Low-charge density ampholytic terpolymers composed of acrylamide (AM), (3-acrylamidopropyl)trimethyl ammonium chloride (APTAC), and N-acryloylvaline were prepared via free-radical polymerization in 0.5 M NaCl to yield terpolymers with random charge distributions. Sodium formate (NaOOCH) was employed as a chain transfer agent during the polymerization to suppress gel effects and broadening of the molecular weight distribution (MWD). Terpolymer compositions were determined by 13 C NMR spectroscopy. Terpolymer molecular weights (MWs) and polydispersity indices (PDIs) were obtained via size exclusion chromatography/multi-angle laser light scattering (SEC-MALLS). Intrinsic viscosity values determined from SEC-MALLS data using the Flory-Fox relationship were compared with those determined by low-shear dilute solution viscometry and found to be in good agreement. SEC-MALLS experiments allowed examination of radius of gyration-MW (R g -M) relationships and the Mark-Houwink-Sakurada intrinsic viscosity-MW ([g]-M) relationships for terpolymers. The R g -M and [g]-M relationships indicated little or no excluded volume effects under SEC conditions indicating that the terpolymers were in near theta conditions in an aqueous buffer solution. Potentiometric titration experiments were performed in deionized (DI) water. These studies revealed that the apparent pK a of the AMVALTAC terpolymers increases with increasing VAL content. The solution properties of low-charge density ampholytic terpolymers have been studied as functions of solution pH, ionic strength, and polymer concentration. The charge-balanced terpolymers exhibit polyampholyte behavior at pH values ! 6.5. As solution pH is decreased, these charge-balanced terpolymers become increasingly cationic due to the protonation of the VAL repeat units. Charge-imbalanced terpolymers generally exhibit polyelectrolyte behavior, although the effects of intramolecular electrostatic interactions (e.g., polyampholyte effects) on the hydrodynamic volume are evident at certain values of solution pH and salt concentration. The solution behavior of the terpolymers in the dilute regime correlates well with that predicted by various polyampholyte solution theories.
Low‐charge‐density amphoteric copolymers and terpolymers composed of acrylamide, (3‐acrylamidopropyl)trimethyl ammonium chloride, and the amino acid derived monomers (e.g., N‐acryloyl valine, N‐acryloyl alanine, and N‐acryloyl aspartate) were prepared via free‐radical polymerization in aqueous media to yield terpolymers with random charge distributions and homogeneous compositions. Sodium formate (NaOOCH) was employed as a chain transfer agent during the polymerization to suppress gel effects and broadening of the molecular weight distribution. Terpolymer compositions were determined by 13C and 1H NMR spectroscopy. Terpolymer molecular weights and polydispersity indices were obtained via size exclusion chromatography/multi‐angle laser light scattering, and hydrodynamic diameter values were obtained via dynamic light scattering. The solution properties of low‐charge‐density amphoteric copolymers and terpolymers have been studied as a function of solution pH, ionic strength, and polymer concentration. The low‐charge‐density terpolymers display excellent solubility in deionized (DI) water with no phase separation. The charge‐balanced terpolymers exhibit antipolyelectrolyte behavior at pH values ≥(6.5 ± 0.2). As solution pH is decreased, these charge‐balanced terpolymers become increasingly cationic because of the protonation of the anionic repeat units. Charge‐imbalanced terpolymers generally demonstrate polyelectrolyte behavior, although the effects of intramolecular electrostatic interactions (e.g., polyampholyte effects) on the hydrodynamic volume are evident at certain values of solution pH and salt concentration. The aqueous solution behavior (i.e., globule‐to‐coil transition at the isoelectric point in the presence of salt and globule elongation with increasing charge asymmetry) of the terpolymers in the dilute regime correlates well with that predicted by the polyampholyte solution theories of Dobrynin and Rubinstein as well as Kantor and Kardar. Examination of comonomer charge density, hydrogen‐bonding ability, and spacer group (e.g., the moiety separating the ionic group from the polymer chain) indicates that conformational restrictions of the amino acid comonomers result in increased chain stiffness and higher solution viscosities in DI water and brine solutions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4479–4493, 2006
Several toughening and crosslinking modifiers were tested in two epoxy resin systems based on the diglycidyl ether of bisphenol A (DGEBA) with the objective to improve the critical stress intensity factor KIC and the glass transition temperature (Tg) simultaneously. An amine hardener (isophorone diamine (IPD)) and a homopolymerization initiator (1‐ethyl‐3‐methylimidazolium acetate (EMIM Ac)) were used as curing agents. The highest effect on the KIC value of the resin system DGEBA/IPD (KIC = 0.72 MPa1/2; Tg = 164°C) was achieved with the dendric polymer Boltorn P501 (10 wt%), but it decreased the Tg (KIC = 1.39 MPa1/2; Tg = 136°C). A high toughening effect with a low decrease of Tg was achieved with a combination of a self‐organized block copolymer (Nanostrength M22N) and silica nanoparticles (Nanopox F400) (KIC =1.15 MPa1/2; Tg =157°C). The KIC value of the resin system DGEBA/EMIM Ac was improved from 0.44 to 0.66 MPa1/2. An improvement of both, the thermal and mechanical properties was established for a combination of a poly(tetrahydrofuran) as toughening modifier (PolyTHF2000) with the post‐crosslinking modifier diethylphosphite (DEP) in the resin system DGEBA/IPD (KIC = 0.86 MPa1/2; Tg = 180°C). A system with chemical linkages between both modifiers was investigated for comparison but yielded inferior results. POLYM. ENG. SCI., 59:86–95, 2019. © 2018 Society of Plastics Engineers
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