Polyphenylene linear

Trilialophenols can be converted to poly(dihaloph.enylene oxide)s by a reaction that resembles radical-initiated displacement polymerization. In one procedure, either a copper or silver complex of the phenol is heated to produce a branched product (50). In another procedure, a catalytic quantity of an oxidizing agent and the dry sodium salt in dimethyl sulfoxide produces linear poly(2,6-dichloro-l,4-polyphenylene oxide) (51). The polymer can also be prepared by direct oxidation with a copper—amine catalyst, although branching in the ortho positions is indicated by chlorine analyses (52). 

The successful development of polyfethylene terephthalate) fibres such as Dacron and Terylene stimulated extensive research into other polymers containing p-phenylene groups in the main chain. This led to not only the now well-established polycarbonates (see Chapter 20) but also to a wide range of other materials. These include the aromatic polyamides (already considered in Chapter 18), the polyphenylene ethers, the polyphenylene sulphides, the polysulphones and a range of linear aromatic polyesters. 

Several substituted linear polyphenylenes have also been prepared but none appear to have the resistance to thermal decomposition shown by the simple poly-p-phenylene. 

Dendrimers, or arborols, or cascade, or cauliflower, or starburst polymers, were first synthesized in the early 1980s [3,4]. In 1985 Tomalia et al. [5] and Newkome et al. [6] presented the first papers dealing with dendrimers. A multitude of dendrimers have been presented in the literature ranging from polyami-doamine [7,8],poly(propylene imine) [9,10], aromatic polyethers [11-13] and polyesters [14, 15], aUphatic polyethers [16] and polyesters [17], polyalkane [18-19], polyphenylene [20], polysilane [21] to phosphorus [22] dendrimers. Combinations of different monomers as well as architectural modifications have also been presented. For example, chirality has been incorporated in dendrimers [23,24]. Copolymers of linear blocks with dendrimer segments (dendrons) [25-27] and block-copolymers of different dendrons have been described [28]. 

One of the first properties of hyperbranched polymers that was reported to differ from those of linear analogs was the high solubility induced by the branched backbone. Kim and Webster [31] reported that hyperbranched polyphenylenes had very good solubility in various solvents as compared to linear polyphenylenes, which have very poor solubility. The solubility depended to a large extent on the structure of the end groups, and thus highly polar end-groups such as carboxylates would make the polyphenylenes even water-soluble. 

The thermal stability of hyperbranched polymers is related to the chemical structure in the same manner as for linear polymers for example, aromatic esters are more stable than aliphatic ones. In one case, the addition of a small amount of a hyperbranched polyphenylene to polystyrene was found to improve the thermal stability of the blend as compared to the pure polystyrene [31]. 

The lack of mechanical strength for thermoplastic hyperbranched polymers makes them more suitable as additives in thermoplast applications. Hyperbranched polyphenylenes have been shown to act successfully as rheology modifiers when processing linear thermoplastics. A small amount added to polystyrene resulted in reduced melt viscosity [31]. (Sect> 3.1). 

Also, linear or cross-linked polyphenylene of type 599 worked efficiently as catalyst in lithiation processes from functionalized chlorinated materials, dichlorinated compounds and benzofused cyclic ethers, with lithium powder in THF at —78 °C to room temperature. Yields are similar to those obtained in solution . 

The effect of blending LDPE with EVA or a styrene-isoprene block copolymer was investigated (178). The properties (thermal expansion coefficient. Young s modulus, thermal conductivity) of the foamed blends usually lie between the limits of the foamed constituents, although the relationship between property and blend content is not always linear. The reasons must he in the microstructure most polymer pairs are immiscible, but some such as PS/polyphenylene oxide (PPO) are miscible. Eor the immiscible blends, the majority phase tends to be continuous, but the form of the minor phase can vary. Blends of EVA and metallocene catalysed ethylene-octene copolymer have different morphologies depending on the EVA content (5). With 25% EVA, the EVA phase appears as fine spherical inclusions in the LDPE matrix. The results of these experiments on polymer films will apply to foams made from the same polymers. 

Finally, just a few words dedicated to the synthesis of polyphenylenes, extremely important polymers, and in particular substituted polyphenylenes such as PPV, which exhibit superb thermal and chemical resihence, semiconduchng properties upon doping and applicahons such as OLEDs. Contrary to their linear acenes counterparts, long polyphenylenes can be obtained e.g., by Bergman s method consisting in the thermal cycloaromatization of enediynes (Lockhart et al, 1981). 

Aromatic cyclic chains are more stable than aliphatic catenated carbon chains at elevated temperatures. Thus linear phenolic and melamine polymers are more stable at elevated temperatures than polyethylene, and the corresponding cross-linked polymers are even more stable. In spite of the presence of an oxygen or a sulfur atom in the backbones of polyphenylene oxide (PPO), polyphenylene sulfide (PPS), and polyphenylene sulfone, these polymers are... 

Eq. (5) in conjunction with Eqs. (8) and (9) have, so far, provided adequate representation of experimental isotherms6 32, which are characterized by an initial con vex-upward portion but tend to become linear at high pressures. Values of K, K2 and s0 have been deduced by appropriate curve-fitting procedures for a wide variety of polymer-gas systems. Among the polymers involved in recent studies of this kind, one may cite polyethylene terephthalate (PET) l2 I4), polycarbonate (PC) 19 22,27), a polyimide l6,17), polymethyl and polyethyl methacrylates (PMMA and PEMA)l8), polyacrylonitrile (PAN)15), a copolyester 26), a polysulphone 23), polyphenylene oxide (PPO)25), polystyrene (PS) 27 28), polyvinyl acetate 29) and chloride 32) (PVAc and PVC), ethyl cellulose 24) (EC) and cellulose acetate (CA) 30,3I>. A considerable number of gases have been used as penetrants, notably He, Ar, N2, C02, S02 and light hydrocarbons. 

Femer sind eine Reihe hochmolekularer Stoffe, wie manche Polyanhydride (HS), Polystilbene (D1), Polyphenylene (M3) oder Poly-tetrafluorathylen (H2), teilweise schon von relativ niedrigen Poly-merisat ionsgraden an, in alien Losungsmitteln unloslich, obwohl sie linear aufgebaut sind. 

Diphenoqinones were concomitant products. This was the first synthesis of a linear polyphenylene ether with high enough molecular weight to have useful physical properties. 

Sulfar fibers are extruded from polyphenylene sulfide) or PPS by the melt-spinning process. The first PPS polymer was made in 1897 by the Friedel-Crafts reaction of sulfur and benzene. Researchers at Dow Chemical, in the early 1950s, succeeded in producing high-molecular weight linear PPS by means of the Ullmann condensation of alkali metal salts of p-bromothiophenol. 

Preparation and characterization of highly branched aromatic polymers, polyphenylenes, polyesters, polyethers, and polyamides, were reviewed. These polymers were prepared from condensation of AB -type monomers, which gave noncrosslinked, highly branched polymers. The polymer properties are vastly different compared to their linear analogs due to their resistance to chain entanglement and crystallization. 

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