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Free-Radical Emulsion Copolymerization of Ethylene and Butyl Acrylate Monomers: Synthesis, Properties, and Application.

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Title: Free-Radical Emulsion Copolymerization of Ethylene and Butyl Acrylate Monomers: Synthesis, Properties, and Application.
Authors: Alsugai, Ibrahim M.1 (AUTHOR), Remanan, Sanjay2 (AUTHOR), Al-Harthi, Mamdouh A.1,2 (AUTHOR) mamdouh@kfupm.edu.sa
Source: Arabian Journal for Science & Engineering (Springer Science & Business Media B.V. ). Jun2026, Vol. 51 Issue 12, p15025-15041. 17p.
Subject Terms: *Copolymerization, *Ethylene, *Acrylates, *Polymer blends, *Polymer structure, *Emulsion polymerization, *Thermal properties
Abstract: This work presents a novel approach for synthesizing ethylene–butyl acrylate (PEBA) copolymers via free-radical emulsion polymerization under high-pressure conditions, using ammonium persulfate (APS) as the initiator. Unlike conventional emulsion systems limited by poor ethylene solubility, we employed a high-pressure autoclave to systematically explore the influence of temperature (60, 70, and 80 °C), ethylene pressure (15, 20, and 25 bar), and butyl acrylate (BA) concentration on ethylene incorporation and resulting copolymer properties. Nuclear magnetic resonance (1H and 13C NMR) analysis confirmed that increasing both temperature and pressure significantly enhances ethylene incorporation into the polymer backbone. The resulting copolymers exhibited a marked reduction in glass transition temperature (Tg) from – 43.9 °C in PBA to as low as – 49.7 °C alongside improved thermal stability, with decomposition temperatures exceeding 400 °C. Morphological studies via SEM and TEM revealed the formation of semi-cylindrical micelle structures with rough surface textures, indicative of structural rearrangement due to copolymerization. Importantly, the synthesized PEBA copolymers were blended with high-density polyethylene (HDPE), leading to a notable increase in storage modulus up to 15 wt% addition, thereby demonstrating potential as mechanical performance modifiers. Water contact angle measurements showed enhanced hydrophobicity (up to 95.5°), suggesting promising applications in water-repellent coatings and polymer blend compatibilization. This work offers a scalable alternative to coordination and controlled radical polymerizations for producing functionalized polyolefins with tunable properties under high-pressure emulsion conditions. [ABSTRACT FROM AUTHOR]
Database: Energy & Power Source
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Header DbId: enr
DbLabel: Energy & Power Source
An: 194774456
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
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  Data: Free-Radical Emulsion Copolymerization of Ethylene and Butyl Acrylate Monomers: Synthesis, Properties, and Application.
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  Data: *<searchLink fieldCode="DE" term="%22Copolymerization%22">Copolymerization</searchLink><br />*<searchLink fieldCode="DE" term="%22Ethylene%22">Ethylene</searchLink><br />*<searchLink fieldCode="DE" term="%22Acrylates%22">Acrylates</searchLink><br />*<searchLink fieldCode="DE" term="%22Polymer+blends%22">Polymer blends</searchLink><br />*<searchLink fieldCode="DE" term="%22Polymer+structure%22">Polymer structure</searchLink><br />*<searchLink fieldCode="DE" term="%22Emulsion+polymerization%22">Emulsion polymerization</searchLink><br />*<searchLink fieldCode="DE" term="%22Thermal+properties%22">Thermal properties</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: This work presents a novel approach for synthesizing ethylene–butyl acrylate (PEBA) copolymers via free-radical emulsion polymerization under high-pressure conditions, using ammonium persulfate (APS) as the initiator. Unlike conventional emulsion systems limited by poor ethylene solubility, we employed a high-pressure autoclave to systematically explore the influence of temperature (60, 70, and 80 °C), ethylene pressure (15, 20, and 25 bar), and butyl acrylate (BA) concentration on ethylene incorporation and resulting copolymer properties. Nuclear magnetic resonance (1H and 13C NMR) analysis confirmed that increasing both temperature and pressure significantly enhances ethylene incorporation into the polymer backbone. The resulting copolymers exhibited a marked reduction in glass transition temperature (Tg) from – 43.9 °C in PBA to as low as – 49.7 °C alongside improved thermal stability, with decomposition temperatures exceeding 400 °C. Morphological studies via SEM and TEM revealed the formation of semi-cylindrical micelle structures with rough surface textures, indicative of structural rearrangement due to copolymerization. Importantly, the synthesized PEBA copolymers were blended with high-density polyethylene (HDPE), leading to a notable increase in storage modulus up to 15 wt% addition, thereby demonstrating potential as mechanical performance modifiers. Water contact angle measurements showed enhanced hydrophobicity (up to 95.5°), suggesting promising applications in water-repellent coatings and polymer blend compatibilization. This work offers a scalable alternative to coordination and controlled radical polymerizations for producing functionalized polyolefins with tunable properties under high-pressure emulsion conditions. [ABSTRACT FROM AUTHOR]
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RecordInfo BibRecord:
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    Identifiers:
      – Type: doi
        Value: 10.1007/s13369-025-10883-7
    Languages:
      – Code: eng
        Text: English
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      Pagination:
        PageCount: 17
        StartPage: 15025
    Subjects:
      – SubjectFull: Copolymerization
        Type: general
      – SubjectFull: Ethylene
        Type: general
      – SubjectFull: Acrylates
        Type: general
      – SubjectFull: Polymer blends
        Type: general
      – SubjectFull: Polymer structure
        Type: general
      – SubjectFull: Emulsion polymerization
        Type: general
      – SubjectFull: Thermal properties
        Type: general
    Titles:
      – TitleFull: Free-Radical Emulsion Copolymerization of Ethylene and Butyl Acrylate Monomers: Synthesis, Properties, and Application.
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            NameFull: Alsugai, Ibrahim M.
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            NameFull: Remanan, Sanjay
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            NameFull: Al-Harthi, Mamdouh A.
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            – D: 15
              M: 06
              Text: Jun2026
              Type: published
              Y: 2026
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              Value: 51
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              Value: 12
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            – TitleFull: Arabian Journal for Science & Engineering (Springer Science & Business Media B.V. )
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