Polycarbonates monomers

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Ttihaloacyl aromatics have been prepared by Friedel-Crafts acylation of aromatics with CX COCl (X = Cl, Br) in the presence of AlCl. They are used as monomers in the preparation of polycarbonates, polyesters, polyamides, polyketones, and polyurethanes (91). 

Examples of photothermoplasts include polyacrylates, polyacrylamides, polystyrenes, polycarbonates, and their copolymers (169). An especially well-re searched photothermoplast is poly(methyl methacrylate) (PMMA), which is blended with methyl methacrylate (MMA) or styrene as a monomer, and titanium-bis(cyclopentadienyl) as a photoinitiator (170). 

During the eady development of polycarbonates, many bisphenols were investigated for potential useftil products. Some of these monomers and polymers are hsted in Table 3. Despite this intensive search, however, no homopolycarbonates other than that of BPA have been produced. Copolymers and blends, on the other hand, have been quite successhil. Blends of polycarbonate with ABS and with poly(butylene terephthalate) (PBT in particular have shown significant growth since the mid-1980s. 

A tme condensation reaction is characterized by elimination of a small molecule when the monomers condense to form the repeating unit. Reacts with phosgene COCl to form the repeat unit shown (see Polycarbonates). 

Alkylphenols have been substituted for phenol as chain teaninatois in polycarbonates. In this role, PTBP (14) competes with the diol monomer for reactive chlorocarbonate sites. The ratio of butylphenol to diol controls the molecular weight of the polymer. 

Donation of a proton to the reactant often forms a carbenium ion or an oxonium ion, which then reacts ia the catalytic cycle. For example, a catalytic cycle suggested for the conversion of phenol and acetone iato bisphenol A, which is an important monomer used to manufacture epoxy resias and polycarbonates, ia an aqueous mineral acid solution is shown ia Figure 1 (10). 

All of the eommereial alkyl eyanoaerylate monomers are low-viseosity liquids, and for some applications this can be an advantage. However, there are instances where a viseous liquid or a gel adhesive would be preferred, sueh as for application to a vertical surface or on porous substrates. A variety of viscosity control agents, depending upon the desired properties, have been added to increase the viscosity of instant adhesives [21]. The materials, which have been utilized, include polymethyl methacrylate, hydrophobic silica, hydrophobic alumina, treated quartz, polyethyl cyanoacrylate, cellulose esters, polycarbonates, and carbon black. For example, the addition of 5-10% of amorphous, non-crystalline, fumed silica to ethyl cyanoacrylate changes the monomer viscosity from a 2-cps liquid to a gelled material [22]. Because of the sensitivity of cyanoacrylate esters to basic materials, some additives require treatment with an acid to prevent premature gelation of the product. 

Bisphenol A is a solid material in the form of white flakes, insoluble in water but soluble in alcohols. As a phenolic compound, it reacts with strong alkaline solutions. Bisphenol A is an important monomer for producing epoxy resins, polycarbonates, and polysulfones. It is produced by the condensation reaction of acetone and phenol in the presence of HCI. (See Chapter 10, p. 273)... 

Phenol was the 33rd highest-volume chemical. The 1994 U.S. production of phenol was approximately 4 billion pounds. The current world capacity is approximately 15 billion pounds. Many chemicals and polymers derive from phenol. Approximately 50% of production goes to phenolic resins. Phenol and acetone produce bis-phenol A, an important monomer for epoxy resins and polycarbonates. It is produced by condensing acetone and phenol in the presence of HCI, or by using a cation exchange resin. Figure 10-8 shows the Chiyoda Corp. bisphenol A process. 

These compds may be modified by monocar-boxy lie acids or poly hydroxy alcohols. This definition includes the polycarbonates (qv), which are a well-defined segment of the general class of polyesters. Unsaturated polyesters, which are produced when any of the reactants contain non-aromatic unsaturation, can be cross-linked or copolymerized with an un-saturated copolymerizable monomer. The formulas and properties of the class polyester are as varied and extensive as the reactants themselves. For specific information on the various sub-classes and sub-sub classes, the following refs should be consulted 9, 10, II, 16a, 17,18,... 

Fig. 22. Deuteron NMR spectra at room temperature for the phenyl groups in polycarbonate itself and in mixtures of polycarbonate and para-dichlorobenzene and polychlorinated biphenyls as indicated. Note that the additives block the phenyl motion for a substantial fraction of the monomer units...

Nearly all of the polymers produced by step-growth polymerization contain heteroatoms and/or aromatic rings in the backbone. One exception is polymers produced from acyclic diene metathesis (ADMET) polymerization.22 Hydrocarbon polymers with carbon-carbon double bonds are readily produced using ADMET polymerization techniques. Polyesters, polycarbonates, polyamides, and polyurethanes can be produced from aliphatic monomers with appropriate functional groups (Fig. 1.1). In these aliphatic polymers, the concentration of the linking groups (ester, carbonate, amide, or urethane) in the backbone greatly influences the physical properties. 

Economic and ecological aspects of chemical recycling are examined, and the application of such processes to the recovery of monomers and intermediates from PETP, polyamides, polyurethanes, polycarbonates, unsaturated polyesters, polyacetals, PMMA and PS is discussed. 17 refs. SNIA... 

Fig. 6.4. Vogel-Fulcher plot of the chain diffusion constants D for the three different polycarbonate modifications, as indicated in the figure, for N = 20 model monomers...

Extraction or dissolution almost invariably will cause low-MW material in a polymer to be present to some extent in the solution to be chromatographed. Solvent peaks interfere especially in trace analysis solvent impurities also may interfere. For identification or determination of residual solvents in polymers it is mandatory to use solventless methods of analysis so as not to confuse solvents in which the sample is dissolved for analysis with residual solvents in the sample. Gas chromatographic methods for the analysis of some low-boiling substances in the manufacture of polyester polymers have been reviewed [129]. The contents of residual solvents (CH2C12, CgHsCI) and monomers (bisphenol A, dichlorodiphenyl sulfone) in commercial polycarbonates and polysulfones were determined. Also residual monomers in PVAc latices were analysed by GC methods [130]. GC was also... 

In an attempt to identify new, biocompatible diphenols for the synthesis of polyiminocarbonates and polycarbonates, we considered derivatives of tyrosine dipeptide as potential monomers. Our experimental rationale was based on the assumption that a diphenol derived from natural amino acids may be less toxic than many of the industrial diphenols. After protection of the amino and carboxylic acid groups, we expected the dipeptide to be chemically equivalent to conventional diphenols. In preliminary studies (14) this hypothesis was confirmed by the successful preparation of poly(Z-Tyr-Tyr-Et iminocarbonate) from the protected tyrosine dipeptide Z-Tyr-Tyr-Et (Figure 3). Unfortunately, poly (Z-Tyr-Tyr-Et iminocarbonate) was an insoluble, nonprocessible material for which no practical applications could be identified. This result illustrated the difficulty of balancing the requirement for biocompatibility with the need to obtain a material with suitable "engineering" properties. 

Figure 5. Each monomer shown in Figure 4 was used in the synthesis of a polyiminocarbonate and a polycarbonate, resulting in the preparation of eight structurally related polymers.

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