Poly sulfonic lithium

Another dramatic example of the usefulness of DPE end-capping of polymeric organolithium compounds to promote efficient functionalization reactions is the sulfonation reaction using sultones [142]. A careful examination of the functionalization of poly(styryl)lithium with 1,3-propane sultone showed that the corresponding sulfonated polymer (see Eq. 32) was obtained in maximum yields of only 30% and 53% in benzene or tetrahydrofuran, respectively [142] ... 

It was proposed that the low yields of sulfonated polymer resulted from the competing metalation reaction of poly(styryl)lithium with the acidic a-hydro-gens of the sultone as shown in Eq. (33) [143] ... 

When poly(styryl)lithium was end-capped with 1,1-diphenylethylene prior to sulfonation with the sultone, the corresponding sulfonated polymer was obtained in 93% yield (Scheme 10). Both the increased steric requirements of the chain end and the more stable 1,1-diphenylalkyllithium chain end appar-... 

In this chapter, we briefly review our work on the synthesis and conducting properties of complexes of lithium perchlorate and polysiloxane comb polymers with oligooxyethylene side chains. Included in the discussion are blends with high-molecular-weight poly(ethylene oxide) (PEO) and some preliminary work on cation-conducting polymers with bound sulfonate groups. 

Fig. 11 a Polymer composites consisting of polystyrene-fr/ocA -poly(4-vinylpyridine) (PS-b-PVP) and oligo(ethylene oxide)sulfonic acid. These composites can complex with LiCl04, exhibiting high lithium ion conductivity, b PS-b-PVP polymers mixed with alkylphenol and toluenesulfonic acid, instead of oligo (ethylene oxide) sulfonic acid, exhibit proton conductivity... 

Supramolecular approaches [5,7,20-22] are also effective for ion conduction in polymers. Ikkala and ten Brinke prepared the complex of polystyrene-frZock-poly(4-vinylpyridine) (PS-fr-PVP) and oligo(ethylene oxide)sulfonic acid 11 [71,72]. The polymer self-assembles into lamellar nanostructures consisting of glassy hydrophobic polystyrene and hydrophilic PEO layers, as shown in Fig. 11. When LiCl04 is dissolved in the polymer composites, lithium ions are complexed and transported in the hydrophilic PEO layers, resulting in high ionic conductivities on the order of 10-6 S cm-1 at ambient temperature. 

Poly(amino acids)2892 and polypeptides2893 can also be grafted onto starch. Starch was first alkylated in the presence of lithium naphthalene, and then the alkoxy derivatives were reacted with /V-carboxy anhydrides. Poly(amide amines) were produced by reacting amines with dioic acids on starch and then crosslinking with epichlorohydrin or 1,2-dichloroethane 2894 Grafting of starch with a synthetic polymer chain, for instance, polystyryl carboxylate anions prepared by an anionic polymerization, can be carried out on a blend of starch and cellulose functionalized by sulfonation, mesylation, or tosylation. In this manner, cellulose-starch graft copolymers were prepared.2895... 

A variety of dimensionally stable solid electrolytes consisting of a mixture of organic plasticizers such as EC, PC etc., along with structurally stable polymers such as poly( acrylonitrile) (PAN) or poly( vinyl sulfone) (PVS), or polyvinyl pyrrolidine (PVP) or polyvinyl chloride (PVC) and several lithium salts have been tested and found to have excellent ionic conductivities at ambient temperatures [155-156]. In these gel type electrolytes the primary role of the polymers PAN, PVS, PVP or PVC is to immobilize the lithium salt solvates of the organic plasticizer liquids. However, with polymers such as PAN a coordination interaction with Li+ is also quite likely. 

As shown in Fig. 7.10A, the PLEC was fabricated with a simple sandwiched structure of ITO/polymer/Al. The active layer contained an alkoxyphenyl substituted poly(l,4-phenylene vinylene) (AP-PPV), trimethylolpropane trimethacrylate (TMPTMA), and lithium trifluoromethane sulfonate (LiTf). When a bias voltage was initially applied, the PIN junction was formed by electrochemical doping (Fig. 7.1 OB). At the same time, the ionic conduction channels would be cut off due to the polymerizing of small molecules... 

Self-doped polyanilines are advantageous due to properties such as solubility, pH independence, redox activity and conductivity. These properties make them more promising in various applications such as energy conversion devices, sensors, electrochromic devices, etc. (see Chapter 1, section 1.6). Several studies have focused on the preparation of self-doped polyaniline nanostructures (i.e., nanoparticles, nanofibers, nanofilms, nanocomposites, etc.) and their applications. Buttry and Tor-resi et al. [51, 244, 245] prepared the nanocomposites from self-doped polyaniline, poly(N-propane sulfonic acid, aniline) and V2O5 for Li secondary battery cathodes. The self-doped polyaniline was used instead of conventional polyaniline to minimize the anion participation in the charge-discharge process and maximize the transport number of Li". In lithium batteries, it is desirable that only lithium cations intercalate into the cathode, because this leads to the use of small amounts of electrolyte... 

PMMA/PEO, polyethylene oxide PC/lithium salt of sulfonated polystyrene PS/polyphenylmethyl siloxane Chlorinated PE/chlorinated polybutadiene PS/carboxylated PPO PPO/poly(alpha-methylstyrene)... 

Electrical properties have been reported on numerous carbon fiber-reinforced polymers, including carbon nanoflber-modified thermotropic liquid crystalline polymers [53], low-density polyethylene [54], ethylene vinyl acetate [55], wire coating varnishes [56], polydimethyl siloxane polypyrrole composites [50], polyacrylonitrile [59], polycarbonate [58], polyacrylonitrile-polycarbonate composites [58], modified chrome polymers [59], lithium trifluoromethane sulfonamide-doped polystyrene-block copolymer [60], boron-containing polyvinyl alcohols [71], lanthanum tetrafluoride complexed ethylene oxide [151, 72, 73], polycarbonate-acrylonitrile diene [44], polyethylene deoxythiophe-nel, blends of polystyrene sulfonate, polyvinyl chloride and polyethylene oxide [43], poly-pyrrole [61], polypyrrole-polypropylene-montmorillonite composites [62], polydimethyl siloxane-polypyrrole composites [63], polyaniline [46], epoxy resin-polyaniline dodecyl benzene sulfonic acid blends [64], and polyaniline-polyamide 6 composites [49]. 

The sodium salt of poly(styrene sulfonate) with a narrow molecular weight distribution (PSS77, GPC standard grade, Mw 77 kg/mol) has been obtained from Fluka. The powder was evacuated to remove any residual water content. The lithium salt of poly(styrene sulfonate) (30% wt in H2O, M , 75 kg/mol) and poly(styrene sulfonic acid) (18% wt in H2O, Mw 75 kg/mol) have been purchased from Aldrich. Both samples have been concentrated in a rotary evaporator and subsequently dried under vacuum. For all experiments a concentration of 5 mmol/1 (monomer) in deuterated solvents (D2O, CD3OD and their mixtures) has been used. 

As discussed previously in the section on primary batteries, an acrylate is often used as a crosslinkable monomer to form a polymer matrix for a nonaqueous electrolyte. The salt-in-polymer type polymer electrolyte made by dissolving trifluoroethylene glycol methacrylate into methoxy poly(ethylene glycol methacrylate) forms a comb-like network structure at the covalently bonded portion. The ethylene oxide chain consists of 22 monomer units, and the ionic conductivity at room temperature is reported to be 10 S/cm. If sodium thiocyanate is used [30] instead of lithium trifluoromethane sulfonate, the ionic conductivity reduced to 10 S/cm. However, by adding 50 wt% of PC as a plasticizer, the ionic conductivity reaches 10 " S/cm. 

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