Synthesis and analysis of phase segregation of polystyrene-block-poly(methyl methacrylate) copolymer obtained by Steglich esterification from semitelechelic blocks of polystyrene and poly(methyl methacrylate)

Here, an alternative route to successfully synthesize polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) is reported. Steglich esterification was used as an effective, metal free approach for coupling carboxylic terminated PS and the hydroxyl end-functionalized PMMA chains obtained by nitroxide-mediated polymerization and atom transfer radical polymerization, respectively. α-Functionalization was obtained using 4,4′-azobis(4-cyanovaleric acid) and 2,2,2-tribromoethanol as initiators. The synthesis of PS-b-PMMA was confirmed by gel permeation chromatography and nuclear magnetic resonance (NMR), while the dependence of the diffusion coefficients of the polymers (PS, PMMA, PS/PMMA blend, and PS-b-PMMA) with their corresponding molecular weights was discussed based on the results of atomic force microscopy-based infrared spectroscopy, differential scanning calorimetry, and spectra of diffusion-ordered NMR spectroscopy. Differently from PS-b-PMMA, a partial segregation was observed for the PS/PMMA blend, affecting its thermal behavior and diffusion coefficient. The study here presented provides an easier and efficient strategy for the synthesis of PS-b-PMMA and new insights into the diffusion of polymers.     

Synthesis and characterization of a poly(acrylic acid)‐graft‐methoxy poly(ethylene oxide) comblike copolymer

A methoxy poly(ethylene oxide) (MPEO) grafted poly(acrylic acid) (PAA) comblike copolymer was synthesized by the direct condensation of MPEO onto the PAA backbone in the presence of dicyclohexyl dimethylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Its chemical structure was characterized by Fourier transform infrared and ¹H‐NMR spectroscopies. The effects of different catalysts, solvents, reaction temperatures, and reaction times on the grafting degree of the PAA‐g‐MPEO comblike copolymer were investigated. Compared to p‐toluene sulfonic acid, DMAP/DCC as a catalyst markedly increased the grafting degree. The optimum reaction conditions were a tetrahydrofuran/water mixture solvent, a reaction temperature of 50°C, and a reaction time of 168 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,spectral analysis,and catalytic activity of poly(aniline‐co‐congored)–metal oxide nanocomposites

Electrically conducting, water‐soluble fluorescent copolymer nanocomposites were synthesized by a solution polymerization method under different experimental conditions in the presence of CuO and V₂O₅ nanoparticles. The prepared copolymer nanocomposites were characterized with analytical tools, including Fourier transform infrared spectroscopy, ultraviolet–visible (UV–vis) spectroscopy, and fluorescence emission spectroscopy. The order of copolymerization was determined on the basis of the UV–vis absorption spectra and fluorescence emission spectra. The copolymer–CuO nanocomposite system exhibited the highest electrical conductivity. The scanning electron microscopy image showed the presence of more CuO nanoparticles on the surface of the copolymer. Furthermore, the catalytic activity of the copolymer nanocomposites was tested for the reduction of p‐nitrophenol. All three types of polymer systems exhibited almost the same apparent rate constant values. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46469.     

The effects of processing variables on electrospun poly(ethylene glycol) fibrous hydrogels formed from the thiol-norbornene click reaction

Electrospinning has been used to create scaffolds with tunable micro/nano architecture, stiffness, and porosity to mimic native extracellular matrix. This study investigated the effects of electrospinning parameters and hydrogel formulation (solvent and crosslinker type) on the architecture and properties of fibrous poly(ethylene glycol) (PEG) hydrogels formed from a photoclick thiol-norbornene reaction. Fibrous hydrogels were prepared using hydrogel precursors (four-arm PEG norbornene and multi-thiol crosslinker), sacrificial poly(ethylene oxide) (PEO, 400 kDa), and photoinitiator (I2959) in either 2,2-triflouroethanol (TFE) or water. Three thiol crosslinkers- 2,2′-(ethylenedioxy)diethanethiol (EDT), pentaerythritol tetrakis(3mercaptopropionate) (PTMP), and PEG dithiol (PEGDT)- were investigated. Fibrous PEG networks with uniform fibers were produced at applied voltages of 10 or 12 kV for TFE and 16 kV for water. Fiber diameters of electrospun hydrogels were largely affected by the solvent when combined with PEO concentration and ranged from 0.5 to 3.5 mm in dry state. While the effect of crosslinker type on fiber diameter, morphology, and porosity of the fibrous hydrogel was minimal, it did modulate its shear modulus. To this end, this study provides the groundwork for selecting processing parameters to achieve desired properties of fibrous PEG thiol-norbornene hydrogels for intended tissue engineering applications ranging from neural, cardiovascular to musculoskeletal.     

Poly(acrylic acid)/poly(acrylamide) hydrogel adsorbent for removing methylene blue

Cationic dye can cause severe damage to the environment due to their refractory degradation, complex composition and strong stability. Hydrogels as adsorbents have been widely used to treatment the wastewater with dyestuff for their low prices, simple operations, and high efficiency. This work uses poly(acrylic acid) (PAA)/poly(acrylamide)(PAM)/calcium hydroxide nanoparticles (CHN) polymeric hydrogel absorbent to eliminate methylene blue (MB) dye. First, PAM/PAA/CHN hydrogel is produced through copolymerization of acrylic acid monomer and acrylamide monomer using inorganic CHN as cross-linker. And then, the adsorption performance of such PAM/PAA/CHN hydrogel adsorbent for adsorbing MB dye is explored at different conditions including pH, contacting time, adsorbent dosage, initial concentration of MB, and temperature. A maximum adsorption capability for adsorbing MB reaches 1,056 mg/g. Furthermore, the pseudo-first-order mode and Langmuir isotherm model can well describe adsorption behavior of MB dye onto such PAA/PAM/CHN hydrogel adsorbent. Thereby, as-prepared PAA/PAM/CHN hydrogel could be a potential adsorbent for eliminating organic dyes from wastewater.     

氨基化单甲氧基聚乙二醇的合成研究

首先合成了单甲氧基聚乙二醇对甲苯磺酸酯(mPEG-OTs),然后根据盖布瑞尔合成法原理,以邻苯二甲酰亚胺钾盐(PPI)为亲核试剂与mPEG-OTs反应,生成单甲氧基聚乙二醇的邻苯二甲酰亚胺衍生物(mPEG-PI),mPEG-PI与水合肼反应肼解生成伯胺,合成了一端为氨基的单甲氧基聚乙二醇(mPEG-NH2)。讨论了缚酸剂、溶剂、反应条件对反应的影响。通过红外、液质联用、核磁共振谱图证实了产物与目标分子的结构相吻合。     

Tailoring the thermal and mechanical properties of injection-molded poly (lactic acid) parts through annealing

The effect of cold-crystallization on poly (lactic acid) (PLA) injection-molded parts was systemically investigated at different annealing temperatures (80/100/120°C) and annealing times (0.5/1/1.5/2 hr). The relative crystallinity (X_c) and crystal form (α' and α) of samples was investigated by differential scanning calorimetry (DSC) and wide X-ray angle diffraction (WAXD). The dependence of the thermal and mechanical performance on relative crystallinity and crystal form/morphology was discussed in detail. A linear relationship between the increment of heat distortion temperature (HDT) and that of X_c was found. The tensile strength, tensile modulus and storage modulus all increased with annealing time and annealing temperature, while the tensile toughness presented a different behavior. The elongation at break for specimens reached a maximum value of 16.9% after annealing at 80°C for 2 hr, which is a threefold improvement compared to PLA samples prepared without annealing. This work suggests that annealing is an effective method for tailoring the physical properties of PLA products.     

Synthesis and In vitro cytotoxicity of poly(ethylene glycol)–epothilone B conjugates

Natural epothilone B (EPOB) is currently in clinical trials for treatment of advanced cancers. In this study, two poly(ethylene glycol) (PEG)–EPOB conjugates were synthesized with carbodiimide chemistry with linear PEG Methoxy‐PEG‐Carboxymethy(mPEG‐COOH) with different molecular weights (5 and 20 kDa). The products were confirmed by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy and ¹H‐NMR, which showed that PEGylation only took place at the 7‐OH site of EPOB. The solubilities of PEG5K–EPOB the conjugate of mPEG‐COOH (MW 5,000) and epothilone B and PEG20K–EPOB the conjugate of mPEG‐COOH (MW 20,000) and epothilone B were determined to be 4.93 × 10^?2 and 1.58 × 10^?2 mmol/mL; this showed improvements of 35 and 11 times, respectively, over that of free EPOB (1.4 × 10^?3 mmol/mL). Moreover, the conjugates were more stable than that of free EPOB in plasma. The cytotoxicity of conjugates was evaluated on human breast cancer MCF‐7 cells with an 3‐(4,5)‐dimethylthiahiazo (‐z‐y1)‐3,5‐di‐ phenytetrazoliumromide(MTT) based assay. The half maximal inhibitory concentration of a substance(IC50) values of EPOB, PEG5K–EPOB, and PEG20K–EPOB were 6.0 × 10^?4, 0.57, and 8.4 × 10^?3 μM, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41123.     

Synthesis and characterization of copolymers of carbazolylalkyl(meth)acrylates and methacrylic acid

Summary The copolymerization of 2-(9-carbazolyl)ethylmethacrylate, 3-(9-carbazolyl)propyl-2-methacrylate and 2-(9-carbazolyl)ethylacrylate with methacrylic acid has been studied obtaining the reactivity ratios of the monomers in benzene. For the estimation of molar masses and copolymer compositions esterification of the copolymers has been performed. A thermal study of the obtained copolymers related to the carbazolylalkyl(meth)acrylate content has been carried out taking into account several theories predicting the dependence of the glass transition temperature on the copolymers composition. The copolymers in which the molar fraction of methacrylic acid did not exceed ca. 65 mol % exhibit glass transition. Glass transition temperatures increase with the increase of molar fraction of methacrylic acid. Received: 7 August 2000/Revised version: 19 September 2000/Accepted: 22 December 2000     

Synthesis of propylene glycol monoesters of docosahexaenoic acid and eicosapentaenoic acid by lipase-catalyzed esterification in organic solvents

Propylene glycol monoesters (PGM) of docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) are potentially health-beneficial water-in-oil emulsifiers useful in the food industry. These esters were synthesized enzymatically to overcome the problems associated with chemical processes. The products were analyzed by gas chromatography. The immobilizedMucor miehei lipase was found to be the best enzyme for the synthesis of both propylene glycol monoesters of EPA and DHA among nine lipases tested. The anhydrous enzyme and hydrophobic organic solvents were favored for the production of both monoesters. The yields of monoesters were also affected by temperature, pH memory, fatty acid/propylene glycol ratio, and reaction time. The yields of PGMDHA and PGMEPA with 50 mM fatty acid and 225 mM propylene glycol as substrates in 1 mL solvent mixture (hexane/t-butyl alcohol=9:1), catalyzed by Lipozyme IM-20 (50 mg) at 40°C for 24 h, were 47 and 49 mM, respectively. The enzyme still retained over 60% of its original activity after 10 d of batch-type operation (1 d per cycle) at 40°C for the synthesis of both PGMDHA and PGMEPA.     

New degradable polyesters from deoxycholic acid and oligo(ethylene glycol)s

A new class of polyesters was prepared by polycondensation of a bile acid, deoxycholic acid, and an oligo(ethylene glycol) (OEG) with molar mass ranging from 100 to 1500. The chemical structure and composition of the polyesters were confirmed by ¹H‐NMR, Fourier transform infrared spectroscopy and HPLC analysis. Polyester molar masses measured by gel permeation chromatography were between 5000 and 20 000. Thermal stability and glass transition temperature decreased with increasing length of OEG. Hydrolytic degradation was also enhanced by the presence of longer chain OEG. Polyesters obtained from OEG with molar mass ≥ 1000 were water soluble, semicrystalline and thermosensitive. As a function of the OEG length used for their preparation, the new polyesters can be useful for biomedical or industrial applications. © 2012 Society of Chemical Industry     

Evaluation of the antifouling and photocatalytic properties of novel poly(vinylidene fluoride) membranes with a reduced graphene oxide–Bi2WO6 active layer

Immobilization of reduced graphene oxide (RGO)–Bi₂WO₆ is an ideal method for obtaining antifouling membranes for membrane distillation (MD) processes. Poly(vinylidene fluoride) membranes modified with RGO–Bi₂WO₆ were successfully obtained with a double‐layer coating method through non‐solvent‐induced phase separation. The water contact angle was improved by about 30° by RGO–Bi₂WO₆; this indicated that the surface modification obviously increased the membrane hydrophobicity. The high desalination rate proved that all of the prepared membranes were appropriate for the MD process. The RGO–Bi₂WO₆‐modified membranes achieve 26.26%–59.95% removal rates in 10 mg/L aqueous ciprofloxacin under visible light for 7.5 h. It was possible to erase strongly bound foulants and recover the prepared membrane's permeation flux by 3 h of visible‐light irradiation. The RGO–Bi₂WO₆‐modified membrane with a high hydrophobicity, fouling mitigation, and photocatalytic capability presents huge potential for the treatment of high‐salt antibiotic wastewater use in the MD process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45426.     

Simple and efficient anionic polymerization of N-phenylmaleimide with fluorides as an initiator

The facile anionic polymerization of N-phenylmaleimide (N-PMI) using fluorides as an initiator has been discovered and systematically investigated. Effect of different solvents such as dioxane, tetrahydrofuran, dichloromethane (DCM), dimethyl sulfoxide (DMSO), N-methylpyrrolidone, acetonitrile, toluene, and acetone and effect of anionic initiators such as tetra-n-butylammonium fluoride (TBAF), cesium fluoride, and potassium fluoride have been studied. The kinetics of polymerization using TBAF as an initiator in DMSO is also studied. Some of the resulting poly(PMI)s are characterized by gel permeation chromatography, solubility test, attenuated total reflection-Fourier transform infrared, nuclear magnetic resonance (NMR), and ¹³C-NMR spectral analysis. The thermal behaviors are studied by thermogravimetric and differential scanning calorimetric analysis. A proposed polymerization mechanism is also discussed. Our results show fluoride can effectively induce the polymerization of N-PMI in various solvents under very mild conditions with good to excellent yields. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48909.     

Production of 2-hydroxyethyl methacrylate-g-poly(ethylene terephthalate) nanofibers by electrospinning and evaluation of the properties of the obtained nanofibers

Nanofiber production was investigated from poly(ethylene terephthalate) (PET) polymers functionalized with hydroxyethyl methacrylate (HEMA) by grafting of HEMA monomers onto the PET fibers. HEMA grafted PET (PET-g-HEMA) copolymers were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy. PET and PET-g-HEMA were dissolved in trifluoroacetic acid and nanofibers were obtained by electrospinning. It was found that the PET and PET-g-HEMA polymers having grafting yield 20 and 55% could be converted to continuous, smooth, and beadles nanofibers. For characterization of the nanofiber membranes, thermogravimetric analysis, differential scanning calorimeter analysis, surface contact angle measurement, porosity analysis, and mechanical tests were applied. When compared with the original PET nanofibers, the thermal properties and degradation process of PET-g-HEMA nanofibers changed according to the amount of HEMA present in the structure of nanofibers. The contact angles of the nanofibers obtained from PET-g-HEMA polymers decreased whereas the water retention ability of the nanofibers increased compared to original PET nanofibers. The porosity of PET-g-HEMA nanofibers was found be high compared to PET nanofibers and whereas the mechanical properties of PET was higher than PET-g-HEMA nanofibers. The obtained nanofibers can be used in many fields such as biomaterial applications.     

异端基遥爪聚乙二醇的合成

采用3种新式引发剂,即2-(苄氧基）乙醇钾、2-(四氢-2H-吡喃-2-氧基)乙醇钾、单丙烯基乙二醇钾引发环氧乙烷阴离子开环聚合,反应条件为25 ℃、48 h、醇与萘钾摩尔比例1∶1,得到3种异端基遥爪聚乙二醇。以2-(苄氧基）乙醇钾引发聚合所得产物为起始物,经一系列反应,得到两种两端均为活性基团的异端基遥爪聚乙二醇,这种方法具有普适性。通过1HNMR及GPC手段,表征了产物的结构、分子量及分子量分布。结果表明可以得到高产率、分子量可控且分布窄的异端基遥爪聚乙二醇。     

Tuning the thermoresponsive properties of poly(oligo(propylene glycol) methacrylate) hydrogels via gradient copolymerization with 2-hydroxyethyl methacrylate

Gamma radiation was used to prepare copolymer hydrogel libraries based on oligo(propylene glycol) methacrylate (OPGMA) and 2-hydroxyethyl methacrylate (HEMA); a complete screening in composition of P(OPGMA/HEMA) copolymers was elaborated from 0% to 100% of OPGMA. Determination of gel fraction was performed as the first step after radiation induced synthesis. Tuning of the volume phase transition temperature (VPTT) of P(OPGMA/HEMA) copolymeric hydrogels was investigated by swelling study. Additional characterization of structure and properties was conducted by FTIR, DSC, and UV-Vis spectroscopy. All results indicate that new P(OPGMA/HEMA) copolymeric hydrogels have wide diversity in thermoresponsive properties which strongly depend on their composition.     

Effects of solvent on structures and properties of electrospun poly(ethylene oxide) nanofibers

Poly(ethylene oxide) (PEO) nanofibers were prepared by electrospinning PEO solution with a mixed solvent of ethanol and deionized water. The results show that the mixed solvent system has noteworthy influences on structures and properties of electrospun PEO nanofibers, including molecular chain orientation, crystallinity degree, surface morphology, fiber diameter, diameter distribution, spinnability, and productivity. With increasing ethanol content in the mixed solvent, wrinkly morphologies appear on the surface of PEO nanofibers due to a high evaporation rate of ethanol during electrospinning process. The dielectric constant, dipole moment, conductivity, density, boiling point, and solubility parameter of the mixed solvent become lower with the ethanol content increasing. Besides, the hydrogen‐bonding interactions between PEO and solvents become weaker. As a result, PEO nanofibers with larger diameters, lower molecular chain orientation, and crystallinity degree are obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45787.     

Copolyester of trimellitic acid,glycerol, and poly(ethylene glycol): Synthesis and characterization

A series of copolyesters having a broad range of biodegradable crosslinks were synthesised by FeCl₃‐catalyzed polyesterification of trimellitic acid and glycerol containing a small mol percent of poly(ethylene glycol) (PEG) of varied molecular weights. The polymer samples designated as I (1.5% PEG 2000), II (4.5% PEG 2000), III (7.5% PEG 2000), IV (1.5% PEG 4000), V (4.5% PEG 4000), VI (7.5% PEG 4000), VII (1.5% PEG 6000), VIII (4.5% PEG 6000), and IX (without PEG) are insoluble and moderately tough‐to‐elastic solids and were characterized by their swelling values in ethanol, glass transition temperatures (T_g), IR spectra, and X‐ray diffractograms. Sample IX (0% PEG) has the lowest equilibrium swelling (12% at 25°C) and the highest T_g (155°C) and, therefore, the highest crosslink density. The swelling increases and the T_g decreases as the PEG content or PEG molecular weight in a glycerol–PEG combination increases, indicating a corresponding decrease in the crosslink density of the polymers. Further, the equilibrium swelling value increases with increasing temperature. The IR spectra of the polymers indicate the formation of ester bonds at the expense of COOH and OH groups. The X‐ray diffractograms show their semicrystalline nature. The percent crystallinity values of 53, 52, 49, and 46 for II, III, V, and VII, respectively, and 54 for IX showed that the percent crystallinity decreases with an increasing PEG content and molecular weight in the same way as do the T_g values. Thus, higher T_g values are associated with a higher percent crystallinity, that is, with structures of higher order. The synthesized polymer samples with varied crosslink (biodegradable) densities are expected to be very suitable as matrices for controlled drug delivery over a varied period of time. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 343–346, 2004     

Thermal characteristics of IPNs composed of poly(propylene glycol) and poly(acrylic acid)

Interpenetrating polymer networks (IPNs) based on poly(propylene glycol) (PPG) and poly(acrylic acid) (PAAc) were prepared by UV irradiation and characterized using fourier transform infrared (FTIR), differential scanning calorimetry (DSC), dielectric analysis (DEA), and thermogaravimetry (TGA). The glass transition temperatures (T_gs) of these IPNs exhibited a relatively higher temperature with an increased PAAc content. The decomposition temperature of PAAc is lower than that of PPG. PAAc affects the thermal stability of IPN more than PPG. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2570–2574, 2003     

Synthesis of a bio-based plasticizer from vanillic acid and its effects on poly(vinyl chloride)

A new bio-based plasticizer, VA8-8, was prepared derived from vanillic acid, and its structure was verified by nuclear magnetic resonance. It was incorporated into poly(vinyl chloride) (PVC) to replace dioctyl phthalate (DOP), and its plasticizing performance was evaluated. The results indicated that VA8-8 shows good compatible with PVC resin, and has a excellent plasticizing effect for PVC. When DOP was partially or completely substituted with VA8-8, the T_g value PVC blends dropped from 34.6 to 24.3°C and the elongation at break increased from 196.4% to 301.9%, suggesting the enhanced plasticizing efficiency of plasticizer. The plasticizing mechanism was also simulated, and the interactions between VA8-8 and PVC molecules were discussed. The thermogravimetric analysis showed VA8-8 can more effectively improve the thermal stability of PVC than DOP. In addition, the migration resistance of VA8-8 was generally superior to that of DOP. Therefore, VA8-8 is a comparable to or better plasticizer than DOP, and it is a promising alternative plasticizer for PVC.