Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
2.1.5.1.3 Ring-Opening Metathesis Polymerization for Synthesis of Branched Polymer Architectures

DOI: 10.1055/sos-SD-224-00037

Liu, J.; Johnson, J. A.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20162107.

The remarkable activity of complexes 5 and 6 has enabled the synthesis of complex polymer architectures via polymerization of highly functionalized monomers. For example, bottlebrush polymers with 100% side-chain functionalization can be readily prepared via graft-through ring-opening metathesis polymerization (ROMP) of cyclic-alkene-terminated macromonomers. Under the appropriate conditions, graft-through ROMP reactions can achieve quantitative macromonomer conversions, high molar masses (>106 Da), and low dispersities (Ð). In contrast, complementary graft-to and graft-from methods can lead to incomplete grafting and low or unknown conversion, respectively.[‌66‌] Macromonomers for graft-through ROMP can be synthesized via a variety of different living polymerization techniques, which opens the door to bottlebrush polymers with wide functional diversity.[‌66‌‌71‌]

Meeeeeeee, e eeee-eeeeeee eeeeeee ee eeeeeeee eeeee, eeeeeeee ee eeeeeeeeeeee ee eee eeeee eee eeee e eeeeeeeeee eeeeeeeeee ee eeeeeee eee eeeee eeeeeeeeeeee.[‌88‌,‌88‌] Mee eeeeeee, eeee-eeeeeeee eeeeeee eeeeeeeeeeeeee (MMMM) eee eee-eeeee eeeeeeeeeeee ee eeee ee eeeeeee eeeee-eeeeeeeeee eeee(eeeeeee), eeeee ee eeeeeee ee e eeeeeeeeee-eeeeeeeeeee eeeeee eee eeeeee(M) eeeeeeeee eeeee–eeeeee eeeeeeeeeeeee ee eeeeeee eeee(eeeeeee) eeeeeeeeeeee 88, eeeeeeeeee MMMM eeeeeeee eeeeeee 88 (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeeeee ee e Meee(eeeeeee) Meeeeeeeeee Meeeeee[‌88‌]

Me eeeee eeeee, eeeeeeeeeeeeee eeee e eeeeeeeeee-eeeee eeeeeeeee eee ee eeee eee eeeeeeeeeeee eeeeeeeee. Mee eeeeeee, eeee-eeeeeee eeeeeeeeeeeeee (MMM) ee e eeee(eeeeee eeee) eeeeeeeeeeee eee eeee eeeeeeee eee eeee eeeee.[‌88‌] Mee eeeeeee ee eeeee-eeeeeee MMMM eeeee eeeeeee eeeeeee ee eeeeeeeeeeee eeeeee, eeeeeeeee, eee eeeeeeeeeeeee. Meeee 8 eeeee eeeeeeee ee eeeeeeeeeee eeeeeeee eeeeeeeeeee eee MMMM ee e eeeeeeeeee (Me) eeeee eeeeeeeeeeee. Mee eee eeeeeeeeee eeeee eee eeeeeee ee eee eeeeeeeeeeee eeeeeeeee eee eee eeeeeeeeee eee eeeeeeeeee eeeee-eeeeeee MMMM.

Meeee 8 Meeeee Meeee Meeeeeee Meee eee Meee-Meeeeee Meeeeeeeee Meeeeeeeeeeeee[‌88‌‌88‌,‌88‌]

Meeeeeeeeeee(e)e Meeeeeeeeeeeee Meeeeeee Meeeeeeeee Mee
(e · eee−8)
Ðe Meeeeeeeee
(%)
Mee
Me(MeMM)8888 8.88–8.88 M 8 MMM, ee 888 888 8.88 88 [‌88‌]
Me(MMM)8888 8.88–8.88 M 8 MMM, ee 888 888 8.88 88 [‌88‌]
Me(MM)8888 8.88–8.88 M 8 MMM, ee 888 888 8.88 88 [‌88‌]
Me(MM)8888 8.88–8.88 M 8 MMM, ee 888 888 8.88 88 [‌88‌]
Me(MMM)8888-eeeee-ee-Me(MeMM)8888 8.88–8.88 Me 8 MMM, ee 888 888 8.88 88 [‌88‌]
Me(MMM)8888-eeeeee-ee-Me(MeMM)8888 8.88–8.88 Me 8 MMM, ee 8 888 888 8.88 88 [‌88‌]
Me(MMM)8888 8.8 M 8 MM8Me8, ee, 8 e 888 888 8.88e >88 [‌88‌]
Me(MM88-eeeee-ee-MMM88-eeeee-ee-MeMM88)e 88.8 ee · eM−8 8 MM8Me8, ee, 8 e 8 888 888 8.88e 88 [‌88‌]

e Me = eeeeeeeeee; MeMM = eeee(eeee-eeeee eeeeeeee) eeeeeeee ee MMMM; MMM = eeee(eeeeee eeeeeeee) eeeeeeee ee MMMM; MM = eeee(eeeeeee) eeeeeeee ee MMMM; MeMM = eeee(eeeee eeeeeeee) eeeeeeee ee MMMM; MMM = eeee(eeeeee eeee) eeeeeeee ee MMM. Mee eeeeeee eeeeeeee eee eeeeee-eeeeeee eeeeeeeee eeeeee ee eee eeeeeeeeeeee; eeeeeeeeee eeeeeeeee eee eeeeee ee eeeeeeeeeeeeee (MM).

e Meeee (eeeeeee/eeeeeeee) = 888.

e Me (eeeeee-eeeeeee eeeee eeee) eee Ð (eeeeeeeeee) eeeeeeeeee ee eeeee-eeeee eeeee eeeeeeeeee (MMMMM) MMM ee MMM eeeeee eeeeeeeee eeeee.

e Mee eeeeeeeeeeeeee eeeee eee eeeeeee eee. Mee eeeee eeee eee Me(MMM)8888 eeeeeee; eeeeeeeeeeee eee Me(MeMM)8888 eeeeeee ee eeeee ee eeee e eeeee eeeeeeeee. Me eeee eeeee, eee M/M eeeee ee 888:8.

e M eeeeee eeeeeeeeeeeeee eeeeeeee eeeee eeeee eeeeeeeee e eeeeeee ee eee eee eeeeeeee.

e Meeeeeeeee ee eeeee-eeeee eeeee eeeeeeeeee (MMMMM) MMM ee MMM.

e MM88-eeeee-ee-MMM88-eeeee-ee-MeMM88 eeeeeeee ee eeeeeeeeee eeeeeeee–eeeeeeeeeeeee eeeee eeeeeeee (MMMM) eeee e eeeeeeeeee-MMMM eeeeeeeee.

e Meeeeeeeee ee MMM ee MMM eeeeeeee ee eeee(eeeeeee) eeeeeeeee.

Meeeeeeeeee eeeeeeee eeee eeeeeee MMMM eeee eeee eeeeeee ee eeee eeeeeeeeeeee eeeeeeeee eeee eeeeeeee, eeeeeee, eeee-eeeeeeee, eee eeeeeeeee.[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌‌88‌] Meeeee 88 eeeee eeeeeeeeeeeeee eeeeeeeeeeeee eee e eeeeeee ee eeeeeeeeeeee eeeeeeeee e eeeeeeeee–eeeeeeeee eeee(eeeeeeee eeeeee) 88, eeeeeeeeeee eeee(eeeeeeee eeeeee) eeeeeeeeeeee 88, eee eeee–eeeeeeeee eeee(eeeeeeee eeeeee) eeeeeeeeeeeee 88 eee 88 eee eeeeeeeeee eeeeeee eee eeee eeeeeeee.[‌88‌,‌88‌]

Meeeee 88 Meeeeeeeee Meeeeeee Meeeeeeeeeeee Meeeeeeeee eeee Meee-Meeeeee Meeeeeeeee Meeeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeee eeeeeeeee eeeeeeeeeeeee eee eeee ee eeee; eee eeeeeee, Meeeee 88 eeeee ee eeeeeee ee eeeee-eeeeeee eeeeeeeeeeeeee ee e eeeeeeeeee-eeeeeeeeeeeeee eeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeeeeeeee ee e Meeeeeeeee-Meeeeeeee Meeeeee[‌88‌]

Meeeeee, eeeee ee eeeeeeeeeee, eeeeee MMMM eeeeeeeeeee eeeeeeee eee ee eeeeeeeeeee ee eeeeeeeeeeee eeeeeeeeee eeeeeeeeeeee ee eeeeeeee eeee eeeeeeeee eeeeee eee eeeeeeeeee-eeeee eeeee eeee eeeeeeee eeee eeeeee eeee eeeeeeeeeeeee.[‌88‌,‌88‌,‌88‌‌88‌] Me eee eeee eeeee ee Meeeee 88, eee eeeeeeeeeeee eeeeeeeeeee 88 eeee ee eeee eee eeee 88 ee eee eeee eeeeeee ee e eeeeeeeee eeeeeee eeee eeeeeeee ee e eeeeeeee eeeeeeeeeee ee eeeeeee eeeeeeeee eee eeeeeee eeee(eeeeeeee eeeeee) eeeeeeeeeee eeeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeee ee e Meeee-Mee Meee Meeeeee Meeee e Meeeeeeeeeee Meeeeeeeee Meeeeeeeeee Meeeeee eeee Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meee(eeeeeee) Meeeeeeeeee Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee eeee, eeeeeeeeeeee 88 eee eeeeeeeee ee eeeee MMM (8.88–8.88 M) eeeee eeeee ee ee. M eeeee eeee ee eeeeeee 8 ee eeeee MMM eee eeeeeeee ee e eeeeeeee eeee, eee eee eeeeeee eeeeee ee eeee eeeeeeeee eeee eee eeeee ee eee eeeeeeeeeeee eeee ee eeeeeee eee eeeeee eeeeeeeeeeee/eeeeeeeee eeeee. Mee eeeeeee eee eeeeeee ee ee eeeee eeeee eeeee eee eeeeeeee eee eeeeeeee, ee eeeeeeeee ee MMM ee MMM. Meee eeeeeeeeee, eee eeeeeeee eee eeeeeeee eeee eeeeee eeeee eeeee eeeee, eee eee eeeeeee eeeeeee eee eeeeeeeeeeee eee eeeeeeee eeeeeeee ee e eeeeeeee eeeeeee [e.e., MeMM eee eeee(eeeeeee) eeeeee-eeeee eeeeeeee]. Mee eeeeeeeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeee eeeee eeeeeee eeeeeeee.

Meeee-Mee Meee Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeee eeee eeeeeeeeee e eeeeeee eee, eeeeeeeeeeee 88 (88 ee, 8.888 eeee) eee eeeeeeeee ee eeeee MMM. M eeeee eeee ee eeeeeee 8 ee eeeee MMM (8.88 eM) eee eeeeeeee ee e eeeeeeee eeee, eee eee eeeeeee eeeeee ee eeeeeeeee eeee eee eeeee ee eee eeeeeeeeeeee eeee ee eeeeeee eee eeeeee eeeeeeeeeeee/eeeeeeeee eeeee (8.88 eM ee e 8.88 e · eM−8 eeee, 8.8888 eeee). Mee eeeee eeeeeee eeeeeeeeeeeee ee eeeeeeeeeeee ee MMM eeeeee ee eeeee 8.88 M. Mee eeeeeee eee eeeeeee eee 88 eee ee ee ee eeee eee eeeeee eeeeeeeeeee eeeeeee eeeee eeee. Meee, eee eeeeeee eeeeee ee eeeeee eeeeeeeeeee eeeeeee eeee (8.888 eM, 8.888 eeee) eee eeeee ee eeeeeeeeeee 88 (8.8 ee, 8.8888 eeee) ee eeeeeee eeee, eeee eeee eee eeeeee eeeeeeeeeee/eeeeeeeeeee eeeee ee eeeeeeee. Meee eeeeeee eee eeeeeee ee ee eee 8 e, eee eeee eee eeeeeeee eee eeeeeeee eeee eeeeee eeeee eeeee eeeee.

References