Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

Mondschein, Ryan J.; Dennis, Joseph M.; Liu, Haoyu; Ramakrishnan, Ramesh; Nazarenko, Sergei; Turner, S. Richard; Long, Timothy Edward

doi:10.1021/acs.macromol.7b01595

Cited by 26 publications

(56 citation statements)

References 40 publications

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“…Substitution of NPG for EG has little to no effect on T g while simultaneously disrupting crystallization much more effectively, allowing the production of high T g amorphous materials. The copolyesters containing both EG and CHDM exhibited unusually low T g ’s given the values typically observed for copolyesters containing 3,4′BB and 4,4′BB, and CHDM traditionally enhances the T g above EG. Copolyester composition 4,4′BB‐50‐NPG‐50‐CHDM produced an amorphous copolyester with the highest T g value in the series.…”

Section: Resultsmentioning

confidence: 72%

“…The presence of 3,4′BB in the copolyester structure also strongly disrupts crystallinity due to the meta substitution producing a kink in the polyester backbone that does not readily fit into crystalline domains. Much like with NPG, incorporation of 3,4′BB produces an amorphous polyester when substituted into PET for more than 10 mol % DMT or when substituted for 4,4′BB in 4,4′BB‐EG by more than 45 mol % …”

Section: Resultsmentioning

confidence: 99%

“…In a 1992 patent, DOW Chemical Company claimed several copolyesters containing both 3,4′BB and 4,4′BB diesters combined with a range of linear aliphatic diols containing 2 – 12 carbons . Copolyester compositions containing 50 mol % or more 3,4′BB were tough, amorphous, and exhibited T g ’s ranging from 104 to 111 °C, and their rheological and gas barrier properties were recently reported by Mondschein et al Compositions containing more than 50 mol % 4,4′BB exhibited high crystallinity, with melting temperatures above 300 °C and T g ’s above 122 °C . The meta substitution of the 3,4′BB moiety produces a “kink” in the polymer backbone that disrupts crystallization and decreases the T g relative to 4,4′BB based polyesters.…”

Section: Introductionmentioning

confidence: 99%

“…The meta substitution of the 3,4′BB moiety produces a “kink” in the polymer backbone that disrupts crystallization and decreases the T g relative to 4,4′BB based polyesters. This is apparent in the 3,4′BB‐EG homopolyester, which is completely amorphous and has improved tensile strength and modulus relative to amorphous 4,4′BB based copolyesters …”

Section: Introductionmentioning

confidence: 99%

“…Early patents by Monsanto claimed copolyester compositions where PET was modified with 4,4′BB comonomer, however, very little property analysis was reported on these compositions. Over the years, both 3,4′BB and 4,4′BB were investigated for their potential to enhance gas barrier, and our recently reported work modified PET with 4,4′BB, 3,4′BB, and isophthalate moieties in an effort to improve its thermal, mechanical, and barrier properties . PET copolyesters containing 15 – 40 mol % 4,4′BB were amorphous with T g ’s ranging from 89 to 98 °C.…”

Section: Introductionmentioning

confidence: 99%

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Amorphous copolyesters based on bibenzoic acids and neopentyl glycol

Edling

Mondschein

Davis

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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High Tg amorphous copolyester thermoplastics were synthesized by incorporating 4,4′‐bibenzoate (4,4′BB) and 3,4′‐bibenzoate moieties into the polyester backbone via melt polycondensation. The high levels of crystallinity typically associated with 4,4′BB containing polyesters were suppressed through copolymerization of ethylene glycol, 1,4‐cyclohexane dimethanol, and neopentyl glycol (NPG) diols. NPG was shown to be highly effective in suppressing crystallization and was used to produce amorphous compositions with Tg’s as high as 129 °C. Diol ratios were determined by 1H NMR spectroscopy and molecular weights were assessed with inherent viscosity (ηinh). Thermogravimetric analysis showed single‐step weight losses in the range of 395–419 °C. Differential scanning calorimetry was used to determine melting points and glass transition temperatures over a wide range of copolyester compositions and identified amorphous compositions. Dynamic mechanical analysis confirmed Tg’s and was used to study β‐relaxations below the Tg. Rheological analysis revealed the effect of NPG structures on shear thinning and thermal stability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 579–587

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Section: Resultsmentioning

confidence: 72%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Amorphous copolyesters based on bibenzoic acids and neopentyl glycol

Edling

Mondschein

Davis

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Oxygen Scavenging and Oxygen Barrier Poly(1,2‐butadiene) Films Containing an Iron‐Complex Catalyst

Wang

Shoda

Hisama

et al. 2019

Macro Chemistry & Physics

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film containing linoleic acid without any change in the physical properties of PET and that the oxidation of linoleic acid suppressed the oxygen permeation, [9] although the amount of suppression was small. Multilayer active films with an oxygen scavenging layer sandwiched between passive barrier layers have been reported. [10][11][12] However, their oxygen absorption capacity was low and the fabrication procedure was tedious.Poly(1,4-butadiene) (1,4-PB) is oxidized upon exposure to atmospheric oxygen at room temperature [13,14] ; however, the low oxygen scavenging capacity of 1,4-PB severely limits its use in oxygen scavenging films. 1,4-PB has been examined as an oxygen scavenging material after the addition of a small amount of a transition metal catalyst, typically cobalt neodecanoates, to accelerate oxidation. [15,16] The oxygen scavenging capacity of 1,4-PB was explained by the oxidative consumption of its double bond. Tung et al. fabricated an oxygen scavenging film consisting of a styrene-butadiene-styrene copolymer and a cobalt complex catalyst, and the film had an oxygen scavenging capacity of 26 mL (oxygen gas at STP) g(film) −1 . [15] The 1,4-PB polymer substrate acted as a reducing agent for oxygen in the presence of a cobalt complex. The oxygen scavenging capacity of this type of film was increased to 90 mL (oxygen gas at STP) g(film) −1 by using homopolymer 1,4-butadiene. [16] However, although cobalt complexes, such as cobalt naphthenate, show high catalytic activity, their practical applications are limited due to their high toxicity. Furthermore, the oxygen scavenging capacity of the 1,4-PB/cobalt neodecanoate film was still below 100 mL (oxygen gas at STP) g(film) −1 and the oxidation reaction yield (i.e., consumption of the double bond) was less than 15%.In this paper, we select an iron complex as a less-toxic and environmentally friendly metal catalyst to incorporate into the polymer film and we tune its catalytic activity for the oxidation of double bonds. [17] In addition, we investigate poly(1,2-butadiene) (1,2-PB) as both the film substrate and the oxygen scavenging agent. The oxidative reactivity of the double bond in the side chain of 1,2-PB are expected to be much higher than that of 1,4-PB. Furthermore, solvent solubility and film formation of 1,2-PB are excellent due to the syndiotactic structure of the side chain. A small amount of the unsaturated hydrocarbon, methyl linoleate (ML), is added as a plasticizer for the polymer film and trigger for the 1,2-PB oxidation. Tough films of poly(1,2-butadiene) are prepared by introducing small amounts of the less toxic iron complex N,N′-bis(salicylidene)ethylenediamine-benzylimidazole and methyl linoleate. The catalytic activity of the iron complex for air oxidation of unsaturated groups is substantially higher than those of previously reported films. The oxygen scavenging capacity of the films is up to 200 mL (oxygen gas at STP) g(film) −1 after 1 month, based on oxidative consumption of the poly(1,2-butadiene) double bonds, which is more t...

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Designing novel semi‐aromatic polyesters with dimethyl 3,3′‐bibenzoate

Heifferon

Weyhrich

Mondschein

et al. 2023

Polymer International

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Melt polycondensation of dimethyl 3,3′‐bibenzoate (3,3'BB) with various linear and cycloaliphatic diols enabled the synthesis of a series of semi‐aromatic polyesters. Size exclusion chromatography analysis confirmed high molecular weight (Mn > 20 kg mol−1). Compression molding resulted in ductile films and further established molecular weights desirable for mechanical performance. 1H NMR spectroscopy confirmed polymer structure and retainment of the cis/trans ratios for the cyclohexyldimethylene‐based polyesters before and after polymerization. Thermogravimetric analysis revealed high onset of weight loss temperatures for the novel semi‐aromatic polymers (Td,5% > 380 °C). Differential scanning calorimetry and dynamic mechanical analysis were used to determine glass transition temperatures and melting temperatures. Further evaluation of these thermal transitions against previously synthesized 4,4'BB, 3,4'BB, and isophthalate‐based polymers elucidated the structure–property relationships of these systems. © 2023 Society of Industrial Chemistry.

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Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

Cited by 26 publications

References 40 publications

Amorphous copolyesters based on bibenzoic acids and neopentyl glycol

Amorphous copolyesters based on bibenzoic acids and neopentyl glycol

Oxygen Scavenging and Oxygen Barrier Poly(1,2‐butadiene) Films Containing an Iron‐Complex Catalyst

Designing novel semi‐aromatic polyesters with dimethyl 3,3′‐bibenzoate

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