Structure–Property Relationships of Water‐Soluble Ammonium–Ionene Copolymers

Abstract

Water-soluble random copolymer ammonium ionenes with M w in the range of 17.4 to 20.8 kg mol − 1 and various charge densities are synthesized from 1, 12-dibromododecane, N , N , N ′ , N ′ -tetramethyl-1,6-hexanediamine, and 1,12-bis( N,N -dimethylamino)dodecane. Anion exchange of the bromine counterion forms ionenes with TFSI, TFO, and BF 4 anions. The nature of the counteranion and charge density tailor the thermal and rheological properties of 12,6/12-ionenes, respectively. X-ray scattering reveals microphase separation with a correlation length of ≈ 7 nm for ionenes with 50 to 90% N , N , N ′ , N ′tetramethyl-1,6-hexanediamine content. Ionene copolymers display polyelectrolyte behavior in methanol based on a predicted scaling relationship between specifi c viscosity ( η sp ) and concentration. dihalide (Figure 1 ). Another type of ionenes is termed segmented [7][8][9][10][11][12] ionenes that have low glass transition temperature ( T g ) oligomeric spacers (e.g., poly(tetramethylene oxide) PTMO, poly(propylene glycol) PPG, and poly(ethylene glycol) PEG) between their ionic sites, which imparts elastomeric properties. Long and co-workers [ 12 , 13 ] demonstrated the synthesis of PPG-based ionenes and imidazoliumcontaining PTMO-based ionenes and established structure-property relationships as a function of hard segment content.Cationic polyelectrolytes having quaternary ammonium groups act as antimicrobial agents. [14][15][16] Rembaum [ 17 ] studied the toxicity and antimicrobial properties of high-charge-density linear and crosslinked ammonium ionenes in comparison with lower-molecular-weight ammonium salts. Moreover, polyelectrolytes were widely used for water treatment purposes to eliminate major fl occulants. [ 18 ] Casson and Rembaum [ 19 ] studied the effect of molecular weight and charge density of nonsegmented x , y -ionenes on fl occulation ability in dilute clay suspensions. Furthermore, ionenes were explored as viable candidates for gene delivery due to effi cient DNA complexation. Zelikin et al. [ 20 ] demonstrated that the degree of polymerization (DP) and charge density of nonsegmented x , y -ionenes directly impacted transfection effi ciency.Macromol. Chem. Phys. 2012, 213, 965−972

Influence of Counterion on Thermal, Viscoelastic, and Ion Conductive Properties of Phosphonium Ionenes

“…The TGA traces shown in Figure B also corroborate previous literature reports on ammonium or imidazolium ionenes, which indicate that the thermal stability is dependent upon the basicity of the associated counterion . Similarly, 4P,12 ionenes showed an improvement in thermal degradation beyond 400 °C for 4P,12‐TfO and 4P,12‐Tf 2 N materials.…”

“…Similarly, 4P,12 ionenes showed an improvement in thermal degradation beyond 400 °C for 4P,12‐TfO and 4P,12‐Tf 2 N materials. Recent publications from our research group comparing ammonium and phosphonium polymerized ionic liquids present phosphonium‐based polymerized ionic liquids as more resistant to degradation through a reverse Menschutkin reaction leading to enhanced thermal stability . The temperature at 5% weight loss (T d,5% ; summarized in Table ) was enhanced nearly 100 °C upon anion metathesis from bromide to Tf 2 N ‐ counterions, which confirms that counterion exchange heavily influences the thermal properties of ionenes.…”

“…Wilkes and co‐workers demonstrated the dependence of elastomeric behavior of segmented ammonium ionenes on the poly(tetramethylene oxide) soft segment molecular weight . Tamami et al also showed that the solubility and resulting solution behavior of ammonium‐based ionenes is variable as a function of alkyl spacer length and counterion . Hemp and co‐workers reported structure‐property relationships as a function of alkyl spacer length for novel phosphonium‐based ionenes where increasing the alkyl spacer length decreased the charge density of phosphonium ionenes and resulted in dramatic differences in viscoelastic response …”

Association of Nucleobase‐Containing Ammonium Ionenes

“…Scheme and illustrate the polymerization of acrylamide‐containing amine monomer and acrylate‐containing amine monomer with 1,12‐dibromo­dodecane to yield four‐bond spacer and nine‐bond spacer ionenes, respectively. Both polymerizations occurred in DMF and reached high conversion in 24 h. In our earlier report, we monitored the reaction progress for the synthesis of non‐segmented 12/6,12‐ammonium ionenes using the C‐N + stretch at ≈905 cm −1 , and FTIR spectroscopy confirmed reaction completion within 24 h. In the current study, we followed the reaction progress using 1 H NMR spectroscopy with the appearance of methyl protons on the quaternized nitrogen at ca. 3.10 ppm, and 1 H NMR confirmed the chemical structures of ionene homopolymers upon completion of the polymerization (Figure S3 and S7, Supporting Information).…”

Photopolymerization of Ionic Liquids – A Mutually Beneficial Approach for Materials Fabrication

“…[34] While there are some examples for the polymerization of cationic vinyl monomers since 1970s, [35,36] it was only around the year 2000, pioneered by Ohno et al, that vinylimidazolium and vinylpyridinium salts were pursued as monomers for the creation of solid polymer electrolytes. [37][38][39] Since then, polymeric ionic liquids have become ubiquitous in the literature with research led by Long, [40][41][42][43] Texter, [44,45] Yuan, [46][47][48] Merceyyes, [30,49,50] Shaplov, [51][52][53][54][55] Drockenmuller, [56][57][58] and others to name a few. [59,60] The improved processability of polymers combined with the chemical utility and derivatizability of ionic liquids is the cornerstone for their interest and broader use.…”