Bisphenol-A, polymerization

Two crosslinkable perfluorinated bisphenol A polymeric derivatives having nonlinear optical chromophores containing thiophene have been prepared. Both crosslinked polymers had higher Tg s and greater mechanical stability than their noncrosslinked analogues and were used as light-emitting diodes. 

Numerous avenues to produce these materials have been explored (128—138). The synthesis of two new fluorinated bicycHc monomers and the use of these monomers to prepare fluorinated epoxies with improved physical properties and a reduced surface energy have been reported (139,140). The monomers have been polymerized with the diglycidyl ether of bisphenol A, and the thermal and mechanical properties of the resin have been characterized. The resulting polymer was stable up to 380°C (10% weight loss by tga). 

DMSO is an effective solvent for the polymerization as it affords good solubiUty for both the polymer and disodium bisphenol A [2444-90-8]. Typical polymerization temperatures for polysulfone are in the range 130—160°C. At temperatures below 130°C, the polymerization slows down considerably due to poor solubiUty of the disodium bisphenol A salt. 

The reaction of NaOH with bisphenol A generates water. This water must be thoroughly removed from the system to allow the reaction to be driven to completion, and more importandy, to preclude any residual water in the system from hydrolyzing part of the DCDPS monomer (2). Before the introduction of DCDPS for the polymerization step, all but traces of water must be removed. Failure to do so results in regeneration of NaOH, which rapidly reacts with DCDPS to form the monosodium salt of 4-chloro-4 -hydroxydiphenylsulfone [18995-09-0] (3) (6). 

The addition—reaction product of bisphenol A [80-05-07] and glycidyl methacrylate [106-91-2] is a compromise between epoxy and methacrylate resins (245). This BSI—GMA resin polymerizes through a free-radical induced covalent bonding of methacrylate rather than the epoxide reaction of epoxy resins (246). Mineral fillers coated with a silane coupling agent, which bond the powdered inorganic fillers chemically to the resin matrix, are incorporated into BSI—GMA monomer diluted with other methacrylate monomers to make it less viscous (245). A second monomer commonly used to make composites is urethane dimethacrylate [69766-88-7]. 

Commercial aromatic polyester resins or polyarylates are a combination of bisphenol A with isophthahe acid or terephthahe acid (79). The resins are made commercially by solution polymerization or melt transesterification (47). 

Bisphenol A Polycarbonate Resins. These resins are manufactured by interfacial polymerization (84,85). A small amount of resin is produced by melt-polymerization of bisphenol with diphenyl carbonate in Russia and the People s RepubHc of China. Melt technology continues to be developmental in Japan and the West, but no commercial activities have started-up to date, although some were active in the late 1960s. No reports of solvent-based PC manufacture have been received. 

The terminal R groups can be aromatic or aliphatic. Typically, they are derivatives of monohydric phenoHc compounds including phenol and alkylated phenols, eg, /-butylphenol. In iaterfacial polymerization, bisphenol A and a monofunctional terminator are dissolved in aqueous caustic. Methylene chloride containing a phase-transfer catalyst is added. The two-phase system is stirred and phosgene is added. The bisphenol A salt reacts with the phosgene at the interface of the two solutions and the polymer "grows" into the methylene chloride. The sodium chloride by-product enters the aqueous phase. Chain length is controlled by the amount of monohydric terminator. The methylene chloride—polymer solution is separated from the aqueous brine-laden by-products. The facile separation of a pure polymer solution is the key to the interfacial process. The methylene chloride solvent is removed, and the polymer is isolated in the form of pellets, powder, or slurries. 

Bisphenol F Resin. Bisphenol F [2467-02-9] epoxy resin is of the same general stmcture as the epoxy phenol novolaks. Bisphenol F is 2,2Emethylene bisphenol. Whereas the epoxy phenol novolaks vary from viscous Hquids to soHd materials, the bisphenol F resin has a low viscosity (ca 4 Pa-s (40 P)) and 165 epoxy equivalent weight. Its n value (degree of polymerization) is about 0.15 and crystallization, often a problem with low viscosity conventional bisphenol A resins, is reduced with the bisphenol F resin. 

Advancement Process. In the advancement process, sometimes referred to as the fusion method, Hquid epoxy resin (cmde diglycidyl ether of bisphenol A) is chain-extended with bisphenol A in the presence of a catalyst to yield higher polymerized products. The advancement reaction is conducted at elevated temperatures (175—200°C) and is monitored for epoxy value and viscosity specifications. The finished product is isolated by cooling and cmshing or flaking the molten resin or by allowing it to soHdify in containers. 

The degree of polymerization is dictated by the ratio of Hquid resin (cmde DGEBPA) to bisphenol A an excess of the former provides epoxy terminal groups. The actual molecular weights attained depend on the purity of the starting material. Reactive monofunctional groups act as chain terrninators. 

Diphenol/thiophenol is one of the most important polymer precursors for synthesis of poly(aryl ethers) or poly-(aryl sulfides) in displacement polymerizations. Commonly used bisphenols are 4,4 -isopropylidene diphenol or bisphenol-A (BPA) due to their low price and easy availability. Other commercial bisphenols have also been reported [7,24,25]. Recently, synthesis of poly(aryl ethers) by the reaction of new bisphenol monomers with activated aromatic dihalides has been reported. The structures of the polymer precursors are described in Table 2. Poly(aryl ether phenylquinoxalines) have been synthesized by Connell et al. [26], by the reaction of bisphenols containing a preformed quinoxaline ring with... 

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. 

Various bisphenol derivatives were also polymerized by peroxidase under selected reaction conditions, yielding soluble phenolic polymers. Bisphenol-A was polymerized by peroxidase catalyst to give a polymer soluble in acetone, DMF, DMSO, and methanol. The polymer was produced in higher yields using SBP as a catalyst. This polymer showed a molecular weight of 4 x 10 and a 7g at 154°C. The HRP-catalyzed polymerization of 4,4 -biphenol produced a polymer showing high thermal stability. ... 

Diphenylcarbonate (DPC) is a key monomer for producing LEXAN polycarbonate resin by melt polymerization reaction of DPC with Bisphenol A. Currently, DPC is produced by General Electric Company (GE) in Cartagena, Spain, using a two-step process (Eq. 1) The stoichiometric carbonylation of... 

Bisphenol A, whose official chemical name is 2,2-bis(4-hydroxyphenyl)propane, is a difunctional monomer with two reactive hydroxyl groups, as shown in Fig. 20,2. It polymerizes svith dicarbonyl organic monomers, such as phosgene or diphenyl carbonate, which are illustrated in Fig. 20.3. During polymerization, shown in Fig. 20.4, the hydroxyl groups of the bisphenol A deprotonate in the presence of a base. After deprotonation, the oxygen atoms on the bisphenol A residue form ester bonds with the dicarbonyl compounds. The polymerization process terminates when a monohydric phenol reacts with the growing chain end. 

Figure 20.4 Polymerization of polycarbonate from bisphenol A and phosgene...

At the start of interfacial polymerization, bisphenol A is dissolved in methylene chloride, then introduced into a reactor. Phosgene is injected into the reactor as a liquefied gas together with an aqueous solution of sodium hydroxide. The methylene chloride and the aqueous solutions are immiscible polymerization occurs at the interface between them. The reactants are combined in a rapidly stirred reactor as shown in Fig. 20.7. The sodium hydroxide neutralizes the hydrochloric acid that is generated by polymerization, while the organic phase serves as a solvent for the polymer. The organic phase is separated and washed to remove traces of the base or salts after which the solvent is removed. 

Fluorescence Intensities. The fluorescence from polymeric films of bisphenol A-epichlorohydrin condensate 1 (Eponol-55-B-40,... 

Figure 14.4.1 The repeating units of the monomer bisphenol A used to construct the polymeric thermoset material used in shatterproof glass.

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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