Bisphenol manufacture

The Brominated Flame Retardants Industry Panel (BFRIP) was formed ia 1985 within the Flame Retardant Chemicals Association (FRCA) to address such concerns about the use of decabromodiphenyl oxide. Siace 1990 the BFRIP has operated as a Chemical Self-Funded Technical Advocacy and Research (CHEMSTAR) panel within the Chemical Manufacturers Association (CMA) (64). As of 1993, members of BFRIP are Ak2o, Amerihaas (Dead Sea Bromine Group), Ethyl Corp., and Great Lakes Chemical. Siace its formation, BFRIP has presented updates to iadustry on a regular basis (65,66), and has pubhshed a summary of the available toxicity information on four of the largest volume brominated flame retardants (67,68) tetrabromo bisphenol A, pentabromodiphenyl oxide, octabromodiphenyl oxide, and decabromodiphenyl oxide. This information supplements that summarized ia Table 11. 

Polycarbonates. Currently, all audio CDs (CD-AD), all CD-ROM, and the biggest fraction of substrate disks for WORM and EOD worldwide are manufactured from a modified bisphenol A—polycarbonate (BPA-PC) (3). In 1991, some 1.3 x 10 compact disks were produced, equivalent to an annual amount of about 35,000 t BPA-PC. WORM and EOD disks are manufactured mainly from BPA-PC for sizes of 5.25 in. and below, and glass for larger form factors (eg, 12 in.), partially also from BPA-PC, and in some cases from aluminum or from cross-linked polymers (epoxy resins) (190). 

Polycarbonates are prepared commercially by two processes Schotten-Baumaim reaction of phosgene (qv) and an aromatic diol in an amine-cataly2ed interfacial condensation reaction or via base-cataly2ed transesterification of a bisphenol with a monomeric carbonate. Important products are also based on polycarbonate in blends with other materials, copolymers, branched resins, flame-retardant compositions, foams (qv), and other materials (see Flame retardants). Polycarbonate is produced globally by several companies. Total manufacture is over 1 million tons aimuaHy. Polycarbonate is also the object of academic research studies, owing to its widespread utiUty and unusual properties. Interest in polycarbonates has steadily increased since 1984. Over 4500 pubflcations and over 9000 patents have appeared on polycarbonate. Japan has issued 5654 polycarbonate patents since 1984 Europe, 1348 United States, 777 Germany, 623 France, 30 and other countries, 231. 

These solvents include tetrahydrofuran (THF), 1,4-dioxane, chloroform, dichioromethane, and chloroben2ene. The relatively broad solubiHty characteristics of PSF have been key in the development of solution-based hoUow-fiber spinning processes in the manufacture of polysulfone asymmetric membranes (see Hollow-fibermembranes). The solvent Hst for PES and PPSF is short because of the propensity of these polymers to undergo solvent-induced crysta11i2ation in many solvents. When the PES stmcture contains a small proportion of a second bisphenol comonomer, as in the case of RADEL A (Amoco Corp.) polyethersulfone, solution stabiHtyis much improved over that of PES homopolymer. 

Process Raw Material. Industrial solvents are raw materials in some production processes. Eor example, only a small proportion of acetone is used as a solvent, most is used in producing methyl methacrylate and bisphenol A. Alcohols are used in the manufacture of esters and glycol ethers. Diethylenetriamine is also used in the manufacture of curing agents for epoxy resins. Traditionally, chlorinated hydrocarbon solvents have been the starting materials for duorinated hydrocarbon production. 

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

Thioglycohc acid is recommended as a cocatalyst with strong mineral acid in the manufacture of bisphenol A by the condensation of phenol and acetone. The effect of the mercapto group (mercaptocarboxyhc acid) is attributed to the formation of a more stable carbanion intermediate of the ketone that can alkylate the phenol ring faster. The total amount of the by-products is considerably reduced (52). 

Benzene is alkylated with propylene to yield cumene (qv). Cumene is catalytically oxidized in the presence of air to cumene hydroperoxide, which is decomposed into phenol and acetone (qv). Phenol is used to manufacture caprolactam (nylon) and phenoHc resins such as bisphenol A. Approximately 22% of benzene produced in 1988 was used to manufacture cumene. 

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). 

The acetone supply is strongly influenced by the production of phenol, and so the small difference between total demand and the acetone suppHed by the cumene oxidation process is made up from other sources. The largest use for acetone is in solvents although increasing amounts ate used to make bisphenol A [80-05-7] and methyl methacrylate [80-62-6]. a-Methylstyrene [98-83-9] is produced in controlled quantities from the cleavage of cumene hydroperoxide, or it can be made directly by the dehydrogenation of cumene. About 2% of the cumene produced in 1987 went to a-methylstyrene manufacture for use in poly (a-methylstyrene) and as an ingredient that imparts heat-resistant quaUties to polystyrene plastics. 

Another important bisphenol is dichlorophene (dichlorophane, methylene-bis(4-chlorophenol)) [97-23-4]. Whereas it is not as active against bacteria as hexachlorophane, it has found miscehaneous apphcations, eg, as a rot preservative for textiles (89) as a treatment for athlete s foot and for tapeworm in humans and domestic animals as a slimicide in paper manufacture and as an antibacterial agent in water-cooling systems (90). 

The manufacture of the majority of fluorocarbon elastomer gums includes the addition of an incorporated cure system comprising an organic onium cure accelerator, such as triphenylbenzylphosphonium chloride [1100-88-5] and a bisphenol cross-linking agent, such as... 

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. 

Bisphenol F epoxy resins are used in high-soHds-high-build systems such as tank and pipe linings, industrial floors, road and bridge deck toppings, stmctural adhesives, grouts, coatings, and electrical varnishes. Bisphenol F epoxy resins are manufactured in Europe and Japan. 

In addition to electrical uses, epoxy casting resins are utilized in the manufacture of tools, ie, contact and match molds, stretch blocks, vacuum-forrning tools, and foundry patterns, as weU as bench tops and kitchen sinks. Systems consist of a gel-coat formulation designed to form a thin coating over the pattern which provides a perfect reproduction of the pattern detail. This is backed by a heavily filled epoxy system which also incorporates fiber reinforcements to give the tool its strength. For moderate temperature service, a Hquid bisphenol A epoxy resin with an aHphatic amine is used. For higher temperature service, a modified system based on an epoxy phenol novolak and an aromatic diamine hardener may be used. 

While phenol is the most common monomer for novolac manufacture, it is far more common to see incorporation of other phenolic materials with novolacs than with resoles. Cresols, xylenols, resorcinol, catechols, bisphenols, and a variety of phenols with longer alkyl side chains are often used. While most resoles are made with a single phenolic monomer, two or more phenolic materials are often seen in novolac formulae. These additional monomers may be needed to impart special flow characteristics under heat, change a glass transition temperature, modify cure speed, or to adjust solubility in the application process among others. 

Staples, C.A. (1998). Analysis of Surface Water Receiving Streams for Bisphenol A Manufacturing and Processing Sites, Technical Report to Bisphenol A TaskGroup by the Society of the Plastics Industry, Inc., Washington, D.C. 

Virtually all epoxy resins are made with starting materials based on epichlorohydrin, principally by reaction with bisphenol A. It is also used for the preparation of resins to increase the wet strength of paper. Both epichlorohydrin and glycidol are used in the manufacture of pharmaceuticals. 

Taking the manufacture of polycarbonates as an example, two manufacturing routes are shown in Scheme 3.1. In the first route phosgene is reacted with bisphenol A in dichloromethane. The main environmental concern with this process is the large-scale use of phosgene. In the second... 

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... 

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). 

Paper mill whitewaters and effluents are rich in bisphenol A (BPA), which is used in great quantities for the production of epoxy resins and polycarbonate plastics. Its presence in effluents has been reported as a result of its use in the manufacture of thermal paper or due to migration from plastic containers at the high water temperatures of whitewaters [35]. This compound is preferably analysed by GC-MS. The levels encountered in paper mill effluents are between 28 and 72 pg/L [36,37]. Another study revealed levels up to 226 pg/L [33]. Special in vitro test systems and animal experiments have demonstrated a weak oestrogenicity for BPA. Since aquatic wildlife could be endangered by paper mill waste discharges at the concentration that BPA is found, its survey in paper mill effluents should be taken into consideration. 

Bisphenol A-derived epoxy resins, 10 356 Bisphenol A epoxy novolacs, 10 370 Bisphenol A manufacture, microporous catalysts and, 14 420 Bisphenol A moiety, 10 355-356 Bisphenol A polycarbonate (BPA-PC),... 

Micropore diffusion, 1 596, 597-599 Microporous catalysts, in bisphenol A manufacture, 14 420 Microporous metal membranes, 15 813t Microporous particles, apparent effective diffusivity and, 15 729-730 Microporous range, pore diameters within, 16 812... 

Precautionary action to reduce the exposure of humans and wildlife to the oestrogenic plastics intermediate bisphenol A looks closer following an EC technical meeting in March. Member States rejected risk assessments put forward by the UK which set aside evidence of low-dose effects on fish and laboratory animals. Bisphenol A is an important plastics intermediate used in polycarbonates and epoxy resins. Global manufacturing capacity stands at two million tonnes per year. 

Bisphenols is a broad term that includes many chemicals with the common chemical structure of two phenolic rings joined together by a bridging carbon. Bisphenol A is a monomer widely used in the manufacture of epoxy and phenolic resins, polycarbonates, polyacrylates and corrosion-resistant unsaturated polyester-styrene resins. It can be found in a diverse range of products, including the interior coatings of food cans and filters, water containers, dental composites and sealants. [4]. BPA and BP-5 were selected for testing by the whole... 

Phenol is both a man-made chemical and produced naturally. It is found in nature in some foods and in human and animal wastes and decomposing organic material. The largest single use of phenol is as an intermediate in the production of phenolic resins. However, it is also used in the production of caprolactam (which is used in the manufacture of nylon 6 and other synthetic fibers) and bisphenol A (which is used in the manufacture of epoxy and other resins). Phenol is also used as a slimicide (a chemical toxic to bacteria and fungi characteristic of aqueous slimes), as a disinfectant, and in medicinal preparations such as over-the-counter treatments for sore throats. Phenol ranks in the top 50 in production volumes for chemicals produced in the United States. Chapters 3 and 4 contain more information. 

Bisphenol A (BPA) (Figure 14.1a) is a starting substance utilized in the manufacture of most types of epoxy resins, which are then crosslinked and used to coat food cans. Another application of BPA is in the manufacture of plastic materials, in particular polycarbonates. BPA serves also as an antioxidant or stabilizing material for many types of plastics, e.g., polyvinyl chloride (PVC). 

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