H-Bonding Effect in Radical Terpolymerization of Maleic anhydride, Acrylic acid Methyl acrylate and Vinyl acetate

Abstract

The ternary copolymerization of vinyl acetate VA , maleic anhydride MA and acrylic acid AA or methylacrylate MAc as a model comonomer , considered as donor-acceptor-acceptor systems, was carried out in p-dioxane in the presence of benzoyl peroxide BPO as initiator in nitrogen atmosphere at 70ºC. Constants of copolymerization and complex formation for the monomer systems studied were determined by the Kelen-Tüdös, UV H-complex and 1H-NMR CTC, charge transfer complex methods, respectively. Analogous H-complex effect is evidenced from comparison of copolymerization of both MA-AA H-complex and MA-MAc binary systems in which are realized alternating and random copolymerization, respectively. Hydrolyzed VA- MA-AA terpolymers with different composition containing regular H-complexed fragments in side-chain of macromolecules are displayed different thermal properties, including glass-transition and melting crystalline phase behaviors, depending on content of H-bonding fragment. Structural peculiarities FTIR analysis and structure-thermal properties DSC and TGA analyses and crystalline X-ray diffraction analysis relationship of terpolymers synthesized are also discussed.

Keywords

• Copolymerization,terpolymerization,H-complex,charge transfer complex,structure-property relationship,thermal properties

Maleik Anhidrit, Akrilik Asit Metil Akrilat ve Vinil Asetat Terpolimerizasyonunda H-bağı Etkisi

Abstract

V inil asetat VA , Maleik Anhidrit MA ve Akrilik Asit AA veya Metil akrilat MAc, model komonomer alıcıverici-alıcı sisteminde; benzoil peroksit BPO başlatıcısı varlığında p-dioksan içerisinde azot atmosferinde 70oC’de üçlü kopolimerizasyon gerçekleştirilmiştir. Kopolimerizasyona ait sabitler ve monomer sistemlerinin oluşturduğu kompleks oluşumu Kelen-Tüdös, UV H-kompleksi ve 1H-NMR CTC, Yük Transfer Kompleksi yöntemleri kullanılarak belirlenmiştir. MA-AA H-kompleksi ve MA-MAc sistemlerinin ardışık ve gelişigüzel ikili kopolimerizasyon oluşumunda H-kompleksinin etkisi karşılaştırma yapılarak açıklanabilmektedir. Makromolekülün yan gruplarında, düzenli H-kompleksi içeren hidroliz olmuş farklı kompozisyonlara sahip VA-MA-AA terpolimeri; H-bağının içeriğine bağlı olarak, camsı geçiş sıcaklığı ve erime sıcaklığı kristal faz gibi farklı ısısal özellikler gösterirler. Sentezlenen terpolimerlerin yapısal farklılıkları FTIR analizi , yapı-ısısal özellikleri DSC ve TGA analizleri ve kristal özellikleri XRD analizi tartışılmıştır

Keywords

• Kopolimerizasyon,Terpolimerizasyon,H-kompleksi,Yük transfer kompleksi,Yapı-özellik ilişkileri,Isısal özellikler

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