Cocatalyst <i>versus</i> precatalyst impact on the vinyl-addition polymerization of norbornenes with polar groups: looking at the other side of the coin

Bermesheva, Evgeniya V.; Nazarov, Ivan V.; Kataranova, Ksenia D.; Khrychikova, Anna P.; Zarezin, Danil P.; Melnikova, Elizaveta K.; Asachenko, Andrey F.; Topchiy, Maxim A.; Rzhevskiy, Sergey A.; Bermeshev, Maxim V.

doi:10.1039/d1py01039e

Cited by 12 publications

(6 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, it has been demonstrated that (NHC)Pd-based systems cat-alyze vinyl-addition polymerization of various functionalized norbornenes [14][15][16][17][18][19][20][21]. For instance, these systems showed good catalytic activity in polymerization of norbornenes with hydroxy [20,22], ether [21], ester [14,15,[18][19][20]23,24], imide [14,16,17], silyl [14,19,20,24], and alkyl/alkenyl [19,20,22,24,25] functionality. At the same time, to the best of our knowledge, the polymerization of norbornene-type monomers with reactive halogen-containing groups over (NHC)Pd-catalysts has not yet been reported.…”

Section: Vinyl-addition Polymerization Of 5-bromoalkylnorbornenesmentioning

confidence: 99%

“…The molecular weights of such polymers were usually insufficient to cast freestanding and robust polymer films. Recently, it has been demonstrated that (NHC)Pdbased systems catalyze vinyl-addition polymerization of various functionalized norbornenes [14][15][16][17][18][19][20][21]. For instance, these systems showed good catalytic activity in polymerization of norbornenes with hydroxy [20,22], ether [21], ester [14,15,[18][19][20]23,24], imide [14,16,17], silyl [14,19,20,24], and alkyl/alkenyl [19,20,22,24,25] Intriguing results were obtained when studying the polymerization of M1-M4 on these (NHC)Pd-catalysts.…”

Section: Vinyl-addition Polymerization Of 5-bromoalkylnorbornenesmentioning

confidence: 99%

See 1 more Smart Citation

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups

Lunin,

Andreyanov,

Makarov

et al. 2023

Polymers

Self Cite

View full text Add to dashboard Cite

Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer’s reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst’s nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (Mn up to 1.4 × 106). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.

show abstract

Section: Vinyl-addition Polymerization Of 5-bromoalkylnorbornenesmentioning

confidence: 99%

Section: Vinyl-addition Polymerization Of 5-bromoalkylnorbornenesmentioning

confidence: 99%

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups

Lunin,

Andreyanov,

Makarov

et al. 2023

Polymers

Self Cite

View full text Add to dashboard Cite

show abstract

“…The influence of the cocatalyst was largely determined by the nature of the utilized monomer. The obtained polymers exhibited satisfactory film‐forming properties 6 . In addition, diverse functionalized polynorbornenes, which are not realizable via the conventional post‐polymerization functionalization or the direct polymerization strategies, were also synthesized through the vinyl‐addition copolymerization of norbornene and alkenyl‐norbornenes by employing α‐substituted benzylic complexes of palladium (II) catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…The obtained polymers exhibited satisfactory film-forming properties. 6 In addition, diverse functionalized polynorbornenes, which are not realizable via the conventional post-polymerization functionalization or the direct polymerization strategies, were also synthesized through the vinyl-addition copolymerization of norbornene and alkenyl-norbornenes by employing α-substituted benzylic complexes of palladium (II) catalysts. The incorporation of desired functional groups into the polymer skeleton was further accomplished through hydrosilylation or hydroboration reactions.…”

Section: Introductionmentioning

confidence: 99%

Shedding light on the poly(5‐ethylidene‐2‐norbornene) microstructural differences: Skeleton rearrangements during polymerization

Omidvar,

Mansouri,

Mortazavi

et al. 2023

J of Applied Polymer Sci

View full text Add to dashboard Cite

Here, an attempt is made to study one of the less noticed aspects of the polymerization of 5‐ethylidene‐2‐norbornene (ENB) by nickel α‐diimine catalysts. Therefore, several (co)polymerization runs using MMAO‐activated binuclear catalyst (BNC) and mononuclear catalyst (MNC) were undertaken. Catalyst activities as high as 561.1 and 925.0 (kgpol mol−1Ni h−1) were observed for ENB polymerization by MNC and BNC, respectively. However, the utilization of comonomer (norbornene [NB]) led to a dramatic decline in the catalyst activities, reaching low levels of 69.4 and 144.4 (kgpol mol−1Ni h−1), respectively. Structural characterization (NMR and FTIR) corroborated the occurrence of ring opening via β‐C elimination and the subsequent β‐H elimination. Additionally, tandem transannular polymerization and ring‐opening metathesis polymerization of ENB were evidenced. The findings demonstrated that the transannular polymerization prevailed during the polymerization, albeit the MNC catalyst showed a higher contribution of ring opening via β‐C elimination. Importantly, comonomer (NB) was displayed to alter the governing polymerization mechanism. According to DMTA analysis, the structures of the monomer and catalyst were found to significantly influence the polymer damping behavior and microstructure heterogeneity. That is, the NB‐ENB copolymer obtained by MNC exhibited the lowest Tg value and highest tan δ along with the diminished microstructure heterogeneity.

show abstract

“…Recently, we have shown that two-and three-component systems based on N-heterocyclic carbene Pd-complexes ((NHC)Pd-complexes) with allyl ligands exhibited high catalytic activity, good tolerance to functional groups, and catalyzed VAP of various norbornenes in air. 55,56 Based on these results and taking into account the literature data indicating that cationic Pd-complexes with a Pd−C bond, a labile ligand, and a weak coordinating anion can serve as onecomponent VAP catalysts, we have developed a set of cationic (NHC)Pd(allyl)-complexes as new one-component VAP catalysts. The synthesized complexes had a good stability in air in solutions and in the solid state, which made it possible to carry out polymerization in air.…”

Section: ■ Introductionmentioning

confidence: 99%

Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes

et al. 2022

Self Cite

View full text Add to dashboard Cite

Well-defined single-component and tolerant Ru-, Mo-, and W-catalysts have been earlier developed for ring-opening metathesis polymerization of norbornene and its derivatives. Another way of norbornene polymerization�vinyl-addition polymerization (VAP)�is a more thermodynamically favorable process and gives polymers with saturated and rigid main chains. Single-component catalysts for VAP are required, which combine good activity, tolerance to functional groups, resistance to oxygen, and air moisture and are capable of catalyzing living VAP of norbornenes. Herein, we have shown that cationic Pd-complexes with N-heterocyclic carbene ligands (NHC ligands) and weak coordinating anion ligands ([(NHC)Pd(allyl)L] + A − , where allyl is an allyl group, L = CO, CH 3 CN, CH 2 Cl 2 , and A − = SbF 6 − or BARF − ) are highly efficient single-component catalysts for VAP of both norbornene and various substituted norbornenes. These complexes, being stable in the solid state and in solutions, have exhibited several important features as VAP catalysts. They are capable of catalyzing VAP of norbornenes in air and are tolerant to functional groups. The complexes have shown high catalytic activity and have allowed polymerizing monomers at very low catalyst loadings, as low as 2 ppm. The versatility of [(NHC)Pd(allyl)L] + A − complexes as catalysts of VAP has been demonstrated by successful polymerization of monomers with polar and bulky groups, containing alkyl, vinyl, alkylidene, ether, ester, imide, or organosilicon motifs, affording high-molecular-weight products in good and high yields. Tuning the nature of NHC and allyl ligands in [(NHC)Pd(allyl)L] + A − complexes let perform living VAP, yielding block copolymers.

show abstract

Cocatalyst versus precatalyst impact on the vinyl-addition polymerization of norbornenes with polar groups: looking at the other side of the coin

Abstract: Polymers derived from norbornenes with polar groups are of interest as modular templates and materials for membrane processes and microelectronic applications due to the attractive combination of their properties. However,...

Cited by 12 publications

References 36 publications

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups

Shedding light on the poly(5‐ethylidene‐2‐norbornene) microstructural differences: Skeleton rearrangements during polymerization

Air-Stable Single-Component Pd-Catalysts for Vinyl-Addition Polymerization of Functionalized Norbornenes

Contact Info

Product

Resources

About