Poly bisphenol

Most polyesters (qv) are based on phthalates. They are referred to as aromatic-aHphatic or aromatic according to the copolymerized diol. Thus poly(ethylene terephthalate) [25038-59-9] (PET), poly(butyelene terephthalate) [24968-12-5] (PBT), and related polymers are termed aromatic-aHphatic polyester resins, whereas poly(bisphenol A phthalate)s are called aromatic polyester resins or polyarylates PET and PBT resins are the largest volume aromatic-aHphatic products. Other aromatic-aHphatic polyesters (65) include Eastman Kodak s Kodar resin, which is a PET resin modified with isophthalate and dimethylolcyclohexane. Polyarylate resins are lower volume specialty resins for high temperature (HDT) end uses (see HeaT-RESISTANT POLYAffiRS). 

FIGURE 5 Molecular structures of poly(Bisphenol A carbonate) and poly(Bisphenol A iminocarbonate). The poly(iminocarbonates) are, in a formal sense, derived from polycarbonates by replacement of the carbonyl oxygen by an imino group. 

Blends of enzymatically synthesized poly(bisphenol-A) and poly(p-r-butylphenol) with poly(e-CL) were examined. FT-IR analysis showed the expected strong intermolecular hydrogen-bonding interaction between the phenolic polymer with poly(e-CL). A single 7 was observed for the blend, and the value increased as a function of the polymer content, indicating their good miscibility in the amorphous state. In the blend of enzymatically synthesized poly(4,4 -oxybisphenol) with poly(e-CL), both polymers were miscible in the amorphous phase also. The crystallinity of poly(e-CL) decreased by poly(4,4 -oxybisphenol). 

Figure 2. Molecular structures of poly(Bisphenol A carbonate) and poly(Bisphenol A iminocarbonate).

Recent developments have allowed atomic force microscopic (AFM) studies to follow the course of spherulite development and the internal lamellar structures as the spherulite evolves [206-209]. The major steps in spherulite formation were followed by AFM for poly(bisphenol) A octane ether [210,211] and more recently, as seen in the example of Figure 12 for a propylene 1-hexene copolymer [212] with 20 mol% comonomer. Accommodation of significant content of 1-hexene in the lattice allows formation and propagation of sheaf-like lamellar structure in this copolymer. The onset of sheave formation is clearly discerned in the micrographs of Figure 12 after crystallization for 10 h. Branching and development of the sheave are shown at later times. The direct observation of sheave and spherulitic formation by AFM supports the major features that have been deduced from transmission electron and optical microscopy. The fibrous internal spherulite structure could be directly observed by AFM. 

Montaudo and co-workers have used direct pyrolysis mass spectrometry (DPMS) to analyse the high-temperature (>500°C) pyrolysis compounds evolved from several condensation polymers, including poly(bisphenol-A-carbonate) [69], poly(ether sulfone) (PES) and poly(phenylene oxide) (PPO) [72] and poly(phenylene sulfide) (PPS) [73]. Additionally, in order to obtain data on the involatile charred residue formed during the isothermal pyrolysis process, the pyrolysis residue was subjected to aminolysis, and then the aminolyzed residue analysed using fast atom bombardment (FAB) MS. During the DPMS measurements, EI-MS scans were made every 3 s continuously over the mass range 10-1,000 Da with an interscan time of 3 s. 

As an example of the form of the information that may be derived from a pyrolysis-MS, Figure 26 [69] shows the structure of the polycarbonate (PC) and the EI-MS spectra of pyrolysis compounds obtained by DPMS of poly(bisphenol-A-carbonate) at three different probe temperatures corresponding to the three TIC (total ion current) maxima shown in Figure 27(b) Figure 27 compares the MS-TIC curve with those obtained from thermogravimetry. (The TIC trace is the sum of the relative abundances of all the ions in each mass spectrum plotted against the time (or number of scans) in a data collection sequence [70].)... 

Figure 26 Structure of PC and El mass spectra of pyrolysis compounds obtained by DPMS of poly(bisphenol-A-carbonate) at probe temperatures of (a) 380°C, (b) 500°C and (c) 550°C. Reprinted with permission from Puglisi et al. [69]. Copyright 1999, American Chemical Society.

Figure 15.1. MALDI spectrum of a polycarbonate sample along with peak assignment. In the inset, an expansion of the spectral region from 3.0 up to 3.7 kDa is shown. (Reproduced from Puglisi, C. et al., 1999. Analysis of Poly(bisphenol A Carbonate) by Size Exclusion Chromatography/Matrix-Assisted Laser Desorption/lonization. I. End Group and Molar Mass Determination. Rapid Communications in Mass Spectrometry, 13 2260-2267. With permission of John Wiley Sons, Inc.)...

J. A. Talla, D. Zhang, S. A. Curran, Electrical transport measurements of highly conductive nitrogen-doped multiwalled carbon nanotubes/poly(bisphenol A carbonate) composites, Journal of Materials Research, vol. 22, pp. 2854-2859, 2011. 

Usually poly (bisphenol - A carbonate, commercially - lexan) is used as a polymer matrix. 

The blend of poly(bisphenol A carbonate)-(poly(caprolactone) PC-PCL is particularly unusual in that both polymers are capable of crystallization and FT-IR has been used to study the state of order in these blends as a function of the method of preparation 254,255). In this case, PCL is a macromolecular plasticizer for PC. The PCL becomes progressively less crystalline as the concentration of PC increases. PC is amorphous if the blend is cast from methylene chloride but semicrystalline if cast from tetrahydrofuran. When PC in the pure form is exposed to acetone, it will not crystallize, but in the blend, exposure of acetone causes the PC to crystallize which emphasizes the additional mobility of the PC in the blend. 

Carr, S. H., Geil, P. H., Baer, E. The development of spherulites from structural units in glassy poly(bisphenol-A-carbonate). J. Macromol. Sci.-Phys. B2,13-28 (1968). 

Gross, S. M. Roberts, G. W. Kiserow, D. J. DeSimone, J. M. Crystallization and Solid State Polymerization of Poly(bisphenol A carbonate) Facilitated by Supercritical C02. Macromolecules 2000, 33, 40 -5. 

The Idemitsu Kosan Co. Ltd developed an original process of grafting of monomers (for example styrene) onto aromatic polyesters like poly bisphenol A terephthalate. In this process, the time of treatment of the cited polymer remains long what is due to its aromatic character well known to be more resistant to ozone than aliphatic polymers [146]. It can be noted that... 

Poly(bisphenol-A-carbonate) under pseudoideal reaction conditions was investigated, and the cyclic polycarbonate was obtained as the main product. In the system, the interface of the water/toluene mixture might have favored the cyclization reaction between the polar end groups [88]. Cyclic carbonates during the (Salen)CrCl catalyzed CCh/cyclohexene oxide copolymerization process in the presence of ionic initiators was also obtained [89]. The cyclic carbonate is produced via the backbiting mechanism, and the process is assumed to take place via a metal alkoxide (polymer chain) intermediate. Subsequent ring-opening of the cyclic carbonate with concomitant formation of polyether and CO2 was fast at the reaction temperatures from 80 to 100 °C). 

Acceptor polymers (TV) = poly(l,6-hexanediol-5-nitroisophthalate), (V) = poly(bisphenol A 5-nitroisophthalate), (VI) = poly[bis(2-hydroxyethyl)-5-nitroisophthalate-bisphenol A carbonate]... 

Estimate, the optical-stress coefficient for poly(bisphenol-A carbonate), [Ci6Hi403]n. with Vw = 144 cm3/mol unit. 

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