Bisphenol A polyarylate

TABLE 2.13 Topical Properties of Ardel D-100 Bisphenol-A Polyarylate and of Liquid Crystalline Polyesters Vectra A-950 and Xydar SRT-500... 

High molar masses (Mw = 80,000-100,000)311 are reported for soluble polyesters such as bisphenol-A polyarylates, but terephthalates give much lower... 

Amorphous bisphenol-A polyarylates are soluble in dioxane and in chlorinated solvents such as CH2C12, 1,2-dichlororethane, 1,1,2-trichloroethane, and 1,1,2,2-tetrachloroethane while semicrystalline and liquid crystalline wholly aromatic polyesters are only sparingly soluble in solvents such as tetrachloroethane-phenol mixtures or pentafluorophenol, which is often used for inherent viscosity determinations. 

Ardel D-100 bisphenol-A polyarylate, 48 Arenesulfonyl chlorides, 329 Aromatic-aliphatic alternating... 

Bisphenol-A benzoxazine reaction, under acidic conditions, 416-417 Bisphenol-A polyarylates, 77 synthesis of, 109-113 Bisphenol-A polysulfone, 327 nucleophilic synthesis of, 337 Bisphenolic monomer, 354 Biurets, 227... 

The first polymer with a flexible backbone was synthesized by a process known in the literature for making bisphenol A polyaryl ether under phase transfer catalysis conditions. We used this procedure to couple BPC with l,4-dichloro-2-butene (DCB) or 1,5-dibromopentane in ort/io-dichlorobenzene (o-DCB) to yield polyethers 7 and 8 (Fig. 12). 

Abbreviations for the polymeric units in Table 2.10 (C H )- - phenyl ring, a-MS - alpha-methyl styrene, AN, acrylonitrile, BMA - butylmethacrylate, CHMA - cyclohexylmethacrylate. Cl - caprolactone, C(VC) - unit of chlorinated PVC, DNS - 2,4-dini-trostyrene-co-styrene, DTC -2,2-dimethyltrimethylenecarbonate, HFPC - hexafluoro bisphenol-A polycarbonate, MA - maleic anhydride, MMA - methylmethacrylate, PAr - unit of polyarylate, Phenoxy - unit of polyhydroxy ether of bisphenol-A, PPE - unit of poly(2,6-dimethyl-1,4-phenylene ether), S - styrene, TMPAr - unit of tetramethyl bisphenol-A polyarylate, TMPC - unit of tetramethyl bisphenol-A polycarbonate, VAc - vinyl acetate, VC - vinyl chloride, VCVAc90 - VC-co-VAc copolymer with 90 wt% VC, VME - vinylmethylether. 

The property profile (mechanical, electrical, thermal, and combustion) of Ardel D-lOO (Bisphenol A polyarylate) is listed in Tables I through IV, respectively. The dynamic mechanical data are illustrated in Figure 3 for Ardel D-lOO showing the high glass transition temperature and consistent modulus over a large temperature range. 

Another property recently reported in detail for polyarylate is in the polymer blend area. An early French patent [33] noted that Bisphenol A polyarylate and poly(ethylene terephthalate) yield interesting mixtures. Further studies by Kimura et al. [34] and Robeson [35] found that with modest ester-exchange polyarylate and poly(ethylene terephthalate) form miscible mixtures (thus transparent with Tg values between the constituent values). Polyarylate and poly(butylene terephthalate) were noted to be miscible without ester-exchange [36]. Miscibility of three different cyclohexane dimethanol based polyesters with polyarylate was observed under minimum time and temperature exposure conditions [35]. 

Guggenheim, et al demonstrated that the cyclic arylates can be polymerized at elevated temperature (360° C) in the presence of an anionic initiator. The polymerization of a cyclics/polymer mixture, which has a lower melting point, can be carried out at a somewhat lower temperature. The individual cyclics melt at about 385° C with polymerization occurring, even in the absence of catalyst. Polymerization leads to polyaiylates with wt. avg. MW of about 40-60,000, and the expected glass transition temperatures (bisphenol A polyarylate, Tg = 167° C, spirobiindane polyarylate, Tg = 242° C). 

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. 

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). 

For a part to exhibit stmctural stiffness, flexural moduH should be above 2000 N/mm (290,000 psi). Notched l2od impact values should be deterrnined at different thicknesses. Some plastics exhibit different notch sensitivities. For example, PC, 3.2 mm thick, has a notched l2od impact of 800 J/m (15 fdbf/in.) which drops to 100 J/m (1.9 fflbf/in.) at 6.4-mm thickness. On the other hand, one bisphenol A phthalate-based polyarylate resin maintains a 250-J /m (4.7-fdbf/in.) notched l2od impact at both thicknesses. Toughness depends on the stmcture of the part under consideration as well as the plastic employed to make the part. Mechanical properties, like electrical properties, ate also subject to thermal and water-content changes. 

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). 

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). 

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. 

Although many other monomers have been utilized, the typical commercial amorphous polyarylate is a polyester containing bisphenol-A units and nearly equal proportions of isophthalate and terephthalate units (Formula 2.1).6... 

Statistical copolymerization of ethylene glycol and 1,4-butanediol with dimethyl ter-ephthalate results in products with improved crystallization and processing rates compared to poly(ethylene terephthalate). Polyarylates (trade names Ardel, Arylon, Durel), copolymers of bisphenol A with iso- and terephthalate units, combine the toughness, clarity, and proce-sibility of polycarbonate with the chemical and heat resistance of poly(ethylene terephthalate). The homopolymer containing only terephthalate units is crystalline, insoluble, sometimes infusible, and difficult to process. The more useful copolymers, containing both tere- and isophthalate units, are amorphous, clear, and easy to process. Polyarylates are used in automotive and appliance hardware and printed-circuit boards. Similar considerations in the copolymerization of iso- and terephthalates with 1,4-cyclohexanedimethanol or hexa-methylene diamine yield clear, amorphous, easy-to-process copolyesters or copolyamides,... 

POLYARYLATES. These are clear, amorphous thermoplastics that combine clarity, high heat deflection temperatures, high impact strength, good surface hardness, and good electrical properties with inherent ultraviolet stability and flame retardance. No additives or stabilizers are required to provide these properties. Polyarylates are aromatic polyesters that are manufactured from various ratios of iso- and terephthalic acids with bisphenol A.1 The resultant products are free-flowing pellets which can be processed by a variety of thermoplastic techniques in transparent and... 

Synthesis. Five different polyaryl ethers were made from the condensation product, resulting from the reaction of phenol and levulinic acid, commonly referred to as diphenolic acid, and one or more of the following monomers bisphenol A, dichlorodiphenyl sulfone, 2,6-dichloro-benzonitrile, and 4,4 -difluorobenzophenone. The resulting polymers were subsequently methylated such that the common monomer becomes (1) ... 

Six more polyaryl ethers were made from 2,6-dichlorobenzonitrile (2) and one of the following monomers l,l -bis(4-hydroxy-3,5-dimethyl phenyl) cyclohexane 2,2 -bis (4-hydroxyphenyl) -2-phenyl ethane 1,3-bis(4-hydroxyphenyl)-1-ethyl cyclohexane 2- ( hydroxyphenyl)-2-[3-(4-hydroxyphenyl) -4-methyl cyclohexyl ] propane 2,2 -bis (4-hydroxy-3,5-dimethyl phenyl) propane and bisphenol A. 

To the range of engineering plastics were added polyethylene and polybutylene tereph-thalates (PET and PBT), as well as General Electric s polyethers, the PPO (polyphenylene oxide) produced through polymerization of 2,6-xylenol and the Noryl plastic produced by blending PPO with polystyrene. Other special polymers, derived like the polycarbonates from bisphenol A, were added to this range polyarylates, polysul-fones, polyetherimides. 

Kanemitsu and Einami (1990) investigated the role of the polymer on hole transport in a series of 2-(p-dipropylaminophenyl)-4-(p-dimethylaminophenyl)-5-(o-chlorophenyl)-l,3-oxazole (OX) doped polymers. The polymers were a polyarylate (PA), bisphenol-A polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene) PS, poly(vinyl chloride) (PVC), polyethylene terephthalate) (PET), and poly(vinyl butyral) (PVB). The glass transition temperatures of the polymers range from 322 (PVB) to 448 K (PA). The temporal features of the photocurrent transients were strongly dependent on the polymer. Figure 76 shows the results. The field was 4.0 x H)5 V/cm and the temperature 295 K. The transients were near rectangular for PS, PET, PA, and PMMA, and highly dispersive for PVC land PVB. This was attributed to the fact... 

A whole series of high-performance polyester LCPs was introduced in 1985. They were assembled from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Polyarylates (PARs) - amorphous phenolic esters derived from aromatic dicarboxylic acids (mixtures of terephthalic acid and isophthalic acid) and biphenols such as bisphenol A - are produced by Amoco (Ardel ), Celanese (Durel ) and DuPont (Arylon ) at a volume of approx. 2000 t/a. 

FDA has approved the use of Bisphenol A as an component used to make polyarylate or 4,4 -Isopropylidenediphenol-epichlorohydrin resins to be used for single and repeated use food contact surfaces as outlined in 21CFR177, Parts 1440 and 1555. OSHA PEL in Shipyards ceiling concentration 0.5 ppm (2.8 mg/m3). 

Bisphenol A is used in large quantities for fabrication of epoxy resins, polycarbonates and polyarylates. 

A plot of the logarithim of the oxygen permeability coefficients versus the reciprocal of the SFVs, as proposed by Lee, shows a fair correlation between these values. Data for the polyetherimides and polyarylates (Figure 3) is meager, but does allow some general conclusions to be drawn. The model does apparently overestimate the permeability for the bisphenol A based PEI 24. In addition, the fit of the polyarylate data with the calculated model is favorable except for an overestimation of the permeability of the bis(4-hydroxy-... 

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