Bisphenol acetone

Toughness Enhancement by Introduction of Silicone Blocks into Polycarbonates of Bisphenol Acetone and Bisphenol Fluorenone... 

Two families of transparent polycarbonate-silicone multiblock polymers based on the polycarbonates of bisphenol acetone (BPA) and bisphenol fluorenone (BPF) were synthesized. Incorporation of a 25% silicone block in BPA polycarbonate lowers by 100°C the ductile-brittle transition temperature of notched specimens at all strain rates silicone block incorporation also converts BPF polycarbonate into a ductile plastic. At the ductile-brittle transition two competing failure modes are balanced—shear yielding and craze fracture. The yield stress in each family decreases with silicone content. The ability of rubber to sustain hydrostatic stress appears responsible for the fact that craze resistance is not lowered in proportion to shear resistance. Thus, the shear biasing effects of rubber domains should be a general toughening mechanism applicable to many plastics. 

The para and ortho positions of phenols condense at the carbonyl group of acetone to make bisphenols, eg, bisphenol A, 4,4 -(l-methylethyhdene)bisphenol [80-05-07]). If the H atom is activated, CICH— compounds add to the carbonyl group in the presence of strong base chloroform gives chloretone (l,l,l-trichloro-2-methyl-2-propanol [57-15-8]). 

Bisphenol A. One mole of acetone condenses with two moles of phenol to form bisphenol A [80-05-07] which is used mainly in the production of polycarbonate and epoxy resins. Polycarbonates (qv) are high strength plastics used widely in automotive appHcations and appHances, multilayer containers, and housing appHcations. Epoxy resins (qv) are used in fiber-reinforced larninates, for encapsulating electronic components, and in advanced composites for aircraft—aerospace and automotive appHcations. Bisphenol A is also used for the production of corrosion- and chemical-resistant polyester resins, polysulfone resins, polyetherimide resins, and polyarylate resins. 

The yield of hydroquinone based on bisphenol A is close to 90%. The phenol and the acetone formed can easily be recycled. However, this process has not been industrialized. 

Methyl Isobutyl Ketone. Methyl isobutyl ketone (MIBK) (4-methyl-2-pentanone), (CH2)2CHCH2COCH2, is an industrially important solvent which after methyl methacrylate and bisphenol A is the third largest tonnage product obtained from acetone. 

The most important commercial chemical reactions of phenol are condensation reactions. The condensation reaction between phenol and formaldehyde yields phenoHc resins whereas the condensation of phenol and acetone yields bisphenol A (2,2-bis-(4-hydroxyphenol)propane). PhenoHc resins and bisphenol A [80-05-7] account for more than two-thirds of U.S. phenol consumption (1). 

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. 

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). 

Fig. 1. Catalytic cycle for synthesis of bisphenol A from phenol and acetone in the presence of a dissociated mineral acid (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. 

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. 

For commercial application, diepoxides such as those derived from bisphenol A are employed, and they are cured via ring-opening crosslinking reactions, into which the epoxy group enters readily. Bisphenol A is so-called because it is formed from two moles of phenol and acetone (Reaction 1.7). 

They are also important chemical intermediates. For example, acetone is used to make methyl methacrylate (the starting material for Plexiglas and Lucite plastics), methyl isobutyl ketone, and Bisphenol A (used in epoxy and polycarbonate resins). 

Almost all of the isopropylbenzene produced is used for making phenol and acetone. The largest use of acetone is as a chemical intermediate to methyl methacrylate and along with phenol to make bisphenol A for preparation of polymers. Acetone is also used widely as a solvent. 

Epoxy resins are widely used in high-strength adhesives, corrosion-resistant coatings, and corrosion-resistant pipes and tanks. The simplest starting material for these thermoset polymers is made from phenol, acetone (to bisphenol A), and epichlorohydrin. 

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. ... 

Miller et al. (1981) studied the kinetics of the reaction of phenol and acetone to bisphenol A in the presence of hydrogen chloride (see Fig. 5.4-31) in an isothermal batch reactor. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

CT-BISA [Chiyoda Thoroughbred bisphenol-A] A catalytic process for making Bisphenol-A from phenol and acetone. The catalyst is an acidic ion-exchange resin. The product is used for making polycarbonate resins. Developed and offered by Chiyoda Corporation, Japan. The first plant was operated in Tobata, Japan, in 1997. 

The solubility is generally improved by the introduction of fluorine atoms into aromatic condensation polymers. Poly(carbonate)s containing hexafluoroisopropylidene units are much more soluble than Bisphenol A poly(carbonate) (3). All of the hexafluoroisopropylidene-unit-containing poly(carbonate)s become soluble in acetone, ethyl acetate, chloroform, and dimethyl sulfoxide (DMSO) in addition to the solvents of Bisphenol A poly(carbonate) (3). Colorless, transparent, and flexible films are prepared from hexafluoroisopropylidene-unit-containing poly(carbonate)s by casting or pressing. 

Bisphenol-A-derived poly(formal) (6) shows poor solubility and is only soluble in dichloromethane, chloroform, THF, HMPA, and NMP. However, poly(formal)s containing the Bisphenol AF moiety are easily soluble in a wide variety of organic solvents, such as acetone, ethyl acetate, benzene, toluene,... 

The use of maleic anhydride as a compatiblizer between wood particles and bisphenol A-based polyesters resins has been investigated (Han etal., 1991). In this study, the MA was added directly to the composition of woody matrix filler and resin rather than by pre-modification of the wood. It was found that composite properties were improved by addition of MA, probably due to esterification of the wood occurring during the kneading process. The modification of sawdust using maleic anhydride has been performed in order to provide a compatible filler for polyester resins (Marcovich etal., 1996). Modification was performed at room temperature using a solution of maleic anhydride in acetone, in some cases catalysed with sulphuric acid. It was claimed that bonding occurred under these mild conditions from IR spectroscopic evidence only. 

Ketones.have the characteristic -C- signature group imbedded in them. Acetone, CH3COCH3, comes from two different routes. It is a by-product in the cumene to phenol/acetone process. It is the on-purpose product of the catalytic dehydrogenation of isopropyl alcohol. Acetone is popular as a solvent and as a chemical intermediate for the manufacture of MIBK, methyl methacrylate, and Bisphenol A. 

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