Carbon from polycondensation

PLA can be synthesized by two routes polycondensation of lactic acid or ringopening polymerization of its cyclic dimer, lactide [12]. PLA prepared from polycondensation has low molar mass and poor mechanical properties and Is therefore not suitable for many applications [13]. High-molar-mass PLA Is most commonly made by ring-opening polymerization of lactide. In both cases, lactic acid is the feedstock for PLA production. Lactic acid has an asymmetric carbon atom, which leads to two optically active forms called L-lactic acid and D-lactic acid. When producing PLA from lactide, polymerization can start from three types of monomers LL-lactide made from two L-lactic acid molecules, DD-lactide from dimerization of D-lactic acid, and LD or wieso-lactide made from a combination of one L- and one D-lactic acid molecules [14,15]. The chemical structures of lactic acid and lactide molecules are illustrated in Figure 5.1. 

Nucleophilic Substitution Route. Commercial synthesis of poly(arylethersulfone)s is accompHshed almost exclusively via the nucleophilic substitution polycondensation route. This synthesis route, discovered at Union Carbide in the early 1960s (3,4), involves reaction of the bisphenol of choice with 4,4 -dichlorodiphenylsulfone in a dipolar aprotic solvent in the presence of an alkaUbase. Examples of dipolar aprotic solvents include A/-methyl-2-pyrrohdinone (NMP), dimethyl acetamide (DMAc), sulfolane, and dimethyl sulfoxide (DMSO). Examples of suitable bases are sodium hydroxide, potassium hydroxide, and potassium carbonate. In the case of polysulfone (PSE) synthesis, the reaction is a two-step process in which the dialkah metal salt of bisphenol A (1) is first formed in situ from bisphenol A [80-05-7] by reaction with the base (eg, two molar equivalents of NaOH),... 

Aromatic polycarbonates are currently manufactured either by the interfacial polycondensation of the sodium salt of diphenols such as bisphenol A with phosgene (Reaction 1, Scheme 22) or by transesterification of diphenyl carbonate (DPC) with diphenols in the presence of homogeneous catalysts (Reaction 2, Scheme 22). DPC is made by the oxidative carbonylation of dimethyl carbonate. If DPC can be made from cyclic carbonates by transesterification with solid catalysts, then an environmentally friendlier route to polycarbonates using C02 (instead of COCl2/CO) can be established. Transesterifications are catalyzed by a variety of materials K2C03, KOH, Mg-containing smectites, and oxides supported on silica (250). Recently, Ma et al. (251) reported the transesterification of dimethyl oxalate with phenol catalyzed by Sn-TS-1 samples calcined at various temperatures. The activity was related to the weak Lewis acidity of Sn-TS-1 (251). 

Polycarbonates are polyesters resulting from the polycondensation of carbonic anhydride (furnished by phosgene) and a bisphenol. 

It has become the custom to name linear aliphatic polyamides according to the number of carbon atoms of the diamine component (first named) and of the dicarboxylic acid. Thus, the condensation polymer from hexamethylenedi-amine and adipic acid is called polyamide-6,6 (or Nylon-6,6), while the corresponding polymer from hexamethylenediamine and sebacoic acid is called polyamide-6,10 (Nylon-6,10). Polyamides resulting from the polycondensation of an aminocarboxylic acid or from ring-opening polymerization of lactams are indicated by a single number thus polyamide-6 (Nylon-6) is the polymer from c-aminocaproic acid or from e-caprolactam. 

A solution of 3 ml (14 mmol) of freshly distilled sebacoyl dichloride (for preparation see above) in 100 ml of carbon tetrachloride is placed in a 250 ml beaker. A solution of 4.4 g (38 mmol) of hexamethylenediamine in 50 ml of water is carefully run on to the top of this solution, using a pipette. (The aqueous solution can be made more readily visible by coloring it with a few drops of phenolphthalein solution.) A polyamide film is immediately formed at the interface and can be pulled out from the center with tweezers or clamps and laid over some glass rods it can now be pulled out continuously in the form of a hollow thread and wound up on to a spool driven by a slow-running motor. The polycondensation comes rapidly to a standstill if the motor is stopped, but immediately recommences, even after some hours, when the motor is restarted. 

Cyclic carbonates are not commercially available and have to be synthesized prior to use. As a result, commercially available carbonates such as diethyl carbonate [55-57] or diphenyl carbonate [93] were evaluated in polycondensation reactions with diols to prepare polycarbonates since they allow a broader spectrum of polymers to be accessed. Unfortunately, polymerizations employing diethyl carbonate require the use of an excess diethyl carbonate [55]. Nevertheless, polymers with molecular weight of 40kDa were achieved within 16 h. Also, the polymerization of diphenyl carbonate with butane-1,4-diol or hexane-1,6-diol via the formation of a cyclic dimer produced polymers with molecular weights ranging from 119 to 339kDa [93]. 

Hyperbranched polymers of polybenzene type can be rendered water-soluble like the above-mentioned monodisperse species by introduction of carboxyl groups [62]. Starting from 3,5-dibromophenylboronic acid 1 as AB2 monomeric building block (Fig. 4.34), the polycondensate 2 was assembled in an aryl-aryl coupling analogous to Suzuki coupling in the presence of Pd(0), and subsequently reacted with carbon dioxide to form the hyperbranched compounds 3 with terminal carboxylate groups ... 

Regioselective polycondensations with transition-metal catalysts were also reported. Nomura et al. developed palladium-catalyzed allylation polycondensation, in which nucleophile predominantly reacted with jt-allyl palladium at the terminal allylic carbon to give fi-linear products [122,123]. On the other hand, polymerization with an iridium catalyst selectively proceeded at the internal allylic carbon to yield branched polymers with pendant vinyl groups (Scheme 30). These polycondensations demonstrate that polymers having different structures can be synthesized from the same monomers by changing the catalyst [124],... 

CycUc polyamides were reported to be isolated from Nylon 6 polymers in 1956 [18,19]. Thermal polycondensation of co-amino acid (carbon number > 6) gave a cycUc and linear polymer [82]. Moreover, upon heating polyamide in the presence of a transamidation catalyst, the cyclization equilibrium is eventually reached, and both Unear and cyclic constituents are present [83]. The proportion of the latter depends on the concentration, and cycUc compounds predominate in high dilute solutions. 

Coordination carbonylation polycondensation has been extended from the synthesis of polyamides [scheme (15)] and polyarylates [scheme (16)] to reactions using other nucleophilic monomers that, with dihaloarenes and carbon monoxide, yield poly(imide-amide)s, poly(acylhydrazide)s, and poly(benzoxa-zole)s [165,170,171],... 

Diatoms are unicellular, photosynthetic microalgae that are abundant in the world s oceans and fresh waters. It is estimated that several tens of thousands of different species exist sizes typically range from ca 5 to 400 pm, and most contain an outer wall of amorphous hydrated silica. These outer walls (named frustules ) are intricately shaped and fenestrated in species-specific (genetically inherited) patterns5,6. The intricacy of these structures in many cases exceeds our present capability for nanoscale structural control. In this respect, the diatoms resemble another group of armored unicellular microalgae, the coccolithophorids, that produce intricately structured shells of calcium carbonate. The silica wall of each diatom is formed in sections by polycondensation of silicic acid or as-yet unidentified derivatives (see below) within a membrane-enclosed silica deposition vesicle 1,7,8. In this vesicle, the silica is coated with specific proteins that act like a coat of varnish to protect the silica from dissolution (see below). The silica is then extruded through the cell membrane and cell wall (lipid- and polysaccharide-based boundary layers, respectively) to the periphery of the cell. 

Figure 3 shows a histogram which depicts field desorption mass-spectra of a benzene solution of protoparticles formed on benzene polycondensation [5]. Thirteen main peaks were noted. Sample temperature 20, 50, 90 °C. It can be seen that the composition and the ratio of the constituents vary with rising temperature, i.e. carbon-containing compounds and associates are partly destroyed by desorption. In this case, certain regularities are observed. For instance, the high m/z values are divisible by some low m/z values or can be made up from several lower m/z values, for example ... 

The manufacture of the large variety of polyamides (commonly referred to as nylons) occurs through polycondensation of amino carboxylic acids (or functional derivatives of them, e.g. lactams) and from diamines and dicarboxylic acids. Labeling the amino groups with A and the carboxyl groups with B allows differentiation of the different chemical structures between the two types AB (from amino carboxylic acids) and AA-BB (from diamines and dicarboxylic acids). The number of C atoms in the monomers acts as a code number for the identification of the polyamides. The polycaprolactam manufactured from caprolactam (type AB) is then called polyamide 6 (PA 6). The number of carbon atoms in the diamine is given first for type AA-BB followed by the number of atoms in the dicarboxylic acid, e.g. PA 66 for polyhexamethylenedia-dipic amide from hexamethylenediamine and adipic acid. For copolymers the components are separated by a slash, e.g. PA 66/6 (90 10) is a copolymer composed of 90 parts PA 66 and 10 parts PA 6. 

Catalytic Cracker Bottoms (CCB) which is the heavy residue from the catalytic cracking of petroleum distillate is a common aromatic feedstock used for synthetic carbons and pitch production. CCB, like other heavy aromatic feedstock, is composed of alkyl-substituted polycondensed aromatics with a very wide molecular weight distribution. 

The initial oligomer as an aqueous solution is obtained from the reaction of urea and formaldehyde at 100°C and pH = 5.8-6 [130]. The process of polycondensation occurs in the presence of acidic catalyst and yields a tri-dimensional polymer, releasing water and formaldehyde [131]. Surfactants are added as foaming agent to the initial composition for the formation of urea polymer foams [125,130]. Various additives are employed to improve the sanitary properties of these plastics. For example, ammonium carbonate reduces the content of free formaldehyde, while addition of carbonates of alkaline metals inhibits corrosion [125]. 

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