Studies on the Charge-Transfer Complex and Polymerization. XVII. The Reactivity of the Charge-Transfer Complex in Alternating Radical Copolymerization of Vinyl Ethers and Maleic Anhydride

Kokubo, T; Iwatsuki, Shouji; Tamashita, Yuya

doi:10.1021/ma60006a005

Cited by 124 publications

(39 citation statements)

References 6 publications

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“…K and E were 0.44 and 172.5 for MAn, 0.96 and 107.4 for CAn, and 0.59 and 58.1 for IAn, respectively. Equilibrium constants for these pairs were from 0.1-1.0, which were classified to groups of spontaneous alternating copolymerization near/at room temperature reported by Yamashita et al 31 …”

Section: Charge Transfer Complex (Ctc) Formationmentioning

confidence: 94%

“…90%) relative to trans 1,4-structure. 31 In the IR spectra of copolymer la, only a strong peak at 1657 ( VH-C=c-H) was observed, indicating that the polymers mostly consist of cis 1,4-structure because the peak of trans 1,4-structure may appear at 1675. These results strongly suggested that alternating copolymerization of BdTMS and MAn took place via the CTC complex.…”

Section: Copolymerization Of Bdtms or Bdtbdms With Manmentioning

confidence: 95%

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Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides

Takasu

Inoue

Inai

et al. 2001

Polym J

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ABSTRACT:1-Silyloxy-1,3-dienes, i.e., 1-butadienyloxytrimethylsilane (BdTMS) or 1-butadienyloxytertbutyldimethylsilane (BdTBDMS) and unsaturated cyclic anhydrides, containing maleic anhydride (MAn), citraconic anhydride (CAn), and itaconic anhydride (!An) were found to form charge transfer complexes (CTC) in benzene. Equilibrium constants, K, of the complexes were calculated by the Benesi-Hildebrand equation using UV spectroscopy to be 0.4 -1.0. Spontaneous copolymerizations of silyloxydienes with unsaturated cyclic anhydrides were established from 25 to 75 mol% of BdTMS in the feed. All polymers obtained had molar composition of 50/50 irrespective of feed molar ratios. Interestingly, molar ratio of 1,4-and 3,4-addtion structure seems to be influenced by K of CTC. Desilylation and successive lactonization of poly(BdTMS-alt-MAn) were conducted. Conversions of lactonization were beyond Flory's limit (86.5%) being nearly 100% due to intramolecular reactions of neighboring hydroxyl groups and cyclic anhydride in alternating copolymers.

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Section: Charge Transfer Complex (Ctc) Formationmentioning

confidence: 94%

Section: Copolymerization Of Bdtms or Bdtbdms With Manmentioning

confidence: 95%

Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides

Takasu

Inoue

Inai

et al. 2001

Polym J

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“…13 The LUMO and HOMO of BOT are a-0.2728/3 and a+ 1.0000{3, respectively, and those of DEB are a-0.4009{3 and a+0.5455{3. In such a case of a strong donor-acceptor system, the dative bond is known to induce an ionic polymerization of Molecular Interaction between BOT and DEB vinyl monomers, for instance, homopolymerization ofvinylidene cyanide and vinyl ether, 14 although a combination of the strongest donor and acceptor seems to be favorable for formation of stable complexes but not for alternating copolymerization. However, the present system is quite different from the system of the usual vinyl monomers.…”

Section: (B-trans-trans) Compoundmentioning

confidence: 99%

“…Toluene may simply act as a donor instead of BDT. 14 As the model system, combinations between TP-PA, TP-DEB, and BDT-PA are studied as shown in Table II. Here, the spectroscopic data of addition compounds are also appended.…”

Section: (B-trans-trans) Compoundmentioning

confidence: 99%

Molecular Interaction between 1,4-Benzenedithiol and 1,4-Diethynylbenzene

Kobayashi

Ohashi

Furukawa

1991

Polym J

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ABSTRACT:Molecular interactions of 1,4-benzenedithiol (BDT) and 1,4-diethynylbenzene (DEB) were studied in hexane or in toluene at 23-25°C by a UV-spectroscopy to elucidate the mechanism for the polyaddition of BDT to DEB. The solution containing both BDT and DEB showed a broad absorption at 280-380nm. The magnitude of the absorbance gradually increased during storage of the solution. Both BDT and DEB may have molecular interactions in solution and also in the solid state to make complexes of the charge-transfer (CT) type. The equilibrium constant (K) and extinction coefficient (e) were tentatively estimated to be about 40 and 8000-15000 at 310nm in hexane or 5:8 and 8000 in toluene, respectively, at 5 s after mixing the component solutions. As a model system, spectroscopic investigation was also made with systems of thiophenol (TP}-phenylacetylene (PA), TP-DEB and BDT-PA in hexane. These systems exhibited a large equilibrium constant and large extinction coefficient as well as BDT and DEB. Consequently, CT interactions seem to control the polyaddition of BDT to DEB in solution and also in solid state.KEY WORDS 1,4-Benzenedithiol / 1,4-Diethynylbenzene / Polyaddition / Model Addition Compounds / UV-Spectroscopy / Charge-Transfer Interaction / Equilibrium Constant (K) / Extinction Coefficient (e) / Continuous-Variation Method/ Ketelaar Method/ When strong electron-donating monomers are mixed with strong electron-accepting ones, regular alternating copolymers may be formed either by spontaneous m1tlat10n or more commonly in the presence of a free radical initiator.in the thin layer crystals perhaps induced by molecular interaction between BDT and DEB.Previously, the authors found a novel polymer of BDT and DEB in solution 1 or in solid state 2 under UV-or y-ray irradiation. In the case of solid state polymerization, thin layer crystals of the 1: 1 mixture of BDT and DEB are mounted on a glass plate by sublimation of a 1 : 1 mixture of BDT and DEB. The thin layer crystals are readily polymerized under UV-irradiation in high yield. 2 Both BDT and DEB are assumed to be arranged alternatingly This report deals with molecular interactions ofBDT and DEB studied by UV-spectroscopy in solution. EXPERIMENTAL BDTand DEBBDT and DEB were prepared by the previous method. 1 • 2 BDT was recrystallized from the ethyl acetate solution, and then sublimed at 70°C under reduced pressure prior to use, mp 97-98°C (97-98°C 1 ). DEB was purified by sublimation at 60°C under reduced pressure prior to use, mp 96.5°C (96.5°C 1 ).

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“…This phenomenon suggests that the CT complex is an active polymerizing species, since it is known that the reactivity of the complex increases with the increase in K value of complex formation in alternating radical copolymerizations of vinyl ethers with MAH. 25,26 Furthermore, the failure of CA and DMMAH to copolymerize with F suggests that complex formation might be a necessary prerequisite for these systems to copolymerize.…”

Section: Comparative Study On Various Donors and Acceptors Related Tomentioning

confidence: 99%

Structure study of the furan–maleic anhydride copolymer

Ragab

Butler

1981

J. Polym. Sci. Polym. Chem. Ed.

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A structural study of furan–maleic anhydride copolymer (F–MAH) was undertaken to confirm its alternating nature and to determine its microstructure. The spectral properties of a model compound representing the alternating repeat unit, 2‐(2‐tetrahydrofuranyl)succinic anhydride, were compared with those of F–MAH. Their infrared (IR), 1H, and 13C nuclear magnetic resonance (NMR) spectra (after compensating for the absence of the olefinic double bond) were in good agreement with those of the copolymer. Furthermore, the observed splitting in the 1H‐ and 13C‐NMR spectra of F–MAH were assigned to cis–trans linkages on both the F and MAH units, with cis linkage being favored on both units, especially the former. The structure of 2,5‐dimethylfuran (DMeF)–MAH copolymer is similar to that of F–MAH copolymer, except that the preference of cis linkages is less pronounced. The structure of 2‐methylfuran (MF)–MAH copolymer is a complex structure with numerous 2,3‐furandiyl units. A mechanistic study was undertaken to elucidate the roles of F–MAH Diels–Alder adduct, and the charge‐transfer (CT) complex in the radical initiated copolymerization. The adduct reverted substantially to monomers under the reaction conditions; but, the amount of adduct remaining at equilibrium was quite appreciable; therefore, its participation could be ruled out on this basis alone. However, on polymerizing the adduct in the presence of F‐d4, the latter was incorporated into the copolymer to an extent indicative of free monomer exchange. Therefore, the adduct cannot be directly involved in the polymerization.

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Studies on the Charge-Transfer Complex and Polymerization. XVII. The Reactivity of the Charge-Transfer Complex in Alternating Radical Copolymerization of Vinyl Ethers and Maleic Anhydride

Cited by 124 publications

References 6 publications

Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides

Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides

Molecular Interaction between 1,4-Benzenedithiol and 1,4-Diethynylbenzene

Structure study of the furan–maleic anhydride copolymer

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