High Molecular Weight Aromatic Polyformals Free of Macrocyclic Oligomers. A Condensative Chain Polymerization Reaction

Miyatake, Kenji; Hlil, and Antisar R.; Hay, Allan S.

doi:10.1021/ma002020r

Cited by 49 publications

(52 citation statements)

References 9 publications

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“…The spectroscopic data were in agreement with the proposed structure. 1 Previously, we reported that high-intensity mixing could greatly increase the rate of the polyformal polymerization reaction, presumably by increasing the surface area of the bisphenol salts and thereby increasing the rate of dissolution of the salts. Under high-intensity mixing reaction conditions, very high molecular weight polyformals with very low molecular weight distributions were obtained in a very short time.…”

Section: Resultsmentioning

confidence: 99%

“…Under high-intensity mixing reaction conditions, very high molecular weight polyformals with very low molecular weight distributions were obtained in a very short time. 1 The formation of formals is an irreversible reaction. The first intermediate, bromomethyl ether, has much higher reactivity than the monomer, methylene dibromide, which is also used as a partial solvent for the polymerization.…”

Section: Resultsmentioning

confidence: 99%

“…[1][2][3][4] With a high-intensity mixing methodology, high-molecular-weight aromatic polyformals free of macrocyclic oligomers were recently synthesized. 1 These polymers had polydispersities as low as 1.3, and it was postulated that the polymerization proceeded via a condensation chain polymerization reaction. Aromatic polyformals have properties similar to those of aromatic polycarbonates, except that the glass-transition temperatures (T g 's) are generally 40-60 8C lower and they are stable under basic conditions.…”

Section: Introductionmentioning

confidence: 99%

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High‐molecular‐weight fluorinated aromatic polyformal containing a phthalazinone moiety

Hay

2007

J. Polym. Sci. A Polym. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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High‐molecular‐weight fluorinated aromatic polyformal containing a phthalazinone moiety

Hay

2007

J. Polym. Sci. A Polym. Chem.

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“…The proposed reaction mechanism shows that the reaction took place through a bromomethyl ether intermediate, which is much more reactive than the monomer of methylene dibromide. 88 Ueda and colleagues 89 also studied the kinetics of the polycondensation of 4,4-thiobisbenzenethiol and dibromomethane and found that a high MW poly(phenylene thioether) was successfully obtained under a nonstoichiometric condition. Therefore, it was envisioned that a geminal dihalide functional group can be applied to the B 2 groups in an AB 2 monomer for the synthesis of HBPs with a 100% DB.…”

Section: Meomentioning

confidence: 99%

Synthesis of hyperbranched polymers with controlled degree of branching

Higashihara

Segawa

Sinananwanich

et al. 2011

Polym J

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Hyperbranched polymers (HBPs) have attracted considerable attention during the past decade because of their intrinsic globular structures and unique properties, such as low viscosity, high solubility and a high degree of functionality, compared with linear analogs. As HBPs are generally prepared by one-pot polycondensation of an AB x monomer, where A and B represent two different functional groups, they are regarded as less-expensive alternatives to dendrimers. However, HBPs have randomly branched structures and their degree of branching (DB) is determined by statistics and only reaches B50%. Recently, several research groups have successfully synthesized a 100% DB without any defect mainly by condensation or addition reactions. These methods are based on a new concept in which the ratio of the rate constants, the first reaction rate constant (k 1 )/the second reaction rate constant (k 2 ) of an AB 2 monomer, can be controlled. Recent development in the synthesis of a linear polymer, that is, a 0% DB HBP, from an AB 2 monomer could make it possible to further precisely control the DB from 0 to 100% by using the same AB 2 monomer. In this review article, the backgrounds and methodologies for controlling the DB are described, especially focusing on recent advances in the synthesis of HBPs with a DB of 100, 0% and any percentage between 0 and 100%.

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“…Hay and coworkers showed that bisphenol-A-polyformals could be formed from the bisphenol with base in excess dichloromethane solution: as the first chlorine of a dichloromethane molecule reacted, the second became far more reactive, so the large excess of dichloromethane did not inter- fere. 38,39 Endo and coworkers have provided further examples. [40][41][42] This situation alleviates the need for strict reactant equivalence in polycondensation and is a boon to the experimenter.…”

Section: Mechanism: the Problems And Considerationsmentioning

confidence: 99%

Condensation routes to polyaniline and its analogs

Hall

Padías

Boone

2007

J. Polym. Sci. A Polym. Chem.

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To obtain polyanilines which are more structurally perfect than those obtainable by the oxidation of anilines, polycondensation procedures were investigated. Model reactions gave extensive information about yields and about the physical properties of the putative structural polymer units. Condensation of anthraquinones with aromatic diamines using titanium tetrachloride and the unique base, 1,4-diazabicyclo-[2.2.2]-octane Dabco, gave high molecular weight orange polyquinonimines. Alkoxy groups on the anthraquinone ring aided solubility and molecular weight, and appropriately positioned alkoxy groups afforded stereoregular polymers. A bisthiophene benzoquinone also polymerized successfully. Application of the same procedure to 2,5-dimethyl-p-benzoquinone gave stereoregular poly(arylene benzoquinonimines), close analogs of pernigrani line. The factors causing problems in achieving high yields and high molecular weight were identified. Recent synthetic developments in this field are discussed. Reduction of the obtained polyquinonimines proceeded smoothly to the leucoemeraldine analogs. Unlike the results from pernigraniline obtained by oxidative polymerization, no evidence for the formation of the electrically conductive emeraldine form was obtained. Keywords: conducting polymers; conjugated polymers; polyaniline; polycondensation; polyimines H. K. Hall, Jr., received his B.S. at Brooklyn Polytech, M.S. at Pennsylvania State University, and Ph.D. from the University of Illinois in 1949. Postdoctoral work followed, with Prof. P. J. Flory at Cornell and with Professors S. Winstein and W. G. Young at UCLA. After 17 years at DuPont, he moved in 1969 to the University of Arizona. His research interests have included the ring-opening polymerizations of strained bicyclic molecules, the mechanisms of reactions of donor with acceptor olefins, the polymerization of imines, and the synthesis of electrically conductive, piezoelectric, and nonlinear optical polymers.

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High Molecular Weight Aromatic Polyformals Free of Macrocyclic Oligomers. A Condensative Chain Polymerization Reaction

Cited by 49 publications

References 9 publications

High‐molecular‐weight fluorinated aromatic polyformal containing a phthalazinone moiety

High‐molecular‐weight fluorinated aromatic polyformal containing a phthalazinone moiety

Synthesis of hyperbranched polymers with controlled degree of branching

Condensation routes to polyaniline and its analogs

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