Reactive extrusion of glycerylated starch and starch-polyester graft copolymers

Elodie Hablot, Sudhanwa Dewasthale, Yanjie Zhao, Yang Zhiguan, Xiangke Shi, Dan Graiver, Ramani Narayan

Research output: Contribution to journalArticle

  • 20 Citations

Abstract

Maleated thermoplastic starch (MTPS) was prepared through in situ reactive modification of thermoplastic starch (TPS) with maleic anhydride (MA) as esterification agent and glycerol as a plasticizer. Melt-blends of 60 wt.% poly(butylene adipate-co-terephthalate) (PBAT) with 40 wt.% of TPS or MTPS were then prepared by reactive extrusion to produce PBAT/TPS and PBAT/MTPS, respectively. Soxhlet extraction in acetone was then used to extract any un-grafted glycerol from these blend systems. Analysis of the acetone extracted product was performed using GC, FTIR and TGA. The residues from the soxhlet extractions were analyzed by FTIR and TGA. GC analysis showed that the acetone extraction was a very effective technique to extract free glycerol from the system. Furthermore, the combination of TGA and the gravimetric results after extraction was an effective method to determine the amount of glycerol grafted on the starch backbone. We observed that introducing 2 wt.% of MA to the system significantly increased glycerol grafting onto the starch backbone. Evidence for grafting of PBAT onto the maleated and glycerylated thermoplastic starch was obtained from dichloromethane (DCM) soxhlet extraction on the PBAT/TPS and PBAT/MTPS resins. The DCM soxhlet extracted fraction and the residue remaining in the thimble were analyzed by FTIR and TGA. The presence of MA on the starch backbone was shown to enhance the extent of grafting of PBAT to the starch backbone. Further acetone extraction of the PBAT/MTPS resin blend indicated that the grafting was obtained through transesterification reactions between the grafted glycerol on the starch backbone and PBAT polymeric chains. Finally, stained blends analyzed by TEM analysis supports our analytical analyses and indicated higher grafting yield in the PBAT/MTPS blend compared with the PBAT/TPS blend.

LanguageEnglish (US)
Pages873-881
Number of pages9
JournalEuropean Polymer Journal
Volume49
Issue number4
DOIs
StatePublished - Apr 2013

Profile

Polyesters
starches
Graft copolymers
polyesters
Starch
Extrusion
copolymers
terephthalate
butenes
Thermoplastics
glycerols
Glycerol
Maleic Anhydrides
Acetone
acetone
Maleic anhydride
anhydrides
Methylene Chloride
Dichloromethane
resins

Keywords

  • Poly(butylene adipate-co-terephthalate)
  • Reactive extrusion
  • Soxhlet extraction
  • Starch

ASJC Scopus subject areas

  • Polymers and Plastics
  • Physics and Astronomy(all)
  • Organic Chemistry

Cite this

Hablot, E., Dewasthale, S., Zhao, Y., Zhiguan, Y., Shi, X., Graiver, D., & Narayan, R. (2013). Reactive extrusion of glycerylated starch and starch-polyester graft copolymers. European Polymer Journal, 49(4), 873-881. DOI: 10.1016/j.eurpolymj.2012.12.005

Reactive extrusion of glycerylated starch and starch-polyester graft copolymers. / Hablot, Elodie; Dewasthale, Sudhanwa; Zhao, Yanjie; Zhiguan, Yang; Shi, Xiangke; Graiver, Dan; Narayan, Ramani.

In: European Polymer Journal, Vol. 49, No. 4, 04.2013, p. 873-881.

Research output: Contribution to journalArticle

Hablot, E, Dewasthale, S, Zhao, Y, Zhiguan, Y, Shi, X, Graiver, D & Narayan, R 2013, 'Reactive extrusion of glycerylated starch and starch-polyester graft copolymers' European Polymer Journal, vol 49, no. 4, pp. 873-881. DOI: 10.1016/j.eurpolymj.2012.12.005
Hablot E, Dewasthale S, Zhao Y, Zhiguan Y, Shi X, Graiver D et al. Reactive extrusion of glycerylated starch and starch-polyester graft copolymers. European Polymer Journal. 2013 Apr;49(4):873-881. Available from, DOI: 10.1016/j.eurpolymj.2012.12.005
Hablot, Elodie ; Dewasthale, Sudhanwa ; Zhao, Yanjie ; Zhiguan, Yang ; Shi, Xiangke ; Graiver, Dan ; Narayan, Ramani. / Reactive extrusion of glycerylated starch and starch-polyester graft copolymers. In: European Polymer Journal. 2013 ; Vol. 49, No. 4. pp. 873-881
@article{3e1283a245c842658052a4ffc2b0e670,
title = "Reactive extrusion of glycerylated starch and starch-polyester graft copolymers",
abstract = "Maleated thermoplastic starch (MTPS) was prepared through in situ reactive modification of thermoplastic starch (TPS) with maleic anhydride (MA) as esterification agent and glycerol as a plasticizer. Melt-blends of 60 wt.{\%} poly(butylene adipate-co-terephthalate) (PBAT) with 40 wt.{\%} of TPS or MTPS were then prepared by reactive extrusion to produce PBAT/TPS and PBAT/MTPS, respectively. Soxhlet extraction in acetone was then used to extract any un-grafted glycerol from these blend systems. Analysis of the acetone extracted product was performed using GC, FTIR and TGA. The residues from the soxhlet extractions were analyzed by FTIR and TGA. GC analysis showed that the acetone extraction was a very effective technique to extract free glycerol from the system. Furthermore, the combination of TGA and the gravimetric results after extraction was an effective method to determine the amount of glycerol grafted on the starch backbone. We observed that introducing 2 wt.{\%} of MA to the system significantly increased glycerol grafting onto the starch backbone. Evidence for grafting of PBAT onto the maleated and glycerylated thermoplastic starch was obtained from dichloromethane (DCM) soxhlet extraction on the PBAT/TPS and PBAT/MTPS resins. The DCM soxhlet extracted fraction and the residue remaining in the thimble were analyzed by FTIR and TGA. The presence of MA on the starch backbone was shown to enhance the extent of grafting of PBAT to the starch backbone. Further acetone extraction of the PBAT/MTPS resin blend indicated that the grafting was obtained through transesterification reactions between the grafted glycerol on the starch backbone and PBAT polymeric chains. Finally, stained blends analyzed by TEM analysis supports our analytical analyses and indicated higher grafting yield in the PBAT/MTPS blend compared with the PBAT/TPS blend.",
keywords = "Poly(butylene adipate-co-terephthalate), Reactive extrusion, Soxhlet extraction, Starch",
author = "Elodie Hablot and Sudhanwa Dewasthale and Yanjie Zhao and Yang Zhiguan and Xiangke Shi and Dan Graiver and Ramani Narayan",
year = "2013",
month = "4",
doi = "10.1016/j.eurpolymj.2012.12.005",
language = "English (US)",
volume = "49",
pages = "873--881",
journal = "European Polymer Journal",
issn = "0014-3057",
publisher = "Elsevier Limited",
number = "4",

}

TY - JOUR

T1 - Reactive extrusion of glycerylated starch and starch-polyester graft copolymers

AU - Hablot,Elodie

AU - Dewasthale,Sudhanwa

AU - Zhao,Yanjie

AU - Zhiguan,Yang

AU - Shi,Xiangke

AU - Graiver,Dan

AU - Narayan,Ramani

PY - 2013/4

Y1 - 2013/4

N2 - Maleated thermoplastic starch (MTPS) was prepared through in situ reactive modification of thermoplastic starch (TPS) with maleic anhydride (MA) as esterification agent and glycerol as a plasticizer. Melt-blends of 60 wt.% poly(butylene adipate-co-terephthalate) (PBAT) with 40 wt.% of TPS or MTPS were then prepared by reactive extrusion to produce PBAT/TPS and PBAT/MTPS, respectively. Soxhlet extraction in acetone was then used to extract any un-grafted glycerol from these blend systems. Analysis of the acetone extracted product was performed using GC, FTIR and TGA. The residues from the soxhlet extractions were analyzed by FTIR and TGA. GC analysis showed that the acetone extraction was a very effective technique to extract free glycerol from the system. Furthermore, the combination of TGA and the gravimetric results after extraction was an effective method to determine the amount of glycerol grafted on the starch backbone. We observed that introducing 2 wt.% of MA to the system significantly increased glycerol grafting onto the starch backbone. Evidence for grafting of PBAT onto the maleated and glycerylated thermoplastic starch was obtained from dichloromethane (DCM) soxhlet extraction on the PBAT/TPS and PBAT/MTPS resins. The DCM soxhlet extracted fraction and the residue remaining in the thimble were analyzed by FTIR and TGA. The presence of MA on the starch backbone was shown to enhance the extent of grafting of PBAT to the starch backbone. Further acetone extraction of the PBAT/MTPS resin blend indicated that the grafting was obtained through transesterification reactions between the grafted glycerol on the starch backbone and PBAT polymeric chains. Finally, stained blends analyzed by TEM analysis supports our analytical analyses and indicated higher grafting yield in the PBAT/MTPS blend compared with the PBAT/TPS blend.

AB - Maleated thermoplastic starch (MTPS) was prepared through in situ reactive modification of thermoplastic starch (TPS) with maleic anhydride (MA) as esterification agent and glycerol as a plasticizer. Melt-blends of 60 wt.% poly(butylene adipate-co-terephthalate) (PBAT) with 40 wt.% of TPS or MTPS were then prepared by reactive extrusion to produce PBAT/TPS and PBAT/MTPS, respectively. Soxhlet extraction in acetone was then used to extract any un-grafted glycerol from these blend systems. Analysis of the acetone extracted product was performed using GC, FTIR and TGA. The residues from the soxhlet extractions were analyzed by FTIR and TGA. GC analysis showed that the acetone extraction was a very effective technique to extract free glycerol from the system. Furthermore, the combination of TGA and the gravimetric results after extraction was an effective method to determine the amount of glycerol grafted on the starch backbone. We observed that introducing 2 wt.% of MA to the system significantly increased glycerol grafting onto the starch backbone. Evidence for grafting of PBAT onto the maleated and glycerylated thermoplastic starch was obtained from dichloromethane (DCM) soxhlet extraction on the PBAT/TPS and PBAT/MTPS resins. The DCM soxhlet extracted fraction and the residue remaining in the thimble were analyzed by FTIR and TGA. The presence of MA on the starch backbone was shown to enhance the extent of grafting of PBAT to the starch backbone. Further acetone extraction of the PBAT/MTPS resin blend indicated that the grafting was obtained through transesterification reactions between the grafted glycerol on the starch backbone and PBAT polymeric chains. Finally, stained blends analyzed by TEM analysis supports our analytical analyses and indicated higher grafting yield in the PBAT/MTPS blend compared with the PBAT/TPS blend.

KW - Poly(butylene adipate-co-terephthalate)

KW - Reactive extrusion

KW - Soxhlet extraction

KW - Starch

UR - http://www.scopus.com/inward/record.url?scp=84875222850&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84875222850&partnerID=8YFLogxK

U2 - 10.1016/j.eurpolymj.2012.12.005

DO - 10.1016/j.eurpolymj.2012.12.005

M3 - Article

VL - 49

SP - 873

EP - 881

JO - European Polymer Journal

T2 - European Polymer Journal

JF - European Polymer Journal

SN - 0014-3057

IS - 4

ER -