Polymeric borane catalyst

Hydrosilylation ofmethyldiundecenylailane (68) yielded hyperbranched polymer (69) having terminal olefins [40]. Subsequent hydroboration with bis(pentafluoroph-enyl) borohydride (70) gave the polymeric borane catalyst (71) [41] (Scheme 19.17). The polymeric borane was tested as cocatalyst in the metallocene-catalyzed polymerization of propylene. Activation through the polymeric borane (71) led to higher activities compared to that of B(C6Fs)3. 

Kumagai, T., Itsuno, S. Asymmetric Aiiyiation Polymerization Novel Polyaddition of Bis(allylsilane) and Dialdehyde Using Chiral (Acyloxy)borane Catalyst. Macromolecules 2000, 33,4995-4996. 

Ni catalysts for olefin polymerization incorporating a-iminocarboxamide ligands are activated by the formation of borane-carbonyl adducts (153).542 Structure/reactivity relationships are similar to Brookhart s dimine catalysts. 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

The key to highly active metallocene catalysts is the use of cocatalysts. In an activation step, the cocatalyst creates out of the metallocene a polymerization-active species. At first, methylaluminoxane (MAO) was usually used to activate metallocenes. Nowadays an alternative activation via borane and borate is becoming more and more important [20, 24, 25]. 

Cross-linked polymers bearing IV-sulfonyl amino acids as chiral ligands were converted to polymer bound oxazaborolidine catalysts by treatment with borane or bromoborane. In the cycloaddition of cyclopentadiene with methacrolein, these catalysts afforded the same enantioselectivities as their non-polymeric counterparts238. 

A Ni based catalyst for addition polymerization can be prepared from nickel(2-ethylhexanoate), methylaluminoxane, and triethyl-borane (34). The polymerization is carried out in toluene as a solvent under pressure. 

The following amine boranes are manufd by the Callery Chemical Co a)Dimethylamine-borane, (CH,)aNH BHS, wh solid b)Tri-methylamine-borane, (CHS)SN BH, wh solid e)Pyridine-borane, CBHSN BHb, col liquid These amine-boranes are relatively stable complexes and are of interest because they act as selective reducing agents, polymerization catalysts, anti-oxidants and stabilizing agents. They may also be used for the prepn of diborane and as petroleum additives. Further information may be obtained from Tech Bull C-200(Ref 2)... 

Based on the excellent solubility and reducing properties of amine boranes, they are often used for the stabilization and purification of industrial materials. Further, they are applied as additives in hydrocarbon fuels and in lubricating oils, as polymerization catalysts, as ingredients in photographic processing and in the electroplating industry.169 High stability towards hydrolysis and oxidation makes cationic boron chelates useful as water-soluble dyes.170... 

In addition to the familiar and extensive role perfluoroaryl boranes and borates fill as co-catalysts for the coordination polymerization of ethylene and a-olefins, these compounds can act as initiators for other polymerization reactions due to their high Lewis acidity. 

C to form the dinuclear (butadienyl)zirconium system 120. Treatment with B(C6F5)3 leads to the formation of a mono-addition product (121), even in the presence of excess borane. Complex 121 (Scheme 40) shows only a marginal ethene polymerization activity. This led to the notion that such formation of dimeric zirconium complexes might represent desactivation pathways in homogeneous Ziegler-Natta catalyst chemistry.125... 

In scientific and patent literature on diene polymerization the following Nd(III)-salts are most often cited as catalyst precursors halides, carboxylates, alcoholates, phosphates, phosphonates, allyl compounds, cyclopentadienyl derivatives, amides, boranes and acetylacetonates. The catalyst systems based on these Nd-sources are reviewed in the following subsections. 

Nd-boranate-based catalysts were also used in the polymerization of dienes. Nd(BH4)3 (THF)3/TEA yields poly(butadiene) with a frans/cz s-ratio 50/50. If Nd(BH4)3 (THF)3 is combined with a stoichiometric amount of MgBu2 catalyst activities are increased, control of molar masses is improved and poly(diene)s with a trans- 1,4-content of up to 99% are obtained. [348, 349]. 

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