Polymerization of aliphatic disubstituted acetylenes by MoOCl4–n‐Bu4Sn–EtOH catalyst: Formation of polymers with narrow MWDs and confirmation of the living character

Kubo, Hideki; Hayano, Shigetaka; Masuda, Toshio

doi:10.1002/1099-0518(20000801)38:15<2697::aid-pola90>3.3.co;2-f

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“…[5] Recently we found that living polymerization of "internal" alkynes such as 2-nonyne proceeds in the presence of the same catalyst when using anisole as the solvent. [6] This background prompted us to carry out the polymerization of diyne monomers, particularly diethyl di-2-butynyl malonate ((EtOCO) 2 C(CH 2 CCMe) 2 , DEDBM), by using our molybdenum-based ternary catalysts. The present study reveals that living polymerization of DEDBM does indeed proceed in the presence of suitable MoOCl 4 -based catalysts.…”

Section: Introductionmentioning

confidence: 99%

Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

Kubo¹,

Hayano²,

Misumi³

et al. 2002

Macromol. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

Kubo¹,

Hayano²,

Misumi³

et al. 2002

Macromol. Chem. Phys.

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“…As an alternative to MoCl 5 -derived initiators, we investigated the use of MoOCl 4 -based systems. With such systems, living polymerizations of various 1-alkynes have already been reported, [23][24][25][26][27] nevertheless, the use of a MoOCl 4 -based initiator for the cyclopolymerization of DEDPM only resulted in gel-type polymers so far. 28 Our investigations started with MoOCl 4 -n-Bu 4 Sn-EtOH (1:1:2).…”

Section: Resultsmentioning

confidence: 99%

First Controlled Cyclopolymerization of Diethyl Dipropargylmalonate by MoCl₅−n-Bu₄Sn−EtOH−Quinuclidine and MoOCl₄−n-Bu₄Sn−EtOH−Quinuclidine To Give Highly Regular Polyenes Consisting Exclusively of 1,2-(Cyclopent-1-enylene)−Vinylene Units

et al. 2003

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Diethyl dipropargylmalonate (DEDPM) was cyclopolymerized by MoCl 5-n-Bu4Sn-EtOHquinuclidine (1:1:5:1) and MoOCl4-n-Bu4Sn-EtOH-quinuclidine (1:1:2:1), respectively, to produce poly-(DEDPM) exclusively based on 1,2-(cyclopent-1-enylene)vinylene units (EtOH ) ethanol). The exact ratio of five-to six-membered rings was determined by quantitative 13 C NMR measurements. The initiator efficiency of MoOCl4-n-Bu4Sn-EtOH-quinuclidine (1:1:2:1) was as high as 91%, the highest value ever reported for such systems, whereas the efficiency for the corresponding MoCl5-based initiator was e67%. The absorption maximum λmax for poly(DEDPM) was 587 nm. A maximum effective conjugation length (Neff) of 49 was estimated therefrom. Molecular weights and polydispersity indices (PDIs) of the polymers were determined in CHCl3 by size exclusion chromatography (SEC) vs polystyrene (PS). Additionally, light-scattering (LS) data were collected at λ ) 690 nm in order to calculate absolute molecular weights. Polydispersities e1.9 were obtained. A plot of number of monomers (N) added vs molecular weights as determined by LS shows a linear dependence for both initiators. Multistage polymerizations of DEDPM indicated for both initiator systems that the catalytic species were active for at least 6 h in the presence of monomer yet do not fulfill the criteria of a truly living polymerization. The 1 H NMR spectrum of the in situ prepared MoCl5-based initiator showed two triplet carbene resonances at δ ) 11.27 and 11.02 ppm, indicating the presence of more than one butylidene species. Accordingly, the 13 C NMR spectrum of the MoCl5-based initiator showed carbene resonances at δ ) 276.0, 275.9, 272.4, 271.3, 262.7, and 261.6 ppm. Identical triplet resonances were observed for the MoOCl4-based initiator at δ ) 11.27 and 11.07. The corresponding 13 C NMR spectrum revealed carbene resonances at δ ) 276.1, 262.7, and 261.6 ppm.

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Polymerization of aliphatic disubstituted acetylenes by MoOCl4–n‐Bu4Sn–EtOH catalyst: Formation of polymers with narrow MWDs and confirmation of the living character

Cited by 2 publications

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Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

First Controlled Cyclopolymerization of Diethyl Dipropargylmalonate by MoCl₅−n-Bu₄Sn−EtOH−Quinuclidine and MoOCl₄−n-Bu₄Sn−EtOH−Quinuclidine To Give Highly Regular Polyenes Consisting Exclusively of 1,2-(Cyclopent-1-enylene)−Vinylene Units

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Polymerization of aliphatic disubstituted acetylenes by MoOCl4–n‐Bu4Sn–EtOH catalyst: Formation of polymers with narrow MWDs and confirmation of the living character

Cited by 2 publications

References 0 publications

Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

Living Metathesis Polymerization of Diethyl Di-2-butynyl Malonate by Molybdenum-Based Ternary Catalysts

First Controlled Cyclopolymerization of Diethyl Dipropargylmalonate by MoCl5−n-Bu4Sn−EtOH−Quinuclidine and MoOCl4−n-Bu4Sn−EtOH−Quinuclidine To Give Highly Regular Polyenes Consisting Exclusively of 1,2-(Cyclopent-1-enylene)−Vinylene Units

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First Controlled Cyclopolymerization of Diethyl Dipropargylmalonate by MoCl₅−n-Bu₄Sn−EtOH−Quinuclidine and MoOCl₄−n-Bu₄Sn−EtOH−Quinuclidine To Give Highly Regular Polyenes Consisting Exclusively of 1,2-(Cyclopent-1-enylene)−Vinylene Units