Polymerization hydroboration

Figure 7 Some 77-conjugated fluorescent organoboron polymers (7) synthesized by the hydroboration polymerization reaction. (Adapted from ref. 27.)...

In one of their notable examples, the hydroboration polymerization of low molecular weight allyl-telechelic polyisobutylene with tripylborane (trip = 2,4,6-triisopropylphenyl) was found to yield air-stable organoboron segmented block copolymers. These boron main-chain polymers (8) (Fig. 8), unlike the general ones, were stable to air. The stability was due to the steric hindrance of the bulky tripyl groups preventing oxygen attack of the borons.28... 

Figure 8 The air-stable 77-conjugated organoboron segmented block copolymer (8) obtained by the hydroboration polymerization of allyl-telechelic polyisobutylene, 1,9-decadiene, and tripylborane. (Adapted from ref. 28.)...

Hydroboration polymerization between diene monomers and 2,4,6-trimethylphenylborane (mesitylborane)6 or 2,4,6-triisopropylphenylborane (tripyl-borane)7 gave organoboron main-chain polymers (scheme 3). The polymerization was... 

B. Reactions of Organoboron Polymers Prepared by Hydroboration Polymerization... 

The preparation of a functional segmented block copolymer was also investigated (scheme ll).15 First hydroboration polymerization of the oligomer using thexylborane was carried out. Then the obtained organoboron polymer was subjected to a chain-transformation reaction (DCME rearrangement). DCME and lithium alkoxide of 3-ethyl-3-pentanol in hexane was added to a THF solution of the polymer at 0°C. 

Conjugated boron polymers containing platimnn or palladium atom in the main chain were also prepared by hydroboration polymerization between tetrayne/ metal complex monomers and tripylborane (scheme 16).30 From gel permeation chromatographic analysis [THF, polystyrene (PSt) standards], the number-average molecular weights of the polymers obtained were found to be 9000. The polymers were soluble in common organic solvents such as THF, chloroform, and benzene. The absorption peaks due to tt-tt transition were observed around 390 nm in the UV-vis spectra of these polymers. The fluorescence emission spectra exhibited intense peaks at 490 nm in chloroform. 

E. Poly(cyclodiborazane)s Prepared by Hydroboration Polymerization of Dicyano Monomers... 

Generally, during hydroboration polymerization of dicyano compounds, the formation of the borazine structures that have a six-membered boron-nitrogen ring (scheme 19a) and dihydroborated end groups (scheme 19b) as a structural defect is unavoidable. The borazine cross-linked structures often cause the gelation, and dehydroboration causes a decrease in molecular weight. 

The organoboron polymer complex was prepared as follows. First, poly(organoboron halide)55 was prepared according to the reported method, by hydroboration polymerization between 1,7-octadiene and the monobromoborane dimethylsuffide complex. The polymer obtained was then reacted with half an equivalent of methanol and 1-methylimidazole to give the corresponding copolymer efficiently (scheme 4). The structure of the polymer was characterized by H- and UB-NMR spectra. 

A variety of organoboron polymer electrolytes were successfully prepared by hydroboration polymerization or dehydrocoupling polymerization. Investigations of the ion conductive properties of these polymers are summarized in Table 7. From this systematic study using defined organoboron polymers, it was clearly demonstrated that incorporation of organoboron anion receptors or lithium borate structures are fruitful approaches to improve the lithium transference number of an ion conductive matrix. 

M. Matsumi, K. Naka, and Y. Chujo, Extension of ir-conjugation length via the vacant p-orbital of the boron atom. Synthesis of novel electron deficient ir-conjugated systems by hydroboration polymerization and their blue light emitting, J. Am. Chem. Soc., 120 5112-5113, 1998. 

N. Matsumi, M. Miyata, and Y. Chujo, Synthesis of organoboron Tr-conjugated polymers by hydroboration polymerization between heteroaromatic diynes and mesitylborane and their light emitting properties, Macromolecules, 32 4467-4469, 1999. 

Table 1. Hydroboration Polymerization of Aromatic Diynes Using Mesilylborane. ...

---