Bisphenol-A-polycarbonate-bisphenol-A-polysulfone block copolymers

Multiblock , block copolymers of bisphenol-A-polycarbon ate and bisphenol-A-polysulfone were prepared by three different synthesis routes. The in situ method consisted of forming the polycarbonate block in the presence of hydroxyl terminated polysulfone oligorner. The coupled oligomer technique utilized phosgene to link up the two preformed oligomers to high molecular weight. In one case, a perfectly alternating block copolymer was formed by reacting a ～9, 000 M _n chloroformate terminated polycarbonate with a ～9, 000 M _n hydroxyl terminated polysulfone. Block sizes from ～4, 000 to ～26, 000 were investigated. The oligomers and copolymers were characterized by potentiometric titrations and UV end group analysis. Membrane osmometry and gel permeation chromatography were also employed. Dynamic mechanical behavior of solvent cast and compression molded films was assessed via rheovibron measurements. The copolymers were ductile and transparent and displayed essentially only a single intermediate glass transition temperature, that is, microphase separation was not observed. This is in contrast to simple physical blends of the homopolymers or oligomers, which are opaque and display two glass transition temperatures.     

The interfacial polycarbonate reactions. I. Defining the critical process parameters

Polycarbonate is prepared by the interfacial phosgenation and polycondensation of bisphenol A (BPA) in methylene chloride with caustic using triethylamine as a catalyst. In a typical batch reactor, where phosgenation and oligomerization proceed simultaneously, the critical process parameters are intermingled and are difficult to determine. Therefore, a semicontinuous process consisting of a series of static mixers for continuous phosgenation, followed by a batch reactor for oligomerization and polycondensation, was developed for better understanding of the reaction mechanisms. Phosgene hydrolysis was reduced greatly going from a batch to a continuous reactor (excess phosgene was reduced from 30 to 5%). Variables which influence the composition of intermediates are linear velocity, organic to aqueous volume ratio, PH (BPA to NaOH ratio), and phosgene to BPA ratio. These variables also affect BPA conversion, amount of phosgene hydrolysis, terminator capping efficiency, molecular weight, and molecular weight distribution of the resulted polycarbonate. Oligomerization takes place at the interface, and monochloroformates (HO-B_n-OCOCI) which contain both hydrophilic and lipophilic end groups, stay at the interface and, hence, react preferentially. Oligomers are analyzed by a newly developed HPLC technique.     

Bisphenol-A polycarbonate/polydimethylsiloxane multiblock copolymers. I. Synthesis and characterization

Aminopropyl-terminated polydimethylsiloxane (PDMS)-bisphenol-A polycarbonate block copolymers were synthesized by interfacial phosgenation reaction of 2,2-bis(4-hydroxyphenyl) propane (BPA) and aminopropyl-terminated PDMS. A new synthetic procedure shows better conversion yield of PDMS oligomer. IR, ¹H, ¹³C, and ²⁹Si nuclear magnetic resonance spectra were used to identify the exact chemical structures of the PDMS-PC block copolymers. The conversions of PDMS of these copolymers were ∼ 90% and independent of the PDMS content. The intrinsic viscosities, IV, [γ] studied were in the range between 0.23 and 2.25 dL/g in dichloromethane at 25°C with different reaction conditions. The intrinsic viscosity and the glass transition temperature decreased with increasing PDMS content at the same reaction temperature, while the melting flow indices increase with increasing PDMS content. Transparent and colorless films, which showed good oxygen-to-nitrogen permselectivity, could be cast from dichloromethane. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 57–66, 1997     

Precipitative polymerization for polycarbonate: A simultaneous reaction–precipitation technique

A novel phenomenon, termed precipitative polymerization, is described. In it, the BPA—phosgene reaction is conducted with simultaneous precipitation of polycarbonate granules. Very low organic-to-aqueous phase ratio and high pH medium are primarily required to cause this in-situ precipitation.     

The fire-resistance properties of polycarbonates

Summary The present paper describes two types of polycarbonates possessing fire-resistance. The first type is obtained by reacting dialkyl bis(hydroxy-4-phenyl) alkyl phosphonates with phosgene and the second type is a copolymer of bisphenol A and dialkyl bisphenol phosphonates.We show that the incorporation of dialkyl bisphenol phosphonates into the bisphenol A polycarbonate chains can be satisfactorily carried out using interfacial polycondensation.The products with groups-P (OCH₃)₂ possess high oxygen indices (OI).     

Synthesis of Polycarbonate Precursors over Titanosilicate Molecular Sieves

A novel catalytic application of titanosilicate molecular sieves (TS-1 and TiMCM-41), in the synthesis of polycarbonate precursors like cyclic carbonates and dimethyl and diphenyl carbonates, avoiding toxic chemicals like phosgene or CO, is reported. Cyclic carbonates were prepared, over TS-1 and TiMCM-41, in high yields, by cycloaddition of CO₂ to epoxides, like epichlorohydrin, propylene oxide and styrene oxide, at low temperatures and pressures. Further, transesterification of the cyclic carbonates with methanol and phenol, over TiMCM-41, yielded other polycarbonate precursors like dimethyl carbonate (DMC) and diphenyl carbonate (DPC). The cyclic carbonates could also be synthesized from the olefins in the same reactor by reacting the olefins, in the presence of TiMCM-41, with a mixture of an epoxidizing agent (like H₂O₂ or tert-butyl hydroperoxide) and CO₂.     

Effects of ethylene-octene copolymer (POE) on the brittle to ductile transition of high-density polyethylene/POE blends

Three kinds of ethylene-octene copolymers (POE) were melt-blended with high-density polyethylene (PE-HD) in different proportions. Detailed characterizations were conducted to analyze their structural differences of POE and its effects in toughening PE-HD. The higher molecular weight POE can improve the toughness of PE-HD. 60:40 PE-HD/POE is elongated to break up to 700% while impact strength is 84.7 kJ/m² at −30°C, which is 21-fold of PE-HD. In the brittle to ductile transition (BDT) during impact, the fracture mechanism changes from the crazing mode to the shear yield-plastic deformation mode. The BDT temperature decreases as the POE molecular weight and its content increase. The interface strength in tension is estimated to access their effects. The Boltzmann-type models were successfully extended to describe the typical S-shaped curves in BDT of notched impact strength vs POE content or temperature. The supplementary decay model is suggested for the attenuation in toughening. Transition map in impact is proposed to select the use range of composition (c ) and temperature (T ) for high toughness. The curves are converted into 3D graph of T -c -impact strength for illustrating their coupling-separate effects, and further into the contour map of impact strength in T -c space for finding their partial equivalence.     

Synthesis and properties of novel biodegradable triblock copolymers of poly(5-methyl-5-methoxycarbonyl-1,3-dioxan-2-one) and poly(ethylene glycol)

Novel biodegradable triblock copolymers of poly(5-methyl-5-methoxycarbonyl-1,3-dioxan-2-one) (PMMTC) with poly(ethylene glycol) (PEG), PMMTC-b-PEG-b-PMMTC, were synthesized by the ring-opening polymerization of MMTC in bulk, using the dihydroxyl PEG as initiator and Sn(Oct)₂ as catalyst. The triblock copolymers with different compositions were characterized by IR and ¹H NMR, their molecular weight was measured by gel permeation chromatography (GPC). The results showed that the molecular weight of triblock copolymers increased either with the increase of the molar ratio of MMTC in feed while the PEG chain length kept constant, or by lengthening the backbone chain of PEG block with the same ratio of MMTC in feed. The hydrophilicity of copolymers was greatly improved by incorporation of PEG block into polycarbonate. The in vitro hydrolytic/enzymatic degradation and controlled drug release properties of the triblock copolymers were also investigated.     

A convenient laboratory preparation of aromatic polycarbonate

Summary An experimentally simple method for the synthesis of aromatic polycarbonates is described. Reaction of commercially available p-nitrophenyl chloroformate with bisphenol A afforded BPA polycarbonate in good yields with M _n= 26,000 g/mol. This laboratory procedure avoids the use of phosgene or phosgene equivalents in the laboratory. The process requires the use of 2 equivalents of triethylamine and a catalytic amount of 4-dimethylaminopyridine. Received: 31 July 2001/ Revised version: 16 November 2001/ Accepted: 28 November 2001     

Structure and properties of ultra‐high molecular weight bisphenol a polycarbonate synthesized by solid‐state polymerization in amorphous microlayers

The structure and properties of ultrahigh molecular weight polycarbonate synthesized by solid‐state polymerization in micro‐layers (SSP_m) are reported. A low molecular weight prepolymer derived from the melt transesterification of bisphenol A and diphenyl carbonate as a starting material was polymerized to highly amorphous and transparent polycarbonate of molecular weight larger than 300,000 g mol^?1 in the micro‐layers of thickness from 50 nm to 20 µm. It was observed that when the polymerization time in micro‐layers was extended beyond conventional reaction time, insoluble polymer fraction increased up to 95%. Through the analysis of both soluble and insoluble polymer fractions of the high molecular weight polycarbonate by ¹H NMR spectroscopy and pyrolysis‐gas chromatography mass spectrometry (Py‐GC/MS), branches and partially crosslinked structures have been identified. The thermal, mechanical and rheological properties of the ultra‐high molecular weight nonlinear polycarbonates synthesized in this study have been measured by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and rheometry. The nonlinear chain structures of the polymer have been found to affect the polymer's thermal stability, mechanical strength, shear thinning effect, and elastic properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41609.     

Two-Component initiator systems for the ring-opening polymerization of oligomeric cyclic bisphenol-A carbonates. Studies with in situ generated wittig salts

A two-component initiator system based on the in situ generation of Wittig salts (alkytriarylphosphonium bromides) has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers for potential use in composite applications so that the prepolymer can suitably wet the composite material before being converted to high molecular weight polymer. The Wittig salt precursors (an alkyl bromide, such as hexadecyl bromide, and a triarylphosphine, such as triphenylphosphine) did not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. However, when the two mixtures of cyclic BPA carbonate oligomers and initiator component were combined, a high molecular weight polymer (M_w = ∼ 65,000) was produced. The polymerization initiating species is thought to be hexadecyltriphenyl-phosphonium bromide. Consistent with this hypothesis is the observation that authentic Wittig salts did initiate ring-opening polymerization to provide high molecular weight polycarbonate. The effects of structure and concentration of the initiator components, reaction temperature, time, etc. on polymerization were studied; in general, the degree of polymerization ranged from 65 to 85%. © 1996 John Wiley & Sons, Inc.     

Synthesis,characterization, and degradation of a novel L‐tyrosine‐derived polycarbonate for potential biomaterial applications

A novel class of pseudo‐poly(amino acid)s was synthesized with a cyclic dipeptide as new diphenole. Nonpeptide bonds alternating with a peptide bond structure were introduced into the backbone of the pseudo‐poly(amino acid)s. The cyclic dipeptide in this study was obtained from natural L ‐tyrosine. L ‐Tyrosine is a major nutrient amino acid with a phenolic hydroxyl group, so a polycarbonate derived from the cyclic dipeptide should possess more optimum mechanical properties, bioactivity, and biocompatibility. The hydrolytic specimen of the resulting polycarbonate was prepared by a modified solvent evaporation process. Under strongly alkaline conditions, degradation testing was performed. The tyrosine‐derived polycarbonate possessed a low glass‐transition temperature value and a high thermal decomposition temperature value, which formed a broad mean thermal processing range. The most important results of our study were the effects of the polycarbonate degradation on the local pH values, which were smaller than those of other biodegradable polymers [e.g., poly(lactic acid), poly(glycolic acid), and poly(lactic glycolic acid)]. The synthesized polymer and cyclic dipeptide were characterized with Fourier transform infrared, ¹³C‐NMR, and ¹H‐NMR spectroscopy to determine their chemical structures; by differential scanning calorimetry and thermogravimetric analysis to determine the thermal properties of the polymer; by gel permeation chromatography to determine the polymer's molecular weight; and by X‐ray diffraction to determine the polymer's morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flocculation of kaolin from aqueous suspension using low dosages of acrylamide-based cationic flocculants

Flocculation of kaolin from aqueous streams has become very important in view of its wide range of applications. In this work, cationic flocculants based on copolymers of acrylamide (AM) and 3-acrylamidopropyltrimethylammonium chloride (APTMAC) were synthesized with two different mole ratios of monomers, 80 mol % of AM (CP-8020) and 40 mol % of AM (CP-4060). The chemical structures of copolymers were confirmed by ¹H and carbon-13 nuclear magnetic resonance (¹³C NMR) spectroscopy. The molecular weight (MW) and zeta potential of the copolymers were determined. High MW was obtained for copolymer with high content of AM (CP-8020) and high zeta potential was observed for copolymer with high content of APTMAC (CP-4060). Flocculation of kaolin suspension was performed using both CP-8020 and CP-4060 and the flocculation was correlated to the zeta potential and MW of the copolymers. The optimum dosages of flocculants were determined. The mechanism of flocculation was discussed in terms of charge neutralization and bridging. The flocs of kaolin were characterized in terms of moisture content and size. To the best of our knowledge, this copolymer system was used for the first time for kaolin flocculation and found out to be efficient. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47286.     

Surface behavior and micelle morphology of novel nonionic polyurethane bolaform amphiphilic block copolymers

A novel series of nonionic bolaamphiphiles—polyurethane amphiphilic block copolymers were synthesized by addition polymerization. Their chemical structures were characterized using FTIR and ¹H-NMR spectra. The critical micelle concentration was determined by surface tensiometer and UV-vis absorption spectra. The surface behaviors of copolymers at air/water interface were also investigated including the effects of concentration, molecular structure, electrolytes, and rest time. The results show that these bolaform polyurethane amphiphilic block copolymers exhibited excellent surface activity: PU₃₄ could attain surface tension as low as 35.6 mN m⁻¹. According to the images of Transmission Electron Microscopy (TEM), the copolymers could self-assemble star-like aggregates comprised of hydrophobic block PPO surrounded by hydrophilic block PEO. Moreover, variation of concentration, the weight fraction of the hydrophilic block (f_phil), and the molecular weight of the copolymers could lead to the transformation of micelle (or premicelle) morphology. This provides a new and simple way to obtain nanoparticles with control over structure on the nanometer scale.     

Siloxane modification of polycarbonate for superior flow and impact toughness

Reactive modification of polycarbonate (PC) with a small amount of ultra-high molecular weight polydimethylsiloxane (PDMS) provides an effective route to a novel blend polymer with superior flow and excellent impact toughness. Low temperature impact toughness for such a blend was found to be comparable to polycarbonate copolymers made by interfacial copolymerization of bisphenol A and specialty silicones with phosgene. Interestingly, the blend also showed strong shear thinning behavior and a viscosity that is almost an order of magnitude lower than the starting PC resin. Analysis of the blend composition and blend morphology revealed the presence of both PC-PDMS copolymer and un-grafted siloxane as a dispersed phase in the polycarbonate matrix. The PC-PDMS copolymer provides a compatibilization effect for the stable sub-micron blend morphology in an otherwise immiscible PC-PDMS blend system. Improvement of low temperature ductility (e.g., at −40 °C) by PDMS was thus made possible. The lubricating effect from siloxane and the possibility of fibrillation flow at high shear stress are suspected to be the main reasons for high flow characteristics of these blends.     

Viable utilization of polycarbonate as a phosgene equivalent illustrated by reactions with alkanedithiols,mercaptoethanol, aminoethanethiol,and aminoethanol: A solution for the issue of carbon resource conservation

Methods for the chemical recycling of polycarbonate (PC) wastes in the forms of bisphenol A (BPA) and cyclic heterocarbonates, such as 1,3‐dithiolan‐2‐one (DTO), 1,3‐dithiane‐2‐one (DTA), and cyclic unsymmetric heterocarbonates, were investigated to prove that PC can be utilized as a phosgene equivalent for industrial purposes. Treatment of PC pellets or waste PC compact discs with 1,2‐ethanedithiol and a catalytic amount of base (e.g., 1.5 mol % NaOH) in dioxane for a short period at 40°C produced DTO and BPA, both in nearly quantitative yields. The reaction could also be carried out in DTO, which saved the use of conventional solvents. Other cyclic heterocarbonates, that is, DTA, 1,3‐oxathiolan‐2‐one, 1,3‐thiazolidine‐2‐one, and N‐methyl‐1,3‐oxazolidine‐2‐one, were prepared in high yields under analogous conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2959–2968, 2003     

Copolymers of unsaturated and saturated poly(ether ester amide)s: Synthesis,characterization, and biodegradation

A series of biodegradable random unsaturated/saturated poly(ether ester amide)s copolymers (USPEEAs) were synthesized by an active solution polycondensation of unsaturated and saturated dicarboxylic acid‐based diester monomers with diamine salts of phenylalanine and saturated oligo(ethylene glycol) (OEG). These USPEEA copolymers were obtained with fairly good yields in DMA solvent. The chemical structures of the USPEEA copolymers were confirmed by both IR and NMR spectra. The molecular weights (M_n and M_w) of USPEEAs measured by GPC ranged from 3 to 27 kg/mol with the molecular weight distribution (MWD) ranging from 1.52 to 2.13. USPEEA copolymers obtained had T_g lower than that of the pure UPEEAs but higher than that of pure saturated poly(ether ester amide)s (SPEEA). An increase in the unsaturated component in USPEEAs led to an increase in their T_g. A preliminary in vitro biodegradation property of USPEEA copolymers were investigated in both pure PBS buffer and α‐chymotrypsin solutions. The USPEEA copolymers showed a pronounced weight loss in enzyme solutions, but a smaller weight loss in a pure PBS. The biodegradation rates of USPEEA copolymers in α‐chymotrypsin solution were much slower than those of pure PEEAs. Therefore, upon adjusting monomers feed ratio, USPEEA copolymers could have controlled chemical, physical, and biodegradation properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Random copolymers of propylene with 1,5-hexadiene containing only cyclopentane units in main chain and tailoring structure and mechanical properties of the copolymers

In the presence of [Ph₃C][B(C₆F₅)₄] and Triisobutylaluminium, dimethyl pyridylamidohafnium complex exhibited remarkable catalytic activity in the copolymerization of propylene with 1,5-hexadiene, affording high molecular weight copolymers with unimodal molecular weight distributions. More noticeably, the resultant copolymers contain absolutely cyclo-group in the polymer chains without pendent vinyl groups and crosslinking. The solid state structures and properties of the homogeneous copolymers were studied by examining melting behavior, wide-angle X-ray scattering, and tensile deformation. Chain microstructures were analyzed by ¹³C NMR spectra, and further confirmed by the measurement of reactivity ratios of the two monomers. These copolymers display a random distribution of the comonomer, and crystallinity decreases with increasing comonomer content. The copolymers contain variable amounts of comonomeric units, showing desired physical properties ranging from thermoplastic to elastoplastomeric to elastomeric.     

Polyelectrolytes with various charge densities: Synthesis and characterization of diallyldimethylammonium chloride-acrylamide copolymers

The synthesis of defined polyelectrolyte models by radical copolymerization of diallyldimethylammonium chloride (DADMAC, M₁) and acrylamide (AAM, M₂) in aqueous solution is impeded by a large difference of the reactivity ratios (r₁ ? r₂) leading to a strong conversion dependence of the copolymer composition. For the synthesis of normally distributed polyelectrolytes of the same molecular weight with various charge densities, a general algorithm based on a feeded polymerization with dosage of the more reactive monomer was therefore developed. Various copolymer compositions predictable by the Mayo-Lewis equation and determined by chloride potentiometry were obtained. The sequence lengths distributions investigated by ¹³C NMR spectroscopy followed a Markov statistic of first order. The ¹³C NMR spectroscopy is shown as alternative method to gravimetry in determining reactivity ratios. The partial specific volumes and the refractive index increments of the copolymers correspond to the additivity principle. Further molecular and dynamic parameters are determined by membrane osmometry, static and dynamic light scattering, analytical ultracentrifugation, gel permeation chromatography, and viscometry. Monomodal molecular weight distributions, small polydispersities only for copolymers with high content of DADMAC are obtained at given comonomer and initiator concentration. The number-average molecular weight is almost constant for a broad copolymer composition range. R_g-M and [η]-M relations could be established for practical use at high ionic strength, despite the various chemical compositions. Some indications for a higher stiffness of copolymers with high contents of DADMAC despite the shielding of the electrostatic interactions are, however, given. At low ionic strength the electrostatic interactions prevail. Their influence with increasing charge density is stronger on the Huggins constants (intermolecular interactions) than their effect on the intrinsic viscosities (intramolecular interactions).     

Synthesis and characterization of some copolycarbonates of 2,2-bis(4-hydroxyphenyl) propane (bisphenol A) and 1,4-bis-(hydroxymethyl) decafluoro-bicyclo(2.2.1) heptane

The preparation and properties of the copolycarbonates of bisphenol A (I) and 1,4-bis(hydroxmethyl) decafluoro-bicyclo (2.2.1) heptane (II) are described. Most of the copolymers were prepared by reaction with phosgene in a mixture of pyridine and methylene dichloride. Bisphenol A polycarbonate molecular weights could be controlled by the use of small quantities of p-cresol. Increasing quantities of II led to a slight reduction in the glass transition temperature (T_g) of the copolymers and to an increased solubility in, for example, acetone. At the same time the heat stability, as measured thermogravimetrically, increased. Even small quantities of II in the copolymer have a substantial effect in reducing the tendency to crystallize and in limiting annealing effects. When heated at 120–140°C polycarbonate (I) shows an increase in yield strength and develops a substantial peak in the d.s.c. curve at T_g. These changes are much reduced by small amounts of copolymerized II. Dynamic mechanical properties were measured on a Rheovibron dynamic viscoelastometer.