BISPHENOL A COPOLYMER

The most interesting aminomethyl derivative of condensation polymers that we have prepared to date Is derived from direct reduction of poly(2-cyano-l,3-phenylene arylene ether), 20. Enchainment of benzonitrile repeat units Is accomplished by coupling 2,6-dichlorobenzonitrile with the potassium salt of bisphenol-A copolymers with lower nitrile contents can be produced by copolycondensation of bisphenol-A, 2,6-dichlorobenzonitrile and 4,4 -dichlorodiphenyl sulfone.21 The pendent nitrile function provides an active site for further elaboration. 

Thermoplastic multilayer laminate composed from an outer layer of resorcinol arylate poly(ester)s, a middle layer comprising a polycarbonate), e.g., LEXAN 131, and an inner-tie layer made from ASA or ABS have been described (37). Resorcinol arylate poly(es-ter)s may be understood as an isophthalic terephthalic resorcinol bisphenol A copolymer. 

Durethan RM PA-6 blended with methacrylate-butyl acrylate-bisphenol-A copolymer, with glass fiber or not Bayer AG/Miles Inc. 

Polystyrene is immiscible with PC however, tetramethyl Bisphenol A polycarbonate (TMPC) is miscible and exhibits lest behavior [439]. The CPMAS NMR analysis gave indication of homogeneity of the TMPC/PS blend at the level of a few nanometers [440], consistent with SANS data of 2 nm [441]. Styrene-MMA copolymers are immiscible with PC, but miscible with TMPC [442]. Miscibility maps for SMMA copolymer blends with hexafluorobisphenol A-tetramethyl bisphenol A copolymers show areas of single phase behavior. TMPC miscibility windows with a series of styrene copolymers (SAN, SMA, styrene-allyl alcohol (SAAl)) have been reported [443 ]. Miscibility of the copolymers with TMPC was maintained for SAN (0-13 wt% AN), SMA (0-8 wt% MA) and SAAl (0-19 wt% aUyl alcohol). Dimethyl bisphenol A-tetramethyl bisphenol A PC copolymer blends with SMMA yielded miscibility with SMMA (< 37 wt%) and PC copolymer with > 60 wt% tetramethyl bisphenol A content [444]. Tetramethyl Bisphenol S polycarbonate is not miscible with polystyrene, but is miscible with styrene-acrylonitrile copolymers (range estimated to be 14 to 42 wt% AN) [445]. Miscibility was also observed with an a-methyl styrene-acrylonitrile copolymer (31 wt% AN). 

Displacement reactions with oxygen nucleophiles are of potential commercial interest. Alkaline hydrolysis provides 2-fluoro-6-hydroxypyridine [55758-32-2], a precursor to 6-fluoropyridyl phosphoms ester insecticides (410—412). Other oxygen nucleophiles such as bisphenol A and hydroquinone have been used to form aryl—pyridine copolymers (413). 

Fig. 26. Qualitative compatison of substrate materials for optical disks (187) An = birefringence IS = impact strength BM = bending modulus HDT = heat distortion temperature Met = metallizability WA = water absorption Proc = processibility. The materials are bisphenol A—polycarbonate (BPA-PC), copolymer (20 80) of BPA-PC and trimethylcyclohexane—polycarbonate (TMC-PC), poly(methyl methacrylate) (PMMA), uv-curable cross-linked polymer (uv-DM), cycHc polyolefins (CPO), and, for comparison, glass.

Polycarbonate (PC) Resins. Polycarbonates (qv) based on bisphenol A are sold in large quantities. Other bisphenols can be incorporated, but do not give the same favorable combination of properties and cost (82). Small quantities of PC based on tetramethylbisphenol A are used as blending resins (83) and polyester carbonate copolymers are used for appHcations requiring heat-deflection temperatures above those of standard PC resins (47). 

Polyester C rbon te Copolymers. Polyester carbonate resins have molecular stmctures composed of iso- and terephthalate units in conjunction with the standard bisphenol A PC moieties. 

Another approach to increase the heat distortion temperature is to produce cocondensates of bisphenol A with bishydroxyphenyl fluorene. Some variations of this copolymer had heat distortion temperatures in excess of 200°C and with the potential to be produced at lower cost than such temperature-resistant thermoplastics as polysulphones and polyetherimides. Plans to develop this material were however abandoned when it was found, during trials of test materials, that workers developed skin rashes said to be similar to those encountered on contact with poison ivy. 

Polycarbonates with superior notched impact strength, made by reacting bisphenol A, bis-phenol S and phosgene, were introduced in 1980 (Merlon T). These copolymers have a better impact strength at low temperatures than conventional polycarbonate, with little or no sacrifice in transparency. These co-carbonate polymers are also less notch sensitive and, unlike for the standard bis-phenol A polymer, the notched impact strength is almost independent of specimen thickness. Impact resistance increases with increase in the bis-phenol S component in the polymer feed. Whilst tensile and flexural properties are similar to those of the bis-phenol A polycarbonate, the polyco-carbonates have a slightly lower deflection temperature under load of about 126°C at 1.81 MPa loading. 

In the 1980s a number of copolymers became established, known as polyester carbonates, which may be considered as being intermediate between bisphenol A polycarbonates and the polyarylates discussed in Chapter 25. 

A different variety of copolymer has been prepared by Gramain and Frere who treated 1,10-diaza-l 8-crown-6 with the bisglycidyl ether of bisphenol A. The reaction was conducted at reflux in a mixture of THF and methanol. The polymer, illustrated in Eq. (6.24) was formed 83% yield. The polymer was appparently quite stable, surviving aging tests conducted over a two-year period. 

Bisphenol A, epoxy resins from, 673 polymers from, 821 Bloch, Konrad Emil, 1084 Block copolymer, 1212 sy nthesis of, 1212... 

Robeson and Matzner were the first to report the synthesis of the sulfonation of DCDPS.205 This work makes it possible to synthesize sulfonated poly(arylene ether sulfone) with well-controlled structures. Ueda et al. used this monomer (Scheme 6.27) as a comonomer of DCDPS to react with bisphenol A and high-molecular-weight bisphenol-A-based copolymers with up to 30 mol % sulfonation achieved.206 Biphenol-based copolymers with up to 100 mol % sulfonation were recently reported by Wang et al.207... 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

Preparation of siloxane-carbonate segmented copolymers by interfacial polymerization involves the reaction of carboxypropyl-terminated siloxane oligomers with bisphenol-A and phosgene, in the presence of a strong base and a phase transfer catalyst, in water/methylene chloride solvent system l50 192), as shown in Reaction Scheme XIV. 

Poly(arylester)-polysiloxane multiblock copolymers have also been synthesized by the interfacial polymerization of aminopropyl terminated polysiloxane oligomers with bisphenol-A and a mixture of isophthaloyl and terephthaloyl chlorides117, 193-1951 as illustrated in Reaction Scheme XV. In these reactions the poly(arylester) blocks are formed in situ during the copolymerization, so the control of their block sizes is not very precise. It is also important to note that since aminopropyl terminated siloxane oligomers are employed, the linkages which connect the arylester and siloxane blocks are amide linkages. 

Table 16 shows various characteristics of segmented siloxane-(aryl ester) block copolymers. The effect of the variation in the polyester backbone was also studied by replacing bisphenol-A with tetramethyl substituted bisphenol-A. The major difference in these systems was an increase in the high temperature Tg to around 210 to 215 °C 193). 

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. 

Lipase CA catalyzed the polymerization of cyclic dicarbonates, cyclobis (hexamethylene carbonate) and cyclobis(diethylene glycol carbonate) to give the corresponding polycarbonates [105]. The enzymatic copolymerization of cyclobis(diethylene glycol carbonate) with DDL produced a random ester-carbonate copolymer. As to enzymatic synthesis of polycarbonates, reported were polycondensations of 1,3-propanediol divinyl dicarbonate with 1,3-propanediol [110], and of diphenyl carbonate with bisphenol-A [111]. 

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