Selective Formation of Poly(<i>N</i>,<i>O</i>-acetal) by Polymerization of 1,3-Benzoxazine and Its Main Chain Rearrangement

Sudo, Atsushi; Kudoh, Ryoichi; Nakayama, Hiroshi; Arima, Kazuya; Endō, Takeshi

doi:10.1021/ma8013178

Cited by 169 publications

(147 citation statements)

References 23 publications

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“…Different accelerators, which lower benzoxazine curing temperature, may bear different functional groups capable of initiating or catalyzing the oxazine ring opening. This is why several mechanisms were proposed for benzoxazine curing [13,14,26,[33][34][35]. Regardless to the type of the accelerator used, the mechanism of the curing process involves several steps, which complicate the kinetics.…”

Section: Results and Discussion 31 Curing Reactionmentioning

confidence: 99%

“…Lower curing temperature would therefore lead to a significant process and resulting material improvement. In order to respond to this issue, a considerable amount of different catalysts have been applied to promote ringopening polymerization, including nucleophilic catalysts and Lewis acids [12][13][14]. Also the use of carboxylic acid groups as accelerators have been extensively studied and a significant decrease in the polymerization temperature has been observed [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, it is of great importance to understand the nature of the cured material and the effect certain functional group has on the curing process, i.e. on the ring-opening, polymerization and cross-linking mechanisms [1,2,12,14,[19][20][21][22][23][24][25][26][27][28][29]. The terminology used for accelerators is varied and may sometimes cause confusion since the terms accelerator, catalyst, promoter, initiator, etc., are sometimes used loosely even though they can apply to very specific types of materials having distinctly different characteristics and functions.…”

Section: Introductionmentioning

confidence: 99%

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Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Ručigaj¹,

Alič²,

Krajnc³

et al. 2015

Express Polym. Lett.

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Abstract. The curing of bisphenol A-aniline based benzoxazine was studied applying different accelerators (4,4"-thiodiphenol, o-dianisidine, 2-mercaptobenzimidazole and 4-mercaptophenol) to initiate the catalytic ring-opening of benzoxazine. Possible pathways of benzoxazine ring-opening, polymerization and cross-linking without and with the addition of different accelerators are presented. The curing kinetics was investigated by model-free kinetic analysis of experimental data obtained by differential scanning calorimetry (DSC). The addition of different accelerators significantly reduced the onset temperature of curing in dynamic experiments. The effects of accelerators on the results of isothermal conversion prediction were studied and discussed in detail. Among the used accelerators, thiodiphenol showed the best accelerating efficiency and was consequently used in further studies, where its amount was varied. By low heating rate DSC analysis the catalytic ring-opening, thermally accelerated ring-opening and the diffusion-controlled steps were identified. The amount of added accelerator affected particularly the ring-opening and diffusion-controlled steps.

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Section: Results and Discussion 31 Curing Reactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Ručigaj¹,

Alič²,

Krajnc³

et al. 2015

Express Polym. Lett.

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“…Polybenzoxazines appear to incorporate the best properties from conventional phenolics, and may find application in a number of their traditional niches, whilst improving on shelf life and offering the potential for greater toughness properties through their greater molecular flexibility; the relative cheapness of the monomer is also an important factor influencing their adoption. Unlike many other commercial thermosetting resins, which evolve condensation products such as water or ammonia, benzoxazine monomers react relatively cleanly to form a polymer with few reaction by-products 2 . Polymerisation may be effected thermally without the need for initiation, although several catalytic studies have also been conducted 3 .…”

Section: Methodsmentioning

confidence: 99%

Examining the influence of bisphenol A on the polymerisation and network properties of an aromatic benzoxazine

Hassan

Liu

Howlin

et al. 2016

Polymer

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General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/about/ebr-terms ABSTRACT: A series of reactive blends, comprising a commercial benzoxazine monomer, 2,2- bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine)propane, and bisphenol A is prepared andcharacterized. Thermal analysis and dynamic rheology reveal how the introduction of up to 15 wt % bisphenol A lead to a significant increase in reactivity (the exothermic peak maximum of thermal polymerization is reduced from 245 ºC to 215 ºC), with a small penalty in glass transition temperature (reduction of 15 K), but similar thermal stability (onset of degradation = 283 ºC, char yield = 26 %). With higher concentrations of bisphenol A (e.g. 25 wt %), a significantly more reactive blend is produced (exothermic peak maximum = 192 ºC), but with a significantly lower thermal stability (onset of degradation = 265 ºC, char yield = 22 %) and glass transition temperature (128 ºC). Attempts to produce a cured plaque containing 35 wt % bisphenol A were unsuccessful, due to brittleness. Molecular modelling is used to replicate successfully the glass transition temperatures (measured using thermal analysis) of a range of copolymers.

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“…27 This intermediate was a polymer having N,O-acetal-type linage in the main chain, which underwent the main chain rearrangement into the Mannich-type polymer upon heating. As shown in Figure 2, Scheme 1.…”

Section: Benzoxazines: a New Class Of Monomers For Networked Polymermentioning

confidence: 99%

Development and application of novel ring‐opening polymerizations to functional networked polymers

Endō

Sudo

2009

J. Polym. Sci. A Polym. Chem.

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This Highlightgives an overview of the recent progress in development of new ring-opening polymerizations (ROPs) and their applications to functional networked polymers in our group. The described ROPs involve thermally induced polymerization of 1,3-benzoxazine, anionic alternating copolymerizations of epoxides and lactones, and those exhibiting equilibrium nature. These ROPs were successfully applied to the syntheses of the relevant networked polymers, leading to their distinctive features such as high thermal stability, small volume shrinkage, and selective decrosslinking ability, which enabled design and development of next generation materials.

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Selective Formation of Poly(N,O-acetal) by Polymerization of 1,3-Benzoxazine and Its Main Chain Rearrangement

Cited by 169 publications

References 23 publications

Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Examining the influence of bisphenol A on the polymerisation and network properties of an aromatic benzoxazine

Development and application of novel ring‐opening polymerizations to functional networked polymers

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