Synthesis of monodisperse porous poly(divinylbenzene) microspheres by distillation-precipitation polymerization

Highly crosslinked monodisperse porous poly(divinylbenzene) (PDVB) microspheres were prepared by distillation-precipitation polymerization in acetonitrile containing up to 25 vol% of toluene as porogen with 2,2′-azobisisobutyronitrile (AIBN) as initiator in the absence of any stabilizer or surfactant. The porous polymer microspheres were formed through a precipitation manner during the distillation of the solvent from the reaction system. Monodisperse porous polymer particles with spherical shape and smooth surface were synthesized with diameters in the range of 1.86 and 3.06 μm, total porosity of up to 0.30 cm³/g and specific surface area as high as 762 m²/g. The growth procedure of porous PDVB microsphere was characterized by SEM technique for morphological observation and isotherm nitrogen adsorption for the determination of the special surface area and porosity. The resultant porous polymer microspheres had a novel structure with the gradual increasing of pore volume during distillation of the solvent out of the reaction system.     

Synthesis and characterization of a polystyrenic resin functionalized by catechol: Application to retention of metal ions

Chelating solid phase extraction is a preconcentration method adapted for metal ions extraction in water and requires functionalization of a solid sorbent by an organic ligand. A new chelating resin has been prepared by grafting catechol on Amberlite^® XAD-4 with an imine bridge and reducing it to enhance stability of the modified resin. Synthesis was first carried out at molecular level to validate experimental conditions, optimize yields and facilitate characterization of solid sorbent (particularly by FTIR). Each synthesis step of grafting on Amberlite^® XAD-4 was characterized by FTIR, Py-GC–MS and TGA-DSC. BET measurements showed a decrease in specific area after grafting from 865 to 425 m² g⁻¹ and in total pore volume from 1.19 to 0.66 cm³ g⁻¹. The grafting rate of 33% was determined by back titration of –OH (0.31 ± 0.03 mmol g⁻¹ of resin) and –NH-functions (0.93 ± 0.02 mmol g⁻¹ of resin). The increase in the sorbent hydrophilicity was confirmed by evaluating the water regain. Finally the retention properties of Cd(II), Cu(II), Ni(II) and Pb(II) were determined by ICP-AES at a pH range from 2 to 9. Retention rates of 94% and 98% were found at pH 8 for Cu(II) and Pb(II), respectively. Sorption capacities of 25.8 ± 2.5 μmol g⁻¹ for Cd(II), 89.7 ± 8.4 μmol g⁻¹ for Cu(II), 49.0 ± 10.5 μmol g⁻¹ for Ni(II) and 31.5 ± 1.6 μmol g⁻¹ for Pb(II) were measured.     

Synthesis and characterization of poly(fluorene vinylene) copolymers containing thienylene–vinylene units

Narrow‐band‐gap 2,5‐thienylene‐divinylene (ThV) units were incorporated into the poly(fluorene vinylene) backbone via a Gilch reaction as an energy trap with various feed ratios; this yielded pronounced changes in the electrochemical and optical properties of the material. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the polymers {poly(9,9‐di‐iso‐octylfluorene vinylene) [poly(fluorene vinylene‐co‐thiophene vinylene (FV))], C1, and C2 } were estimated to be ?5.53 to ?5.10 eV and ?2.98 to ?2.84 eV, respectively, by cyclic voltammetry measurements. In comparison with poly(FV), the HOMO energy levels of polymers poly(fluorene vinylene‐co‐thiophene vinylene (FV) (90 : 10) ( C1 ) and poly(fluorene vinylene‐co‐thiophene vinylene (FV) (80 : 20) ( C2 ) were significantly increased, but their LUMO energy levels were slightly decreased. The optical properties were investigated by absorption and emission spectra of the polymers. The good spectral overlap between the emission of poly(FV) and the absorption of polymers C1 and C2 revealed a sufficient energy transfer from the majority of 9,9‐di‐iso‐octylfluorene vinylene units to the minority of ThV units. The reduction of self‐absorption losses of polymers C1 and C2 due to spectral separation caused by the incorporation of ThV units could be indirectly confirmed by nonlinear optical (NLO) properties. The result of the NLO properties of the polymers showed that the third‐order NLO coefficients of poly(FV), C1, and C2 were 8.1 × 10^?10, 1.35 × 10^?9, and 1.51 × 10^?9 esu, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Highly sensitive and simultaneous determination of hydroquinone and catechol at poly(thionine) modified glassy carbon electrode

A simple and highly sensitive electrochemical method for the simultaneous and quantitative detection of hydroquinone (HQ) and catechol (CT) was developed, based on a poly(thionine)-modified glassy carbon electrode (GCE). The modified electrode showed excellent electrocatalytic activity and reversibility towards the oxidation of both HQ and CT in 0.1 M phosphate buffer solution (PBS, pH 7.0). The peak-to-peak separations (ΔE_p) between oxidation and reduction waves in CV were decreased significantly from 262 and 204 mV at the bare GCE, to 63 and 56 mV, respectively for HQ and CT at the poly(thionine) modified GCE. Furthermore, the redox responses from the mixture of HQ and CT were easily resolved in both CV and DPV due to a difference in the catalytic activity of the modified GCE to each component. The peak potential separation of ca. 0.1 V was large enough for the simultaneous determination of HQ and CT electrochemically. The oxidation peak currents of HQ and CT were linear over the range from 1 to 120 μM in the presence of 100 and 200 μM of HQ and CT, respectively. The modified electrode showed very high sensitivity of 1.8 and 1.2 μA μM⁻¹ cm⁻² for HQ and CT, respectively. The detection limits (S/N = 3) for HQ and CT were 30 and 25 nM, respectively. The developed sensor was successfully examined for real sample analysis with tap water and revealed stable and reliable recovery data.     

Application of electrosynthesized poly(aniline-co-p-aminophenol) as a catechol sensor

Poly(aniline-co-p-aminophenol) (copolymer) film was used as a sensor to determine the presence of catechol, taking advantage of the ability of the film to effectively catalyze the oxidation of catechol. The copolymer served as an electron transfer mediator between the electrode surface and catechol in the solution. The response current of the catechol sensor depended on the applied potential, pH and temperature at a given concentration of catechol. At optimum conditions, the catechol sensor displayed an excellent electrocatalytic response to the detection of catechol in a concentration range from 5 to 500 μM with a detection limit of 0.8 μM. The effects of selected organic compounds on the response of the catechol sensor were studied. Together, these findings show that the catechol sensor exhibits a better selectivity towards interfering species and a better operational and storage stability.     

Synthesis and characterization of poly(pyridinium salt)s with oxyalkylene units exhibiting amphotropic liquid-crystalline and photoluminescence properties

Several novel poly(pyridinium salt)s with oxyalkylene moieties in the main chain with bulky organic counterions (tosylate and triflimide) were prepared by either the ring-transmutation polymerization of phenylated bis(pyrylium tosylate) salt with a series of oxyalkylene containing diamines in dimethyl sulfoxide on heating for 48 h or the metathesis reaction of the corresponding tosylate polymers with lithium triflimide in methanol. Their chemical structures were determined by elemental analysis and ¹H and ¹³C NMR spectroscopies, and their polyelectrolyte behavior in dimethyl sulfoxide was determined by solution viscosity measurements. Their weight average molecular weights were in the range 14,000-22,000 and polydispersity indices were in the range 1.20-1.70 as determined by gel permeation chromatography. They were characterized both for their thermotropic and lyotropic liquid-crystalline properties by using differential scanning calorimetry and polarizing optical microscopy. Since these polymers exhibited liquid-crystalline phase both in the melt and in solution, they can be appropriately classified as amphotropic class of ionic polymers. Their light-emitting properties were also determined by using spectrofluorometry.     

Synthesis and characterization of adamantane-containing poly(enaminonitriles)

The first aliphatic bis(chlorovinylidene cyanide) monomer, 1,3-bis(1-chloro-2,2-dicyanovinyl)adamantane, has been synthesized and polymerized with appropriate diamines to give adamantane-containing aromatic-aliphatic and all aliphatic poly(enaminonitriles) (PEANs) via vinylic nucleophilic substitution polymerization. The PEANs showed excellent solubility in polar aprotic solvents and good thermal stability (10% weight loss in air > 320 °C), despite the aliphatic contents of the polymers. Solution inherent viscosities of 0.23-0.90 dL/g were obtained.Three other new PEANs containing the adamantane-based cardo group were also synthesized via vinylic nucleophilic substitution polymerization from the adamanaine-containing cardo diamine 2,2-bis[4-(4-aminophenoxy)phenyl]adamantane. The cardo PEANs showed better solubility in common organic solvents than the corresponding cardo polyamides. They also showed good thermal stabilities (10% weight loss in air > 339 °C) comparable to those of the corresponding cardo polyamides.     

Synthesis and characterization of poly(catechol) catalyzed by porphyrin and enzyme

Catalytic polymerization of catechol was performed employing the cationic porphyrin and horseradish peroxidase (HRP) as catalysts. The obtained results demonstrate that the cationic metalloporphyrin is a more-efficient catalyst than the HRP in the catechol polymerization. The oxidative polymerization was carried out in the presence of polystyrene sulfonate (PSS) as a template. According to TGA data, poly(catechol) that is synthesized by porphyrin catalyst exhibits more thermal stability than the enzymatic catalyzed product. The GPC indicate higher molecular weight of polymer synthesized by porphyrin as a catalyst. Cyclic voltammetry measurements show that the synthesized polymers have convenient electroactivity. The poly(catechol) and its methyl and methoxy derivatives that are synthesized by porphyrin catalyst show low electrical conductivity.     

Synthesis of a novel histidine‐targeting poly(ethylene glycol) and modification of lysozyme

A simple and highly efficient method was developed to prepare a synthetic poly(ethylene glycol) (PEG) derivative, which can be used for conjugation to histidine residue. This derivative reacted with sodium nitrite and the intermediate 4‐diazo‐N‐mPEG‐benzamide proved to have a good performance for histidine modification of lysozyme. Then the pegylated lysozyme was separated and its bacteriolytic activities were determined. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of composite resin by vinyl chloride grafted onto poly(BA-EHA)/poly(MMA-St)

Crosslinked poly(butyl acrylate-co-2-ethylhexyl acrylate)/poly(methyl methacrylate-co-styrene) (ACR I) latex was synthesized by multi-stage emulsion polymerization. A series of grafting vinyl chloride (VC) composite latices were prepared by emulsion copolymerization in the presence of core-shell ACR I latex. The effects of ACR I amount and its core/shell ratio on particle diameters of the composite latices and mechanical properties of the prepared materials were investigated. The grafting efficiency (GE) of VC grafted onto ACR I increases with an increasing ACR I content. Transmission electron microscope (TEM) study indicates that ACR I latex particles have a regular core-shell structure obviously. However, when styrene content in the shell of ACR I is more than 70 percent of the shell by weight, ACR I latex particles have an irregular core-shell morphology like sandwich. The composite latex particles synthesized by core-shell ACR I latex grafting VC have a clear three-layered core-shell structure. Dynamic mechanical analysis (DMA) study reveals that the compatibility between ACR I and PVC is well improved. With increasing ACR I content, the loss peak in low temperature range for every composite sample becomes stronger and stronger and gradually shifts to a higher temperature. Scanning electron microscope (SEM) graphs showed that the fractured surface of the composite sample exhibited better toughness of the material. TEM graphs showed that ACR I was uniformly dispersed in the PVC matrix.     

Synthesis of hyperbranched P poly(glycerol-diacid) oligomers

Novel oligomeric prepolymers were synthesized by acid-catalyzed condensation of glycerol with iminodiacetic, azelaic, or succinic acid. The prepolymers were obtained, on average, in 62% yield and were characterized by ¹³C NMR, ¹H NMR, matrix-assisted laser desorption ionization-time of flight-mass spectrometry, and gel permeation chromatography. The synthesized oligomers had an average M.W. of 1543 Daltons (average polydispersity (PD)=1.34, average degree of polymerization (DOP)=5.5). Hyperbranching was evident in the oligomers produced when using azelaic acid and succinic acid as co-monomers with glycerol, whereas the reaction between iminodiacetic acid and glycerol resulted in linear products bearing cyclic urethane structures.     

Synthesis and characterization of poly(pyridylurea) and poly(pyridylthiourea), potentially semiconducting polymers

Poly(pyridylureas) and poly(pyridylthioureas) were synthesized by reacting 2,6‐diaminopyridine with phosgene and thiophosgene, respectively, using THF and pyridine as solvent. The synthesized polymers were characterized by IR‐spectroscopy, elemental analysis, and X‐ray photoelectron spectroscopy. Thermal stability of the polymers was determined by thermal degradation between 35°C and 700°C. The 50% weight loss of polypyridylureas was above 400°C while for the polypyridylthioureas it was above 450°C. Undoped poly(pyridylureas) and poly(pyridylthioureas) behave as semiconductors, σ = 10^?9 (Ω cm)^?1. After doping with I₂ and SbF₅, the electrical conductivity increases several orders of magnitude, σ = 10^?7(Ω cm)^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Properties of carbon fiber sized with poly(phthalazinone ether ketone) resin

We studied thermoplastic poly(phthalazinone ether ketone) (PPEK) resin as a sizing agent on carbon fiber, with emphasis on its thermal stability, surface energy, wetting performance, and interfacial shear strength (IFSS). X‐ray photoelectron spectroscopy characterization was carried out to study the chemical structure of sized/unsized carbon fibers. Scanning electron microscopy and atomic force microscopy were used to characterize surface topography. TGA was used to analyze the thermal stability. Meanwhile, contact angle measurement was applied to analyze the compatibility between the carbon fibers and PPEK and the surface energy of carbon fibers. IFSS of carbon fiber/PPEK composite was examined by microbond testing. It is found that carbon fibers uniformly coated with PPEK resin had better thermal stability and compatibility with PPEK resin than the uncoated fiber. The contact angle is 57.01° for sized fibers, corresponding to a surface energy of 49.96 mJ m^?2, much smaller than that for unsized ones with contact angle value of 97.05°. The value of IFSS for sized fibers is 51.49 MPa, which is higher than the unsized fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of poly(ferrocenylsilane) high polymers

Ring-opening polymerization of strained, ring-tilted cyclic ferrocenylsilanes has recently provided access to the first examples of high molecular weight poly(ferrocenylsilanes) [1], which possess backbones of alternating ferrocenyl groups and silicon atoms. In this paper we provide an overview of the progress to date on the synthesis and properties of these unusual polymers.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Synthesis and characterization of diblock,triblock, and multiblock copolymers containing poly(3‐hydroxy butyrate) units

A poly[(R,S)‐3‐hydroxybutyrate] macroinitiator (PHB‐MI) was obtained through the condensation reaction of poly[(R,S)‐3‐hydroxybutyrate] (PHB) oligomers containing dihydroxyl end functionalities with 4,4′‐azobis(4‐cyanopentanoyl chloride). The PHB‐MI obtained in this way had hydroxyl groups at two end of the polymer chain and an internal azo group. The synthesis of ABA‐type PHB‐b‐PMMA block copolymers [where A is poly(methyl methacrylate) (PMMA) and B is PHB] via PHB‐MI was accomplished in two steps. First, multiblock active copolymers with azo groups (PMMA‐PHB‐MI) were prepared through the redox free‐radical polymerization of methyl methacrylate (MMA) with a PHB‐MI/Ce(IV) redox system in aqueous nitric acid at 40°C. Second, PMMA‐PHB‐MI was used in the thermal polymerization of MMA at 60°C to obtain PHB‐b‐PMMA. When styrene (S) was used instead of MMA in the second step, ABCBA‐type PMMA‐b‐PHB‐b‐PS multiblock copolymers [where C is polystyrene (PS)] were obtained. In addition, the direct thermal polymerization of the monomers (MMA or S) via PHB‐MI provided AB‐type diblocks copolymers with MMA and BCB‐type triblock copolymers with S. The macroinitiators and block copolymers were characterized with ultraviolet–visible spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, cryoscopic measurements, and thermogravimetric analysis. The increases in the intrinsic viscosity and fractional precipitation confirmed that a block copolymer had been obtained. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1789–1796, 2004     

Synthesis of macroporous poly(styrene-divinyl benzene) microspheres by surfactant reverse micelles swelling method

Macroporous poly(styrene-divinyl benzene) microspheres with pore size of about 500 nm were prepared by a new method, surfactant reverse micelles swelling method. The macroporous microspheres were prepared by convenient suspension polymerization. The difference from conventional suspension polymerization was that a higher concentration of surfactant was added in the oil phase. The effects of the amount and type of surfactants on the morphology of microspheres were investigated, and the formation mechanism was also discussed. Macropores were formed when the concentration of surfactant was much higher than critical micelle concentration (cmc). It was proposed that a large amount of reverse micelles formed by adding a large amount of surfactant in the oil droplet phase, and the reverse micelles could absorb water from the external aqueous phase. The water in the oil phase formed macropores after polymerization. The method developed in this study was convenient to prepare microspheres with larger pore size than the conventional method such as agglomeration method of nanoparticles.     

Synthesis and properties of a new type of unsaturated poly(ester amide)

A new type of unsaturated poly(ester amide), maleic anhydride–phthalic anhydride–ethylene glycol–neopentylene glycol–anthranilic acid copolymer, was prepared by melt polycondensation. The copolymer was characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The viscosity of the polymer was measured with a Ubbelohde viscometer. The compressive strength of the crosslinked unsaturated poly(ester amide) under different heat‐treatment conditions was measured. Studies of its degradation behavior were carried out in simulated body fluid at pH 7.4 (37°C), and the compressive strength loss of the crosslinked unsaturated poly(ester amide) was also measured after different degradation times. The copolymer was hydrolyzed in a 1.0‐mol/L NaOH standard solution at room temperature. All of the preliminary results suggest that the new unsaturated poly(ester amide) might potentially be used as a new type of bone‐fixation material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of carbon quantum dots to fabricate ultraviolet-shielding poly(vinylidene fluoride) films

The paper presents a simple and effective approach to fabricating a poly(vinylidene fluoride) (PVDF) film with excellent ultraviolet (UV) shielding performance. Carbon quantum dots (CQDs) with a highly UV absorbing property were made via a hydrothermal reaction and were then added to a poly(vinyl alcohol) (PVA) solution. The PVDF membrane pretreated with an alkaline solution was immersed in the prepared CQD/PVA solution to coat a UV-shielding layer on the film surface. Fourier transform infrared spectroscopy, X-ray photoelectron spectrometry, X-ray diffraction, transmission electron microscopy, and UV–visible spectrophotometry were applied to study the structure, morphology, and optical performance of the CQD particles. The stability and UV-shielding performance of the obtained PVDF-OH@CQDs/PVA composite film were further investigated. The results showed that the CQD particles with diameter of 18 nm could be well dispersed in solution. Additionally, the CQDs had fairly high UV absorbance, and the PVDF-OH@CQDs/PVA composite film could shield the UV light completely. The method described in this paper is a promising one for fabricating UV-shielding composite films. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47555.     

Synthesis and properties of novel poly(coumarin‐amide)s

A novel monomer diacid, 6,6′‐methylenebis(2‐oxo‐2H‐chromene‐3‐carboxylic acid), was synthesized and used in a direct polycondensation reaction with various aromatic diamines in N‐methyl‐2‐pyrrolidone solution containing dissolved LiCl and CaCl₂, using triphenyl phosphite and pyridine as condensing agents to give a series of novel heteroaromatic polyamides containing photosensitive coumarin groups in the main chain. Polyamide properties were investigated by DSC, TGA, GPC, wide‐angle X‐ray scattering, viscosity, and solubility measurements. The copolymers were soluble in aprotic polar solvents, and their inherent viscosities varied between 0.49 and 0.78 dL g^?1. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 27,500–43,900 g mol^?1 and 46,500–66,300 g mol^?1, respectively, and polydispersities in the range of 1.48–1.69. The aromatic polyamides showed glass‐transition temperatures (T_g) ranging from 283 to 329°C and good thermal properties evidenced by no significant weight loss up to 380°C and 10% weight loss recorded above 425°C in air. All the polyamides exhibited an amorphous nature as evidenced by wide‐angle X‐ray diffraction and demonstrated a film forming capability. Water uptake values up to 3.35% were observed at 65% relative humidity. These polymers exhibited strong UV‐vis absorption maxima at 357–369 nm in DMSO solution, and no discernible photoluminescence maxima were detected by exciting with 365 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

甲基丙烯酸甲酯-丁二烯-苯乙烯树脂的合成及其对聚氯乙烯的改性

采用种子乳液接枝聚合技术合成了甲基丙烯酸甲酯(MMA)-丁二烯-苯乙烯树脂(MBS),考察了复合乳化剂浓度、CO2用量对丁苯胶乳粒径及其分布、胶乳稳定性的影响;研究了接枝单体滴加方式和接枝聚合反应温度对MBS体系稳定性和接枝效率的影响;讨论了MBS改性聚氯乙烯(PVC)的影响因素;提出了丁苯胶乳的碳酸化扩径附聚法和MBS胶乳的SO2凝聚新工艺。结果表明:在丁二烯/苯乙烯(质量比)为90/10、阴离子/非离子复合乳化剂浓度为35~40g/L、丁苯胶乳采用CO2附聚扩径、部分MMA预溶胀和其余MMA连续滴加的方式以及MBS胶乳SO2凝聚新工艺的条件下,所得MBS树脂粉料颗粒均匀,40~180目的颗粒质量分数达96%,堆积密度在0.4g/cm3以上;PVC/MBS(质量比为100/8)共混物的冲击强度达22.6kJ/m2。