolecules and the optimum composition is attained at the molar ratio of components Z equal to 1:1. In semidilute solutions, the addition of aluminoxane particles to the copolymer brings about formation of the gel featuring viscoelastic properties. For all copolymers, the maximally elastic properties of the gels are attained at Z ≈ 1.     

The synthesis and solution behaviors of novel amphiphilic block copolymers based on d-galactopyranose and 2-(dimethylamino)ethyl methacrylate

A series of novel stimuli-responsive AB, ABA, and BAB type block copolymers based on 6-O-methacryloyl-1,2:3,4-di-O-isopropylidene-d-galactopyranose (MAIpGP:A block) and 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA: B block) were synthesized via ATRP techniques using ethyl 2-bromoisobutyrate (EBiB) as monofunctional ATRP initiator in the case of diblock copolymer and diethyl meso-2,5-dibromoadipate (DEDBA) as bifunctional ATRP initiator in the case of triblock copolymers. The PMAIpGP blocks of the AB, ABA, and BAB type linear block copolymers were converted to water soluble PMAGP blocks via deprotection process under mild acidic conditions. Both proton NMR and DLS studies demonstrated that block copolymers were temperature-sensitive, whereby the lower critical solution temperature (LCST) of polymers varied with the polymerization degrees of comonomers in the block copolymers. LCST was determined to be between ∼35 °C and 55 °C depending on the type and the comonomer compositions of the block copolymers. It was observed that an increase on the percentage of hydrophilic PMAGP block in block copolymer caused an increase on the LCST value as expected.     

Attractive double-layer forces and charge regulation upon interaction between electrografted amine layers and silica

Chitosan (CS) and poly(acrylic acid) (PAA) were crosslinked by an ionic gelation method to form super absorbent polymers (SAPs). CS and PAA form amide bonds between the amino and carboxyl groups. The CS-PAA copolymers were synthetically engineered by varying the feed ratios of the prepolymer units. The copolymer materials possess tunable sorption and mucoadhesive properties with a backbone structure resembling proteinaceous materials. The sorption properties of the copolymers toward methylene blue (MB) in aqueous solution were studied using UV-Vis spectrophotometry at ambient pH and 295 K. The copolymers showed markedly varied interactions with MB, from physisorption- to chemisorption-like behavior, in accordance with their composition, surface area, and pore structure characteristics. The sorption isotherms were evaluated with the Sips model to provide estimates of the sorption properties. The sorbent surface area (271 and 943 m²/g) and the sorption capacity (Q_m = 1.03 and 3.59 mmol/g) were estimated for the CS-PAA copolymer/MB systems in aqueous solution.     

High conductive copolymers of polypyrrole-α,ω-diamine polydimethylsiloxane

Block copolymers of α,ω-diamine polydimethylsiloxane (DA · PDMS) and polypyrrole have been produced by the polymerization of pyrrole with the redox system of ceric salt/DA · PDMS. The properties of the copolymers may be regulated by the ratio of DA · PDMS/Pyrrole/Ce₄(NH₄)₂(NO₃)₆. The copolymers with lower conductivities are soluble in solvents such as DMF and acetone but higher conductive copolymers are insoluble. A block copolymer with unusually high conductivity (4000 S/cm) was produced under one specific polymerization condition. The chemical structure and the surface morphology of the copolymer particles seem to be important for high conductivity.