Quaternary copolymers

Acrylic polyols represent a special group of amorphous polyols, of molecular weight (MW) of 8000-13000 daltons, obtained by radical copolymerisation of acrylic monomers (ternary or quaternary copolymers), such as acrylic or methacrylic acids and esters. The source of hydroxyl groups in these acrylic polyols is the utilisation in the radical copolymerisation reaction of hydroxyalkyl acrylates or hydroxyalkyl methacrylates [1,2] as comonomers. The acrylic polyols are used in high performance polyurethane (PU) coatings. 

Two representative acrylic polyols, quaternary copolymers of various acrylic monomers, are shown in Figures 10.2 and 10.3. 

Transparent ABS is a quaternary copolymer composed of butadiene, styrene, acrylonitrile, and methyl methacrylate. It is composed of a core-shell structure, where the core component uses butadiene rubber or... 

Ion-exchange separations can also be made by the use of a polymer with exchangeable anions in this case, the lanthanide or actinide elements must be initially present as complex ions (11,12). The anion-exchange resins Dowex-1 (a copolymer of styrene and divinylben2ene with quaternary ammonium groups) and Amherlite IRA-400 (a quaternary ammonium polystyrene) have been used successfully. The order of elution is often the reverse of that from cationic-exchange resins. 

Strong Base Anion Exchangers. As ia the synthesis of weak base anion exchangers, strong base resias are manufactured from styrenic as well as acryhc copolymers. Those based on copolymers of styrene and divinylben2ene are chloromethylated and then aminated. These reactions are the same as for the styrenic weakbase resias. The esseatial differeace is the amine used for amination. Trimethyl amine [75-50-3] N(CH2)3, and /V, /V- dim ethyl eth a n ol amine [108-01 -0] (CH2)2NCH2CH20H, are most commonly used. Both form quaternary ammonium functional groups similar to (8). 

The most successful of these products contain high ratios of VP to DMAEMA and are partially quatemized with diethyl sulfate (Polyquaternium 11) (142—144). They afford very hard, clear, lustrous, nonflaking films on the hair that are easily removed by shampooing. More recendy, copolymers with methyl vinyl imidazoliiim chloride (Polyquaternium 16) (145) or MAPTAC (methacrylamidopropyltrimethyl ammonium chloride) (Polyquaternium 28) have been introduced. Replacement of the ester group in DMAEMA with an amide analog as in Polyquaternium 28 results in a resin resistant to alkaline hydrolysis and hence greater utility in alkaline permanent-wave and bleach formulations (see Quaternary ammonium compounds). 

The existence of an azeotropic composition has some practical significance. By conducting a polymerization with the monomer feed ratio equal to the azeotropic composition, a high conversion batch copolymer can be prepared that has no compositional heterogeneity caused by drift in copolymer composition with conversion. Thus, the complex incremental addition protocols that arc otherwise required to achieve this end, are unnecessary. Composition equations and conditions for azeotropic compositions in ternary and quaternary eopolymerizations have also been defined.211,21... 

The organic resin material is often a styrene divinylbenzene (DVB) copolymer in a network or matrix, to which are attached functional groups such as a sulfonic acid, carboxylic acid, and quaternary ammonium. The nature of these groups determines whether the resin is classified as a strong/weak acid (cation resin) or strong/weak base (anion resin) ion-exchanger. 

Poly(l-acryloyl-4-methyl piperazine and copolymers of l-acryloyl-4-methyl piperazine quaternary salts with acrylamide quaternary salts) OiW ... 

The cationic monomer can be a diallyldimethyl ammonium halide, a di-methylaminoethyl acrylate quaternary salt, or a dimethylaminoethyl methacrylate quaternary salt [1635]. The copolymers may be in solid, dispersion, latex, or solution form. 

Copolymers. Copolymers have also been studied (16-18). While one comonomer contains 1-2 quaternary nitrogen in a flexible pendant chain, the other comonomer was nonionic. Copolymers of the methyl chloride salt of dimethylaminoethyl methacrylate (one quaternary nitrogen atom) and dimethylaminoethyl methacrylate (DMAEMA) and of MDTHD (2 quaternary nitrogen atoms) and DMAEMA, N,N-dimethylacryl-amide (NNDMAm) or dimethylaminopropyl methacrylate (DMAPMA) have been studied and the results summarized in Table VI. 

The observation that the quaternary ammonium monomer content of MDTHD.-DMAEMA and DMAEMA CH3C1 DMAEMA copolymers had little effect on their silica fines stabilization properties of prompted an investigation of nonionic polymers as mineral fines stabilizers (17,18). A series of N-vinylpyrrolidinone (NVP) copolymers with DMAEMA have been studied. Results are summarized in Table VII. 

When the DMAEMA content of NVP - DMAEMA copolymers was reduced from 20% to 8%, the silica fines stabilization effectiveness appeared to improve slightly. When the 80/20 NVP - DMAEMA copolymer was converted to a terpolymer containing 8% DMAEMA (CH SO, silica fines stabilization was substantially unaffected. However, stabilization of silica/kaolinite fines was greatly improved. This suggested that the interaction of polymer quaternary nitrogen atoms with anionic sites on mineral surfaces was important for the stabilization of migrating clays but a different interaction was important for the stabilization of silica fines. Calcite fines stabilization improved while hematite fines stabilization effectiveness decreased. This also indicated the nature of the adsorbed polymer - fine particle complex varied for different minerals. 

The results summarized in Table IX indicated that another copolymer which does not contain quaternary nitrogen atoms, poly (DMAEMA - co - methyl acrylate) was also an effective silica fines stabilizer. 

Another way for covalent immobilisation is to synthesise indicator chemistry with polymerizable entities such as methacrylate groups (Figure 4). These groups can then be copolymerized with monomers such as hydrophobic methyl methacrylate or hydrophilic acryl amide to give sensor copolymers. In order to obtain self-plasticized materials, methacrylate monomers with long alkyl chains (hexyl or dodecyl methacrylate) can be used. Thus, sensor copolymers are obtained which have a Tg below room temperature. Similarly, ionophores and ionic additives (quaternary ammonium ions and borates) can be derivatised to give methacrylate derivatives. 

In an extension of this work, the reuse of the polymeric catalyst was addressed and several new PE-poly(alkene) glycol copolymers were prepared [68]. Commercially available oxidized polyethylene (CO2H terminated, both high and low molecular weight) was converted to the acid chloride and reacted with Jeffamine D or Jeffamine EDR, and subsequently converted to the tributylammonium bromide salt with butyl bromide. These new quaternary salts were shown to catalyze the nucleophihc substitution of 1,6-dibromohexane with sodium cyanide or sodium iodide. While none of the polymeric quaternary salts catalyzed the reaction as well as tetrabutylammonium bromide, the temperature-dependent solubility of the polymers allowed removal of the polymer by simple filtration. 

Plastic film membranes can also contain fixed ion-exchange groups. Jyo and coworkers [79] chloromethylated Amberlite XAD-2 (cross-linked styrene-divinylbenzene copolymer of the macroreticular type) and formed quaternary ammonium groups in the product by treatment with dimethyltetradecylamine. They converted the substance into the chloride, nitrate or perchlorate form and saturated it with nitrobenzene. The presence of hydrophobic ion-exchange sites... 

Note 4 The use of the term polymer alloy for a polymer blend is discouraged, as the former term includes multiphase copolymers but excludes incompatible polymer blends. Note 5 The number of polymeric components which comprise a blend is often designated by an adjective, viz. binary, ternary, quaternary, etc. 

Lu and coworkers have synthesized a related bifunctional cobalt(lll) salen catalyst similar to that seen in Fig. 11 that contains an attached quaternary ammonium salt (Fig. 13) [36]. This catalyst was found to be very effective at copolymerizing propylene oxide and CO2. For example, in a reaction carried out at 90°C and 2.5 MPa pressure, a high molecular weight poly(propylene carbonate) = 59,000 and PDI = 1.22) was obtained with only 6% propylene carbonate byproduct. For a polymerization process performed under these reaction conditions for 0.5 h, a TOF (turnover frequency) of 5,160 h was reported. For comparative purposes, the best TOF observed for a binary catalyst system of (salen)CoX (where X is 2,4-dinitrophenolate) onium salt or base for the copolymerization of propylene oxide and CO2 at 25°C was 400-500 h for a process performed at 1.5 MPa pressure [21, 37]. On the other hand, employing catalysts of the type shown in Fig. 12, TOFs as high as 13,000 h with >99% selectivity for copolymers withMn 170,000 were obtained at 75°C and 2.0 MPa pressure [35]. The cobalt catalyst in Fig. 13 has also been shown to be effective for selective copolymer formation from styrene oxide and carbon dioxide [38]. 

Upon dissolving the copolymer/catalyst mixture in ethylbutylamine (EtBuNH) the introduction of CO2 at atmospheric pressure results in formation of an equilibrium mixture of carbamic acid and the quaternary ammonium salt of carbamate. The carbamic acid serves to remove the copolymer from the metal center, at which time it precipitates in the ionic liquid and is isolated by filtration. The metal catalyst... 

Aromatic electrophilic substitution is used commercially to produce styrene polymers with ion-exchange properties by the incorporation of sulfonic acid or quaternary ammonium groups [Brydson, 1999 Lucas et al., 1980 Miller et al., 1963]. Crosslinked styrene-divinyl-benzene copolymers are used as the starting polymer to obtain insoluble final products, usually in the form of beads and also membranes. The use of polystyrene itself would yield soluble ion-exchange products. An anion-exchange product is obtained by chloromethylation followed by reaction with a tertiary amine (Eq. 9-38) while sulfonation yields a cation-exchange product (Eq. 9-39) ... 

Over the years it has been shown that complexes prepared from organophosphorous ligands in combination with peroxotungstic acid or its quaternary ammonium salts exhibit efficient catalytic properties. In order to make an efficient recycling of the catalyst possible and get tungsten-free products and effluents, some of these catalysts were immobilized onto polystyrene, poly benzimidazole and polymethacrylate copolymers modified by the introduction of the phosphorous(V)-containing ligands. 

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