Synthesis and Characterization of α,ω‐bi[2,4‐dinitrophenyl (DNP)] poly(2‐methoxystyrene) Functional Polymers. Initial Evaluation of the Interaction of the Functional Polymers with RBL Mast Cells

Two series of functional polymers, α,ω‐bi[2,4‐dinitrophenyl][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (DNP‐PEO‐P2MS‐PEO‐DNP) and α,ω‐bi[2,4‐dinitrophenyl caproic][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (CDNP‐PEO‐P2MS‐PEO‐CDNP), were synthesized by anionic living polymerization. The polymers were characterized by FT‐IR, ¹H‐NMR and Gel Permeation Chromatography (GPC). The molecular weight distributions for the lower molecular weight functional polymers were slightly broad (1.3–1.5). However, the molecular weight distributions for higher molecular weight polymers were narrower (1.1–1.2). Differential scanning calorimetry (DSC) studies showed thermal transitions indicative of the presence of microphases in the polymer solid state. The polymers were white powders and soluble in tetrahydrofuran. The binding affinity of DNP‐PEO‐P2MS‐PEO‐DNP ligands towards anti DNP IgE was determined by titrations with fluorescently labeled FITC‐IgE. A water soluble CDNP‐PEO‐P2MS‐PEO‐CDNP/DMEG (dimethoxyethylene glycol) complex binds and achieves steady state binding with solution IgE within a few seconds. This strongly suggests that CDNP functional polymers with improved water solubility have potential in therapeutics. Higher molecular weight (water insoluble) CDNP‐PEO‐P2MS‐PEO‐CDNP polymers were electrosprayed as fibers (500 nm) on silicon surface. Fluorescence spectroscopy clearly showed that RBL mast cells were interacting with the fibers suggesting that the cell‐surface receptors were clustered along the fiber surface. These observations suggest that the functional polymers hold promise for developing an antibody detection device.     

High-speed aqueous gel-permeation chromatography

High-speed gel-permeation chromatography (GPC) of water-soluble polymers has been investigated by using TSK-GEL, type-PW columns packed with small porous particles. Being semirigid, the column packing could be operated under high pressure and, therefore, it was possible to achieve high-speed GPC. A resolution higher than that of ordinary GPC in organic solvent system was attained when the measurement of one sample was completed within 40 min with a 6-ft column set. Samples with a wide range of molecular weights, from oligomers to polymers having a molecular weight greater than 10⁶, could be fractionated. Dextran, polyethylene glycol, polyacrylamide, poly(vinyl alcohol), and poly(vinyl pyrrolidone) were separated according to molecular size with no evidence of adsorption. Investigation of other water soluble polymers is now in progress.     

Synthesis and characterization of poly(ϵ-caprolactone)-poly(ethylene glycol) block copolymer

Poly(ϵ-caprolactone)–poly(ethylene glycol)–poly(ϵ-caprolactone) triblock copolymers (PECL) covering a wide range of poly(ethylene glycol) (PEG) lengths were synthesized with alkali metal alkoxide derivatives of poly(ethylene glycol). The effects of various factors, such as amount of the initiator, reaction time and temperature, polarity of solvent, length of PEG segment, and counterion on the polymerization were investigated. The copolymers were characterized by ¹H-NMR, IR, GPC, and DSC. It was found that THF system is superior to toluene system. The conversion of the monomer increased with increase of the initiator concentration. High molecular weight of the copolymer and high conversion of the monomer was obtained at below 30°C within 5 min. The polymerization process was studied by GPC and the coexistence of propagation and transesterification reaction was found, which leaded to relatively broad molecular weight distribution of the copolymers. © 1997 John Wiley & Sons, Inc.     

Evaluation of matrix-assisted laser desorption ionization mass spectrometry for polymer characterization

A protocol for the preparation of polymeric samples for time-of-flight matrix-assisted laser desorption ionization mass spectrometry (TOF-MALDI-MS) analysis was developed. Dithranol was identified as a good matrix for polystyrene (PS), and the addition of silver for cationization of molecules was determined to be necessary. Based on this preparative method, low molecular weight samples of other polymers [polyisoprene, polybutadiene, poly(ethylene oxide), poly(methyl methacrylate), and polydimethylsiloxane] were analyzed with molecular weights up to 49 ku. The effects of laser intensity were determined to influence the molecular weight distribution of intact oligomers, most significantly for low molecular weight polymers. Linear and reflectron modes of analysis were evaluated; better signal intensity and resolution were obtained in the reflectron mode. The TOF-MALDI-MS measurements are compared with time-of-flight secondary ion mass spectrometry (TOF-SIMS) and gel permeation chromatography (GPC) for the same polymers. The M _n values calculated by TOF-MALDI-MS consistently are higher than values calculated by TOF-SIMS for all classes of polymers with molecular weights up to 8 ku. The molecular weights of the PS calculated from TOF-MALDI-MS are in good agreement with GPC (±10%). The composition of the terminal group on a polymer chain may affect the ion yields. The ion yields of intact oligomers were evaluated as a function of end group composition for both TOF-MALDI-MS and TOF-SIMS. The slight disparity of results between TOF-SIMS and TOF-MALDI-MS for the perfluoroalkyl-terminated PS suggests that the oligomers are desorbed preferentially from the surface in the TOF-SIMS analysis, rather than having an increased ionization probability.     

Novel synthesis of biodegradable amphiphilic linear and star block copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol)

Biodegradable, amphiphilic, diblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol) (PCL‐b‐PEG), triblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol)‐block‐poly(ε‐caprolactone) (PCL‐b‐PEG‐b‐PCL), and star shaped copolymers were synthesized by ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) methyl ether or poly(ethylene glycol) or star poly(ethylene glycol) and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature to yield monomodal polymers of controlled molecular weight. The chemical structure of the copolymers was investigated by ¹H and ¹³C NMR. The formation of block copolymers was confirmed by ¹³C NMR and DSC investigations. The effects of copolymer composition and molecular structure on the physical properties were investigated by GPC and DSC. For the same PCL chain length, the materials obtained in the case of linear copolymers are viscous whereas in the case of star copolymer solid materials are obtained with low T_g and T_m temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3975–3985, 2007     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Universal Calibration and Molecular Weight Averages in Gel Permeation Chromatography Illustrated by Cellulose Nitrate and Poly(oxypropylene)

Abstract

The nature of the averaging process in the analysis of gel permeation chromatograms was examined for cases where the molecules in the detector cell of the apparatus were of different molecular weight and of the same molecular weight. When the molecules have the same molecular weight, the hydrodynamic volume (1), [?]M, averaged across a chromatogram was found to become KM^a+1 for any molecular weight average at the elution volume corresponding to that average. [η] is intrinsic viscosity, M is molecular weight, and K and a are the appropriate Mark-Houwink constants. Thus when size separation is by molecular weight, the universal GPC calibration functions include KM_n ^a+1 where M_n is the number average molecular weight.

Cellulose nitrate and poly(oxypropylene) were analyzed using three sets of columns and two GPC instruments. KM_n ^a+1, KM_w ^a+1, and [η]M_w were found to represent the hydrodynamic volume since these functions fell on the universal calibration plot for nearly nono-disperse polystyrene standards. The function [η]M_n was displaced from the polystyrene universal calibration plot by factor which equaled M_w/M_n. The slopes and intercepts of the universal calibration plots were found to be completely consistent with the slopes and intercepts of the molecular weight calibration plots showing that the Mark-Houwink constants were correct. Intrinsic viscosity - molecular weight relations were presented for 12.0–12.6%N cellulose nitrate and for low molecular weight poly(oxypropylene), the latter relation being a correction of that of Sholtan and Lie (18).     

Microwave‐Assisted Single‐Step Synthesis of Poly(alkylene hydrogen phosphonate)s by Transesterification of Dimethyl Hydrogen Phosphonate with Poly(ethylene glycol)

Summary: Poly(alkylene hydrogen phosphonate)s with a number‐average molecular weight of about 3 000 Da were obtained by a transesterification of dimethyl hydrogen phosphonate with poly(ethylene glycol) (PEG 400) under microwave irradiation with a very short reaction time (55 min) relative to that of classical thermal heating (9 h). The structure of the resulting polymer was confirmed by ¹H, ³¹P, and ¹³C NMR spectroscopy. The molecular weight was determined by ¹H, ³¹P{H} NMR spectroscopy, MALDI‐TOF, and GPC.

The transesterification of dimethyl hydrogen phosphonate with poly(ethylene glycol).     

Generalized Universal Molecular Weight Calibration Parameter in GPC

Abstract

In this report we show by experimental and theoretical investigations that the commonly used GPC universal calibration parameter, the intrinsic viscosity multiplied by the weight average molecular weight ([η] M^w) is incorrect. The error which can arise by using [η] M to calculate the molecular weight across the GPC chromatogram for nonuniformly branched polymers [poly(vinyl acetate) and low density polyethylene] and copolymers with compositional drift, could be very large. We also show conclusively that the number average molecular weight M_n is the correct average to use for the universal calibration parameter. We therefore recommend that our general universal Calibration parameter [η] M_n be used for calculating the molecular weight across the chromatogram for all polymer systems (linear and branched homopolymers, copolymers with or without compositional drift and for polymer blends).     

Separation of Bufotalin and Cinobufotalin by Preparative Liquid Chromatography

Abstract

Complete resolution of bufadienolides by traditional column chromatography, or by thin-layer chromatography (TLC), is quite difficult. Separation of various bufadienolide conjugates by high performance liquid chromatography (HPLC) has been described, but not for resolution of the corresponding genins. A preparative HPLC procedure has been developed for resolving the difficultly separable bufotalin (1) and cinobufotalin (2). A Lobar B column packed with LiChromprep Si-60 was used to separate these bufadienolides employing a recycling procedure.     

Novel synthesis of biodegradable star poly(ethylene glycol)‐block‐poly(lactide) copolymers

Biodegradable star‐shaped poly(ethylene glycol)‐block‐poly(lactide) copolymers were synthesized by ring‐opening polymerization of lactide, using star poly(ethylene glycol) as an initiator and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature. Two series of three‐ and four‐armed PEG‐PLA copolymers were synthesized and characterized by gel permeation chromatography (GPC) as well as ¹H and ¹³C NMR spectroscopy. The polymerization under the used conditions is very fast, yielding copolymers of controlled molecular weight and tailored molecular architecture. The chemical structure of the copolymers investigated by ¹H and ¹³C NMR indicates the formation of block copolymers. The monomodal profile of molecular weight distribution by GPC provided further evidence of controlled and defined star‐shaped copolymers as well as the absence of cyclic oligomeric species. The effects of copolymer composition and lactide stereochemistry on the physical properties were investigated by GPC and differential scanning calorimetry. For the same PLA chain length, the materials obtained in the case of linear copolymers are more viscous, whereas in the case of star copolymer, solid materials are obtained with reduction in their T_g and T_m temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3966–3974, 2007     

Synthesis and characterization of biodegradable poly(ester anhydride) based on ε‐caprolactone and adipic anhydride initiated by potassium poly(ethylene glycol)ate

Novel biodegradable poly(ester anhydride) block copolymers based on ε‐caprolactone (ε‐CL) and adipic anhydride (AA) were prepared by sequential polymerization. ε‐CL was first initiated by potassium poly(ethylene glycol)ate and polymerized into active chains (PCL‐O^?K⁺), which were then used to initiate the ring‐opening polymerization of AA. The effects of the AA feed ratio, solvent polarity, monomer concentration, and temperature on sequential polymerization were investigated. The copolymers, obtained under different conditions, were characterized by Fourier transform infrared, ¹H NMR, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The GPC results showed that the weight‐average molecular weights of the block copolymers were approximately 6.0 × 10⁴. The DSC results indicated the immiscibility of the two components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1511–1520, 2003     

One‐Step Synthesis of Multiphase Block Copolymers via Simultaneus Free Radical and Ring Opening Polymerization Using Poly(ethylene oxide) Possessing Azo Group

Multiphase block copolymers having the structure of poly(?‐caprolacton‐b‐etyhlene glycol‐b‐styrene‐b‐ethylene glycol‐b‐?‐caprolacton) were synthesized from poly(ethylene oxide) possesing azo group in the main chain by the combination of free radical polymerization (FRP) of styrene (S) and ring opening polymerization (ROP) of ?‐caprolacton (?‐CL) in one‐step. The block copolymers were characterized ¹H‐NMR and FT‐IR spectroscopy and gel permeation chromatography (GPC). ¹H‐NMR and FT‐IR spectroscopy and GPC studies of the obtained polymers indicate that multiphase block copolymers easily formed as a result of combination FRP and ROP in one‐step.     

The synthesis of poly[6,8‐dioxabicyclo[3.2.1]octane‐b‐(ethylene glycol)‐b‐6,8‐dioxabicyclo[3.2.1]octane] by controlled cationic ring‐opening polymerization

The triblock copolymer poly[6,8‐dioxabicyclo[3.2.1]octane‐b‐(ethylene glycol)‐b‐6,8‐dioxabicyclo[3.2.1]octane] was prepared by the controlled cationic ring‐opening polymerization of 6,8‐dioxabicyclo[3.2.1]octane (6,8‐DBO) from a macroinitiator. The macroinitiator, poly(ethylene glycol) (PEG) di(1‐chloroethyl ether), was prepared via the addition of HCl to PEG divinyl ether and was characterized with ¹³C NMR, ¹H NMR, and gel permeation chromatography (GPC). Upon preparation, a small fraction of the chain ends underwent a cyclization reaction to form inactive chain ends. When the macroinitiator was used in polymerizations of 6,8‐DBO with ZnI₂ as an activator, linear kinetic plots were observed, a linear increase in the copolymer molecular weight with conversion was seen, and the molecular weight distributions of the copolymer samples remained constant at about 1.40. Confirmation of the triblock structure of the final product was obtained with ¹H NMR spectra, ¹³C DEPT spectra, and GPC chromatograms. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4081–4087, 2000     

Synthesis of side‐chain liquid‐crystalline homopolymers and triblock copolymers with p‐methoxyazobenzene moieties and poly(ethylene glycol) as coil segments by atom transfer radical polymerization and their thermotropic phase behavior

A series of side‐chain liquid‐crystalline (LC) homopolymers of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with different degrees of polymerization were synthesized by atom transfer radical polymerization (ATRP), which were prepared with a wide range of number‐average molecular weights from 5.1 × 10³ to 20.6 × 10³ with narrow polydispersities of around 1.17. Thermal investigation showed that the homopolymers exhibit two mesophases, a smectic phase, and a nematic phase, and the phase‐transition temperatures of the homopolymers increase clearly with increasing molecular weights. A series of novel LC coil triblock copolymers with narrow polydispersities was synthesized by ATRP, and their thermotropic phase behavior was investigated with differential scanning calorimetry and polarized optical microscopy. The LC coil triblocks were designed to have an LC conformation of poly[6‐(4‐methoxy‐4′‐oxy‐azobenzene) hexyl methacrylate] with a wide range of molecular weights from 3.5 × 10³ to 1.7 × 10⁴ and the coil conformation of poly(ethylene glycol) (PEG) (number‐average molecular weight: 6000 or 12,000) segment. Their characterization was investigated with ¹H NMR, Fourier transform infrared spectra, and gel permeation chromatography. Triblock copolymers exhibited a crystalline phase, a smectic phase, and a nematic phase. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased, and the crystallization of PEG depressed with increasing molecular weight of the LC block. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2854–2864, 2003     

Investigation of the synthesis of poly-D,L-lactide-co-poly(ethylene glycol) flexible thermoplastic

A series of biodegradable poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s with various lactide-to-poly(ethylene glycol) (LA/PEG) mole ratios has been successfully synthesized by ring-opening polymerization (ROP) followed by chain extension reaction through formation of urethane linkage. Resulting FT-IR spectra indicate complete polymerization of lactide monomers, while NMR analysis quantitatively marks the chain length of polymer blocks. The molecular weight and dispersion index of copolymers were investigated by GPC analysis. DSC thermogram and XRD diffractogram of the prepared copolymers were studied as well for revealing the thermal and crystallinity behavior of the copolymer as LA/PEG mole ratios varied.     

Polymerization behavior and gel properties of ethane,ethylene and acetylene-bridged polysilsesquioxanes

Soluble bridged polysilsesquioxanes with a range of molecular weight were synthesized from bis(triethoxysilyl)ethane, ethylene, and acetylene (BTES-E1, -E2, and -E3) via hydrolysis and polycondensation reaction by adjusting the water amount. Polymerization behavior of these three trialkoxysilanes was investigated by monitoring the reaction progress by GPC, and ²⁹Si NMR spectrometry of the resulting polymers, poly(BTES-E1), poly(BTES-E2), and poly(BTES-E3), showing that BTES-E1 generated cyclic oligomers at the early stage. In contrast, polymerization of BTES-E2 and BTES-E3 provided no detectable amounts of cyclic oligomers, but afforded linear polymers only. Bulk gels were also prepared by curing the polymers. The gel from poly(BTES-E3) exhibited high thermal stability derived from the rigid acetylene spacer with respect to thermogravimetric analysis. On the other hand, the polymer film of BTES-E1 showed the highest pencil hardness index among the polymers, indicating the tight siloxane network of poly(BTES-E1).     

Amphiphilic Biodegradable Poly(ϵ-caprolactone)-Poly(ethylene glycol) – Poly(ϵ-caprolactone) Triblock Copolymer Synthesis by Maghnite-H+ as a Green Catalyst

Amphiphilic biodegradable (PCL-PEG-PCL) triblock copolymers have been successfully prepared by the ring opening polymerization of ?-caprolactone (CL) in the presence of poly(ethylene glycol) (PEG) at 80°C employing Maghnite-H⁺ a non-toxic Montmorillonite clay as catalyst. Maghnite-H⁺ reacts as a solid source of protons to induce ?-caprolactone polymerization. The triblock architecture, molecular weight and thermal properties of the copolymers were characterized by NMR spectra, GPC and DSC analyses. The effect of Maghnite-H⁺ proportion and PEGs on the rate of copolymerization and on average molecular weight of resulting copolymers was studied. A cationic mechanism for the copolymerization reaction was proposed.     

Characterization of Nylons by Gel Permeation Chromatography and Low Angle Laser Light Scattering in 2,2,2-Trifluoroethanol

Abstract

A GPC method was developed for the analysis of several commercial nylons in trifluoroethanol + 0.05M LiBr using a styrene-divinylbenzene column custom-packed by Jordi Associates.

A broad molecular weight standard method was developed by interfacing GPC with LALLS to give the absolute molecular weight for each data point or elution volume along the chromatographic peak from a nylon sample of known molecular weight. The integrity of the interface was verified by static LALLS measurements; no loss or adsorption of solute was found in the chromatographic system.

A strong ionic effect was observed for nylon samples and the method to alleviate it was described. The molecular weights and distribution of the following nylons were determined by this method: nylon 6, nylon 4,6, and nylon 6,6. Much higher than quoted molecular weights were obtained for nylons when polymethyl methacrylates and ethylene glycols were used as standards; this necessitated the use of this broad molecular weight method for column calibration. The ambient operating conditions offered several advantages over the conventional m-cresol solvent which required operation at higher than 100 C in order to reduce the viscosity, possessed a strong odor, and occasionally resulted in degradation of polyamides.     

Peculiarities of polyacrylamide analysis by aqueous GPC

Various commercially available stationary phases of gel permeation chromatography (GPC) were tested to determine their effectiveness in aqueous exclusion chromatography. It was found that controlled pore glass (GPG) is the most suitable material for the separation of polyacrylamides and poly(acry1amide-co-sodium acrylate), dextrans, and poly(sodium styrene–sulfonates) in 0.1M aqueous Na₂S0₄ solutions of ionic strength 0.3. A calibration curve was established by using broad molecular weight distribution polyacrylamide standards in a trial and error procedure. To avoid artificial oscillations on the evaluated distribution curves a cubic B-spline representation of the calibration curve was used instead of the conventional polynomials. By applying this system the solution instability of polyacrylamides was observed by GPC and is discussed because of its general importance to the applicability of indirect molecular weight determination methods for polyacrylamides. The effectiveness of aqueous GPC was demonstrated in an evaluation of thermal degradation measurements of polyacrylamides. Finally, the feasibility of universal calibration of aqueous GPC by means of poly(sodium styrene–sulfonates) was investigated. It is apparent that in spite of some problems concerning adsorption of the polymer universal calibration is a successful tool for calibrating aqueous GPC.