Polymerization of 1,3‐dienes containing functional groups: 8. Free‐radical polymerization of 2‐triethoxysilyl‐ 1,3‐butadiene

Abstract

The presence of a bulky substituent at the 2‐position of 1,3‐butadiene derivatives is known to affect the polymerization behavior and microstructure of the resulting polymers. Free‐radical polymerization of 2‐triethoxysilyl‐1,3‐butadiene (1) was carried out under various conditions, and its polymerization behavior was compared with that of 2‐triethoxymethyl‐ and other silyl‐substituted butadienes. A sticky polymer of high 1,4‐structure ($E:Z \approx 8:2$) was obtained in moderate yield by 2,2′‐azobisisobutyronitrile (AIBN)‐initiated polymerization. A smaller amount of Diels–Alder dimer was formed compared with the case of other silyl‐substituted butadienes. The rate of polymerization (Rp) was found to be Rp = k[AIBN]0.5[1]1.2, and the overall activation energy for polymerization was determined to be 117 kJ mol−1. The monomer reactivity ratios in copolymerization with styrene were r1 = 2.65 and rst = 0.26. The glass transition temperature of the polymer of 1 was found to be −78 °C. Free‐radical polymerization of 1 proceeded smoothly to give the corresponding 1,4‐polydiene. The 1,4‐E content of the polymer was less compared with that of poly(2‐triethoxymethyl‐1,3‐butadiene) and poly(2‐triisopropoxysilyl‐1,3‐butadiene) prepared under similar conditions. Copyright © 2010 Society of Chemical Industry

Highly Cis-1,4-Selective Living Polymerization of 3-Methylenehepta-1,6-diene and Its Subsequent Thiol–Ene Reaction: An Efficient Approach to Functionalized Diene-Based Elastomer

“…Since butadiene derivatives bearing electronically withdrawing polar groups are difficult to be synthesized, and easily dimerized to form Diels–Alder adduct during polymerization process, the (co)­polymerization of polar butadiene derivatives has been far from successful . Hirao and Takenaka reported the anionic living polymerization of a series of silicon-containing butadiene derivatives and systematically investigated the influences of polymerization conditions on the microstructure of the resulting polymer . Stadler et al opened the door to access N , N -dialkyl-2-aminomethyl-1,3-butadiene polymers through anionic and radical polymerization techniques and further quaternized the tertiary amino groups to obtain ionic polymers .…”

α,ω-Bis(trialkoxysilyl) difunctionalized polycyclooctenes from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization

“…Increasing the COE and CTA 2 loading up to 48 000 and 800 equiv, respectively, confirmed a high productivity of all ruthenium catalysts with effective turnover numbers (TONs) up to 48 000 (Table 2, entries 7-15). HG2 and G3 catalysts, the amount of CNF remained low (818wt%) (entries[16][17][18][19].…”

Synthesis of 1,3-Butadiene and Its 2-Substituted Monomers for Synthetic Rubbers

“…Sato et al [147] reported a synthetic route of 2-(triisopropoxysilyl)-l,3-butadiene in 1984; since then, this kind of functional diene has attracted wide interest. In this route, 2-(triisopropoxysilyl)-1,3-butadiene is prepared using 1,4-dichloro-2-(trichlorosilyl)-2-butene and isopropyl alcohol as starting materials (Figure 14) [148,149]. Firstly, the solution of isopropyl alcohol in triethylamine is added dropwise to a THF solution of l,4-dichloro-2-(trichlorosilyl)-2-butene ( Figure 14a) at 0 • C. After stirring overnight at 20 • C, the mixture is heated to 60 • C and kept for several hours, followed by cooling to 0 • C. Hexane is applied to precipitate the inorganic salt, which is removed using Hyflo-Super-Cel" (Johns-Manville Co.).…”