Xylylenes

Several studies have concerned the microstnicture of lamellae in materials such as the block copolymers polystyrene-h/oc/r-poly-l-vinylpyridine [139] and polystyrene-h/oc/r-polybutadiene [140], as well as single crystals of poly-para-xylylene [139], and reveal features (such as intersecting lamellae (figure Bl.19.29)) that had not been previously observed. 

Two efficient syntheses of strained cyclophanes indicate the synthetic potential of allyl or benzyl sulfide intermediates, in which the combined nucleophilicity and redox activity of the sulfur atom can be used. The dibenzylic sulfides from xylylene dihalides and -dithiols can be methylated with dimethoxycarbenium tetrafiuoroborate (H. Meerwein, 1960 R.F. Borch, 1968, 1969 from trimethyl orthoformate and BFj, 3 4). The sulfonium salts are deprotonated and rearrange to methyl sulfides (Stevens rearrangement). Repeated methylation and Hofmann elimination yields double bonds (R.H. Mitchell, 1974). 

PX forms j xylylene when heated above 1200°C. The stmctuie of J-xylylene is represented by a i)-quinoid stmcture or as a i)-ben2enoid brtadical. Condensation yields poly(p-xylylene) (19—22) (see Xylene polymers). 

When the pyrolysis gases are quenched with a molar excess of iodine vapor, a yield of greater than 50% -xylylene diiodide is recovered. The observation of this effect offered the first direct chemical support for the idea that DPX pyrolysis results in PX (1) (3). 

Moreover, where i r-acetjldi- -xyljlene [10029-00-2]( is pyroly2ed, by adjusting temperatures in the deposition region, it is possible to isolate two different polymeric products, ie, poly(acetyl-/)-xylylene) [67076-72-6] (8) and poly(p-xylylene) (PPX) (2). This of course requires the cleavage of the original dimer into two fragments. 

A particularly useful property of the PX monomer is its enthalpy of formation. Conventional means of obtaining this value, such as through its heat of combustion, are, of course, excluded by its reactivity. An experimental attempt was made to obtain this measure of chemical reactivity with the help of ion cyclotron resonance a value of 209 17 kJ/mol (50 4 kcal/mol) was obtained (10). Unfortunately, the technique suffers from lack of resolution in addition to experimental imprecision. It is perhaps better to rely on molecular orbital calculations for the formation enthalpy. Using a semiempirical molecular orbital technique, which is tuned to give good values for heat of formation on experimentally accessible compounds, the heat of formation of /5-xylylene has been computed to be 234.8 kj/mol (56.1 kcal/mol) (11). 

Successful />Xylylene VDP Monomers. Within the limits mentioned above, it is frequentiy possible, and often desirable, to modify the /5-xylylene monomer by attaching to it certain substituents. Limitations on such modifications He ia three areas reactivity, performance ia the coater, and cost. 

Fig. 3. Isolatable y)-xylylene derivatives (12), Thiele s hydrocarbon - 1904 [26392-12-1] (13), tetracyanoquiuodimethane [1518-16-7] (TCNQ) (14), tetrakis(methoxycarbonyl)-quiaodimethan [65649-20-9]-, (15), tetrakis(ethy1sii1fony1)quinodimethan [84928-90-5].

It is also possible to iaterfere with the polymerization by attaching at the alpha positions either too many groups, or groups which are too bulky. Four chlorine atoms (12) or four methyl groups (13) seem to be sufficient to hinder the production of polymer. These crowded -xylylene monomers can be polymerized, but not through a VDP process. 

The widely used Parylene C owes its popularity ptincipaHy to the room temperature volatiUty of its monomer. The Parylene C monomer, chloro-A-xylylene, has become the de facto performance standard. By comparison, the Parylene N monomer, A"xylylene itself, is too volatile and would perform better ia a sub-ambient temperature deposition system. The Parylene D monomer, dichloro-A-xyljlene [85586-88-5] is too heavy, and causes distribution problems ia larger deposition systems. 

Manufacture. For the commercial production of DPXN (di-/)-xylylene) (3), two principal synthetic routes have been used the direct pyrolysis of -xylene (4, X = Y = H) and the 1,6-Hofmaim elimination of ammonium (HNR3 ) from a quaternary ammonium hydroxide (4, X = H, Y = NR3 ). Most of the routes to DPX share a common strategy PX is generated at a controlled rate in a dilute medium, so that its conversion to dimer is favored over the conversion to polymer. The polymer by-product is of no value because it can neither be recycled nor processed into a commercially useful form. Its formation is minimised by careful attention to process engineering. The chemistry of the direct pyrolysis route is shown in equation 1 ... 

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