Radiation induced terpolymerization of tetrafluoroethylene with propylene and n-butyl vinyl ether in bulk

Terpolymerization of tetrafluoroethylene (TFE) with propylene (P) and n-butyl vinyl ether (NBVE) induced by γ-rays at room temperature at dose rate 5 × 10⁵ rad/h and P/NBVE molar ratio from 49/1 to 10/40 was carried out. An alternating copolymerization between TFE and two α-olefins was found to take place in this system, so that 50 mole % of TFE containing terpolymer is always formed at various monomer compositions. The terpolymer composition can be explained successfully by the treatment by a complex mechanism. The complex reactivity ratios of r_I (TFE–complex) and r_II (TFE-NBVE complex) were calculated to be 0.5 and 0.6, respectively, assuming a complex mechanism. The polymerization rate and molecular weight increase with NBVE concentration in the monomer mixture. Colorless transparent rubber-like polymers were obtained at each monomer composition. The glass transition temperature sharply decreases with NBVE concentration in the terpolymer but the thermal and chemical resistances of the terpolymer slightly decrease. Considering these results together with the mechanical properties it has been concluded that the 45/48/7 terpolymer of TFE/P/NBVE molar ratio is good as a practical elastomer useful at relatively low temperatures.     

Radiation-induced terpolymerization of tetrafluoroethylene with propylene and isobutylene in bulk

Terpolymerization of tetrafluoroethylene (TFE) with propylene (P) and isobutylene (iB) by γ radiation at temperatures of ?78 to 40°C, a dose rate of 5 × 10⁴?5 × 10⁵ rad/hr, and an iB/P molar ratio of 40/10?5/45 in the monomer mixture was carried out. Alternating copolymers of TFE and α-olefins, that is, P and iB, were formed at various monomer compositions. No crystalline structure was observed in the terpolymer obtained below an iB/P molar ratio of 15/35 in the monomer mixture but a partly crystalline order increased with the amounts of iB in terpolymer. The crystal lattice of the TFE–iB copolymer was affected by the introduction of P. The dose rate dependencies of the polymerization rate and inherent viscosity were 0.8 and ?0.2, respectively. The activation energy of polymerization was 2.4 kcal/mole, and the relative reactivity ratio of iB and P for a TFE radical chain end was estimated as 4.50 by the treatment of the free propagating mechanism.     

Synthesis of phosphonated copolymers with tailored architecture by reversible addition‐fragmentation chain transfer polymerization (RAFT)

The synthesis by reversible addition‐fragmentation chain transfer (RAFT) polymerization of three phosphonated terpolymers with tailored architecture has been studied. A phosphonated methacrylate (MAUPHOS) was copolymerized with vinylidene chloride (VC₂) and methyl acrylate (MA) to prepare a gradient terpolymer poly(VC₂‐co‐MA‐co‐MAUPHOS). Besides, hydroxyethyl acrylate (HEA) was used as a functional monomer in RAFT polymerization to prepare a statistical poly(VC₂‐co‐MA‐co‐HEA) terpolymer and a diblock poly(VC₂‐co‐MA)‐b‐poly(HEA) terpolymer. The HEA‐containing polymers were then modified with a phosphonated epoxide to introduce the phosphonated group. The control of the polymerization was proven by kinetic studies (evolution of molecular weight vs. conversion) and by a successful block copolymerization. The architecture of the terpolymers was determined by the reactivity ratios of the monomers: terpolymerization of VC₂, MA, and HEA leading to an ideal statistical terpolymer (no composition drift) whereas terpolymerization of VC₂, MA, and the phosphonated methacrylate led to a gradient terpolymer. These terpolymers were characterized by size exclusion chromatography, ³¹P NMR and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 13–24, 2006     

pH‐Responsive ampholytic terpolymers of acrylamide,sodium 3‐acrylamido‐3‐methylbutanoate,and (3‐acrylamidopropyl)trimethylammonium chloride. I. Synthesis and characterization

Low-charge-density ampholytic terpolymers composed of acrylamide, sodium 3-acrylamido-3-methylbutanoate (NaAMB), and (3-acrylamidopropyl)trimethylammonium chloride were prepared via free-radical polymerization in 0.5 M NaCl to yield terpolymers with random charge distributions. NaOOCH was used as a chain-transfer agent during the polymerization to eliminate the effects of the monomer feed composition on the degree of polymerization (DP) and to suppress gel effects and broadening of the molecular weight distribution. The terpolymer compositions were obtained via ¹³C NMR spectroscopy, and the residual counterion content was determined via elemental analysis for Na⁺ and Cl⁻. The molecular weights (MWs) and polydispersity indices (PDIs) were determined via size exclusion chromatography/multi-angle laser light scattering (SEC–MALLS); the terpolymer MWs ranged from 1.3–1.6 × 10⁶ g/mol, corresponding to DPs of 1.6–1.9 × 10⁴ repeat units, with all terpolymers exhibiting PDIs of less than 2.0. Intrinsic viscosities determined from SEC–MALLS data and the Flory–Fox relationship were compared to intrinsic viscosities determined via low-shear dilute-solution viscometry and were found to agree rather well. Data from the SEC–MALLS analysis were used to analyze the radius of gyration/molecular weight (R_g–M) relationships and the Mark–Houwink–Sakurada intrinsic viscosity/molecular weight ([η]–M) relationships for the terpolymers. The R_g–M and [η]–M relationships revealed that most of the terpolymers exhibited little or no excluded volume effects under size exclusion chromatography conditions. Potentiometric titration of terpolymer solutions in deionized water showed that the apparent pK_a value of the poly[acrylamide-co-sodium 3-acrylamido-3-methylbutanoate-co-(3-acrylamidopropyl)trimethylammonium chloride] terpolymers increased with increasing NaAMB content in the terpolymers and increasing ratios of anionic monomer to cationic monomer at a constant terpolymer charge density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3236–3251, 2004     

Synthesis and characterization of near‐monodisperse electron acceptor homopolymers of 2‐[(3,5‐dinitrobenzoyl)oxy]ethyl methacrylate

Homopolymers of 2‐(trimethylsiloxy)ethyl methacrylate of degrees of polymerization from 5 to 50 were synthesized by group transfer polymerization in tetrahydrofuran (THF) using 1‐methoxy‐1‐(trimethylsiloxy)‐2‐methyl propene as the initiator and tetrabutylammonium bibenzoate as the catalyst. These polymers were first converted to poly[2‐(hydroxy)ethyl methacrylate]s by removal of the trimethylsilyl‐protecting groups by acidic hydrolysis, and subsequently transformed to poly{2‐[(3,5‐dinitrobenzoyl)oxy]ethyl methacrylate}s by reaction with 3,5‐dinitrobenzoyl chloride in the presence of triethylamine. Gel permeation chromatography in THF and proton nuclear magnetic resonance (¹H NMR) spectroscopy in CDCl₃ and d₆ dimethyl sulfoxide were used to characterize the polymers in terms of their molecular weight and composition. The molecular weights were found to be close to the values expected from the polymerization stoichiometry and the molecular weight distributions were narrow, with polydispersity indices around 1.1. The hydrolysis and reesterification steps were found to be almost quantitative for all polymers. Differential scanning calorimetry and thermal gravimetric analysis were also employed to measure the glass transition temperatures (T_g 's) and decomposition temperatures, which were determined to be approximately 80 and 320 °C, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1457–1465, 2000     

Polymerization of o‐quinodimethanes. III. Polymerization of o‐quinodimethanes bearing electron‐withdrawing groups formed in situ by thermal ring‐opening isomerization of corresponding benzocyclobutenes

The substituent effect on the radical polymerization of o‐quinodimethanes, generated by thermal isomerization of benzocyclobutenes, was investigated. Polymerizations of three benzocyclobutenes bearing electron‐withdrawing groups were studied, namely 1‐cyanobenzocyclobutene (1), 1‐chlorobenzocyclobutene (2), and 1‐bromobenzocyclobutene (3). While radical polymerizations of 2 and 3 did not afford any polymer, radical polymerization of 1 afforded n‐hexane‐insoluble polymer(M_n = 5000) in moderate yields at temperatures above 120°C. The structure of the obtained polymer was confirmed to be a ring‐opened polymer(4) by IR, ¹H‐, and ¹³C‐NMR. The yield of the polymer increased with an increase in the initiator concentration. The polymer yield reported in this paper is higher than those of benzocyclobutenes bearing electron‐donating groups, reported previously by the authors. The semi‐empirical molecular orbital calculation supported the contribution of ring‐opening polymerization of spiro‐compounds, rejecting the possibility of 1,4‐polymerization. Lastly, radical copolymerizations of 1 with various comonomers were also performed to obtain the corresponding copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1555–1563, 1999     

Synthesis and characterization of a biodegradable ABC triblock terpolymer as co‐delivery carrier of doxorubicin and DNA

This study is aimed to develop a well‐defined ABC triblock terpolymer, poly(ethylethylene phosphate)‐block‐poly(ε‐caprolactone)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] (PEEP‐b‐PCL‐b‐PDMAEMA), for co‐encapsulating anticancer drug doxorubicin (DOX) and DNA to form polyplexes. The terpolymer is first synthesized via a combination of ring‐opening polymerization and atom‐transfer radical polymerization techniques, and characterized by ¹H NMR and gel permeation chromatography. Subsequently, the self‐assembly behavior of the terpolymer and the micelles loaded with DOX or DNA are investigated by dynamic light scattering, ζ potential, transmission electron microscopy, and gel retardation assay, respectively. In vitro release study reveals that much more DOX is released at pH 5.0 than that at pH 7.4 in the same period. The simultaneous delivery of DOX and green fluorescent protein (GFP)‐labeled DNA is studied by a fluorescence microscope and the results demonstrate that both drug and GFP–DNA can be efficiently delivered into HeLa cells. This system presents a practical and promising carrier for the co‐delivery of drugs and genes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3005–3016     

Linear pentablock quintopolymers (l‐SIDMV) with five incompatible blocks: Polystyrene,polyisoprene‐1,4, poly(dimethylsiloxane), poly(tert‐butyl methacrylate), and poly(2‐vinylpyridine)

Three linear pentablock quintopolymers (l‐SIDMV), where S is polystyrene (PS), I polyisoprene‐1,4 (PI), D poly(dimethylsiloxane) (PDMS), M poly(tert‐butyl methacrylate) (PtBuM), and V poly(2‐vinylpyridine) (P2VP), were synthesized by anionic polymerization high vacuum techniques. The approach involves the following: (a) The synthesis of living triblock terpolymer PS‐b‐PI‐b‐PDMSLi and diblock copolymer P2VP‐b‐PtBuMK by sequential polymerizations of the corresponding monomers with sec‐BuLi and benzyl potassium, respectively; and (b) The selective linking of the living triblock terpolymer with the chlorosilane group of 2‐(chloromethylphenyl)ethyldimethylchlorosilane (CMPDMS), followed by linking of the living block copolymer with the remaining chloromethyl group of CMPDMS. Molecular characterization carried out by size exclusion chromatography, membrane osmometry, solution (in CDCl₃ or d₈‐toluene) and solid‐state ¹H‐NMR spectroscopy indicated a high degree of molecular and compositional homogeneity. Differential scanning calorimetry results on the precursors and final polymers were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3938–3946, 2008     

Synthesis and self‐assembly of diblock copolymers composed of poly(3‐hexylthiophene) and poly(fluorooctyl methacrylate) segments

Regioregular poly(3‐hexylthiophene)‐b‐poly(1H,1H‐dihydro perfluorooctyl methacrylate) (P3HT‐b‐PFOMA) diblock copolymers were synthesized by atom transfer radical polymerization of fluorooctyl methacrylate using bromoester terminated poly(3‐hexylthiophene) macroinitiators in order to investigate their morphological properties. The P3HT macroinitiator was previously prepared by chemical modification of hydroxy terminated P3HT. The block copolymers were well characterized by ¹H NMR spectroscopy and gel permeation chromatography. Transmission electron microscopy was used to investigate the nanostructured morphology of the diblock copolymers. The block copolymers are able to undergo microphase separation and self‐assemble into well‐defined and organized nanofibrillar‐like micellar morphology. The development of the morphology of P3HT‐b‐PFOMA block copolymers was investigated after annealing in solvent vapor and also in supercritical CO₂. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Ethylene–propylene copolymerization behavior of ansa‐dimethylsilylene(fluorenyl)(amido)dimethyltitanium complex: Application to ethylene–propylene–diene or ethylene–propylene–norbornene terpolymers

Copolymerization behavior of ethylene (E) and propylene (P) using ansa‐dimethylsilylene(fluorenyl)(amido)dimethyltitanium complex was investigated. P was more reactive than E regardless of the chain‐end monomer unit, which was very unusual in the coordination polymerization system. The terpolymerizations of E, P and norbornene (NB) or 5‐ethylidene‐2‐norbornene (5E2N) were also performed. The each content in the E/P/NB terpolymer was independently controlled by the initial concentration of NB and E/P feed ratio. Glass transition temperature (T_g) of the terpolymer was raised in proportion to the NB content and close to that of the corresponding NB/E random copolymer with the same NB content. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 685–691     

ROMP‐NMP‐ATRP combination for the preparation of 3‐miktoarm star terpolymer via click chemistry

A combination of ring opening metathesis polymerization (ROMP) and click chemistry approach is first time utilized in the preparation of 3‐miktoarm star terpolymer. The bromide end‐functionality of monotelechelic poly(N‐butyl oxanorbornene imide) (PNBONI‐Br) is first transformed to azide and then reacted with polystyrene‐b‐poly(methyl methacrylate) copolymer with alkyne at the junction point (PS‐b‐PMMA‐alkyne) via click chemistry strategy, producing PS‐PMMA‐PNBONI 3‐miktoarm star terpolymer. PNBONI‐Br was prepared by ROMP of N‐butyl oxanorbornene imide (NBONI) 1 in the presence of (Z)‐but‐2‐ene‐1,4‐diyl bis(2‐bromopropanoate) 2 as terminating agent. PS‐b‐PMMA‐alkyne copolymer was prepared successively via nitroxide‐mediated radical polymerization (NMP) of St and atom transfer radical polymerization (ATRP) of MMA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 497–504, 2009     

Novel dinitroxide mediating agent for stable free‐radical polymerization

A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10^?5 s^?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004     

Effect of biaxial orientation on dielectric and breakdown properties of poly(ethylene terephthalate)/poly(vinylidene fluoride‐co‐tetrafluoroethylene) multilayer films

Polymer films with enhanced dielectric and breakdown properties are essential for the production of high energy density polymer film capacitors. By capitalizing on the synergistic effects of forced assembly nanolayer coextrusion and biaxial orientation, polymer multilayer films using poly(ethylene terephthalate) (PET) and a poly(vinylidene fluoride‐co‐tetrafluoroethylene) [P(VDF‐TFE)] copolymer were produced. These films exhibited breakdown fields, under a divergent field using needle/plane electrodes, as high as 1000 kV mm^?1. The energy densities of these same materials, under a uniform electric field measured using plane/plane electrodes, were as high as 16 J cm^?3. The confined morphologies of both PET and P(VDF‐TFE) were correlated to the observed breakdown properties and damage zones. On‐edge P(VDF‐TFE) crystals induced from solid‐state biaxial stretching enhanced the effective P(VDF‐TFE) layer dielectric constant and therefore increased the dielectric contrast between the PET and P(VDF‐TFE) layers. This resulted in additional charge buildup at the layer interface producing larger tree diameters and branches and ultimately increasing the breakdown and energy storage properties. In addition to energy storage and breakdown properties, the hysteresis behavior of these materials was also evaluated. By varying the morphology of the P(VDF‐TFE) layer, the low‐field dielectric loss (or ion migration behavior) could be manipulated, which in turn also changed the observed hysteresis behavior. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 882–896     

A polymer of bisphenol A and bisphenol A diglycidyl ether and its blends with poly(styrene‐co‐acrylonitrile): In situ polymerization preparation,morphology, and mechanical properties

The poly(hydroxy ether of bisphenol A)‐based blends containing poly(acrylontrile‐co‐styrene) (SAN) were prepared through in situ polymerization, i.e., the melt polymerization between the diglycidy ether of bisphenol A (DGEBA) and bisphenol A in the presence of poly(acrylontrile‐co‐styrene) (SAN). The polymerization reaction started from the initial homogeneous ternary mixture of SAN/DGEBA/bisphenol A, and the phenoxy/SAN blends with SAN content up to 20 wt % were obtained. Both the solubility behavior and Fourier transform infrared (FTIR) spectroscopy studies demonstrate that no intercomponent reaction occurred in the reactive blend system. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electronic microscopy (SEM) were employed to characterize the phase structure of the as‐polymerized blends. All the blends display the separate glass transition temperatures (T_g's); i.e., the blends were phase‐separated. The morphological observation showed that all the blends exhibited well‐distributed phase‐separated morphology. For the blends with SAN content less than 15 wt %, very fine SAN spherical particles (1–3 μmm in diameter) were uniformly dispersed in a continuous matrix of phenoxy and the fine morphology was formed through phase separation induced by polymerization. Mechanical tests show that the blends containing 5–15 wt % SAN displayed a substantial improvement of tensile properties and Izod impact strength, which were in marked contrast to those of the materials prepared via conventional methods. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 525–532, 1999     

Terpolymerization of ethyl methacrylate,N‐phenylmaleimide,and itaconic acid

The terpolymerization of ethyl methacrylate (EMA), N‐phenylmaleimide (NPMI), and itaconic acid (IA) was investigated. The terpolymer composition was determined by elemental analysis and ¹H NMR spectroscopy. The reactivity ratios of the three binary systems (EMA/NPMI, EMA/IA, and NPMI/IA) were calculated and used for the calculation of the terpolymer composition with the terminal model equations. A comparison between the experimental and theoretical compositions was made. The rate of the terpolymerization process was measured dilatometrically at two total monomer concentrations; this was done to establish the presence of intermolecular interactions between the investigated monomers. The thermal analysis of the obtained terpolymers was performed by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3180–3187, 2003     

H‐transfer reaction during decomposition of N‐(2‐methylpropyl)‐ N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐N‐oxyl (SG1)‐based alkoxyamines

Thermal decomposition of four tertiary N‐(2‐methylpropyl)‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl)‐N‐oxyl (SG1)‐based alkoxyamines (SG1‐C(Me)₂‐C(O)‐OR, R = Me, tBu, Et, H) has been studied at different experimental conditions using ¹H and ³¹P NMR spectroscopies. This experiment represents the initiating step of methyl methacrylate polymerization. It has been shown that H‐transfer reaction occurs during the decomposition of three alkoxyamines in highly degassed solution, whereas no products of H‐transfer are detected during decomposition of SG1‐MAMA alkoxyamine. The value of the rate constant of H‐transfer for alkoxyamines 1 (SG1‐C(Me)₂‐C(O)‐OMe) and 2 ( SG1‐C(Me)₂‐C(O)‐OtBu) has been estimated as 1.7 × 10³ M^?1s^?1. The high influence of oxygen on decomposition mechanism is found. In particular, in poorly degassed solutions, nearly quantitative formation of oxidation product has been observed, whereas at residual pressure of 10^?5 mbar, the main products originate from H‐atom transfer reaction. The acidity of the reaction medium affects the decomposition mechanism suppressing the H‐atom transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Characterization and quantification of microstructures of a fluorinated terpolymer by both homonuclear and heteronuclear two‐dimensional NMR spectroscopy

Fluoropolymers are usually insoluble in organic solvents. Insolubility of fluoropolymers limits basic characterization such as microstructural investigations. In the family of fluoropolymers, terpolymer of tetrafluorethylene (TFE), hexafluoropropylene (HFP), and vinylidene fluoride (VDF), named THV is one of the newest members. There are nine grades of THV available. Among the nine grades, THV‐221 G is an ideal model polymer for basic characterization purposes. THV‐221 G is soluble in solvents such as acetone and ethyl acetate. In the current report, both homonuclear and heteronuclear 2D NMR experiments were employed in solution on THV‐221 G. The homonuclear gradient correlation spectroscopy NMR measurement revealed that THV has two adjacent TFE units in addition to TFE‐HFP sequence orders. The fraction of the microstructures is quantified by the analysis of 1D solution ¹⁹F NMR spectrum. Further, the gradient heteronuclear single quantum coherence experiment helped with the clarification of chemical environments of the units TFE, HFP, and VDF. The 1D solution ¹³C NMR spectrum was helpful in clarifying sequence assignments of VDF. It is concluded that THV is a random polymer with a limited fraction of TFE‐TFE and TFE‐HFP sequence orders in addition to head‐to‐tail polymerization of VDF unit. Copyright © 2014 John Wiley & Sons, Ltd.     

Near‐monodisperse α‐hydroxy and α,ω‐dihydroxy amine‐based polymers: Synthesis and characterization

α‐Hydroxy and α,ω‐dihydroxy polymers of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) of various molecular weights were synthesized by group transfer polymerization (GTP) in tetrahydrofuran (THF), using 1‐methoxy‐1‐(trimethylsiloxy)‐2‐methyl propene (MTS) as the initiator and tetrabutylammonium bibenzoate (TBABB) as the catalyst. The hydroxyl groups were introduced by adding one 2‐(trimethylsiloxy) ethyl methacrylate (TMSEMA) unit at one or at both ends of the polymer chain. The ends were converted to 2‐hydroxyethyl methacrylate (HEMA) units after the polymerization by acid‐catalyzed hydrolysis. Gel permeation chromatography (GPC) in THF and proton nuclear magnetic resonance (¹H‐NMR) spectroscopy in CDCl₃ were used to determine the molecular weight and composition of the polymers. These mono‐ and difunctional methacrylate polymers can be covalently linked at the hydroxy termini to form star polymers and model networks, respectively. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1597–1607, 1999     

Free radical and thermal curing of terpyridine‐modified terpolymers

Terpolymers bearing terpyridine as well as (meth)acrylates as free radical curable groups (UV‐curing) or hydroxyl groups (thermal curing with bis‐isocyanates) were synthesized and characterized using ¹H NMR, IR and UV‐vis spectroscopy as well as GPC. Subsequently, the ability of covalent crosslinking via the UV‐initiated polymerization of the acrylate groups was investigated. Moreover, the thermal covalent crosslinking via the reaction of hydroxyl functionalized terpolymer and bis‐isocyanate compounds could be successfully achieved. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4028–4035, 2004     

Preparation and characterization of soluble terpolymers from m‐phenylenediamine,o‐anisidine,and 2,3‐xylidine

A series of terpolymers were synthesized by the chemical oxidative polymerization of m‐phenylenediamine (MPD), o‐anisidine (AS), and 2,3‐xylidine (XY) in hydrochloride aqueous medium. The yield, intrinsic viscosity, and solubility of the terpolymers were studied by changing the MPD/AS/XY molar ratio from 100/0/0 to 53/39/8 to 0/100/0. It was discovered that the MPD/AS/XY terpolymers exhibit a higher polymerization yield and better solubility than MPD/AS and MPD/XY bipolymers having the same MPD molar content. The as‐prepared MPD/AS/XY terpolymer bases were characterized by Fourier transform infrared, ultraviolet–visible, ¹H NMR, and high‐resolution solid‐state ¹³C NMR spectroscopies; wide‐angle X‐ray diffraction; and thermogravimetry. The results suggested that the oxidative polymerization from MPD, AS, and XY is exothermic, and the resulting terpolymers are more easily soluble in some organic solvents than MPD homopolymer. The copolymer obtained was a real terpolymer containing MPD, AS, and XY units, and the actual MPD/AS/XY molar ratio calculated by solid‐state ¹³C NMR spectra of the polymers is very close to the feed ratio, although the AS content calculated on the basis of the ¹H NMR spectrum of the soluble part of the polymer is higher than the feed AS content. The terpolymers and MPD homopolymer exhibit a higher polymerization yield and much higher intrinsic viscosity and are more amorphous than the AS homopolymer. At a fixed MPD content of 70 mol %, the terpolymers exhibit an increased thermostability and activation energy of the major degradation in nitrogen and air with an increasing AS content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3989–4000, 2001