A scheme to predict the morphology of diblock copolymers and their blends

Diblock copolymers of α-methylstyrene and isoprene were synthesized anionically. The morphology of the copolymers and of their blends with the homopolymers was studied by transmission electron microscopy. Based on this, a scheme is proposed to predict the morphological behavior associated with the blending of block copolymers with homopolymers. Two blending systems are discussed. They are (i) copolymer AB with homopolymers A and B and (ii) copolymers AB of two different molecular weights with homopolymer A. Two factors are considered to be the most crucial. One is the morphology of the predominant polymer (50 wt %), and the other is the weight ratio of the blends. The solubilizing effect of the block copolymer AB in the blend must also be taken into account. When the two copolymers are blended, the one with lower molecular weight was emulsified by higher one and restricted around the longer chain. It is shown that the present scheme is successful in predicting the morphology of diblock copolymers and their blends.     

Physical properties of poly(n-alkyl acrylate) copolymers. Part 1. Crystalline/crystalline combinations

The physical properties of n-alkyl acrylate copolymers containing two crystallizeable monomers, including thermal characteristics, structure as determined by small angle X-ray scattering, and gas permeability as a function of temperature, were examined in detail and compared to the corresponding homopolymers. The copolymers exhibit co-crystallization and, thus, for a given average side-chain length have comparable melting temperatures as the corresponding homopolymers. For a given side-chain length, the copolymers have somewhat lower heats of fusion than the corresponding homopolymers because of a reduction in crystallite size as revealed by SAXS. This depression in crystallinity is reflected in the permeability data for the copolymers. Poly(n-alkyl acrylates) exhibit a ‘jump’ in their gas permeability at the T_m of the side-chain lengths that is mainly caused by a switch in the side-chain morphology from crystalline to amorphous upon melting. The depression in crystallinity for the copolymers results in a smaller permeation jump. The jump breadth correlates with the melting endotherms for these polymers as determined by DSC. Ultimately, the melting endotherms for these copolymer systems provide an excellent tool for predicting permeability changes across the melting region.     

2-丙烯酰胺-2-甲基丙磺酸

介绍了2-丙烯酰胺-2-甲基丙磺酸(AMPS)的性质和制备方法,综述了由AMPS单体制备的均聚物或共聚物在油气开采、水处理工业、涂料工业、生物医学、工程材料等领域的应用。AMPS均聚物和共聚物的抗盐性、抗温性和抗剪切性,为我们解决油气田开发中的复杂问题提供了重要的手段,加强AMPS在油田化学剂中开发和应用研究具有广阔的发展前景。     

Distinguishing amorphous polymer blends from copolymers by wide angle X-ray diffraction

Amorphous homopolymer blends were differentiated from the corresponding random copolymers with wide angle X-ray diffraction (WAXRD) using the diffraction angle and the band width at one-half peak maximum. The diffraction angle was also used to determine the composition of copolymers and of mixtures of homopolymers. A procedure has been developed to predict the WAXRD patterns of polyblends and/or random copolymers based on those of the corresponding homopolymers.     

Compatibilization of polystyrene/poly(butyl methacrylate)/poly[(ethylene glycol) dimethacrylate] blends via concentrated emulsion polymerization

Two concentrated emulsions in water containing styrene and butyl methacrylate (BMA) as dispersed phases were prepared. Each of them contained a small amount of an amphiphilic macromonomer, poly[(ethylene glycol) dimethacrylate] (PEGD), in the continuous phase. The two concentrated emulsions were partially polymerized at 50 °C until conversions of about 22.5 % were reached. They were then mixed mechanically and the mixture was subjected to complete polymerization. During the latter polymerization, homopolymers of styrene and BMA and copolymers of the two were generated. The copolymers, particularly the crosslinked structures, which were formed through copolymerization of PEGD with styrene and BMA at the interface of the latexes, provided compatibilizers for the homopolymers. This blend of homopolymers, copolymers and crosslinked structures possessed excellent toughness and processability. The blends were characterized by their gel content, and by X‐ray photoelectron spectroscopy, rheometric testing, dynamic mechanical thermal analysis, transmission electron microscopy and impact strength measurements. Copyright © 2005 Society of Chemical Industry     

Physical properties of poly(n-alkyl acrylate) copolymers. Part 2. Crystalline/non-crystalline combinations

The physical properties of n-alkyl acrylate copolymers containing one crystallizeable monomer and one non-crystallizeable or slightly crystallizeable monomer, including thermal characteristics, structure as determined by small angle X-ray scattering, and gas permeability as a function of temperature, were examined in detail and compared to the corresponding homopolymers and copolymer systems containing two crystallizeable comonomers. The current copolymers exhibit melting point depression and, for a given average side-chain length, have lower heats of fusion than the corresponding homopolymers and crystalline/crystalline copolymers. Limited SAXS experiments revealed an increase in the d-spacings, above and below the melting point, with side-chain length consistent with expectations. The crystallites predominantly exhibit end-to-end packing similar to other poly(n-alkyl acrylates) previously studied. Poly(n-alkyl acrylates) exhibit a ‘jump’ in their gas permeability at the T_m of the side-chain lengths that is mainly caused by a switch in the side-chain morphology from crystalline to amorphous upon melting. The reduced crystallinity of the crystalline/non-crystalline copolymers results in a smaller permeation jump, which in some cases were extremely broad. All jump breadths correlate with the melting endotherms for these copolymers as determined by DSC similar to that for homopolymers and crystalline/crystalline copolymers. The magnitude of the jump correlates with the heat of fusion, irrespective of the comonomer type, in all cases.     

Copolymers of chosen alkyl methacrylates with N-phenylmaleimide and N-(4-halogenphenyl)maleimides: A UV-aging study

Homopolymers and copolymers of ethyl and butyl methacrylates with N-phenylmaleimide, N-(4-chlorophenyl)maleimide, and N-(4-bromophenyl)maleimide were synthesized by free-radical bulk polymerization with benzoyl peroxide as the initiator. The content of imide in the copolymers was about 5–10 or 7.5 wt %. The homopolymers and copolymers were irradiated with ultraviolet (UV) light in a climatic test chamber for various periods to study their aging behavior. After 100, 250, and 500 h, the structure, thermal stability, chemical resistance, and some physicomechanical properties were examined. The influence of UV radiation time on structure and the investigated properties of the homopolymers and copolymers were studied. The experimental results indicate that all investigated copolymers were resistant to UV radiation after 500 h. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3244–3250, 2001     

Characterization and Electrical Properties of Some Hydrochloric Acid-Doped Aniline and 2-Amino-Pyridine Homopolymers and Copolymers

The synthesis of (group I) hydrochloric acid-doped poly(aniline-co-toluidine), poly(aniline-co-thiophene), poly(aniline-co-o-phenylenediamine), and poly(aniline-co-2-aminopyridine) as well as their hydrochloric acid-doped homopolymers of polyaniline, poly-m-toluidine, poly-o-phenylene diamine, and poly-2-aminopyridine and the synthesis of (group II) hydrochloric acid-doped poly (2-aminopyridine-co-o-phenylene diamine) and its hydrochloric acid-doped homopolymers of poly 2-amino pyridine and poly-o-phenylene diamine have been carried out via a chemical oxidation process using ammonium and potassium persulphate as chemical initiators. The synthesized homo- and copolymers were characterized by ultraviolet-visible spectroscopy (UV-VIS), infrared spectroscopy (IR), and thermal analysis. The variation of the electrical conductivity (σ, S cm^?1) with the reciprocal of the absolute temperature (1000/T, K) at different frequencies (1–1000 kHz) for hydrochloric acid homopolymers and copolymers is illustrated.     

Antibacterial poly{(4‐vinyl phenylboronic acid)‐co‐[2‐(dimethylamino)ethyl methacrylate]} copolymers and their application in water‐based paints

Herein, we report the synthesis of poly(4‐vinylphenylboronic acid) (PVPBA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) homopolymers, copolymers, and their methyl, pentyl, and octyl quaternized forms as dopant in water‐based permanent antibacterial paints. Both quaternized and nonquaternized forms of P(VPBA‐co‐DMAEMA) copolymers have reflected higher MIC values relative to PDMAEMA homopolymers. High molecular weight copolymers were more active against Escherichia coli ATCC 25922, contrarily, lower molecular weight copolymers showed higher antibacterial activity against Staphylococcus aureus ATCC 25923. The paint films prepared with quaternized PDMAEMA homopolymers with a weight of 10% showed better antibacterial activity in water and airborne tests than the copolymers. However, it has been shown that the inadequate anti‐biofilm properties of homopolymer‐containing paint films are overcome with the VPBA content of the copolymer structure and the most effective antibacterial and anti‐biofilm properties have been obtained with paint films containing P(VPBA‐co‐5QDMAEMA) copolymers. These paint films, which can maintain antibacterial and anti‐biofilm properties for at least 1 year, have the potential to be an alternative to Ag/Cl based solid surfaces which require the active substance to be regenerated. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46245.     

Interpolymer complexes between hydrophobically modified poly(methacrylic acid) and poly(N-vinylpyrrolidone)

The formation and structure of interpolymer complexes between amphiphilic multi-block copolymers—poly(dimethylsiloxane-N-vinylpyrrolidone) and poly(dimethylsiloxane-methacrylic acid)—were studied using potentiometric and conductometric titration, viscometry and fluorescence spectroscopy. The ratio of hydrophobic/hydrophilic groups in the copolymer and the molecular weight of each sequence were varied in order to establish the influence of these parameters on the interactions between the components. The complexation between pairs of block copolymers, of block copolymers and homopolymers as well as between homopolymer pairs was considered. The complexes were formed through the hydrogen bonding. They have a compact structure with a non-stoichiometric composition of pyrrolidone to methacrylic acid groups ratio around 0.6-0.7, with the exception of complexes formed between pairs of homopolymers and of copolymers with the shortest siloxane block. The difference between the new complexes and the ones formed from homopolymers, with equimolar composition, is explained by the spatial non-complementarity of the copolymers having a ‘flower-like’ structure in aqueous solutions.     

Esterification of hydroxylated polymers with 2-sulfobenzoic acid cyclic anhydride: A facile approach for the synthesis of near-monodisperse strong acid homopolymers and diblock copolymers

A convenient two-step route was developed to prepare a range of low polydispersity strong acid homopolymers and several examples of well-defined diblock copolymers. Atom transfer radical polymerization (ATRP) of either 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate or glycerol monomethacrylate afforded the corresponding near-monodisperse hydroxylated homopolymers, while several diblock copolymer precursors were prepared by either (1) the one-pot ATRP of 2-hydroxypropyl methacrylate and 2-(diethylamino)ethyl methacrylate using sequential monomer addition or (2) the ATRP of either 2-hydroxypropyl methacrylate or glycerol monomethacrylate using a poly(ethylene oxide)-based macro-initiator. Excess 2-sulfobenzoic acid cyclic anhydride was used to fully esterify the hydroxy groups of these homopolymers and diblock copolymers under mild conditions. The resulting zwitterionic diblock copolymers undergo micellar self-assembly on adjusting the pH of the solution, while one of the anionic poly(ethylene oxide)-based diblock copolymers formed colloidal polyelectrolyte complexes in aqueous solution when mixed with a cationic poly(ethylene oxide)-based diblock copolymer.     

Synthesis and luminescent properties of block copolymers based on polyfluorene and polytriphenylamine

For the preparation of block copolymers containing polyfluorene (PF) and hole transporting segment, PF homopolymers with diphenylamine terminals were synthesized by Suzuki coupling polymerization. The terminals of PF were converted to polytriphenylamine (PTPA) block by C–N coupling polymerization to give PTPA-block-PF-block-PTPA (PF-PTPA) triblock copolymers with different PTPA chain lengths. These polymers were soluble in common organic solvents and readily formed thin films by solution processing. All of the polymers exhibited similar UV absorption and PL emission properties both in chloroform solution and in film state. PF-PTPA block copolymers showed relatively high HOMO compared with that of PF by cyclic voltammetry. Compared with corresponding PF homopolymers, the EL devices based on PF-PTPA block copolymers showed higher luminance and current efficiency than those of PF homopolymers because of the improvement of hole injection by the introduction of PTPA segment.     

Glass transitions of some block copolymers

A number of block and graft copolymers have been prepared from several vinyl monomers, and their glass transition temperatures measured. The series included polar, nonpolar and polar-nonpolar pairs. It was found in all cases except one that the glass transition temperatures were close to those found for the individual homopolymers. The exception was a block copolymer of styrene and α-methylstyrene, the only pair whose homopolymers would give clear mixed solutions in a mutual solvent.     

Synthesis and characterization of homopolymers and copolymers of various acrylates and acrylonitrile

Various homopolymers and copolymers of methyl acrylate, ethyl acrylate, butyl acrylate, and acrylonitrile in different feed ratios were synthesized. These were characterized by IR, ¹³C-NMR, DSC, DTA, and TGA. Spectroscopic characterization helped in differentiating copolymers of different mol ratios. Thermal analysis revealed different degradation patterns for homopolymers and copolymers. The temperature and energy changes associated with various phase transitions were dependent on the chemical composition of homo- and copolymers, as expected. © 1993 John Wiley & Sons, Inc.     

New block copolymers of α-amino acids

Triblock cepolypeptides of γ-benzyl-L-glutamate and L-leucine or L-valine of high molecular weight have been prepared. The solid state structure of the block copolymers cast from preferential solvents has been compared with that of random copolymers of similar composition as well as the appropriate homopolymers. Infrared and solid state circular dichroism measurements indicate that the γ-benzyl-L-glutamate and L-leucine blocks assume an α-helical conformation and L-valine blocks a β-sheet structure. The WAXD patterns of the block copolymers show overlapping reflections characteristic of the individual homopolymers. Further evidence for a phase separated morphology is provided by dynamic mechanical spectroscopy.     

Use of the lower critical solution temperature for the characterization of polymer mixtures and the study of their compatibility: Application to polyethylenes,polypropylene, and their copolymers

The Lower Critical Solution Temperature (LCST) of polyethylene (PE), polypropylene (PP), and ethylene-propylene block and random copolymers have been measured in heptanes. A thermogram related to the variation of the turbidity of the solution is obtained between 100 and 210°C. The temperature of the onset of the turbidity peak is defined as the LCST of the system. The width and the area of the turbidity peaks are tentatively associated with the polymer polydispersity and the amount of polymer involved in the phase separation. The thermograms of solutions containing both homopolymers show two distinct turbidity peaks situated at a 70°C interval. Correlations of molecular orientations in the concentrated phase, possible in PE systems but not in PP solutions, are at the origin of the lower LCST values for PE solutions. The LCST of copolymers are situated between those of the homopolymers but the dependence of the LCST on the copolymer ethylene content is different for block and random copolymers. Examples of thermograms are also given for mixtures of copolymers with PE and PP. By analysis of their thermograms, some commercial block EP copolymers were also found to contain PK and PP. This method seems well suited for characterizing polymer mixtures.     

Biodegradable lactone copolymers. II. Hydrolytic study of ε-caprolactone and lactide copolymers

Copolymers of ε-CL/L-LA and ε-CL/DL-LA were allowed to age in a buffer solution of pH 7 at 23 and 37°C. The effects of time and temperature on the rate of hydrolysis were examined by various techniques including weighing (water absorption and weight loss), SEC (molecular weight and polydispersity), and DSC (thermal properties). For comparison, the hydrolytic behavior of PLLA, PDLLA, and commercial PCL homopolymers was investigated by the same methods. SEC measurements showed that molecular weights of the copolymers and PLA homopolymers started to decrease during the first week of hydrolysis, but significant mass losses occurred only much later. As expected, there was no change in either molecular weight or mass of PCL during the hydrolysis study. The kinetic results for copolymers and homopolymers were calculated to study the degradation mechanism. During hydrolysis, the crystallinity of the initially semicrystalline copolymers increased and some crystallinity appeared in the initially amorphous L-LA-containing copolymers. © 1996 John Wiley & Sons, Inc.     

Effect of matrix features on polypropylene layered silicate nanocomposites

The aim of this study was to examine the effect of the polypropylene based resin on the properties of organoclay-PP nanocomposites prepared by melt compounding using a twin screw extruder.The characterization of the obtained materials was performed by X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), melt flow rate (MFR) and mechanical tests.The study has shown the effect of the polymer matrix molecular weight on the possibility of producing by melt compounding nanocomposites based on PP homopolymers or heterophasic PP-PE copolymers and an organically modified montmorillonite, in presence of maleic anhydride-modified polypropylene (PP-g-MAH).An increase of mechanical properties was achieved both for homopolymers and heterophasic copolymers. However the reinforcing effect of clay dispersed in heterophasic copolymers was not as high as found for the homopolymers.     

SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene

This paper systematically describes a LCB determination method that can quantify both LCB content and LCB distribution across the molecular weight distribution in polyethylene homopolymers as well as copolymers. Coupling size-exclusion chromatography with multi-angle light scattering (SEC-MALS), this method quantifies molecular weights (MW) and radii of gyration (R_g) simultaneously. The number of LCB per molecule and LCB frequency as a function of MW can be calculated by comparing R_g of a branched polymer with that of a linear control at the same MW using the Zimm-Stockmayer approach. Because the presence of short-chain branching in copolymers results in changes in R_g of the copolymers, their LCB contents cannot be obtained before the short-chain branching (SCB) effect is corrected. Using well-characterized linear PE copolymers as standards, an empirical method is successfully established in this paper to correct the SCB effect. Consequently, this method can be applied to determine LCB in PE copolymers as well. Some practical aspects, such as the selection of formalism for data processing, the LCB detection sensitivity and precision, and long-term reproducibility of this method are also discussed. Finally, examples are given to demonstrate how this method is applied to determine LCB and LCB distribution in practical PE homopolymers and copolymers.     

Influence of the longest ethylene and isotactic propylene sequences on crystallization elution fractionation of ethylene/propylene copolymers

Crystallization elution fractionation (CEF) is the newest crystallization-based technique for estimating the chemical composition distribution of ethylene/1-olefin copolymers. Understanding the separation mechanism of CEF for ethylene/propylene copolymers over their full compositional range is challenging because the crystallizabilities of the copolymer chains depend on the longest ethylene sequence and on longest isotactic propylene sequence. We developed a mathematical model to describe the CEF mechanism for ethylene/propylene copolymers over the entire compositional range using population balances for the crystallization and dissolution stages. The joint distribution of longest ethylene and isotactic propylene sequences determines how the copolymer populations crystallize and dissolve. The model was validated with experimental CEF profiles of ethylene/propylene copolymers varying from pure ethylene to propylene homopolymers.