Poly Benzocyclobutenes

Another approach adopts a two-step process processable prepolymers are synthesized, and then the prepolymers are cured to drive the polymerization reaction to higher conversions, initiating network formation. Chemically, this 

In the late 1970s, Kirchhoff at Dow Chemical Company developed the use of benzocyclobutenes in polymer synthesis and modification. These efforts culminated in 1985 with the issuance of the first patent describing the use of benzocyclobutene in the synthesis of high-molecular-weight polymer.27 Similar work that involved a thermosetting system based on Diels-Alder cycloaddition between terminal benzocyclobutene and alkyne groups,28,29 was reported separately and independently by Tan and Arnold.28 Since these initial discoveries, the field of benzocyclobutene polymers has expanded rapidly and benzocyclobutene chemistry constitutes the basis of a new and versatile approach to the synthesis of high-performance polymers for applications in the electronics and aerospace industries.30 

Although the mass of the fluorinated benzocyclobutene analogue is significantly higher than that of the hydrocarbon it should be noted that the incorporation of fluorine often enhances the volatility of derivatives beyond the expected levels, e.g., tetrafluorobenzocyclobutene with a mass of 176 boils only 10° higher than o-xylene with a mass of 106 (153°C vs. 143°C). 

By comparision of the calculated carbon ratios and those determined from XPS data, it can be seen that the number of fluorine atoms is lower than the theoretical value, and is approximately C (C—C or C—H)  

Before fluorination, the dielectric constant ofpoly(bisbenzocyclobutene) was 2.8, and this value was reduced to 2.1 after plasma treatment. No data were reported in the paper on characterization of structure or properties, except for the dielectric constant of the modified poly(bisbenzocyclobutene). The authors did report that the thermal stability offluorinatedpoly(vinylidenefluoride) was inferior to the original poly(vinylidenefluoride) when treated in a similar way. One of the probable reasons for the low thermal stability is that the NF3 plasma degraded the polymer. According to their results, the thickness of fluorinated poly(bisbenzo-cyclobutene) was reduced by 30%. The same phenomenon was observed for other hydrocarbon polymers subjected to the NF3 plasma process. A remaining question is whether plasma treatment can modify more than a thin surface layer of the cured polymer Additionally, one of the side products generated was hydrogen fluoride, which is a serious drawback to this approach. 

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Alternative polymers that have certain advantages over polyimides have also been introduced they include poly(phenylquinoxaline), poly(phenylquinoline), and poly(benzocyclobutenes) (PBCBs) (93,116). The PBCBs have a low curing temperature (250 °C), low dielectric constant (2.6), low dissipation factor (0.0045), and low moisture absorption (0.3%) The development of specialty polymers for packaging and high-density interconnections will continue to be an active area of research as polymer manufacturers focus on the needs of the microelectronic industry. 

TABLE 12. Poly cycles through benzocyclobutene ring opening... 

Using a fluorinated benzocyclobutene-based monomer (Figure 18.4) should provide at least one advantage over the already promising properties of fluorinated poly(j9-xylylene). All the desirable properties such as low dielectric constant and low affinity for water should remain but the thermal stability should be enhanced because of the cross-linking that would accompany the generation of these films. The synthesis and polymerization paths for poly(octafluorobisbenzocyclobutene) are depicted in Scheme 5. 

The structure formed through a linear addition of the molecules is Shown at the top of the illustration. The benzocyclobutene groups on either end of the BCB terminated resin molecules react with two other BCB groups as shown to form a poly(o-xylyene) strands. With BCB reactive groups present at both ends of the resin molecules, a double strand of poly(o-xylyene) is formed which is bridged by the aromatic imide chains. 

An alternative polymerization mechanism and polymer architecture has been proposed by Kirchhoff [1, 2, 3], Tan and Arnold [77], By this mechanism, polybenzocyclobutenes which do not contain reactive sites of unsaturation are proposed to polymerize by the 1,4 addition of the o-quinodimethane intermediates to give a substantially linear poly(o-xylylene) structure. Since the monomers all contain at least two benzocyclobutene units the net result of this reaction will to a first approximation be a ladder type polymer as shown in Fig. 17. The formation of a true ladder polymer however would require that all... 

A novel cure chemistry employed for addition poly(imides) has recently been published. The successful preparation of 4-aminobenzocyclobutene allowed the synthesis of benzocyclobutene-terminated imide oligomers and bisfbenzocylobutenes) (17). The benzocyclobutene group is a latent diene which isomerizes to o-guinodimethane at temperatures of about 200 °C and may homo- and/or co-polymerize for example with bismaleimide (83). Details on the benzocyclobutene chemistry are described in chapter I of this book. 

BPAC-BCB2 Poly(bisphenol-A carbonate - bis benzocyclobutene). 

Poly(divinylsiloxane - bis benzocyclobutene) Poly(diketone - bis benzocyclobutene) Poly(bisphenol-A carbonate - bis benzocyclobutene)... 

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