Synthesis and properties of new crystalline poly(arylene ether)s containing pendant benzoyl groups

Poly(arylene ether)s ( 3 ) containing pendant benzoyl groups were prepared by the aromatic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone (2) with hydroquinone ( 1a ) and methylhydroquinone ( 1b ) in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.8 dL/g. The polymer ( 3b ) derived from methylhydroquinone was quite soluble in common organic solvents and could be processed into uniform films from solutions. On the other hand, the polymer ( 3a ) derived from hydroquinone was only soluble in pentafluorophenol and methanesulfonic acid and had a high crystallinity. These polymers showed 10% weight losses at around 420 and 490°C in nitrogen. Polymer 3b also showed good tensile strength and tensile moduli. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 605–611, 1997     

Photochemical behavior of poly(ethylacryloylacetate) and poly(acryloylacetone) films

Films of poly(ethylacryloylacetate) (PEAA) and poly(acryloylacetone) (PAA) were subjected to UV irradiation (λ = 254 nm) at room temperature. The photoinduced structure transfer from cis-enol onto a diketo forms has been investigated. The structure transfer caused by UV light was found to be slower than for the corresponding process in solution. The spectral investigations (UV, IR) showed reversible process of photoketonization. The results were analyzed in terms of the model for the participation of the trans-enol form in the process of the ketonization. Based on the results obtained, some general conclusions were made about the organization of the units in the polymer chain. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3683–3688, 1997     

A one-pot method for the preparation of latices of telechelic oligomers,by ozonolysis of latices of polymers containing main-chain unsaturation

Poly(methyl methacrylate-co-butadiene), Poly(butyl methacrylate-co-butadiene) and Poly(methyl methacrylate-co-2,3-dimethyl butadiene) latices (a.k.a. latexes) were prepared by monomer-starved emulsion polymerization. The polymerizations were followed by GPC. It was found that the molecular-weight distribution did not alter significantly with conversion if the polymerizations were carried out at a feed rate of 0.03 cm³ s⁻¹ per 1000 cm³ of reaction medium and a temperature of 70°C. Slower rates of monomer addition led to broadening of the molecular-weight distribution. The resultant latices were swollen with varying amounts of toluene. Ozonolysis of the swollen and nonswollen latices yielded latices of polymer ozonides. Oxidation, with selenium oxide/hydrogen peroxide reagent, converted the ozonides to latices of carboxylic acid or methyl ketone ended telechelic oligomers. It was found that the molecular weights of the oligomers were a function of toluene concentration. Colloidal stability was found to be a function of end-group structure. Thus, carboxylic acid end groups impart extra stability to the colloid while methyl ketone end groups do not. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3255–3262, 1997     

Synthesis of regiocontrolled poly(4,6-di-n-butoxy-1,3-phenylene) by oxidative coupling polymerization

Poly(4,6-di-n-butoxy-1,3-phenylene) ( 6 ) was prepared by oxidative coupling polymerization of 1,3-di-n-butoxybenzene ( 1 ) or 2,2′,4,4′-tetra-n-butoxy biphenyl (3). Polymerizations were conducted in nitrobenzene in the presence of FeCl₃ at room temperature and produced polymers with number-average molecular weights up to 42,000. The effects of various factors, such as amount of FeCl₃ and reaction temperature and time were studied. The structure of polymer 6 was characterized by 270 MHz ¹H- and 68.5 MHz ¹³C-NMR spectroscopies and was estimated to consist of almost completely 1,3-linkage. The regiocontrolled polymer was readily soluble in common organic solvents. Thermogravimetric analysis of polymer 6 showed 10% weight loss at 390°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Chem 35 : 2259–2266, 1997     

Near‐infrared spectroscopy for the quantitative determination of mass transfer and water absorption kinetics by a polymer solution

This article reports a new method to quantify the water absorption kinetics and the mass transfer in a polymer solution by using near‐infrared (NIR) spectroscopy and partial least‐squares (PLS) models, while it is exposed to a humid atmosphere. Polymer solutions used in this study were made with highly polar solvents exhibiting both a high affinity for water and a low volatility such as dimethylformamide, dimethylacetamide, and N‐methylpyrrolidone. Poly(ethersulfone) and poly(etherimide) were chosen as polymer models as the method could provide useful information for coating process and membrane fabrication monitoring. Whereas gravimetric kinetics yield data on the overall mass transfer, including both water absorption and solvent evaporation, in situ analyses using NIR can quantify separately the solvent and nonsolvent concentration change in the polymer solution. Quantitative models were developed using PLS regression to predict the local water, polymer, and solvent weight fractions in the polymer solution. The method was proved to be suitable for the different studied systems and allowed to infer mass transfers until the onset of the phase separation process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1960–1969, 2010     

Engineering a sharp physiological transition state for poly(n‐isopropylacrylamide) through structural control

Poly(N‐isopropylacrylamide) (pNIPAAm), a well‐studied, biologically inert polymer that undergoes a sharp aqueous thermal transition at 32 °C, has been a subject of widespread interest for possible biological applications. A major hindrance to its successful application is due to the difficulty of maintaining a sharp transition when the polymer is modified for a physiological transition temperature, especially in isotonic solutions. Current copolymer blends raise the transition temperature but also make the transition significantly broader. We have combined the use of reversible addition‐fragmentation chain transfer (RAFT) polymerization with tacticity control to synthesize well‐defined pNIPAAm that demonstrates sharp transitions under physiological conditions. By selecting a RAFT agent with appropriate end groups, controlling molecular weight, and increasing the racemo diad content, we were able to increase the thermal transition temperature of pure pNIPAAm to a sharp transition at 37.6 °C under isotonic conditions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Molecular composite films from polybenzoxazole and crosslinked polymer matrixes

Films consisting of a rigid-rod polymer and thermoset resin matrixes were prepared. Poly{(benzo[1,2-d : 5,4-d′]bis(oxazole-2,6-diyl))-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with 2,6-bis(4-benzocyclobutene) benzo[1,2- d : 5,4-d′]bis(oxazole) ( 1 ), and films were extruded from these solutions. The coagulated films were soluble in methanesulfonic acid (MSA). After heat treatment at 300°C, the films became insoluble in MSA. Crosslinked films were homogeneous and did not show phase segregation between the two components. These were composite films at the molecular level. Transmission electron microscopy (TEM) showed enhanced interlayer integrity and reduced microfibril separation for the molecular composite films as compared to normal PBO film. These films had significantly better torsion and tension delamination resistance. The incorporation of a second component did not sacrifice the tensile properties of PBO film. Thermal stability of these composite films was only slightly lower than that of normal PBO film. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2157–2165, 1997     

Long-term permeation properties of poly(1-trimethylsilyl-1-propyne) membranes in hydrocarbon—Vapor environment

Poly(1-trimethylsilyl-1-propyne) (PTMSP), a high free-volume glassy di-substituted polyacetylene, has the highest gas permeabilities of all known polymers. The high gas permeabilities in PTMSP result from its very high excess free volume and connectivity of free volume elements. Permeability coefficients of permanent gases in PTMSP decrease dramatically over time due to loss of excess free volume. The effects of aging on gas permeability and selectivity of PTMSP membranes continuously exposed to a 2 mol % n-butane/98 mol % hydrogen mixture over a period of 47 days are reported. The permeation properties of PTMSP membranes are quite stable when the polymer is continuously exposed to a gas mixture containing a highly sorbing organic vapor such af n-butane. The n-butane/hydrogen selectivity was essentially constant for the 47-day test period at a value of 29, or 88% of the initial value of the as-cast film of 33. Condensable gases such as n-butane may serve as a “filler” in the nonequilibrium free volume of the polymer, thereby preserving the high level of excess free volume. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1483–1490, 1997     

Radical ring-opening polyaddition of a bifunctional vinylcyclopropane bearing a spiroacetal moiety with dithiols

Radical polyadditions of vinylcyclopropane having spiroacetal moiety, 1,10-divinyl-4,8,12,15-tetraoxatrispiro[2.2.2.2.2.2] pentadecane ( 1 ), and various dithiols were examined. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and pentaerythritol, and radical polyadditions of 1 and dithiols were carried out at 60 and 120°C for 20 h in the presence of an appropriate initiator (3 mol % vs. 1 ) in degassed sealed ampoules or at 20°C under photo irradiation by using a 400 W high-pressure mercury lamp. Poly( 1 ), pale yellow transparent viscous polymers was isolated by reprecipitation with ether containing a small amount of triethylamine to avoid hydrolysis of the polymer. The obtained polymers were soluble in chlorobenzene, DMF, and chloroform but insoluble in ether and n-hexane. The molecular weights of the polymers obtained from aliphatic dithiols were smaller than those from aromatic ones. The structure of the polymer was determined by comparing the NMR spectra with those of the model compounds, which were obtained by radical addition of 1 and benzyl mercaptan. The reaction proceeded through radical polyaddition of dithiol to 1 via radical ring-opening polymerization of the cyclopropane ring. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2487–2492, 1997     

Side‐chain liquid‐crystalline polymers based on flexible rod‐like mesogen directly attached to backbone

In this article, we report the synthesis and characterization of a new end‐on side‐chain liquid crystalline polymer (SCLCP), poly[4‐(4′‐alkoxyphenyloxymethylene)styrene] [denoted as Poly(n‐POMS), where n is the carbon number of the alkyl tail, n = 2, 4, 6, 8, 12, 16], with the flexible rod‐like mesogenic side‐chain directly attached to the polymer backbone without flexible spacer. The polymer was obtained by using free radical polymerization. The chemical structures of Poly(n‐POMS) and the corresponding monomer were characterized using various techniques with satisfactory analysis data. A combination analysis of differential scanning calorimetry, polarized light microscopy, small angle X‐ray scattering, and wide‐angle X‐ray diffraction has been conducted to investigate the phase behavior of Poly(n‐POMS). Poly(2‐POMS), Poly(4‐POMS), and Poly(6‐POMS) are amorphous. Poly(8‐POMS) develops partially into the liquid crystal phase, and Poly(12‐POMS) and Poly(16‐POMS) self‐assembly into the smectic A (SmA) phase. Upon increasing temperature, the phase transition of Poly(16‐POMS) follows the sequence of SmA1 ? SmA2 ? isotropic (I), which may be attributed to the conformation isomerization of the flexible rod‐like mesogens. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of polycarbonates by a silicon-assisted alkoxy/carbonylimidazolide coupling reaction

The investigation of a silicon-mediated coupling reaction between hydroxyl and carbonylimidazolide functional groups in the preparation of carbonate linkages is described. Application of this reaction to the formation of aliphatic polycarbonates was accomplished by the polymerization of an AB monomer unit, which was composed of 1,4-cyclohexanediol, where one of the hydroxyl groups was protected as a dimethylphenylsilyl ether and the other carried the carbonylimidazolide functionality. Reaction of this monomer with cesium fluoride removed the silicon protecting group and the resulting alkoxy anion promoted polymerization. Poly(1,4-cyclohexanecarbonate)s with typical molecular weights of M_w = 20,000 and M_n = 7300 a.m.u. (from GPC based upon polystyrene standards) were prepared in ca. 65% yield. The polymer showed a glass transition temperature at 138°C by DSC. TGA gave 85% mass loss between 275 and 350°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1133–1137, 1997.     

Synthesis of degradable crosslinked polymers based on 1,5-dioxepan-2-one and crosslinker of bis-ϵ-caprolactone type

Poly(lactones) may be crosslinked by ring-opening polymerization of the corresponding cyclic esters in the presence of tetrafunctional bis(ϵ-caprolactone). The homopolymer of 1.5-dioxepan-2-one (DXO) has poor mechanical properties but also some very good properties, such as biocompatibility and degradability. Crosslinking of degradable polymer based on the poly(ether-ester) DXO was performed with crosslinkers having the same reactivity as the monomer. 2,2-Bis(ϵ-caprolactone-4-yl)propane (BCP) and bis(ϵ-caprolactone-4-yl) (BCY) with tetrafunctionalities were synthesized from the corresponding diols and then used as comonomers during the polymerization of DXO. The comonomers showed the same reactivity to the initiator, stanneous 2-ethylhexanoic acid, as DXO and perfectly random crosslinked films were obtained. The crosslinked films showed a high degree of swelling already at 2–3 mol % BCP or BCY. The BCP crosslinker was somewhat less soluble in DXO at lower temperatures, but all BCP was soluble at 180°C. These polymeric films were elastic with no crystallinity and the T_g values increased from −39°C for pure DXO to −35°C for BCP crosslinked films and −21°C for BCY crosslinked ones. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1635–1649, 1997     

Poly[N-(2-aminoethyl)acrylamido] triethylammonium polyhalide derivatives: Preparation and synthetic applications

Poly[N-(2-aminoethyl)acrylamido]triethylammonium dichloroiodate, tetrachloroiodate, and dibromoiodate polyhalides were developed as a new class of solid phase organic reagents. N,N′-methylenebisacrylamide crosslinked polyacrylamide support was utilized to prepare the reagents. The utility of polyhalide reagents for the α-halogenation of carbonyl compounds and oxidation of alcohols at various reaction conditions is described. The reactivity of the polyhalide reagents increased considerably in polar solvents and the optimum temperature for conducting the reactions was 30°C. Studies on halogenation and oxidation reactions using differently crosslinked polyacrylamide-based polyhalide reagents revealed that the reactivity increased up to 10% crosslinking and decreased progressively on further increase in the degree of crosslinking. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1413–1421, 1997     

New water-soluble photo crosslinkable polymers based on modified poly(vinyl alcohol)

Poly(vinyl alcohol) (PVA) was partially modified by polymer analogous reaction with acrylic and methacrylic acid and with 2-vinyl-4,4-dimethyl-azlactone to obtain water-soluble polymers with pendant (meth)acrylate and acrylamide groups. Aqueous solutions of these polymers were crosslinked by UV-irradiation within seconds to form transparent networks with potential for use in contact lenses. The water content of these hydrogels was studied as a function of polymer molecular weight, the acetate, (meth)acrylate, and methacrylamide contents and irradiation conditions. The hydrogels showed good mechanical properties, even at low crosslinker (<5 mol %) and high water contents (60–80%). The formation kinetics and stability of aggregates, investigated by combined GPC/light-scattering measurements of samples annealed and/or stored at different temperatures (−20 to 100°C), give insight into PVA secondary structures. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3603–3611, 1997     

Novel method for the preparation of poly(urethane–imide)s and their properties

A polymer blend consisting of polyimide (PI) and polyurethane (PU) was prepared by means of a novel approach. PU prepolymer was prepared by the reaction of polyester polyol and 2,4-tolylenediisocyanate (2,4-TDI) and then end-capped with phenol. Poly(amide acid) was prepared from pyromellitic dianhydride (PMDA) and oxydianiline (ODA). A series of oligo(amide acid)s were also prepared by controlling the molar ratio of PMDA and ODA. The PU prepolymer and poly(amide acid) or oligo(amide acid) solution were blended at room temperature in various weight ratios. The cast films were obtained from the blend solution and treated at various temperatures. With the increase of polyurethane component, the films changed from plastic to brittle and then to elastic. The poly(urethane–imide) elastomers showed excellent mechanical properties and moderate thermal stability. The elongation of films with elasticity was more than 300%. The elongation set after the breaking of films was small. From the dynamic mechanical analysis, all the samples showed a glass transition temperature (T_g) at ca. −15°C, corresponding to T_g of the urethane component, suggesting that phase separation occurred between the two polymer components, irrespective of polyimide content. TGA and DSC studies indicated that the thermal degradation of poly(urethane–imide) was in the temperature range 250–270°C. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3745–3753, 1997     

Temperature-induced phase transition of poly(N,N-dimethylaminoethyl methacrylate-co-acrylamide)

Copolymers of N,N-dimethylaminoethyl methacrylate (DMAEMA) and acrylamide (AAm) were prepared to demonstrate a temperature-induced phase transition. Poly DMAEMA has a lower critical solution temperature (LCST) around 50°C in water. With copolymerization of DMAEMA with AAm, the LCST shifts to the lower temperature was observed, probably due to the formation of hydrogen bonds between amide and N,N-dimethylamino groups. FT-IR studies clearly show the formation of hydrogen bonds which protect N,N-dimethylamino groups from exposure to water and result in a hydrophobic contribution to the LCST. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 595–598, 1997     

Effects of different acid functional groups on proton conductivity of polymer‐1,2,4‐triazole blends

Proton transfer reactions under anhydrous conditions have attracted remarkable interest due to chemical energy conversions in polymer electrolyte membrane fuel cells. In this work, 1H‐1,2,4‐triazole (Tri) was used as a proton solvent in different polymer host matrices such as Poly(vinylphosphonic acid) (PVPA), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) (PAMPS). PVPATri_x and PAMPSTri_x electrolytes were investigated where x is the molar ratio of Tri to corresponding polymer repeat unit. The interaction between polymer and Tri was studied via FTIR spectroscopy. Thermogravimetry analysis and differential scanning calorimetry were employed to examine the thermal stability and homogeneity of the materials, respectively. PVPATri_1.5 showed a maximum water‐free proton conductivity of 2.3 × 10^?3 S/cm at 120 °C and that of PAMPSTri₂ was 9.3 × 10^?4 S/cm at 140 °C. The results were interpreted in terms of different acidic functional groups and composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3315–3322, 2006     

Polybisaminophosphazene-silver nitrate complexes: Coordination and properties

Poly[bis(propylamino)phosphazene]-silver nitrate complexes and poly[bis-(butylamino)phosphazene]-silver nitrate complexes with various salt contents, which are new polyphosphazene-salt complexes, have been prepared. The complexes were characterized by FTIR, ³¹P-NMR, and ¹³C-NMR spectroscopies, and the thermal properties were studied by DSC, TGA, and TGA/FTIR measurements. It was found that the poly[(bisamino)phosphazene]-silver coordination may occur both at the backbone nitrogen and the side chain nitrogen and incorporation of silver nitrate into the polymer lowered the decomposition temperature. The complexes can be cast as freestanding film with good dimensional stability. Compared to their parent polymers, the highest conductivities of the films are increased three to four orders in magnitude at room temperature. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1023–1031, 1997     

Living anionic homo- and block copolymerization of 2-(tert-butylamino)ethyl methacrylate

Anionic polymerization of 2-(tert-butylamino)ethyl methacrylate (tBAEMA), which bears an unprotected secondary amine moiety, has been investigated in THF at −78°C. The presence of lithium chloride has been shown to be desirable to afford narrow molecular weight distribution as well as a good agreement between theoretical and observed molecular weight. The living character of the polymerization has also been demonstrated, and the synthesis of block copolymers carried out successfully. They have been analyzed by SEC by adding a mixture of secondary and tertiary amines to the eluent (THF) so as to avoid any polymer adsorption during elution. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2035–2040, 1997     

Mutual conversion between stretched and contracted helices accompanied by a drastic change in color and spatial structure of poly(phenylacetylene) prepared with a [Rh(nbd)Cl]2‐amine catalyst

The yellow‐colored poly(phenylacetylene), Poly( Y ), is obtained from phenylacetylene using a [Rh(nbd)Cl]₂‐NEt₃ catalyst in ethanol at 25 °C. The color of Poly( Y ) drastically changes into red Poly( R ) or reddish‐black Poly( B ) by immersion in acetylacetone or exposure to chloroform vapor, respectively. Poly( R ) is also created from Poly( B ) by contact with acetylacetone. Poly( Y ) is regenerated from both Poly( R ) and Poly( B ) by reprecipitation from their chloroform solution into methanol. Wide‐angle X‐ray scattering (WAXS) patterns of Poly( Y ) and Poly( R ) correspond to a pseudohexagonal crystal called a columnar as stretched cis‐transoid and contracted cis‐cisoid helices, respectively. These helical diameters and pitch widths obtained from the WAXS measurements are agreed with those of MMFF94 calculation models. The smallest helical pitch width is 3.3 Å for Poly( R ) and Poly( B ). Moreover, information regarding the size and ordering of the vacant space within each polymer is estimated by using ¹²⁹Xe NMR technique. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 752–759