Grafting of maleic anhydride onto styrene–butadiene–styrene triblock copolymer using supercritical CO2 as a swelling agent

Grafting of maleic anhydride (MA) onto styrene–butadiene–styrene triblock copolymer (SBS) was carried out by free radical polymerization using supercritical carbon dioxide (SC CO₂) as a solvent of MA and swelling agent of SBS. The effect of various factors such as monomer concentration, initiator concentration, SC CO₂ pressure, and reaction time on grafting ratio was studied. SBS and the product (SBS‐g‐MA) were characterized by Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). GPC data showed that the molecular weight of SBS‐g‐MA is bigger than that of SBS. DSC testing indicated that the glass transition temperature (T_g) of SBS‐g‐MA is higher than that of SBS. By SEM photo, we can observe that some particles which contain more oxygen atom grew out from the surface of SBS‐g‐MA when grafting ratio reached at 5.6%, and the amount and diameter of particles increased with increasing of grafting ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4425–4429, 2006     

Grafting of poly(vinyl chloride) and polypropylene with styrene in a supercritical CO2 solvent medium: Synthesis and characterization

Graft copolymerization of styrene onto poly(vinyl chloride) (PVC) and polypropylene (PP) was carried out in a supercritical CO₂ medium using AIBN as a free radical initiator. The supercritical CO₂ medium served as a reaction medium in addition to being a solvent for the styrene monomer and the free radical initiator. The reaction temperature and pressure were kept above the critical points of the solvent‐monomer mixture to form a homogeneous single‐phase medium. The resulting graft copolymers were characterized using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and nuclear magnetic resonance (NMR) techniques. The weight percent of grafting was determined using IR absorbance ratio technique. TGA results showed that the thermal stabilily of grafted copolymer of PVC was better than that of PVC, while grafted copolymer of PP had poorer thermal stability than PP. DSC results showed that glass transition temperatures (T_g's) of the grafted copolymers were higher than those of the starting polymers PVC and PP. The presence of polystyrene attached to the backbone polymer was confirmed by ¹H NMR and ¹³C NMR analyses.     

Fabrication,structures, and properties of acrylonitrile/methyl acrylate copolymers and copolymers containing microencapsulated phase change materials

The polyacrylonitrile‐methyl acrylate (AN/MA mole ratio 100/0–70/30) copolymers and copolymers (AN/MA mole ratio 85/15) containing up to 40 wt % of microencapsulated n‐octadecane (MicroPCMs) are synthesized in water. The MicroPCMs were incorporated at the step of polymerization. The effect of the MA mole ratio and MicroPCMs content on structures and properties of the copolymers were studied by using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹H NMR), scanning electronic microscope (SEM), differential scanning calorimetry (DSC), thermogravimetry analysis (TG), gel permeation chromatography (GPC), and X‐ray diffraction (XRD). The feeding ratio agreed well with the composition of the AN/MA copolymers. The copolymers are synthesized in the presence of MicroPCMs. The melting point moves to lower temperature (206°C), while the decomposition temperature moves to higher temperature (309°C) with increasing of the MA mole ratio and microcapsules content. The number–average molecular weight of the copolymer is ～30,000. The crystallinity of the copolymer decreases with increasing of the MA mole ratio and microcapsules content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2776–2781, 2007     

Synthesis and Characterization of Poly(glycidyl nitrate‐block‐caprolactone‐block‐glycidyl nitrate) (PGN‐PCL‐PGN) Tri‐Block Copolymer as a Novel Energetic Binder

An energetic binder was synthesized through ring opening copolymerization of glycidyl nitrate (GLYN) with polycaprolactone (PCL) as a macroinitiator to form tri‐block copolymer PGN‐PCL‐PGN. Effect of monomer concentration, catalyst, reaction time and solvent was investigated in polymerization. Resulting tri‐block copolymer was characterized by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The DSC result shows that glass transition temperature of tri‐block copolymer (T_g=−56.2 °C) is lower than PGN (T_g=−35 °C). In optimal condition, the M_w of this polymer was obtained 2900 g/mol.     

Synthesis of multi‐block copolymer and its compatibilization to the blends of poly(ether ether ketone) with thermotropic liquid crystalline polymer

A multiblock copolymer (BCP) containing amorphous poly(aryl ether ketone) (PAEK) and thermotropic liquid crystalline polymer (TLCP) segments was synthesized. The chemical structure and properties of BCP were characterized by fourier‐transform infrared spectrometer (FTIR), differential scanning calorimeter (DSC), gel permeation chromatograms (GPC), thermogravimetry analysis, polar light microscope (PLM), and solubility test respectively. BCP can dissolve in chloroform because of soluble PAEK block bonded with TLCP block, which was insoluble. The peak of the original PAEK oligomer was no more present in the GPC traces of the block copolymer. These facts indicated that polymer synthesized should be copolymers of the two components rather than blends. A single T_g at 138.1°C and broad melting endotherm at 315.7°C can be observed. The liquid crystalline texture of BCP showed uniformity in the view after heat treated for 10 min above its T_m under PLM. Ternary blends of poly(ether ether ketone) (PEEK)/TLCP/BCP were prepared by extrusion and characterized by DSC. DSC results showed that the crystallization temperature of PEEK phase in the blends shifted higher with the addition of TLCP. Wide angle X‐ray diffraction investigations indicated that the crystalline structure of PEEK was not disturbed by blending or compatibilizing. Scanning electron microscope and mechanical tests confirmed the compatibilizing effect of BCP. Reduction in dispersed phase TLCP size was observed when 2 phr by weight of compatibilizer was added to the blend. Measurement of the tensile properties showed increased elongation as well as improved modulus and strength to some extent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Grafting of styrene/maleic anhydride copolymer onto PVDF membrane by supercritical carbon dioxide: Preparation,characterization and biocompatibility

Herein we report the surface modification of poly(vinylidene fluoride) (PVDF) microporous membrane via thermally induced graft copolymerization with maleic anhydride (Man)/styrene (St) in supercritical carbon dioxide (SC CO₂). SC CO₂, as a solvent and carrier agent, could accelerate mass transfer of monomers inside polymer matrixes and then facilitate the graft copolymerization on the surface of the membrane and within membrane pores, which were confirmed by FT-IR/ATR and XPS spectra together with SEM photographs. The effects of SC CO₂ pressure and temperature and the monomer concentration on the graft copolymerization were investigated. The modified PVDF membranes containing from 0 to 7 wt.% of grafted St–Man copolymer (SMA) were prepared and analysed in terms of surface microstructure, composition, hydrophilicity and biocompatibility. Solid-state ¹³C CP/MAS NMR and DSC indicated that the grafted SMA on the PVDF membrane had the alternative sequence structure and formed the different phases in the modified membrane, where the grafted SMA was associated with T_g of 122.8 °C and the PVDF matrix with T_m of 161.2 °C. The static contact angle measurements revealed that remarkable and permanent hydrophilicity was obtained upon grafting SMA. The experiments of BSA adsorption and cell growth also showed that the surface of SMA-based PVDF membrane has excellent biocompatibility.     

Synthesis and properties of a new conjugated polymer containing benzodithiophene for polymer solar cells

We have synthesized a new conjugated polymer PBDTDT containing 4,8-dioctyloxybenzo[1,2-b;3,4-b′]di-thiophene and 2,2′-dithiophene via a Stille coupling reaction. The copolymer was characterized by FTIR, NMR, GPC, TGA, DSC, UV–vis absorption, and electrochemical cyclic voltammetry. TGA showed that the copolymer exhibited good thermal stability. The optical, electrochemical, photovoltaic properties, and hole mobility of the copolymer were investigated and discussed. As a result, the polymer solar cell based on PBDTDT with a conventional device configuration of ITO/PEDOT:PSS/PBDTDT:PC₆₁BM/LiF/Al showed a power conversion efficiency of 1.19 %, with a short-circuit current density (J _sc) of 4.72 mA/cm², an open-circuit voltage (V _oc) of 0.6 V and a fill factor of 53.3 % under the AM 1.5G illumination with an intensity of 100 mW/cm² from a solar simulator.     

Supercritical CO2‐assisted synthesis of poly(acrylic acid)/nylon1212 blend

PAA/nylon1212 blend was prepared using supercritical CO₂ as substrate‐swelling agent and monomer/initiator carrier. Both supercritical CO₂/nylon1212 binary system and SC CO₂/monomer/nylon1212 ternary system have been studied. Virgin nylon1212 and blends were characterized through differential scanning calorimetry (DSC), infrared spectroscopy (IR), and scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2040–2044, 2003     

Effect of the maleic anhydride content on the structural,thermal, rheological and film properties of the n-butyl methacrylate–maleic anhydride copolymers

Various copolymers of n-butyl methacrylate (nBMA)-maleic anhydride (MA) were synthesized by free radical solution polymerization using xylene as a solvent, with monomer ratio of (nBMA/MA) 80/20, 65/35 and 50/50 wt%. The nBMA/MA copolymers were analyzed by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (¹H NMR), gel permeation chromatography (GPC) differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), rheology, acid value, microhardness and friction resistance. The formation of the nBMA/MA copolymers was proven by FTIR and ¹H NMR. The conversion percentage, glass transition temperature (T_g), thermal stability, hardness and the friction resistance of the nBMA/MA copolymers increased with the MA contents in the copolymers. All copolymers presented a thinning-shear rheological behavior due to the presence of entanglements. All films of the copolymers showed a good chemical resistance to HCl and NaCl solutions, but in the presence of NaOH solutions the films exhibited a blister.     

Thermal characterization of n‐alkyl maleate‐styrene‐allyl propionate terpolymers

Thermal characterization of maleic anhydride‐styrene‐allyl propionate (MA‐St‐AP) terpolymer and its ester derivatives named as n‐alkyl maleate and shown as nPr MA‐St‐AP, nBu MA‐St‐AP, nPn MA‐St‐AP, and nBz MA‐St‐AP was carried out. The thermal characterization was performed using thermal analysis techniques such as TGA, DTA, DSC, and TMA. Different results were observed between the original terpolymer and its ester derivatives. Thermal stabilities of the terpolymer and its ester derivatives were compared by using various measurements plotted as TGA, DTA, DSC, and TMA curves. The increase in the alcohols' carbon numbers added to the original terpolymer results in ester derivatives with different thermal stability behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 600–604, 2007     

Copolymerization of carbon dioxide and propylene oxide using zinc adipate as catalyst

Zinc adipate was synthesized from zinc oxide with adipic acid by different methods. Their chemical structure and crystalline morphology were determined by Fourier transform infrared spectroscopy (FTIR), wide‐angle X‐ray diffraction (WXRD), and scanning electron microscopy (SEM) techniques. The results showed that the zinc adipate synthesized under magnetic stirring possessed higher degree of crystallinity than that synthesized under mechanical stirring due to the different stirring strength, and therefore exhibited greater catalytic activity for the copolymerization between CO₂ and propylene oxide (PO). The optimum condition for the copolymerization of CO₂ and PO was also investigated. Very high catalytic activity of 110.4 g polymer/g catalyst was afforded under optimizing copolymerization condition. NMR spectra revealed that the synthesized poly(propylene carbonate) (PPC) had a highly alternating copolymer structure. DSC and TGA examinations showed that the glass transition temperature and decomposition temperature of the PPC with M_n = 41,900 Da were 27.7 and 248°C, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 200–206, 2006     

Synthesis,characterization, and electro‐optical properties of a soluble conjugated polymer containing an oxadiazole unit in the main chain

A novel copolymer, poly{[2,5‐diphenylene‐1,3,4‐oxadiazole‐vinylene]‐alt‐[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐phenylenevinylene]}(MEH‐OPPV) containing a high‐electron‐affinity unit of aromatic oxadiazole in the main chain is synthesized through the Wittig condensation reaction. The obtained copolymer is easily soluble in conventional organic solvents. The structure of the copolymer was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and ultraviolet‐visible and photoluminescence spectroscopy. The TGA result indicates that the copolymer has very high thermal stability (stable up to 310°C in nitrogen), while DSC investigation demonstrates that the glass transition temperature (T_g) is 143°C, which might be a merit for the long‐life operation of light‐emitting devices. The absorption spectrum of film sample of the copolymer reveals two peaks at 310 and 370 nm, respectively, and the edge absorption corresponds to a band gap of 2.46 eV. A single‐layer light‐emitting diode device ITO/MEH‐OPPV/Al is successfully fabricated. The device emits visible yellowish‐green light above the bias voltage of 4.0 V under ambient condition. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2618–2623, 2003     

Ring-Opening Polymerization of Epoxidized Soybean Oil

Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by boron trifluoride diethyl etherate (BF₃·OEt₂) in methylene chloride was conducted in an effort to develop useful biodegradable polymers. The resulting polymerized ESO (PESO) were characterized using infrared (IR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), ¹H NMR, ¹³C NMR, solid state ¹³C NMR and gel permeation chromatography (GPC). The results indicated that PESO materials were highly crosslinked polymers. They had glass transition temperatures ranging from −16 to −48 °C. TGA results showed the PESO polymers were thermally stable at temperatures up to 220 °C. Decomposition of the polymers was found to occur at temperature greater than 340 °C. GPC results indicated the extracted soluble substances from PESO polymers were ESO dimers, trimers and polymers with low molecular weights. The resulting crosslinked polymers can be converted into hydrogels by chemical modification, such as hydrolysis. These soy based hydrogels will find applications in personal care and health care areas.     

Synthesis,characterization and thermal dissociation of 2‐butoxyethanol‐blocked diisocyanates and their use in the synthesis of isocyanate‐terminated prepolymers

A series of blocked diisocyanates has been synthesized from toluene diisocyante (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′‐diphenylmethane diisocyanate (MDI) and 2‐butoxyethanol. The synthesis of blocked diisocyanate adducts was confirmed by Fourier transform infrared, ¹H NMR, electron impact mass spectrometry and nitrogen analysis. Differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and carbon dioxide evolution were used to determine the minimum de‐blocking temperatures. De‐blocking temperatures determined by these three techniques were found to be in the order DSC > TGA > CO₂ evolution. The effect of different metal catalysts on thermal de‐blocking reaction of the blocked diisocyanates was studied, using the carbon dioxide evolution method. It was found that iron(III) oxide has the maximum catalytic activity on de‐blocking. The solubility of the blocked diisocyanate adducts was determined in different solvents. The study revealed that at 30 °C blocked IPDI and HDI adducts show better solubility than adducts based on TDI and MDI. Isocyanate‐terminated prepolymers of blocked diisocyanates and hydroxyl‐terminated polybutadiene (HTPB) were prepared. The storage stability and gelation times of the prepolymers were studied. Results showed that all the diisocyanate‐HTPB compositions are stable at 50 °C for more than three months. However, aliphatic diisocyanate‐HTPB compositions require greater gelation time than aromatic diisocyanate‐HTPB compositions at their respective de‐blocking temperatures. Copyright © 2007 Society of Chemical Industry     

Grafting of glycidyl methylacrylate onto chlorinated polypropylene and its bonding to aluminum flake

Glycidyl methacrylate (GMA) was grafted onto chlorinated polypropylene (CPP) in the molten state using benzoyl peroxide (BPO) in the presence of styrene (St) as a comonomer. The differential scanning calorimetry (DSC) results indicated that the thermodynamic curve of unpurified grafted CPP was different from the purified, and showed a new broad endothermic peak at 100°C, which may be attributed to the glass transition temperature (T_g) of remained copolymer of GMA and St. Furthermore, transmission electron microscope (TEM) showed that there were two‐phase structures in the grafted CPP. Because the grafted CPP was to be used as a hot melt adhesive, so the influence of initiator concentration, monomer concentration, and reaction temperature on peel strength was investigated. The experiment results showed that a higher degree of grafting was obtained by using two kinds of monomers, such as GMA and St. Increasing the monomer concentration led to an initial rapid increase in the peel strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2515–2521, 2007     

Graft copolymerization of methylmethacrylate with N‐substituted maleimide‐styrene copolymer by ATRP

Atom transfer radical polymerization (ATRP) was employed to prepare graft copolymers having poly(MBr)‐alt‐poly(St) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches to obtain heat resistant graft copolymers. The macroinitiator was prepared by copolymerization of bromine functionalized maleimide (MBr) with styrene (St). The polymerization of MMA was initiated by poly(MBr)‐alt‐poly(St) carrying bromine groups as macroinitiator in the presence of copper bromide (CuBr) and bipyridine (bpy) at 110°C. Both macroinitiator and graft copolymers were characterized by ¹H NMR, GPC, DSC, and TGA. The ATRP graft copolymerization was supported by an increase in the molecular weight (MW) of the graft copolymers as compared to that of the macroinitiator and also by their monomodal MW distribution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Precipitation polymerization of methyl methacrylate in tetrahydrofuran with compressed CO2 as antisolvent

Precipitation polymerization of methyl methacrylate (MMA) in tetrahydrofuran (THF) with compressed CO₂ as an antisolvent was carried out at 335 K up to 8.5 MPa, and the decomposition rate of the initiator, 2,2′‐azobisisobutyronitrile (AIBN), was studied with UV/vis. Gel permeation chromatography (GPC) and differential scanning calorimetry (DSC) were used to determine the average molecular weights and glass transition temperature (T_g), and scanning electron micrography (SEM) was used to observe the morphologies of the product. The results showed that the average molecular weights of the polymer vary considerably with the volume expansion of the solution induced by compressed CO₂. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2427–2433, 2003     

Syntheses and characterization of starch-poly(methacrylic acid) graft copolymers

Methacrylic acid (MA) was graft polymerized onto starch using Ce⁴⁺ initiator in aqueous medium. The dependence of grafting on the reaction variables, such as monomer and initiator concentration and time and temperature, was studied in detail. Acid hydrolysis and infrared (IR) spectroscopy were used for the confirmation of graft copolymer formation. Further, a representative graft copolymer was characterized by x-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The solubility/swellability and the gelatinization characteristics of the copolymers are also reported. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1399–1403, 1997     

Preparation and characterization of gel polymer electrolyte based on PVA-K2CO3

ABSTRACT

In this study, electrolyte materials were synthesized by mixing a highly conducting salt (K₂CO₃) with the poly(vinyl alcohol) (PVA) in different proportions (from 10 to 50 wt.%). The synthesized electrolyte was characterized using Fourier transform infrared (FTIR) spectroscopy, field-emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) for their functional groups, morphology, thermal stability, glass transition temperature (T_g ), ionic conductivity, and potential window, respectively. Characterization results show that the complex formation between PVA and K₂CO₃ salt has been established by FTIR spectroscopic study, which indicates the detailed interaction between PVA and the salts in PVA-K₂CO₃ composites while the amorphous nature of the electrolyte after incorporation of the salts has been confirmed by FESEM analysis. Similarly, TGA and DSC analysis revealed that both decomposition temperature and T_g of the synthesized electrolytes decrease with the addition of K₂CO₃ due to the strong plasticizing effect of the salt. The results confirm that the electrolytes have sufficient thermal stability for supercapacitor operation, as well as an amorphous phase to effectively deliver high ionic conductivity. The highest ionic conductivity of 4.53 × 10^?3 S cm^?1 at 373 K and potential window of 2.7 V was exhibited by PK30 (30 wt.% K₂CO₃), which can be considered as high value for solid-state electrolytes which are superior to those electrolytes from PVA salts earlier reported. The results similarly show that the prepared electrolyte is temperature-dependent as conductivity increase with increase in temperature. Based on these properties, it can be imply that the PVA-K₂CO₃ gel polymer electrolyte (GPE) could be a promising electrolyte candidate for EDLC applications. The results indicate that the PVA-K₂CO₃ as a new electrolyte material has great potential in practical applications of portable energy-storage devices.     

Synthesis and properties of aliphatic polycarbonates derived from carbon dioxide,propylene oxide and maleic anhydride

Terpolymerization of carbon dioxide (CO₂) with propylene oxide (PO) and maleic anhydride (MA) was successfully carried out using supported zinc glutarate catalyst. Consequently giving high molecular weight poly(propylene carbonate maleate) (PPCMA) in a very high yield (72.5 g polymer/g catalyst). The resulting terpolymers were fully characterized by FTIR, ¹H NMR, ¹³C NMR, and wide‐angle X‐ray diffraction (WAXD) techniques. NMR measurements showed that PPCMA had an almost alternating structure for the components of carbon dioxide and PO. The influence of molecular weight and MA content on the properties of PPCMA was also investigated. Differential scanning calorimetry (DSC) measurements revealed that the glass transition temperature (T_g) of PPCMA increased with increasing molecular weight. Thermogravimetric analysis (TGA) indicated that PPCMA51 exhibited a very high decomposition temperature (263°C) due to the introduction of the double bond of MA into the backbone of terpolymer. The terpolymers with double bonds can be readily subjected to crosslinking reaction in high temperature to give a slightly crosslinked PPCMA, which exhibit superior thermal stability. Tensile tests also showed that the mechanical properties of PPCMA increased with increasing molecular weight. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008