Synthesis of 4-tert-butyldimethylsilyloxystyrene and its copolymerization with styrene using (η5-indenyl)trichlorotitanium in the presence of methylaluminoxane

Abstract

SUMMARY: Poly(styrene-co-4-tert-butyldimethylsilyloxystyrene) as a precursor of hydroxyl-functionalized syndiotactic polystyrene was successfully synthesized via (g 5 -indenyl)trichlorotitanium (IndTiCl 3 )-catalyzed copolymerization of styrene with 4-tert-butyldimethylsilyloxystyrene in toluene at 25 8C in the presence of methylaluminoxane (MAO) ([Al]/[Ti] = 2 000). The amount of styrene derivative incorporated into the polymeric chain for a 20,7 : 1 mole feed ratio of styrene to 4-tert-butyldimethylsilyloxystyrene was found to be 1,8 mol-% from a 1 H NMR analysis. The styrene derivative was successfully prepared from 4-hydroxybenzaldehyde via first protecting the hydroxyl group using tert-butyldimethylchlorosilane followed by the 'Wittig-type' reaction with the 'Tebbe' reagent. The yield was about 82 wt.-% on the basis of the initial amount of 4-hydroxybenzaldehyde used.

Syndiospecific Coordination Polymerization of Si‐H‐Containing Styrenes Catalyzed by Scandium Complex and Synthesis of Styrene‐Based Triblock Copolymers

“…One involves functionalized styrene containing polar group, the other involves functionalized styrene containing reactive group. To date, through the direct polymerization, some polar functional groups such as amino, silyloxy, methoxy, methylthio, and halogen groups have been successfully introduced into sPS to improve its properties. But the direct polymerization of such styrene derivatives is still limited to the combination of polar groups with specific catalyst systems, because the strong Lewis acid–base interaction between polar groups and catalyst centers extremely restricted polymerization stereoselectivity and activity.…”

Precisely Controlled Polymerization of Styrene and Conjugated Dienes by Group 3 Single‐Site Catalysts

“…For example, 4‐ tert ‐butyldimethylsilyloxystyrene was reported to copolymerize with styrene catalyzed by ( η 5 ‐indenyl)trichlorotitanium (IndTiCl 3 ) with methylaluminoxane (MAO) in toluene at 25 °C. The incorporation degree of substituted St in copolymer was only 1.8 % . The copolymerization of 4‐aminostyrene, 4‐aminomethylstyrene, and 4‐[B‐( n ‐butylene)‐9‐BBN]styrene etc.…”

Engineering of Syndiotactic and Isotactic Polystyrene-Based Copolymers via Stereoselective Catalytic Polymerization

“…Murata and co-workers described the synthesis of syndiotactic diblock sP( p -Me)S- b -s( p -HO)S material obtained via sequential block copolymerization of p -methylstyrene and 4-( tert -butyldimethylsilyloxy)styrene (TBDMSS) catalyzed by 14a /B(C 6 F 5 ) 3 /Al(Oct) 3 and subsequent desilylation of the resulting P(TBDMSS) block [ 81 ]. The synthesis of diblock sPS- b -sP(TBDMS)S using (Ind)TiCl 3 ( 13 )/MAO was also described; however, no deprotection of the silyl group was performed on this copolymer [ 82 ].…”