Poly(hydroxy amide ethers):  New High-Barrier Thermoplastics

Abstract

The synthesis of a new class of high-barrier polymers, poly(hydroxy amide ethers), is described. The polymers are formed by the reactions of bisphenol-A diglycidyl ether, OCH2CHCH2OC6H4C(CH3)2C6H4OCH2CHCH2O, and amide-containing bisphenols of the general formula HOC6H4NHC(O)RC(O)NHC6H4OH [R = −(CH2) n −, −CH2C6H4CH2−, or −C6H4−] or HOC6H4NHC(O)C6H4OH at 140−160 °C in propylene glycol monophenyl ether solvent using ethyltriphenylphosphonium acetate as initiator. High-molecular-weight poly(hydroxy amide ethers) of the general structure [−CH2CH(OH)CH2OC6H4C(CH3)2C6H4OCH2CH(OH)CH2OC6H4NHC(O)RC(O)NHC6H4O−] n or [−CH2CH(OH)CH2OC6H4C(CH3)2C6H4OCH2CH(OH)CH2OC6H4NHC(O)C6H4O−] n are readily prepared. The amorphous thermoplastics have glass transition temperatures (T g) of 90−133 °C and oxygen transmission rates (O2TR) which range from 0.7 to 4.6 cc·mil/100 in.2·atm·day (barrier units or BU) at 23 °C and 47−85% relative humidity. The effect that polymer structure has on oxygen barrier properties and T g is described. The characterization, structure determination, and properties of the poly(hydroxy amide ethers), as well as the amide-containing bisphenol precursors, are also presented.

Poly(hydroxyaminoethers): A New Family of Epoxy-Based Thermoplastics

“…[8] Further, although we and others have shown that reactions of ADGE with bisphenols afford a stunning variety of poly(hydroxyethers) (see Sec. 4) comparable in molecular weight to those prepared by the direct sequence of Scheme 1, [9,10] we have found that polymerizations of ADGE with dinucleophilic amines, [11] dicarboxylic acids, [12] dithiols, [6] and disulfonamides [13] often yield polymers with combinations of barrier performance and other properties that cannot be realized with poly(hydroxyethers), at least without resorting to unusual and commercially unavailable bisphenols. [6] Of special interest are poly(hydroxyaminoethers), recently commercialized under the tradename BLOX Adhesive and High-Adhesion Barrier Resins (trademark of the Dow Chemical Company).…”

Water effect on the morphology of EVOH copolymers

“…However, EVOH properties, including barrier properties, are greatly affected by water content. 1,2 Because water is always present in a food packaging system (it forms part of the external atmosphere and is a main constituent of many foodstuffs), EVOH films are always sandwiched between polyolefin layers (barrier to water) to protect EVOH. In some cases, both package and food are subject to thermal treatments such as pasteurization or retorting.…”

High-Barrier Poly(hydroxy amide ethers): Effect of Polymer Structure on Oxygen Transmission Rates. 3

“…32,41,[46][47][48][49][50][51][52][53][54][55][56][57][58] However, various synthetic methodologies were used during their preparation and complete characterization was not carried out in most cases. In this work, diglycidyl ethers 6-22 were prepared using the same synthetic procedure and were fully characterized by a combination of NMR methods and epoxide equivalent weight determination.…”

“…Poly(hydroxy amide ethers) 23-39 (Table Scheme 1 4) were prepared by the reactions of N,N′-bis(3-hydroxyphenyl)adipamide (5) with diglycidyl ethers 6-22 using a previously described synthetic methodology 26 ) with the use of an ethyltriphenylphosphonium acetate-acetic acid complex (70% in methanol) as catalyst. During the polymerization reaction, the phe- nolic groups react with the epoxide functionalities, generating the pendent secondary hydroxyl groups along the polymer backbone.…”