Synthesis,characterization and cytotoxicity of novel modified poly[(maleic anhydride)‐ co‐(vinyl acetate)]/noradrenaline conjugate

Poly[(maleic anhydride)‐co‐(vinyl acetate)] (MAVA) copolymer was synthesized by free radical polymerization reaction, in methyl ethyl ketone at 80 °C, using benzoyl peroxide as the initiator. The copolymer was then modified with a biomolecule, noradrenaline (NA). The modification reaction was performed at 70 °C in dimethylformamide containing triethylamine as the catalyst. The modified polymer was named MAVA/NA. Structural characterization of the copolymer and the modified product was carried out by Fourier transform infrared (FTIR) and ¹H NMR and ¹³C NMR spectroscopy. The FTIR, ¹H NMR and ¹³C NMR spectra confirmed that NA was successfully covalently bound to the MAVA copolymer backbone. Surface morphology was visualized by atomic force microscopy. The cumulative release of NA from MAVA/NA was determined in phosphate buffered saline solution for 7 days at 37 °C and compared with MAVA. Cytotoxicity of the MAVA/NA was evaluated by using a mouse fibroblast cell line (L929). Results obtained indicated that MAVA/NA had almost no toxicity and no negative effect on cell viability at 250 µg mL^?1 concentration. © 2012 Society of Chemical Industry     

Synthesis,characterization and in vitro antibacterial assessments of a novel modified poly[maleic anhydride-alt-acrylic acid]/acriflavine conjugate

Water-soluble maleic anhydride-containing poly[maleic anhydride-alt-acrylic acid] (poly(MA-alt-AA) or MAAA) copolymer was synthesized by free-radical chain polymerization reaction, in 1,4-dioxane in the presence of benzoyl peroxide, 0.1 %, as the radical initiator at 70 °C under a nitrogen atmosphere. The purified copolymer was then modified with an anti-external fungal and anti-cancer active agent, acriflavine (AF). The modification reaction was performed 48 h at 70 °C in dimethylformamide organic media, using triethylamine (TEA or Et₃N) as the catalyst. The modified or conjugated copolymer/drug couple was named as MAAA/AF. Detailed structural characterization of the copolymer (MAAA) and modified product (MAAA/AF) was carried out by Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (¹H-NMR and ¹³C-NMR). The obtained FTIR, ¹H-NMR, and ¹³C-NMR spectra confirmed that AF was successfully bound to the MAAA copolymer backbone by ring-opening reaction. Antimicrobial susceptibility of the MAAA, AF, and MAAA/AF was evaluated by Kirby Bauer Disc Diffusion method on Mueller–Hinton Agar using Enterecoccus faecium, Enterohaemorrhagic Escherichia coli (EHEC), Staphylococcus aureus and Listeria monocytogenes. Results obtained indicated that MAAA/AF had antibacterial activity on EHEC and S. aureus at 50, 40, and 30 µg. A mechanism for MAAA and AF was then also suggested for the conjugation reaction.     

Synthesis,structural characterization and properties of novel functional poly(ether imide)/titania nanocomposite thin films

In this study, the synthesis, morphology, and thermal properties of new poly(ether imide)/titania nanohybrid films were investigated. The novel diamine containing functional nitrile groups was prepared in two steps by the nucleophilic substitution reaction and it was fully characterized by different techniques. Reaction of this diamine with pyromellitic dianhydride and 4-aminobenzoic acid gave poly(ether imide) with carboxylic acid end groups. This acid functionalized poly(ether imide) was condense with different amount of TiO₂ nanoparticles to provide organic-inorganic bonding, and the flexible films of these hybrid were prepared. The obtained materials were characterized by Fourier transform-infrared spectroscopy, thermogravimetry analysis (TGA), differential scanning calorimetry, X-ray powder diffraction, UV–Vis spectroscopy, field emission-scanning electron microscopy, and transmission electron microscopy (TEM) techniques. TEM of the nanohybrid films with 12% of TiO₂ contents confirms well dispersion of nanoparticles in the polymer matrix. TGA data indicated that the thermal behavior of the hybrid materials was increased with an increasing the content of TiO₂ nanoparticles. The tensile stress–strain of the hybrids was investigated and the resulting nanocomposites showed good mechanical properties. The permeability and selectivity of the PEI/TiO₂ membranes as a function of the titania weight percentage were study and the results indicated that the permeabilities of CO₂ and N₂ increase with increasing the titania content.     

Synthesis and characterization of novel poly(dimethylsiloxane)/polyindole composites

A series of composites of polyindole (PIN) and poly(dimethylsiloxane) (PDMS) were synthesized chemically using FeCl₃ as an oxidant agent in anhydrous media. The composites were characterized by FTIR and UV‐visible spectroscopies, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), X‐ray diffraction (XRD), elemental analysis, inductively coupled plasma‐optic emission spectroscopy (ICP‐OES), magnetic susceptibility, stress–strain experiments, and conductivity measurements. The conductivities of PIN at different temperatures were also measured and it was revealed that their conductivities were slightly increased with increasing temperature. Moreover, the freestanding films of PDMS/PIN composites were prepared by casting on glass Petri dishes to examine their stress–strain properties. From thermogravimetric analysis results it was found that PDMS/PIN composites were thermally more stable than PIN. Thermal stabilities of PDMS/PIN composites increased with increasing PIN content. It was found that the conductivities of PDMS/PIN composites depend on the indole content in the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(propylene carbonate)/modified sepiolite nanocomposites

A series of poly(propylene carbonate) (PPC)/modified sepiolite (mSp) nanocomposites with different mSp contents were prepared via a solution‐based processing method. The modified sepiolite was obtained by fabricating sepiolite with methyl trimethoxysilanes (MTMS) gel. The effect of mSp amount, in the range 1–10 wt%, on the morphology, mechanical properties, and thermal degradation of PPC was investigated by means of scanning electron microscopy (SEM), X‐ray diffractometry (XRD), static strenching analysis, thermogravimetric analyses (TGA), differential scanning calorimetry (DSC). Morphological studies showed the homogeneous dispersion of mSp in the PPC matrix whose structure remains amorphous. The nanoscale dispersion of mSp significantly enhanced the mechanical properties and thermal stability. The thermal motion and degradation of the polymer occur at higher temperature in the presence of mSp because of the strong interfacial adhesion between the two components. POLYM. COMPOS., 21–27, 2016. © 2014 Society of Plastics Engineers     

Preparation and characterization study on maleic acid cross-linked poly(vinyl alcohol)/chitin/nanocellulose composites

In the quest on improving composite formulations for environmental sustainability, maleic acid (MA) cross-linked poly(vinyl alcohol) (PVA)-α-chitin composites reinforced by oil palm empty fruit bunch fibers (OPEFB)-derived nanocellulose crystals (NCC) had been successfully prepared. Based on the Fourier transform infrared (FTIR) spectroscopic analysis, it was proven that molecular interactions of the cross-linker to the polymeric networks was through conjugated ester linkage. Differential scanning calorimetry (DSC) showed that the influence of MA was minimal toward crystallization in the PVA/chitin/NCC composite. Maximum tensile strength, elongation at break and Young's modulus of the respective PVA/chitin/NCC composites were achieved at different content of MA, dependent on the PVA/chitin mass ratio. Among all compositions, a maximum Young's modulus was achieved at 30 wt% MA loading in PVA/chitin-30/NCC, amounting to 2,413.81 ± 167.36 MPa. Moreover, the mechanical properties and selected physicochemical properties (swelling, gel content, and contact angle) of the PVA/chitin/NCC composites could be tailored by varying the chitin content (10–30 wt%) and MA content (10–50 wt% based on total mass of composite). In brief, this chemically cross-linked PVA-based biocomposites formulated with sustainable resources exhibited tunable physicochemical and mechanical properties.     

聚(N-异丙基丙烯酰胺)/聚丙烯酸半互穿网络微凝胶的合成及表征

利用IPN技术合成了一种具有温度和pH双重敏感性的聚（N-异丙基丙烯酰胺）/聚丙烯酸半互穿网络微凝胶（PNIPAM/PAAc semi-IPN）。这种微凝胶在酸性条件下发生典型的体积相转变;而在弱碱性条件下,当温度低于聚（N-异丙基丙烯酰胺）（PNIPAM）微凝胶的体积相转变温度（VPTT）时,微凝胶的粒径随着温度的上升而增大,当温度达到VPTT后,粒径突然急剧减小,并随着温度的逐渐上升而减小,最终趋向平衡。     

Synthesis of poly(acrylate-styrene)/poly(acrylate-styrene) core/shell latex and TOPEM-DSC characterization

Poly(acrylate-styrene)/poly(acrylate-styrene) core/shell latex particles were synthesized via seeded semi-continuous emulsion polymerization. Both core polymer (CP) and shell polymer (SP) were copolymerized by using three identical monomers of methyl methacrylate (MMA), butyl acrylate (BA) and styrene (St) with different composition ratios. The synthesized core/shell latex particle presents a phase separated state with the interfacial layer between CP and SP. In this study, the weight fractions and the corresponding thickness of this interfacial layer, CP and SP phase in the core/shell latex particle has be successfully calculated by using multi-frequency temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results indicate that the interfacial layer thickness of the core/shell latex particle is determined by the core/shell structure, such as hard core/soft shell (defined as HC/SS) and soft core/hard shell (defined as SC/HS), the glass transition temperature (T_g) of the “hard” phase (correspondingly core or shell for HC/SS or SC/HS structure, respectively), and the existence of hydrophilic monomer during the copolymerization process such as acrylic acid. Meanwhile, the influence of film-formation-temperature on the microstructure of the latex films was systematically explored in this work.     

Synthesis and characterization of poly(butyl acrylate)/silica and poly(butyl acrylate)/silica/poly(methyl methacrylate) composite particles

Poly(butyl acrylate)/poly(methyl methacrylate) (PBA/PMMA) core–shell particles embedded with nanometer‐sized silica particles were prepared by emulsion polymerization of butyl acrylate (BA) in the presence of silica particles preabsorbed with 2,2′‐azobis(2‐amidinopropane)dihydrochloride (AIBA) initiator and subsequent MMA emulsion polymerization in the presence of PBA/silica composite particles. The morphologies of the resulting PBA/silica and PBA/silica/PMMA composite particles were characterized, which showed that AIBA could be absorbed effectively onto silica particles when the pH of the dispersion medium was greater than the isoelectric potential point of silica. The critical amount of AIBA added to have stable dispersion of silica particles increased as the pH of the dispersion medium increased. PBA/silica composite particles prepared by in situ emulsion polymerization using silica preabsorbed with AIBA showed higher silica absorption efficiency than did the PBA/silica composite particles prepared by direct mixing of PBA latex and silica dispersion or by emulsion polymerization in which AIBA was added after the mixing of BA and silica. The PBA/silica composite particles exhibited a raspberrylike morphology, with silica particles “adhered” to the surfaces of the PBA particles, whereas the PBA/silica/PMMA composite latex particles exhibited a sandwich morphology, with silica particles mainly at the interface between the PBA core and the PMMA shell. Subsequently, the PBA/silica/PMMA composite latex obtained had a narrow particle size distribution and good dispersion stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3425–3432, 2006     

Poly(methyl methacrylate)/poly(ethylene glycol)/poly(ethylene glycol dimethacrylate) micelles: Preparation,characterization, and application as doxorubicin carriers

A crosslinked amphiphilic copolymer [poly(ethylene glycol) (PEG)–poly(methyl methacrylate) (PMMA)–ethylene glycol dimethacrylate (EGDM)] composed of PMMA, PEG, and crosslinking units (EGDM) was synthesized by atom transfer radical polymerization to develop micelles as carriers for hydrophobic drugs. By adjusting the molar ratio of methyl methacrylate and EGDM, three block copolymer samples (P0, P1, and P2) were prepared. The measurement of gel permeation chromatography and ¹H‐NMR indicated the formation of crosslinked structures for P1 and P2. Fluorescence spectroscopy measurement indicated that PEG–PMMA–EGDM could self‐assemble to form micelles, and the critical micelle concentration values of the crosslinked polymer were lower than those of linear ones. The prepared PEG–PMMA–EGDM micelles were used to load doxorubicin (DOX). The drug‐loading efficiencies of P1 and P2 were higher than that of P0 because the crosslinking units enhanced the micelles' stability. With increasing drug‐loading contents, DOX release from the micelles in vitro was decreased, and in the crosslinked formulations, the release rate was also slower. An in vitro release study indicated that DOX release from the micelles for the linear samples was faster than that for crosslinked micelles. The drug feeding amount increased and resulted in an increase in the drug‐loading content, and the loading efficiency decreased. These PEG–PMMA–EGDM micelles did not show toxicity in vitro and could reduce the cytotoxicity of DOX in the micelles; this suggested that they are good candidates as stable drug carriers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39623.     

Synthesis and characterization of poly(vinyl acetate peroxide)

Poly(vinyl acetate peroxide) (PVACP) was prepared from vinyl acetate by free-radicalinitiated oxidative polymerization. The polyperoxide was isolated and characterized by different spectroscopic methods. The extreme instability of PVACP was demonstrated by FTIR spectroscopy. The ¹H-and ¹³C-NMR studies show the irregularities in the polyperoxide chain due to the cleavage reactions of the propagating peroxide radical. Thermal degradation studies using differential scanning calorimetry revealed that PVACP degrades at a lower temperature and the heat of degradation is in the same range as reported for other vinyl polyperoxides. © 1996 John Wiley & Sons, Inc.     

Novel ternary poly(vinyl pyrrolidone)/poly(amide-imide)/ZnO nanocomposite: Synthesis,characterization, thermal and optical performance

The present work describes the synthesis and properties of polymer composites based on poly(vinyl pyrrolidone) (PVP) as polymer shell and poly(amide-imide)(PAI)/ZnO nanocomposite (ZNC) as efficient filler. At first, the alanine amino acid containing dicarboxylic acid was grafted on the surface of ZnO NPs. Then, modified ZnO (12 wt%) was incorporated into the PAI matrix under ultrasonic irradiations. The obtained hybrid ZNC showed high thermal stability and the size of the NPs in the TEM image of ZNC was about 31 nm. Secondly, PVP NCs with different ZNC loadings such as 2, 4 and 6 wt% were prepared via ultrasonication. Transmission electron microscopy (TEM) observations showed that the ZnO NPs were uniformly and highly dispersed in the PVP matrix. The UV–vis results exposed that the high UV-shielding efficiency of the obtained composites. Thermal analysis represented that the onset decomposition temperatures of the obtained PVPNCs had remarkable increasing in compared to the neat PVP due to the presence of both ZnO NPs and PAI.     

Synthesis and characterization of intercalated ladder‐like poly(vinylsilsesquioxanes)/organically modified montmorillonite nanocomposites

In this paper, ladder‐like poly(vinylsilsesquioxanes) (LPVS)/organically modified montmorillonite (OMT) nanocomposites have been synthesized by ultrasonic dispersion and solution blending method. The structures of nanocomposites are characterized by small angle X‐ray scattering (SAXS) and high‐resolution transmission electronic microscopy (TEM). These results indicate that LPVS have already entered the galleries of OMT layers and intercalated LPVS/OMT nanocomposites have been formed. The effects of different reaction conditions, including solution concentration and the advantage of ultrasonic dispersion, are discussed. The intercalated nanocomposite is further treated at 250.0°C for 2 h in order to eliminate surfactant in OMT. On the basis of the SAXS and TGA results, it has been found that the treated product remains in its intercalated structure and presents better thermal stability, which provides potential usage in polymer composites. POLYM. COMPOS., 27: 660–664, 2006. © 2006 Society of Plastics Engineers     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

一种改性聚乙酸乙烯酯乳液的合成与性能

通过在乳液聚合过程中引入单体N-羟甲基丙烯酰胺参与共聚的方法,制得一种改性聚乙酸乙烯酯乳液,实验结果表明,该乳液具有良好的稳定性、耐水性、成膜性、粘接性,N-羟甲基丙烯酰胺的用量以乙酸乙烯酯质量的1%~2%为宜,聚合周期比普通PVAc乳液缩短40%左右。     

Miscibility and crystallization behavior of poly(ethylene-co-vinylalcohol)/poly(maleic anhydride-alt-ethylene) blend

The miscibility of poly(vinylalcohol-co-ethylene) (PEVA) with poly(ethylene-alt-maleic anhydride) (PEMAH) blends was investigated over a wide range of compositions by viscosimetry and DSC analyses using Krigbaum–Wall and Kwei approaches. The results revealed that the blends were completely miscible in all proportions due to the specific interactions between the hydroxyl groups of PEVA and the carbonyl groups of PEMAH. From Nishi equation, the interaction parameter of Flory was found to be −0.89. The nonisothermal crystallization behavior and kinetics of this system were also investigated and compared with those of the pure PEVA. There were strong dependencies of the degree of crystallinity (X_T), peak crystallization temperature (T_p), half time of crystallization (t_1/2), and Ozawa exponent (m) on PEMAH content and cooling rate. The crystallization activation energy (E_c) that was calculated from Kissinger model increased with increasing PEMAH composition in the blend. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis, characterization, and properties of poly(ethylene terephthalate)/poly(1,4-butylene succinate) block copolymers

Reactive blending at 290 °C of a series of mixtures of poly(ethylene terephthalate) (PET) and poly(1,4-butylene succinate) (PBS) led to the formation of block PET/PBS copolyesters. The block lengths of the resulting copolymers decreased with the severity of the treatment. Copolyesters with PET/PBS molar compositions of 90/10, 80/20, 70/30, and 50/50 were prepared by this method and their composition and microstructure were characterized by ¹H and ¹³C NMR, respectively. The T_g, T_m, and crystallinity of the copolymers decreased as the content in PBS and the degree of randomness increased. The elastic modulus and tensile strength of the copolymers decreased with the content of PBS, whereas, on the contrary, the elongation at break increased. The PET/PBS copolymers exhibited a pronounced hydrolytic degradability, which increased with the content in 1,4-butylene succinic units. Hydrolysis mainly occurred on the aliphatic ester groups.     

Synthesis and characterization of novel aromatic poly(benzimidazole-amide)/Ag and Cu nanocomposites through transition metal complexation

A new thermally stable aromatic poly(benzimidazole-amide)s PBIAs was synthesized by low-temperature polycondensation of bis-benzimidazole diamines; 1,4-bis(5-amino-1H-benzimidazol-2-yl)benzene (3a) and 1,3-bis(5-amino-1H-benzimidazol-2-yl)benzene (3b) with two different diacid chlorides. Diamines 3a and 3b were prepared via direct condensation of 1,2-phenylene diamine and terephthalic or isophthalic acid in polyphosphoric acid in high yield. Chemical structures of synthesized monomers were confirmed by elemental analyses and spectroscopic methods. The structures of synthetized polymers were confirmed by FT-IR, ¹H-NMR, elemental and thermogravimetric analysis (TGA), X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Thermal stability of the polymers was ascertained via 10 % weight loss temperatures in the range of 315–380 °C (inert atmosphere). Existence of benzimidazole moieties in polymer’s structure makes them suitable for easy coordination to Lewis acids or metallic ions, whereas the substitution of C–H or N–H protons allows for the synthesis of complex derivatives. As a result, a series of novel nanocomposites, via metal complexation of PBIA6a due to their great solubility with Ag⁺ or Cu²⁺ cations followed by reduction to metals by sodium borohydride (NaBH₄), was prepared. The resulting nanocomposites’ structures were confirmed by FT-IR, XRD, TGA, UV/vis, FE-SEM, TEM and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM–EDX). The FE-SEM, TEM and SEM–EDX results indicated that Cu and Ag particles were dispersed homogenously in nano scale in the polymer matrix.     

聚(苯乙烯/马来酸酐/丙烯酸丁酯)的合成

以过氧化苯甲酰为引发剂,在甲苯介质中引发聚合制备苯乙烯(St),马来酸酐(MAH)/丙烯酸丁酯(BA)三元聚合物[P(St/MAH/BA)].探讨了反应时间、温度和单体配比等对P(St/MAH,BA)产量的影响,并对P(St,MAH,BA)的结构和性能进行了表征.结果表明,共聚单体质量比对三元聚合物的产率有决定性的作用.当m(St)/m(MAH)/m(BA)为1.00:1.00:0.78时,聚合物的产率最高,达到70%,相对分子质量为3.5×105,且热稳定性良好.