Synthesis of functional polyethylene graft copolymers by nitroxide‐mediated living radical polymerization

Mohajery, Shabnam; Rahmani, Sohrab; Entezami, Ali Akbar

doi:10.1002/pat.1161

Cited by 17 publications

(13 citation statements)

References 23 publications

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“…The synthesis of functionalized polyolefins is very important in the development of new materials . The copolymerization of olefins with polar monomers would be the most effective way to attain functionalized polymers . However, both Ziegler–Natta (ZN) and metallocene catalysts are affected by poisoning, due to the interaction between polar groups and the active centers of the catalysts .…”

Section: Introductionmentioning

confidence: 99%

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Rahmatiyan

Bahri‐Laleh

Hanifpour

et al. 2018

Polymer International

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The behaviors of three different catalyst systems, TiCl4/MgCl2, Cp2ZrCl2 and Cp2HfCl2, were investigated in ethylene/1,5‐hexadiene copolymerization. In the Fourier transform infrared spectra of the copolymers, cyclization and branching were detected for 1,5‐hexadiene insertion in the metallocene and Ziegler–Natta systems, respectively. DSC and viscometry analyses results revealed that copolymers with lower Tm and crystallinity and higher molecular weight were obtained with metallocene catalysts. The sequence length distribution of the copolymers was investigated by using the successive self‐nucleation and annealing thermal fractionation technique. The continuous melting endotherms obtained from successive self‐nucleation and annealing analysis were employed to get information about short‐chain branching, the branching dispersity index, comonomer content and lamella thickness in the synthesized copolymers. The results established that metallocene catalysts were much more effective than Ziegler–Natta catalysts in the incorporation of 1,5‐hexadiene in the polyethylene structure. Metallocene‐based copolymers had higher short‐chain branching and comonomer content, narrower branching dispersity index and thinner lamellae. Finally, the tendency of the employed catalysts in the 1,5‐hexadiene incorporation and cyclization reaction was explored via molecular simulation. The energy results demonstrated that, in comparison to Ziegler–Natta, metallocene catalysts have a much higher tendency to 1,5‐hexadiene incorporation and cyclization. © 2018 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Rahmatiyan

Bahri‐Laleh

Hanifpour

et al. 2018

Polymer International

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“…Some examples are described in the literature where the preparation of macroalkoxyamine is carried out by a multi‐step procedure, which is often complex and time‐demanding . For example, Mohajery et al .…”

Section: Nrc Reaction In Peroxide‐initiated Post‐polymerization Modifmentioning

confidence: 99%

Post‐polymerization modification by nitroxide radical coupling

Coiai

Passaglia

Cicogna

2018

Polymer International

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Post‐polymerization modification is an attractive approach to extend applications and convert commodity plastics into products with new, desirable and tunable properties. Among the post‐polymerization modification methods, the nitroxide radical coupling (NRC) reaction has been shown to be a convenient and versatile way to graft specific functionalities onto polymer chains and to control the onset and yield of polymer crosslinking during peroxide‐initiated processes. The use of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) and its derivatives as controllers of scorch in crosslinking and as functionalizers in functionalization reactions is thoroughly described. Examples are also given of graft polymerization from macroalkoxyamines generated by NRC and grafting of nitroxides by irradiation processes. In addition, in this review we attempt to demonstrate the broad applications of the NRC reaction in the preparation of polymers with a multitude of functionalities and elaborate architectures. The examples discussed here concern the use of atom transfer and single electron transfer NRC reactions to design a variety of polymers with asymmetrical structure and the use of the radical crossover reaction, based on the alkoxyamine dynamic covalent bond, to generate reversible polymer structures and switchable functional polymers. © 2018 Society of Chemical Industry

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“…There are only a few reports concerning the synthesis of graft copolymers having polydimethylsiloxane and sPS by anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D 3 ) from a side chain functionalized syndiotactic polystyrene. 23 As a continuation of our extensive previous work related to chemical modification of polyolefines, [24][25][26][27][28] we now report the synthesis of graft copolymers of sPS and polydimethylsiloxane via a post polymerization approach involving the 1) preparation of syndiotactic poly(styrene-co-p-methylstyrene) (sPSMS), 2) anionic grafting from the reaction of hexamethylcyclotrisiloxane by a metallation reagent.…”

Section: Introductionmentioning

confidence: 98%

Grafted polydimethylsiloxane onto syndiotactic poly(styrene-co-p-methylstyrene): Synthesis and characterization

Rahmani

Entezami

2011

Macromol. Res.

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Syndiotactic polystyrene-graft-polydimethylsiloxane copolymers were synthesized using a two-stage process and characterized. First, the syndiotactic polystyrene copolymer, poly(styrene-co-p-methylstyrene) was prepared by the copolymerization of styrene and p-methylstyrene with cyclopentadienyltitanium trichloride/methylaluminoxane catalyst. The obtained copolymer was grafted with polydimethylsiloxane by the anionic ring-opening polymerization of hexamethylcyclotrisiloxane with a metallation reagent. The effect of the solvent on the degree of grafting in the obtained copolymers was investigated. 1 H NMR, 13 C NMR, FTIR spectroscopy and differential scanning calorimetery (DSC) were used to examine the structure and thermal behavior of the copolymers. The degree of graft was higher in THF. The melting, crystallization and glass-transition temperatures of the graft copolymers decreased with increasing degree of graft in the copolymers.

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Synthesis of functional polyethylene graft copolymers by nitroxide‐mediated living radical polymerization

Cited by 17 publications

References 23 publications

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Post‐polymerization modification by nitroxide radical coupling

Grafted polydimethylsiloxane onto syndiotactic poly(styrene-co-p-methylstyrene): Synthesis and characterization

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