Poly aryl methylenes

Prepolymers are produced by the condensation of aryl alkyl ethers or aryl alkyl halides or other aromatic, heterocyclic, or metalloorganic compounds in the presence of Friedel-Crafts catalysts  

The prepolymers can be cross-linked with diepoxides or polyepoxides or with hexamethylene tetramine (elimination of NH3). 

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Poly(aryl ether ketone) Cone, sulfuric acid, trifluorometh-anesulfonic acid, diphenyl sulfone, sulfolane Alcohol, ether, methylene chloride... 

MC MDI MEKP MF MMA MPEG MPF NBR NDI NR OPET OPP OSA PA PAEK PAI PAN PB PBAN PBI PBN PBS PBT PC PCD PCT PCTFE PE PEC PEG PEI PEK PEN PES PET PF PFA PI PIBI PMDI PMMA PMP PO PP PPA PPC PPO PPS PPSU Methyl cellulose Methylene diphenylene diisocyanate Methyl ethyl ketone peroxide Melamine formaldehyde Methyl methacrylate Polyethylene glycol monomethyl ether Melamine-phenol-formaldehyde Nitrile butyl rubber Naphthalene diisocyanate Natural rubber Oriented polyethylene terephthalate Oriented polypropylene Olefin-modified styrene-acrylonitrile Polyamide Poly(aryl ether-ketone) Poly(amide-imide) Polyacrylonitrile Polybutylene Poly(butadiene-acrylonitrile) Polybenzimidazole Polybutylene naphthalate Poly(butadiene-styrene) Poly(butylene terephthalate) Polycarbonate Polycarbodiimide Poly(cyclohexylene-dimethylene terephthalate) Polychlorotrifluoroethylene Polyethylene Chlorinated polyethylene Poly(ethylene glycol) Poly(ether-imide) Poly(ether-ketone) Polyethylene naphthalate Polyether sulfone Polyethylene terephthalate Phenol-formaldehyde copolymer Perfluoroalkoxy resin Polyimide Poly(isobutylene), Butyl rubber Polymeric methylene diphenylene diisocyanate Poly(methyl methacrylate) Poly(methylpentene) Polyolefins Polypropylene Polyphthalamide Chlorinated polypropylene Poly(phenylene oxide) Poly(phenylene sulfide) Poly(phenylene sulfone)... 

We recently have reported our initial studies on step-growth block copolymers containing segments of poly (aryl ethers) and poly (aryl carbonates) (9,10). The multiblock [ A-B ]n block copolymers were prepared by phosgenation in methylene chloride/pyridine solution either by what was termed an in situ or by a coupled oligomer technique (JO). The choice of polycarbonates and poly (aryl ethers) for initial studies was based on the several considerations. Copolymerization is feasible since the end groups in the two oligomers can be identical, as shown in Structures 1 and 2. Considerable information is available in the... 

Fig. I. Poly-aryl m-methylene-bridged macrocyclic compounds...

The oxidation of PASs with ozone leads to the formation of poly(aryl-ene sulfoxide)s with a high selectivity. This reaction takes place although ozone is an extremely strong oxidant. Thus, an appropriate amount of ozone enables either to partially or completely convert the sulfur bond into the sulfoxide bond. ° The oxidation is carried out in an ozone/inert gas stream in which the ozone is present in a concentration of 2-6% by volume. The selection of the suspension medium has a decisive influence. In methylene chloride suspension, complete oxidation to the sulfoxide is achieved in a short time. 

Highly hindered biphenols 1 (R= CH3, Ph, Cl) were synthesized by oxidative coupling of the corresponding phenols. High molecular weight poly(aryl ether)s 3 were prepared from these biphenols by reaction with bis(4-fluorophenyl)sulfone or 4,4 -difluorobenzophenone in polar, aprotic solvents in the presence of potassium carbonate. The polymerization reactions were very slow because of the steric hindrance provided by the pendant phenyl groups in these biphenols. The polymers are amorphous and very thermooxidatively stable. They are very soluble in methylene chloride at room temperature and they can be cast into tough, flexible films. ... 

Fig. 9.59 Plot of temperature of maximum spherulite growth rate, Tmax, against equilibrium melting temperature. I m, for indicated polymers. (1) isotactic poly(styrene) (a) (2) poly(tetramethyl-p-silphenylene siloxane) (b) (3) poly(cis-isoprene) (c) (4) poly(caproamide) (d,e) (5) poly(L-lactic acid) (f) (6) poly(phenylene sulfide) (g,h) (7) poly(R-epichlorohydrin), poly(S-epichlorohydrin), poly(I-RS-epichlorohydrin) (i) (8) poly(ethylene terephthalate) (j,k,l) (9) poly(aryl ether ether ketone) (m,n) (10) poly(ethylene-2,6-naphthalene dicarboxylate) (n) (11) poly(3-hydroxybutyrate) (o) (12) isotactic poly(methyl methacrylate) (q) (13) poly(dioxolane) (r) (14) New TPI poly(imide) (s) (15) poly(methylene oxide) (t) (16) poly(cis-butadiene) (u) (17) poly(propylene oxide) (v,w) (18) poly(imide) BPDA - - 134 APB (x) (19) poly(imide) BPDA - -C12 (x) (20) syndiotactic poly(propylene) (y) (21) poly(3-hydroxy valerate) (z) (22) poly(ethylene succinate) (aa) (23) poly(aryl ether ketone ketone) (bb) (24) poly(phenylene ether ether sulfide) (cc) (25) poly(tetramethylene isophtha-late) (dd) (26) poly(hexamethylene adipamide) (e,ee) (27) poly(tetrachloro-bis-phenol-A adipate) (fQ nylon 6-10 (ee).

In the poly(alkylene arylate) series, Tm decreases with increasing length of flexible — (CH2) — moieties and, as in the aliphatic series, approaches the limiting value of polyethylene melting point for large n values (Table 2.6). Aromatic -aliphatic polyesters with even numbers of methylene groups melt at higher... 

Poly(butylene terephthalate) (PBT), because of the addition of two methylene units in the diol-derived portion, has a lower melting point than PET with a Eg of about 170°C (structure 4.49). Moldability of aryl polyesters has been improved through the use of PBT instead of PET or by use of blends of PET and PBT. These aryl polyesters are used for bicycle wheels, springs, and blow-molded containers. 

The synthetic sequence to methylene-bridged poly(phenylene)s 71 represents the first successful employment of the stepwise process to ladder-type macromolecules involving backbone formation and subsequent polymer-analogous cyclization. As shown, however, such a procedure needs carefully tailored monomers and reaction conditions in order to obtain structurally defined materials. The following examples demonstrate that the synthesis of structurally defined double-stranded poly(phenylene)s 71 (LPPP) via a non-concerted process is not just a single achievement, but a versatile new synthetic route to ladder polymers. By replacing the dialkyl-phenylenediboronic acid monomer 68 by an iV-protected diamino-phenylenediboronic acid 83, the open-chain intermediates 84 formed after the initial aryl-aryl cross-coupling can te cyclized to an almost planar ladder-type polymer of structure 85, as shown recently by Tour and coworkers [107]. 

In this text, we prefer the term arylene ether over aryl ether, in the sense that the aryl group is situated in the backbone of the polymer for example, recall the meaning of the term methylene. There are variants of this t) e of polymer, for example, poly(ether ketone sulfone)s, or poly(ether ether ketone sulfone)s. Basically, a poly(ether ketone sulfone) can be understood as a copol5mier bearing both the poly(ether ketone) moiety, and the poly(ether ketone) moiety in the backbone. This type of polymer could be dealt with either in the poly(ether ketone) chapter or in this chapter it is a matter of taste that we include this type here. Still other variants are summarized in Table 7.1. 

SCHEME 5.9 Structures of polyindenofluorene and a poly(parfl-phenyiene) with bridged pentaphenyl units (the methylene bridges can carry different aryl and alkyl substituents, for simplicity all substituents are given as R). 

In the preparation of the linear analogues, solvents such as nitrobenzene [478] and methylene chloride [479] were used. A new method capable of creating poly(ether ketone) and polyfthioether ketone) was recently disclosed by Ueda et al. [480-482]. Here, the dehydrating power of a mixture of phosphorus pentoxide and methanesulfonic acid (MSA) is the driving force for the direct polycondensation of aromatic dicarboxylic acids with aryl compounds contain-... 

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