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: Research - peer-reviewArticle

    • 16 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
    Graft copolymers
    Starch
    Extrusion
    starches
    polyesters
    copolymers
    Thermoplastics
    butylene glycol adipic acid polyester
    terephthalic acid
    terephthalate
    butenes
    Glycerol
    glycerols
    Acetone
    acetone
    Maleic Anhydrides
    Maleic anhydride
    anhydrides
    Methylene Chloride

    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: Research - peer-reviewArticle

    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",
    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 -