Stereocopolyamides Derived from 2,3-Di-<i>O</i>-Methyl-<scp>d</scp>- and -<scp>l</scp>-Tartaric Acids and Hexamethylenediamine. 2. Influence of the Configurational Composition on the Crystal Structure of Optically Compensated Systems

Iribarren, I.; Alemán, Carlos; Regaño, Celia; Ilarduya, Antxon Martı́nez de; Bou, Jordi J.; Muñoz‐Guerra, S.

doi:10.1021/ma960473j

Cited by 32 publications

(25 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1)2122. Other examples which can form homo-stereocomplex crystallites include enantiomeric polymer pairs of polyester: poly( β -propiolactone)2324, polyamides: poly(γ-alkyl glutamate)25, poly(hexamethylene di- O -methyl tartaramide)262728, polycarbonate: poly(propylene carbonate)29, polyether: poly( tert -butylene oxide)30, polythioether: poly( tert -butylene sulfide)31, polyketones: poly(propylene- alt -carbon monoxide) and poly(1-butene- alt -carbon monoxide)32, and poly(ester-ether): poly(propylene succinate)33. In the case of PLA, the mechanical performance, thermal/hydrolytic degradation-resistance of stereocomplexed materials are higher than those of constituent polymers, L-PLA and D-PLA11121314151617.…”

mentioning

confidence: 99%

Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers

Tsuji

Noda

Kimura

et al. 2017

Sci Rep

View full text Add to dashboard Cite

D-configured poly(D-lactic acid) (D-PLA) and poly(D-2-hydroxy-3-methylbutanoic acid) (D-P2H3MB) crystallized separately into their homo-crystallites when crystallized by precipitation or solvent evaporation, whereas incorporation of L-configured poly(L-2-hydroxybutanoic acid) (L-P2HB) in D-configured D-PLA and D-P2H3MB induced co-crystallization or ternary stereocomplex formation between D-configured D-PLA and D-P2H3MB and L-configured L-P2HB. However, incorporation of D-configured poly(D-2-hydroxybutanoic acid) (D-P2HB) in D-configured D-PLA and D-P2H3MB did not cause co-crystallization between D-configured D-PLA and D-P2H3MB and D-configured D-P2HB but separate crystallization of each polymer occurred. These findings strongly suggest that an optically active polymer (L-configured or D-configured polymer) like unsubstituted or substituted optically active poly(lactic acid)s can act as “a configurational or helical molecular glue” for two oppositely configured optically active polymers (two D-configured polymers or two L-configured polymers) to allow their co-crystallization. The increased degree of freedom in polymer combination is expected to assist to pave the way for designing polymeric composites having a wide variety of physical properties, biodegradation rate and behavior in the case of biodegradable polymers.

show abstract

mentioning

confidence: 99%

Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers

Tsuji

Noda

Kimura

et al. 2017

Sci Rep

View full text Add to dashboard Cite

show abstract

“…Poly(lactide) [i.e., poly(lactic acid) (PLA)] homostereocomplex (HMSC) forms upon blending enantiomeric poly( l ‐lactide) [i.e., poly( l ‐lactic acid) (PLLA)] and poly( d ‐lactide) [i.e., poly( d ‐lactic acid) (PDLA)] or in stereo block PLAs . Recently, HMSC formation has been reported for enantiomeric blends of poly(propylene succinate), poly(hexamethylene‐2,3‐di‐ O ‐methyl‐tartaramide), poly(propylene carbonate), poly(α‐olefin‐ alt ‐carbon monoxide), in addition to enantiomeric polymer pairs summarized in review articles . Normally, HMSC formation of PLA is accompanied by increased melting temperature ( T m ) and thereby elevated thermal‐resistance compared to those of constituent polymers.…”

Section: Introductionmentioning

confidence: 99%

Heterostereocomplex‐ and Homocrystallization and Thermal Properties and Degradation of Substituted Poly(lactic acid)s, Poly(l‐2‐hydroxybutanoic acid) and Poly(d‐2‐hydroxy‐3‐methylbutanoic acid)

Tsuji

Hayakawa

2016

Macro Chemistry & Physics

View full text Add to dashboard Cite

Heterostereocomplex‐ and homocrystallization behavior, thermal properties and degradation of neat poly(l‐2‐hydroxybutanoic acid) [P(l‐2HB)], poly(d‐2‐hydroxy‐3‐methylbutanoic acid) [P(d‐2H3MB)], and their equimolar blend are first investigated. Regime I and II kinetics are observed for neat P(l‐2HB), whereas regime II and III kinetics are seen for the blend. The growth geometry of the neat P(l‐2HB) is linear and circular while that of the blend is spherical, whereas that of the neat P(d‐2H3MB) changes from linear to spherical, depending on crystallization temperature (T c). The main crystalline species is heterostereocomplex (HTSC) in the blend for a wide T c range of 0–180 °C and a very small amount of P(d‐2H3MB) homocrystallites form for melt‐crystallization at T c below 70 °C and solution‐crystallization. The equilibrium melting temperature of P(l‐2HB)/P(d‐2H3MB) HTSC crystallites (234.5 °C) is higher than those of P(l‐2HB) and P(d‐2H3MB) homocrystallites (114.9 and 208.6 °C, respectively). The activation energy values for thermal degradation of the P(l‐2HB)/P(d‐2H3MB) blend (190–219 kJ mol−1) are between those of neat P(l‐2HB) and P(d‐2H3MB) (164–180 and 210–380 kJ mol−1, respectively), reflecting that the interaction between the polymers with opposite configurations is similar to or lower than that between the polymers with the same configurations at a high temperature in the melt.

show abstract

“…This aspect merits special attention and constitutes the subject of the second part of this work, where it will be examined in full detail. 18 …”

Section: Discussionmentioning

confidence: 99%

Stereocopolyamides Derived from 2,3-Di-O-methyl-d- and -l-tartaric Acids and Hexamethylenediamine. 1. Synthesis, Characterization, and Compared Properties

et al. 1996

Self Cite

View full text Add to dashboard Cite

Poly(hexamethylene-2,3-di-O-methyl-D,L-tartaramide)s [P6DM(D,L)T], with enantiomeric D/L ratios ranging from 1:9 to 1:1 and weight average molecular weights up to ∼80 000, were obtained by the active ester polycondensation method. The microstructure of these stereocopolyamides was investigated by 1 H and 13 C NMR using as model compound a copolytartaramide the racemic composition of which was ensured by chemical synthesis. No evidence was observed from these studies which led to the interpretation that the microstructure of P6DM(D,L)T was other than that consisting of a statistical distribution of D and L configurations. All the copolyamides were found to be highly crystalline with melting points close to that of the optically pure polymer, which is about 230°C, and Tg's decreasing from 106 to 68°C as the D/L ratio increased from 0 to 1. Powder X-ray diffraction indicated that a crystal structure very similar to that described for the pure enantiomorph, poly(hexamethylene-2,3-di-O-methyl-L-tartaramide) (P6DMLT), seems to be adopted by all these copolyamides. It was concluded that the replacement of L units by D units is feasible over the whole range of enantiomeric compositions without much distortion of the crystal lattice and properties.

show abstract

Stereocopolyamides Derived from 2,3-Di-O-Methyl-d- and -l-Tartaric Acids and Hexamethylenediamine. 2. Influence of the Configurational Composition on the Crystal Structure of Optically Compensated Systems

Cited by 32 publications

References 25 publications

Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers

Configurational Molecular Glue: One Optically Active Polymer Attracts Two Oppositely Configured Optically Active Polymers

Heterostereocomplex‐ and Homocrystallization and Thermal Properties and Degradation of Substituted Poly(lactic acid)s, Poly(l‐2‐hydroxybutanoic acid) and Poly(d‐2‐hydroxy‐3‐methylbutanoic acid)

Stereocopolyamides Derived from 2,3-Di-O-methyl-d- and -l-tartaric Acids and Hexamethylenediamine. 1. Synthesis, Characterization, and Compared Properties

Contact Info

Product

Resources

About