Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion

Jacqueline Stagner, Vanessa Dias Alves, Ramani Narayan, Adelaide Beleia

    Research output: Contribution to journalArticle

    • 10 Citations

    Abstract

    Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.

    Original languageEnglish (US)
    Pages (from-to)589-597
    Number of pages9
    JournalJournal of Polymers and the Environment
    Volume19
    Issue number3
    DOIs
    StatePublished - Sep 2011

    Profile

    Starch
    Glycerol
    Thermoplastics
    Maleic anhydride
    Extrusion
    Temperature
    Acetanilides
    Dextrothyroxine
    Free radicals
    Hydrodynamics
    Alphavirus
    Molecular weight
    Chemical modification
    Plasticizers
    Esterification
    Extruders
    Dynamic light scattering
    Acetone
    Thermoanalysis
    Fourier transform infrared spectroscopy

    Keywords

    • Biodegradable
    • Maleation
    • Reactive extrusion
    • Thermoplastic starch

    ASJC Scopus subject areas

    • Environmental Engineering
    • Polymers and Plastics
    • Materials Chemistry

    Cite this

    Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion. / Stagner, Jacqueline; Alves, Vanessa Dias; Narayan, Ramani; Beleia, Adelaide.

    In: Journal of Polymers and the Environment, Vol. 19, No. 3, 09.2011, p. 589-597.

    Research output: Contribution to journalArticle

    Stagner, Jacqueline; Alves, Vanessa Dias; Narayan, Ramani; Beleia, Adelaide / Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion.

    In: Journal of Polymers and the Environment, Vol. 19, No. 3, 09.2011, p. 589-597.

    Research output: Contribution to journalArticle

    @article{9862b05f0a334ce48abffcb842fa4de7,
    title = "Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion",
    abstract = "Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.",
    keywords = "Biodegradable, Maleation, Reactive extrusion, Thermoplastic starch",
    author = "Jacqueline Stagner and Alves, {Vanessa Dias} and Ramani Narayan and Adelaide Beleia",
    year = "2011",
    month = "9",
    doi = "10.1007/s10924-011-0307-3",
    volume = "19",
    pages = "589--597",
    journal = "Journal of Polymers and the Environment",
    issn = "1566-2543",
    publisher = "Springer New York",
    number = "3",

    }

    TY - JOUR

    T1 - Thermoplasticization of High Amylose Starch by Chemical Modification Using Reactive Extrusion

    AU - Stagner,Jacqueline

    AU - Alves,Vanessa Dias

    AU - Narayan,Ramani

    AU - Beleia,Adelaide

    PY - 2011/9

    Y1 - 2011/9

    N2 - Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.

    AB - Modified thermoplastic high amylose starch (MTPS) was synthesized by reactive extrusion in the presence of maleic anhydride (MA) as an esterification agent in a twin-screw extruder. The objective of this work was the preparation of reactive thermoplastic starch in the presence of glycerol and with different amounts of maleic anhydride (MA) and free-radical initiator, in order to improve processability and reactivity. The concentration of MA added varied from 2 to 6 wt% (of starch + glycerol), and the free-radical initiator, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, also called Luperox 101, varied from 0.1 to 0.5 wt% (of starch + glycerol). Characterization of maleated thermoplastic starch was performed using dynamic light scattering and thermal analysis. Further, proof of chemically modified extrudate was determined by Fourier transform infrared spectroscopy and by soxhlet extraction with acetone. The modified high amylose corn starch (20 or 30% glycerol) could be pelletized and gave pellets that were more transparent than thermoplastic starches not modified with maleic anhydride. There was negligible change in hydrodynamic radius as the percentage of maleic anhydride increased. However, as the percentage of Luperox 101 increased, the hydrodynamic radius decreased. It could be inferred that the molecular weight decreased as the percentage of free-radical initiator increased. Using the maximum temperature in the extrusion process of 165 °C instead of 135 °C caused a decrease in the hydrodynamic radius, due to the high influence of the temperature profile on the molecular weight of the thermoplastic starch. The MTPS samples presented higher melting temperatures compared to TPS samples. The soxhlet studies indicated that the plasticizer, glycerol, was chemically linked to the starch. Using the maximum temperature of 165 °C versus 135 °C in the extrusion temperature profile resulted in more interaction between glycerol and starch.

    KW - Biodegradable

    KW - Maleation

    KW - Reactive extrusion

    KW - Thermoplastic starch

    UR - http://www.scopus.com/inward/record.url?scp=80052038762&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=80052038762&partnerID=8YFLogxK

    U2 - 10.1007/s10924-011-0307-3

    DO - 10.1007/s10924-011-0307-3

    M3 - Article

    VL - 19

    SP - 589

    EP - 597

    JO - Journal of Polymers and the Environment

    T2 - Journal of Polymers and the Environment

    JF - Journal of Polymers and the Environment

    SN - 1566-2543

    IS - 3

    ER -