4,4 - -bisphenol Copolymerization

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). 

Recently, the pyrazole group containing bisphenols have been synthesized from activated aromatic dihalides and 3,5-bis (4-hydroxy phenyl)-4-phenyl pyrazole or 3,5-bis(4-hydroxy phenyl)-1,4-diphenyl pyrazole. A novel synthesis of imido aryl containing bisphenols has been reported [32]. N-substituted l,4-bis(4-hydroxy phenyl)-2,3-naphthalimides were prepared from phenolphthalein and copolymerized with aromatic sulfone or ketone difluorides to obtain the poly(imidoaryl ether) sulfones/ ketones. 

Structure of bisphenol-A polycarbonate copolymerized with 3% by weight of labile groups... 

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. 

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]. 

The formation of relatively ill-defined catalysts for epoxide/C02 copolymerization catalysts, arising from the treatment of ZnO with acid anhydrides or monoesters of dicarboxylic acids, has been described in a patent disclosure.968 Employing the perfluoroalkyl ester acid (342) renders the catalyst soluble in supercritical C02.969 At 110°C and 2,000 psi this catalyst mixture performs similarly to the zinc bisphenolates, producing a 96 4 ratio of polycarbonate polyether linkages, with a turnover of 440 g polymer/g [Zn] and a broad polydispersity (Mw/Mn>4). Related aluminum complexes have also been studied and (343) was found to be particularly active. However, selectivity is poor, with a ratio of 1 3.6 polycarbonate polyether.970... 

As described earlier, the choice of bisphenols for the polymerization of poly(arylene ether ketone)s is large. In particular, the electrochemical properties of the above monomer copolymerized with bisphenol AF were studied. The fundamental PEM characteristics (water uptake and conductivity) were analogous to those of the BPSH systems for a given lEC. 

Three poly(aryl ethers) were prepared and used as coblocks in imide copolymerizations. The first coblock prepared was poly(aryl ether phenylquinoxaline), since this material has the requisite high Tg ( 280 °C) and thermal stability, and the polymer can be processed from solution or the melt. The synthesis of po-ly(aryl ether phenylquinoxalines) involves a fluoro-displacement polymerization of appropriately substituted fluorophenylquinoxalines with bisphenols, us-... 

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,... 

In a similar way as has been described for syntheses of type al, the majority of examples of type b involve polycondensation of a,ea bifunctional, small molecule reaction partners. Some examples are the reaction of AIBN or AIBN derivatives with 1,4-cyclohexane bismethyl diamine78), 1,2-ethylene diamine78), 1,6-hexamethylene diamine 78-80 , bisphenol A 78,81 and mono-, di- and tetraethylene glycol 55-64 . In almost all case using the AIBN derivative 4,4 -azobis(4-cyano valeryl chloride), an interfacial polymerization was employed. These polymeric azo compounds could be used as initiators for radical block copolymerizations. 

A survey of the extensive literature of kinetic results reported for epoxy-anhydride-tertiary amine systems is surprising. Both nth order and autocatalytic expressions have been reported for the same system. As an example, we analyze the results reported for the copolymerization of a diepoxide based on diglycidyl ether of bisphenol A (DGEBA) with methyl-tetrahydrophthalic anhydride (MTHPA), initiated by benzyldimethylamine (BDMA). 

Poly(bisphenol-A-carbonate) under pseudoideal reaction conditions was investigated, and the cyclic polycarbonate was obtained as the main product. In the system, the interface of the water/toluene mixture might have favored the cyclization reaction between the polar end groups [88]. Cyclic carbonates during the (Salen)CrCl catalyzed CCh/cyclohexene oxide copolymerization process in the presence of ionic initiators was also obtained [89]. The cyclic carbonate is produced via the backbiting mechanism, and the process is assumed to take place via a metal alkoxide (polymer chain) intermediate. Subsequent ring-opening of the cyclic carbonate with concomitant formation of polyether and CO2 was fast at the reaction temperatures from 80 to 100 °C). 

Diaryl phthalides, particularly phenolphthalein 281 and several phthalides derived from it, are widely used for the preparation of cardo polymers. The term is derived from the latin word for hinge or pivot, which is an apt name given that the aryl substituents are hinged on the C-3 carbon of the phthalide. In one application, compound 281 was used to prepare phthalamide 282 and both bisphenols were copolymerized with terephthaloyl chloride 283 to form polyesters. These formed strong flexible fdms with improved thermal stability and solubility <1997PSA3227>. 

The telechelica,(i -bis(2,6-dimethylphenol)-poly(2,6-dimethylphenyl-ene oxide) (PP0-20H) [174-182] is of interest as a precursor in the synthesis of block copolymers [175] and thermally reactive oligomers [179]. The synthesis has been accomplished by five methods. The first synthetic method was the reaction of a low molecular weight PPO with one phenol chain end with 3,3, 5,5 -tetramethyl-l,4-diphenoquinone. This reaction occurred by a radical mechanism [174]. The second method was the electrophilic condensation of the phenyl chain ends of two PPO-OH molecules with formaldehyde [177,178], The third method consists of the oxidative copolymerization of 2,6-dimethylphenol with 2,2 -di(4-hydroxy-3,5-di-methylphenyl)propane [176-178]. This reaction proceeds by a radical mechanism. A fourth method was the phase transfer-catalyzed polymerization of 4-bromo-2,6-dimethylphenol in the presence of 2,2-di(4-hy-droxy-3,5-dimethylphenyl)propane [181]. This reaction proceeded by a radical-anion mechanism. The fifth method developed was the oxidative coupling polymerization of 2,6-dimethylphenol (DMP) in the presence of tetramethyl bisphenol-A (TMBPA) [Eq. (57)] [182],... 

Difunctional cyanate ester monomers were discovered 30 years ago by Ernst Grigat, an organic chemist now retired from Bayer of Levetkusen, Germany, who was also the first to succeed in making organic cyanate esters at all. Bayer licensed dicyanate/polycyanurate technology to Mitsubishi Gas Chemical Co., Tokyo, and to the then Celanese Corp., New York City. Mitsubishi improved the resin by copolymerization of bisphenol A dicyanate with the bis-(maleimide) of 4,4 -methylenedianiline. 

N-heterocyclic carbene/palladium complexes were successfully used as catalysts in the copolymerization of bisphenol and carbon monoxide (Scheme 29)... 

Highly crosslinked polymers are commonly produced from epoxy materials such as diglycidyl ether of bisphenol A (DGEBA). DGEBA is easily copolymerized with various substances such as amines or anhydrides. Copolymerization of DGEBA with a monoamine yields linear polymer chains. When DGEBA is copolymerized with a diamine, polymer chains crosslink. 

Copolymeric aromatic polyesters, though possessing a somewhat lower level of heat resistance are easier to fabricate than are the wholly aromatic polymers they also possess many properties that make them of interest as high-temperature materials. These materials, called polyarylates, are copolyester of terephthalic acid, and bisphenol A in the ratio of 1 1 2. 

Nitrile-functional, (hexafluoroisopropylidene)diphenol-basedpoly(ar-ylene ether) copolymers with pendent sulfonic acid groups can be prepared by the copolymerization of 4,4 -(hexafluoroisopropyUdene)diphenol, 2,6-dichlorobenzonitrile, and 3,3 -disulfonate-4,4 -dichlorodiphenyl sulfone. Hexafluoroisopropylidene)diphenol is a fluorinated bisphenol A. 

Several 2,2, 6,6 -tetrachloro-4,4 -dihydroxy bisphenols were subjected to random copolymerization with bisphenol A at two levels of incorporation. Copolymerization of TCBF with isomeric chlorinated bisphenols was also carried out. 

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