Reactivity of norbornene esters in ring-opening metathesis polymerization initiated by a N-chelating Hoveyda II type catalyst

Kiselev, Stanislav A.; Lenev, Denis A.; Lyapkov, A. A.; Semakin, S. V.; Bozhenkova, G. S.; Verpoort, Francis; Ashirov, R. V.

doi:10.1039/c5ra25197d

Cited by 10 publications

(11 citation statements)

References 25 publications

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“…The literature shows that studies on 5-norbornene-2,3-dicarboxylic ester derivatives are important for the development of new materials, which can be verified by the relevant number of recent publications. 8,[10][11][12][13] In contrast, in this study, the use of air atmosphere makes the means more robust, being a new contribution to science.…”

Section: Discussionmentioning

confidence: 74%

“…A study using N-chelating Hoveyda II type catalyst in the ROMP of eight of norbornene-2,3-dicarboxylic acid esters demonstrated that elongation of the aliphatic substituent affected the reactivity of esters insignificantly. 13 Discoordination of the N-Hoveyda II catalyst allows a fast approach to independent monomeric units.…”

Section: Resultsmentioning

confidence: 99%

“…Demel et al 11 presented an interesting study on the influence of Grubbs' catalysts in the ROMP of (NBE-(COOCH 2 CH 3 ) 2 ), revealing superior activity of the second Grubbs' catalyst and intermediary activity of the first generation catalysts. In addition, Kiselev et al 13 have recently conducted a study with another important focus: the influence of the pendent group of 5-norbornene-2,3-dicarboxylic acid esters derived in its ROMP with 2 nd generation Hoveyda-Grubbs' catalyst.…”

Section: Introductionmentioning

confidence: 99%

“…5-Norbornene-2,3-dicarboxylic acid and its esters are vastly used as monomers in ROMP reactions. 7,8,[10][11][12][13] NBE-(COOCH 3 ) 2 and NBE-(COOCH 2 CH 3 ) 2 are examples of 5-norbornene-2,3-dicarboxylic derived acid esters presented in the literature 8,11,12 in studies of polymerization via metathesis using different metathesis catalysts. Demel et al 11 presented an interesting study on the influence of Grubbs' catalysts in the ROMP of (NBE-(COOCH 2 CH 3 ) 2 ), revealing superior activity of the second Grubbs' catalyst and intermediary activity of the first generation catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Chain Elongation Influence in Copolymerization with Different Diesters of Norbornene 2,3-Dicarboxylic Acid Monomers via ROMP under Air Atmosphere

Braga¹,

Vieira²,

Silva-Neta³

et al. 2017

J. Braz. Chem. Soc.

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Diesters of norbornene 2,3-dicarboxylic acid (NBE-(COOR) 2 ), in which R is an alkyl group, were synthesized from one-pot synthesis method with 5-norbornene-2,3-dicarboxylic acid and methanol and ethanol. The new monomers were, respectively, the dimethyl ester NBE-(COOCH 3 ) 2 and diethyl ester NBE-(COOCH 2 CH 3 ) 2 . Norbornene was mixed with these monomers at different proportions and copolymerized via ring-opening metathesis polymerization (ROMP) with 1 st generation Grubbs' catalyst. All experiments were conducted under air atmosphere to obtain the isolated polymer. Yield results show that elongation of the R group influenced the copolymerization process. At the same co-monomer proportion, the yield decreases as a function of the R group elongation. Thermogravimetric analysis (TGA) was performed and, in all cases, more than one thermal degradation process was observed. The first process was assigned to pendent group degradation, whereas the second process was assigned to main chain degradation. These thermal processes were also influenced by different elongation of the aliphatic group of the pendent chain.

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Section: Discussionmentioning

confidence: 74%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Chain Elongation Influence in Copolymerization with Different Diesters of Norbornene 2,3-Dicarboxylic Acid Monomers via ROMP under Air Atmosphere

Braga¹,

Vieira²,

Silva-Neta³

et al. 2017

J. Braz. Chem. Soc.

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“…The steric hindrances significantly decrease the reactivity of diesters with branching aliphatic radical under interaction with active form of ruthenium complex. In study [35], the researchers attempted to make a quantitative estimation of the initiation and growth constants. Table 5, the increase of aliphatic radical length leads to gradual increase of activation parameters.…”

Section: Correlations Inmentioning

confidence: 99%

Ring Opening Metathesis Polymerization

Lyapkov¹,

Kiselev²,

Bozhenkova³

et al. 2018

Recent Research in Polymerization

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In recent years, the olefins metathesis has established itself as a powerful tool for carboncarbon bonds forming and has found numerous applications in polymer chemistry. One of the important directions of metathesis is the polymerization with cycle opening. A study of new ruthenium catalysts, resistant to the many functional groups effects, has showed the possibility of synthesizing functionalized polymers with unique properties. In this chapter, reactivity and activation parameters of eight different norbornene dicarboxylic acid alkyl esters in the presence of a Hoveyda-Grubbs II catalyst for the ring opening metathesis polymerization were determined by 1 H NMR analysis in-situ. The molecules of esters differ in the aliphatic radical structure and the location of the substituent groups. Kinetic studies have shown that effective polymerization constants and activation parameters strongly depend on the monomer structure. It is shown that the elongation of the aliphatic radical does not significantly affect the reactivity, but significantly changes the activation parameters. The branching of the aliphatic radical significantly affects both the reactivity of the corresponding ester and the activation parameters of the polymerization. The position of the substituents in the norbornene ring of the ester also has a significant effect on the activation parameters of metathesis polymerization.

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A systematic study of stereochemical effects in homologous poly(alkenamer)s: Dewar benzene versus norbornene

Lee

Seo

Bielawski

2020

Journal of Polymer Science

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Two diastereomeric derivatives of norbornene, dimethyl (1R,2R,3S,4S)‐bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylate and dimethyl (1R,2S,3S,4S)‐bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylate, were synthesized and polymerized using ring‐opening metathesis polymerization (ROMP). For comparative purposes, diastereomeric derivatives of Dewar benzene, dimethyl (1R,2S,3R,4S)‐bicyclo[2.2.0]hex‐5‐ene‐2,3‐dicarboxylate and dimethyl (1R,2S,3S,4S)‐bicyclo[2.2.0]hex‐5‐ene‐2,3‐dicarboxylate, were also synthesized and polymerized using ROMP. The polymerization reactions proceeded in a controlled manner as evidenced in part by linear relationships between the monomer‐to‐catalyst feed ratios and the molecular weights of the polymer products. Chain extension experiments were also conducted which facilitated the formation of block copolymers. Although the poly(norbornene) derivatives exhibited glass transition temperatures that were dependent on their monomer stereochemistry (cis: 115°C vs. trans: 125°C), more pronounced differences were observed upon analysis of the polymers derived from Dewar benzene (cis: 70°C vs. trans: 95°C). Likewise, microphase separation was observed in block copolymers that were prepared using the diastereomeric monomers derived from Dewar benzene but not in block copolymers of the norbornene‐based diastereomers. The differential thermal properties were attributed to the relative monomer sizes as reducing the distances between the polymer backbones and the pendant stereocenters appeared to enhance the thermal effects.

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Reactivity of norbornene esters in ring-opening metathesis polymerization initiated by a N-chelating Hoveyda II type catalyst

Abstract: The reactivity and activation parameters for the ROMP of eight norbornene esters in the presence of a N-chelating Hoveyda–Grubbs II type catalyst were determined. Kinetic studies prove that these parameters highly depend on the monomer structures.

Cited by 10 publications

References 25 publications

Chain Elongation Influence in Copolymerization with Different Diesters of Norbornene 2,3-Dicarboxylic Acid Monomers via ROMP under Air Atmosphere

Chain Elongation Influence in Copolymerization with Different Diesters of Norbornene 2,3-Dicarboxylic Acid Monomers via ROMP under Air Atmosphere

Ring Opening Metathesis Polymerization

A systematic study of stereochemical effects in homologous poly(alkenamer)s: Dewar benzene versus norbornene

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