Synthesis and characterization of two novel functional ladder-like polysilsesquioxanes for nonlinear optical response

Two novel functional ladder-like polysilsesquioxanes with double-chain macromolecular backbones and nonlinear optical (NLO) chromophore-containing side chains for NLO applications (NLO-T₁ and NLO-T₂) were synthesized successfully for the first time via the introduction of the NLO chromophores to the side chains of the ladderlike polychloropropylsilsesquioxane (Cl-T₁) and ladderlike poly(4-chloromethylphenyl)ethylsilsesquioxane (Cl-T₂), respectively, by an etherification reaction. The obtained polymers were characterized by FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vapour pressure osmometry (VPO), fluorescence spectroscopy and second-harmonic generation (SHG) measurements. The poled thin films of the above two ladder-like NLO polymers showed d₃₃ coefficients of 9.2 and 9.6 pm V⁻¹, respectively. Compared with the corresponding single main chain polymers, the poled thin films of the synthesized ladder-like NLO polymers demonstrated a much higher thermal stability of SHG.     

Synthesis and characterization of poly(dihalophenylene oxide)s by solid-state thermal-decomposition of manganese phenolate complexes with tetramethylethylenediamine

The characterization of poly(dihalophenylene oxide)s synthesized by solid-state thermal decomposition of manganese phenolate complexes with tetramethylethylenediamine (TMEN) ligand is reported. The complexes prepared with 2,4,6-trichlorophenol (TCP) and 2,4,6-tribromophenol (TBP) have been characterized by FTIR spectroscopy, elemental analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dependence of the polymerization yield on temperature and decomposition time of the complexes has been investigated. Maximum polymerization yield is obtained at 220°C and 48 h. The polymers synthesized from the complexes have been characterized by ¹H-NMR and FTIR spectroscopy, DSC, and viscometric measurements. All polymers have a branched structure, a high T_g and low intrinsic viscosity. © 1999 Society of Chemical Industry     

Synthesis and Characterization of New Polymers Containing Bis 1,2,4-Triazole Ring and Used in the Purification of Wastewater from Copper Ion

In this study, two types of polymers containing bis 1,2,4-triazole were prepared (poly thioether and poly thioester) by condensation polymerization. These polymers were characterized by FTIR, ¹H NMR, DSC and TGA techniques. Also, intrinsic viscosities were measured to estimate the molecular weight of the polymers. We use these polymers in treating wastewater containing heavy metal ion, Cu⁺². The effect of time on the efficiency of Cu⁺² ion removal in 25°C was investigated. Results showed that when researchers used poly thioester to removal the copper ion from wastewater, the ability of removal is better than when poly thioether is used.     

Synthesis and Characterization of New Polyesters Derived from Diphenols and Aromatic Diacids Chlorides

Summary A series of aromatic polyesters, were synthesized under phase transfer conditions. The copolymers were obtained in an essentially quantitative yield. These polyesters were soluble in chloroform and readily form clear, colorless films from solution. The optimum conditions of polymerization were obtained via interfacial polymerization at room temperature and with a reaction time of 4 h in chloroform. All polymers were characterized by FTIR, GPC, viscosity, water contact angle, water absorption, TGA, DSC, X-ray, and NMR. The structures of the polymers were confirmed by NMR and FTIR spectroscopy. The prepared polyesters showed excellent thermal stability as measured by TGA (10% wt. loss) is moderate and ranges from 438 to 473 °C in argon, glass transition temperatures are between 147 and 215 °C, water contact angles for these polymers ranged were from 74^° to 90^°, Inherent viscosity values range obtained from 0.35 to 1.3 dL.g-1 and Mw values range from 30.5 to 159×10³.     

Cationic copolymerization involving NCO-bearing monomers and reaction of the ensuing materials with the superficial hydroxy groups of cellulosic fibres

Summary This paper describes the cationic polymerization of 3-isopropenyl-,-dimethylbenzyl isocyanate (TMI) and its copolymerization with isopropenylbenzene (IPB) in order to synthesize materials with varying amounts of NCO side groups. These polymers were characterized by FTIR, ¹H-NMR, elemental analysis and DSC. Their structure showed an essentially random incorporation of TMI. Preliminary reactions of the copolymers with cellulosic fibers are also reported.     

1,3,5-Triazine-based polymer: synthesis,characterization and application for immobilization of silver nanoparticles

Six s-triazine-based polymers were prepared through the nucleophilic reaction of 2,4-dichloro-6-substituted s-triazine derivatives with 1,4-diaminobutane employing conventional heating and microwave irradiation. The prepared polymers were characterized by using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The microwave irradiation provides the target polymers in less reaction time with higher yields and purities; the results from the TGA revealed that microwave technique enhanced the thermal behavior of the prepared polymers. The effect of substituent on the thermal stability of polymers has the main factor, where incorporation of the aromatic ring on the triazine core in the prepared polymers increased their thermal stability. As a model for immobilization of silver nanoparticles (AgNPs), p-methoxy-s-triazine- 1,4-butadiamine (BDPMA) copolymer was used as an example in the presence and absence of hydrazine-hydrate. AgNPs were characterized by zeta potential, scanning electron microscope (SEM), X-ray powder diffraction analysis (XRD) and transmission electron microscope (TEM). Best results in term of particle size was obtained by using BDPMA in the absence of hydrazine hydrate, where the particle size of AgNPs was less than 20 nm as observed from TEM.

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Block copolymer grafted-silica particles: a core/double shell hybrid inorganic/organic material

Hybrid inorganic/organic materials consisting of a poly(n-butyl acrylate)-b-poly(styrene) diblock copolymer anchored to silica particles were synthesized via ‘grafting from’ technique using a controlled/living free radical polymerization named stable free radical polymerization. XPS and FTIR analysis were used to control the effectiveness of the chemical modification of the silica particles. Thermal characterizations were performed by thermal gravimetric analysis (TGA) and by differential scattering calorimetry (DSC). The TGA permitted the determination of the quantity of grafted polymer and thus the grafting density; DSC was used to study the influence of the silica and blocks of the copolymer on their thermal behaviors. The glass transition temperature of the grafted copolymers was compared to these of free polymers or copolymers homologues.     

Synthesis and properties of new polymaleimides containing allyl groups

Two new polymaleimides containing allyl groups in their backbone were synthesized and characterized. The synthesis of these polymaleimides was carried out by reacting allyl polyamine with maleic anhydride. The monomers were characterized by infrared spectroscopy (IR), ¹³C-NMP, and elemental analysis. Differential Scanning Calorimetry (DSC) of monomers showed that the presence of allyl groups reduces the curing temperature. Thermogravimetric analysis (TGA) revealed that all polymers were stable up to 400°C in air or 500°C in nitrogen atmosphere. Their char yield at 800°C under anaerobic conditions was 58–61%.     

Preparation and characterization of poly (styrene-co-Methacrylic acid) copolymer nanoparticles via precipitation polymerization

Nanoparticls of multifunctional polymers have very promising characteristics that make this type of the polymers have rapidly growing research attentions and innovations due to advantageous high surface area to volume ratio. In this study, poly (Styrene-co-Methacrylic acid) (P)St-co-MAA)) copolymer nanoparticles were synthesized using free radical polymerization method. Copolymerization takes place via a precipitation polymerization technique. Different polymerization factors such as co-monomer concentration and ratio, polymerization temperatures, polymerization time, initiator concentration and solvent composition were studied to obtain the copolymerization conditions that produce the maximum copolymerization conversion yield and the minimum particle size in nanosize range in a very narrow size distribution. The P)St-co-MAA) copolymer nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and Thermogravimetric analysis (TGA). When the copolymerization occurred at a monomer ratio of MAA: St (90:10) we obtained the smallest particle size of 25 nm. The maximum conversion yield reached to 99.5% within 4 h of polymerization in the case of St: MAA (1:1) comonomer ratio and 10% total monomer ratio using water:ethanol (1:1) mixture as a co-solvent system. The results clearly demonstrated that use of water as a co-solvent is indeed very effective to promote the polymerization to high conversion. The MAA content in copolymer composition was investigated by carboxylic content via titration method and also by FTIR.

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Tailoring of energetic groups in acroyloyl polymers

Acryloyl based novel energetic monomers having nitro acrylates and nitro triazole acrylates were synthesized and further used for polymerization. Due to scavanging properties of nitro groups, syntheses of nitro aromatic polymers are not facile at normal conditions. In this regard, we report a simple protocol to synthesize these energetic group embeded acroloyl polymers. These polymers were characterized by FTIR, and NMR spectroscopic techniques. gel permeation chromatography (GPC) technique was employed in order to understand molecular mass of these polymers along with average molecular weight, number average weight and poly dispersity index. Glass transition temperature (T_g) was determined by using DSC analysis. It was observed that with increase in nitro groups in polymers there is a decrease in glass transition temperature. Two steps degradation were depicted in the TGA thermograph in nitro containing polymers. Heat release during this reaction was found up to 951 J/g. Increase in nitrogen content in polymer unit enhanced the heat release of polymers.     

Synthesis of hybrid crosslinked polyphosphazenes and investigation of their properties

Novel organic/inorganic hybrid polyphosphazenes were prepared by free radical UV copolymerization of linear polyphosphazenes and vinyl monomers. In this work, linear polyphosphazenes grafted by allyl amino and n-butylamino groups have been synthesized via nucleophilic substitution reaction at an anhydrous and anaerobic atmosphere. By regulating the molar ratio of allyl amino and n-butylamino groups, five different linear polyphosphazenes were prepared. The hybrid polyphosphazenes have been crosslinked using the linear polyphosphazenes and vinyl monomers including styrene, methyl methacrylate, and lauryl methacrylate as intermediates via free radical UV copolymerization. By changing the quantity of vinyl monomers participating in the crosslinking reaction, series of hybrid polyphosphazene membranes were obtained. The linear polyphosphazenes have been characterized by Nuclear magnetic resonance, Fourier transform infrared (FTIR), Thermogravimetric analysis (TGA), Differential scanning calorimeter, Dynamic mechanical analyzer and Drop Shape Analysis (DSA). The hybrid polyphosphazenes have also been studied via FTIR, TGA and DSA. The test results proved that the linear polymers were successfully synthesized. Moreover, the water contact angles showed that the hybrid crosslinked polyphosphazenes had a better hydrophobicity and thermal stability than the linear polyphosphazenes and the hydrophobicity of hybrid membranes have a regular changing tendency with the quantities of UV-monomers and ratio of allylamino. The initial decomposition temperatures of the hybrid polymers also had a regular change due to the difference and quantities of vinyl monomers.     

Synthesis of multi‐arm star polystyrene with hyperbranched polyester initiators by atom transfer radical polymerization

Multi‐arm star polystyrenes with hyperbranched polyester (HP3) core were prepared by atom transfer radical polymerization (ATRP). The structures of the polymers were investigated with FTIR and ¹H NMR. GPC results showed that the resultant polymers had relatively broad polydispersity indices that arouse from the macromolecular initiator (HP3‐Br). The thermal properties were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC analysis indicated that polystyrene star polymers had only the glass transition temperatures (T_g), which changes with the weight ratio of multi‐functional macroinitiator‐to‐monomer. In addition, these star polymers could form the spherical micelles in the selected solvent (THF/n‐hexane). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 728–733, 2006     

Novel strategies for the synthesis of hydroxylated and carboxylated polystyrenes

Hydroxylated and carboxylated polystyrenes (PHMSt and PCSt, respectively) were synthesized using facile strategies. For this purpose, PSt was synthesized through atom transfer radical polymerization (ATRP) approach and then brominated at the para-position of the aromatic rings to produce PBrSt. The bromination efficiency was calculated to be 37 and 68%, even though there was a degradation of the polymer chains, using 60 or 100 mol% of bromine relative to the PSt, respectively. The brominated polymer was converted into Grignard reagent (PSt-magnesium-Br), and then reacted with anhydrous formaldehyde and solid carbon dioxide (Dry Ice) to afford PHMSt and PCSt, respectively. The chemical structures of all synthesized polymers were characterized using Fourier transform infrared (FTIR) as well as proton nuclear magnetic resonance (¹H NMR) spectroscopies. Furthermore, the thermal behavior of the synthesized PHMSt and PCSt were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Preparation of Cyclosilalkylenesiloxane Monomers and Their Cationic ROP

A novel series of cyclosilalkylenesiloxane monomers was prepared having larger alkylene units, hexanylene, octanylene, decanylene, and tetradecanylene, than previously reported. The rings also contain at least one tetramethyldisiloxanylene unit and undergo ring-opening polymerization via the siloxane bond. Thus, poly(1,1,8,8-tetramethyl-9-oxa-1,8-disilanonanylene), poly(1,1,10,10-tetramethyl-11-oxa-1,10-disilaundecanylene), poly(1,1,12,12-tetramethyl-13-oxa-1,12-disilatridecanylene), and poly(1,1,16,16-tetramethyl-17-oxa-1,16-disilaheptadecanylene) were prepared using a strongly acidic ion exchange resin. The polymers were obtained in yields of 74–86%, similar to that obtained for cyclosiloxane equilibration polymerization. The monomers were characterized using ¹H, ¹³C, and ²⁹Si NMR, FTIR, GC-MS, and elemental analysis. The polymers were characterized using ¹H, ¹³C, and ²⁹Si NMR, DSC, TGA, FTIR, GPC, and refractive index.     

Degradation of graft polymer and blend based on cellulose and poly(L‐lactide)

Degradable polymers were prepared by blending and graft polymerization of cellulose and poly(L‐lactide) (PLLA). The cellulose/poly(L‐lactide) blends and cellulose‐graft‐poly(L‐lactide) polymers were characterized by FTIR, NMR, DSC, and TGA. Wide‐angle X‐ray powder diffraction (WAXD) and degradation tests [by alkaline, phosphate‐buffered saline solution (PBS), and enzyme solution] showed changes in the crystalline structure as a result of degradation. The results indicated that blending and graft polymerization could affect crystallization of the polymers and promote the degradability. The polymers with low degree of crystallinity showed higher degradability. In contrast, enzyme, alkaline, and PBS degradated material decreased rate of polymers degradation. In addition, high levels of PLLA resulted in a decrease in degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2257–2264, 2013     

Simultaneous novel synthesis of conducting,nonconducting, and crosslinked polymers by microwave initiation

A novel synthesis of poly(dibromophenylene oxide) (P), conducting polymer (CP), and/or crosslinked polymer (CLP), and/or radical ion polymers (RIP) was achieved simultaneously from sodium 2,4,6‐tribromophenolate by microwave energy in a very short‐time interval. The synthesized polymers were characterized via elemental analysis, FTIR, ¹H NMR and ¹³C NMR, X‐ray diffraction spectroscopy, SEM, DSC, TGA, ESR, GPC, conductivity measurement, and light scattering. It was found that polymerization proceeds through both 1,2‐ and 1,4‐addition at equal rates. The effects of the energy and time on the % conversion and the polymer synthesis were investigated. The optimum condition for synthesis of P (the highest M_w, 2.97 × 10⁵ g/mol) and CP was 70 W for 5 min in 5 mL water and 100 W for 1 min in 0.5 mL water, having maximum values 23.6% and 27.2%, respectively. In addition, synthesis of CLP and RIP were achieved in 5 mL water at 350 W and 700 W at the end of 1 min, respectively. The direct synthesis of highly conducting polymer, with the conductivity of 1 S cm^?2 was achieved in the absence of applied doping process in a very short time sequence. P, CP, CLP, and RIP had fine granular, sponge‐like, dendrite, and coarse surface structures, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5427–5435, 2006     

Synthesis and Characterization of Thiophen-3-yl Acetic Acid 4-Pyrrol-1-yl Phenyl Ester and its Conducting Polymers

ABSTRACT

Thiophen-3-yl acetic acid 4-pyrrol-1-yl phenyl ester (TAPE) monomer was synthesized via reaction of thiophen-3-yl acetyl chloride with 4-pyrrol-1-yl phenol. Homopolymers were achieved by using electrochemical and chemical polymerization techniques. Copolymers of TAPE with bithiophene or pyrrole were synthesized by potentiostatic electrochemical polymerization in acetonitrile-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. The chemical structures were confirmed by both Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and Thermal Gravimetry Analysis (TGA) were used to examine the thermal behavior of the polymers. The morphologies of the films were investigated by Scanning Electron Microscope (SEM). Two-probe technique was used to measure the conductivities of the samples. Moreover, investigations of electrochromic and spectroelectrochemical properties of poly(TAPE-co-BiTh) carried out and the characteristics of dual type electrochromic device based on poly(TAPE-co-BiTh) and poly(3,4-ethylenedioxythiophene) (PEDOT) were reported.     

Synthesis of water-soluble acryl terpolymers and their anticorrosion properties on mild steel in 1 mol·L~(-1) HCl

Two water soluble acryl terpolymers containing polyvinyl alcohol, acrylamide/acrylic acid and vinyl sulphonic acid(VSA) were synthesized by free radical polymerization in aqueous medium. The morphological structure of the polymers were analysed using FTIR and1 H NMR, while the thermal properties were analysed by TGA and DSC. The inhibitive action of the terpolymers on corrosion of mid-steel in 1 mol·L-1HCl was studied using gravimetric, potentiodynamic polarisation and electrochemical impedance spectroscopy(EIS) at 303 K.Both the polymers provided inhibition efficiency around 90% which clearly demonstrate that the grafted polymers have effective corrosion inhibiting ability on MS corrosion.     

Novel tri- and tetrafunctional cholic acid-based initiators for the synthesis of star-shaped poly(L-lactide)s

In this investigation, two novel multifunctional initiators for ring-opening polymerization were synthesized in three steps starting from cholic acid. Thus, cholic acid (1a) and its methyl ester (1b) were quantitatively transformed, via solvent-free reaction with succinic anhydride, to the corresponding 3, 7, 12-tri-hemisuccinate derivatives (3a-b). The polyacidic compounds (3a-b) were treated with thionyl chloride affording the corresponding acyl chlorides 4a-b which, in turn, were reacted with ethylene glycol to give the derivatives 2a-b having three and four primary alcohol end groups. These compounds, fully characterized by ¹H, ¹³C NMR and mass spectrometry, have been assessed as initiators in the ring-opening polymerization of L-lactide using stannous octanoate as catalyst. The resulting three- and four-armed star-shaped poly(L-lactide)s, which were characterized by ¹H NMR, SEC, DSC and TGA analysis, were amorphous, and their glass transition temperatures ranged from 13.7 to 36.5 °C. Additionally, some cholic acid-based star-shaped polylactic structures recently published have been critically reconsidered showing that these molecules, described as star polymers, were actually linear polymers.     

Synthesis and comparative study of thermal stabilities of the imidization of some maleic anhydride copolymers

In the present study, first, maleic anhydride‐styrene (MA‐St), maleic anhydride‐allyl phenyl ether (MA‐APhE), maleic anhydride‐heptene‐1(MA‐Hp), and maleic anhydride‐allyl propionate (MA‐AP) copolymers have been synthesized in different solvents in the presence of azobisisobutyronitrile (AIBN) at 70°C. Then, these four copolymers have been reacted with aniline at 60°C in N,N‐dimethyl formamide (DMF), and maleamidic acid derivatives of these copolymers have been synthesized. Next, they have been obtained from their maleimide derivatives by heating under vacuum at 150°C. All these polymers have been characterized by Fourier Transform infrared spectroscopy (FTIR) and investigated their thermal properties by using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) methods. The analyses results showed that thermal properties of maleimide derivatives of maleic anhydride copolymers changed as depend on the neighbor monomers of maleic anhydride. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2250–2254, 2006