Synthetic cationic polyelectrolytes (CPEs) serve as coagulation and flocculation agents in wastewater treatment due to a synergy of inherent electrostatic interactions and hydrophilic properties. In wastewater treatment, CPEs act as coagulation and flocculation agents to aggregate impurities and enable water purification. New health and environmental-related regulations provide motivation for government agencies and industrial companies to reuse wastewater. Chemical structure, molecular weight, charge density and functionality of CPEs provide tailorability for specific purification needs. Cationic polyacrylamides, ammonium-based polymers, poly(allyldimethyl-ammonium chloride) and epichlorohydrin/dimethylamine-based polymers are the most common CPEs used as coagulation and flocculation agents because they are economical and water soluble with tunable charge densities at high molecular weights. Free radical polymerization, step-growth polymerization and post-polymerization modification methods afford each polymer system. This review highlights recent advancements in synthetic methods to yield CPEs, structure−property relationships as related to flocculation efficiency and a summary of their toxicity and environmental impact.
Fabrication
of personalized dosage oral pharmaceuticals using additive
manufacturing (AM) provides patients with customizable, locally manufactured,
and cost-efficient tablets, while reducing the probability of side
effects. Binder jetting AM has potential for fabrication of customized
dosage tablets, but the resulting products lack in strength due to
solely relying on the binder to produce structural integrity. The
selection of polymeric binders is also limited due to viscosity restraints,
which limits molecular weight and concentration. To investigate and
ameliorate these limitations, this article reports a comprehensive
study of linear and 4-arm star poly(vinyl pyrrolidone) (PVP) over
a range of molecular weights as polymeric binders for binder jetting
AM and their effect on physical tablet properties. Formulation of
varying molecular weights and concentrations of linear and 4-arm star
PVP in deionized water and subsequent jetting revealed relationships
between the critical overlap concentrations (C*)
and jettability on binder jetting systems with thermal inkjet printheads.
After printing with a commercially available ZCorp Spectrum Z510 printer
with an HP11 printhead with a lactose and powdered sugar powder bed,
subsequent measurement of compressive strength, compressive modulus,
and porosity revealed structure–property relationships between
molecular weight, polymer concentration, and linear and 4-arm star
architectures with physical properties of binder jetted tablets. This
study elucidated that the dominating factor to increase compressive
strength of a tablet is dependent on the weight percent of the polymer
in the binder, which filled interstitial voids between powder particles.
Because 4-arm star polymers have lower solution viscosities compared
to linear analogues at the same molecular weights, they were jettable
at higher concentrations, thus producing the strongest tablets at
a compressive strength of 1.2 MPa. Finally, the inclusion of an active
pharmaceutical ingredient (API), acetaminophen, revealed maintenance
of the tablet physical properties across 5–50 total wt % API
in each tablet.
New polymers with a phosphazene backbone
and both 2,2,2-trifluoroethoxy-
and phenoxy-functionalized cyclotriphosphazene substituents exist
in three phases depending on the side group ratios. At low concentrations
of the bulky substituents (up to ∼7 mol %), the polymers are
semicrystalline thermoplastics, with properties that are minor variations
of poly[bis(2,2,2-trifluoroethoxy)phosphazene]. However, after the
incorporation of between ∼7 mol % and ∼20 mol % of the
bulky cyclic trimeric side groups, the polymers lose their semicrystalline
properties and become amorphous elastomers. At still higher trimer
loadings (>20 mol %) the materials develop gum-like behavior. The
elastomeric phase appears to be generated by interdigitation or agglomeration
of the bulky aryloxy-cyclotriphosphazene side groups, which act as
quasi-physical cross-links between the polymer chains. The presence
of these interactions allows the materials to experience high strain
values before rupture (up to 1000%), and elastic recovery of more
than 85% of the original dimensions when stressed up to 60% of the
break elongation over four cycles. In addition, the chemical and physical
nature of the substituents on the cyclic trimeric side groups alters
the physical characteristics of the polymer in a way that provides
a facile method to tune the properties.
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