• Title/Summary/Keyword: copolymerization kinetics

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Novel Superabsorbent Hydrogel Based on Natural Hybrid Backbone: Optimized Synthesis and its Swelling Behavior

  • Pourjavadi, Ali;Soleyman, Rouhollah;Bardajee, Ghasem Rezanejade;Ghavami, Somayeh
    • Bulletin of the Korean Chemical Society
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    • v.30 no.11
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    • pp.2680-2686
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    • 2009
  • The synthesis of a novel superabsorbent hydrogel with natural hybrid backbone via graft copolymerization of acrylamide (AAm) onto kappa-carrageenan (kC, as a polysaccharide) and gelatin (as a protein) under classic thermal conditions is described. The Taguchi method as a strong experimental design tool was used for synthesis optimization. A series of hydrogels were synthesized by proposed conditions of Qualitek-4 Software. Considering the results of 9 trials according to analysis of variance (ANOVA), optimum conditions were proposed. The swelling behavior of optimum hydrogel was measured in various solutions with pH values ranging from 1 to 13. In addition, swelling kinetics, swelling in various organic solvents, various salt solutions and On–Off switching behavior were investigated. The hydrogel formation was confirmed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetrical analysis (TGA). Surface morphology of the synthesized hydrogels was assessed by scanning electron microscope (SEM).

Kinetic Studies on Homopolymerization of $\alpha$-Methylstyrene and Sequential Block Copolymerization of Isobutylene with $\alpha$-Methylstyrene by Living/Controlled Cationic Polymerization (리빙/조절 양이온중합에 의한 알파메틸스티렌 호모중합 및 이소부틸렌과의 블록공중합에 대한 반응속도론 연구)

  • Wu, Yibo;Guo, Wenli;Li, Shuxin;Gong, Huiqing
    • Polymer(Korea)
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    • v.32 no.4
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    • pp.366-371
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    • 2008
  • The controlled/living cationic polymerization of $\alpha$-methylstyrene (${\alpha}MeSt$) and sequential block copolymerization of isobutylene (IB) with ${\alpha}MeSt$ were achieved using 2-chloro-2,4,4-trimethylpentane (TMPCl)/titanium tetrachloride ($TiCl_4$)/titanium isopropoxide ($Ti(OiPr)_4$)/2,6-ditert-butylpyridine (DtBP) initiating system in $CH_3Cl$/hexane(50/50 v/v) solvent mixture at $-80^{\circ}C$. The polymerization rate decreased with increasing $[Ti(OiPr)_4]/[TiCl_4]$ ratio in the homopolymerization of ${\alpha}MeSt$. The effects of $[Ti(OiPr)_4]/[TiCl_4]$ ratios and $PIB^+$ molecular weight on the polymerization rate and blocking efficiency were also investigated. Well-defined poly(isobutylene-b-$\alpha$-methylstyrene)s were demonstrated by $^1H$-NMR and triple detection SEC; refractive index (RI), multiangle laser light scattering (MALLS) and ultraviolet (UV) detectors. Blocking efficiencies for the poly(isobutylene-b-$\alpha$-methylstyrene)s of almost 100% were obtained when ${\alpha}MeSt$ was induced by PIB's of $M_n\;{\geq}\;41000$ at $[Ti(OiPr)_4]/[TiCl_4]=1$. Differential scanning calorimetry (DSC) of the block copolymers showed two glass transition temperatures, thereby demonstrating microphase separation.

Catalyzed Transesterification Kinetics in Early Stage of Polycarbonate Melt Polymerization (폴리카보네이트 용융중합 초기의 촉매기반 에스터 교환반응 동력학)

  • Jung, Ju Yeon;Lee, Ji Mok;Hong, Sung Kwon;Lee, Jin Kuk;Jung, Hyun Min;Kim, Yong Seok
    • Polymer(Korea)
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    • v.39 no.2
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    • pp.235-239
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    • 2015
  • In this work, we evaluated catalytic activity of LiOH, $Cu(acac)_2$ and n-butyltin hydroxide oxide hydrate in the early stage of the melt transesterification of isosorbide and bisphenol A as diol monomers and diphenylcarbonate for the melt polymerizaiton of polycarbonate. $Cu(acac)_2$ proved to be the most active catalyst for homopolymerization process, while the catalytic activity of LiOH was higher than the others in case of melt copolymerization depending on the catalytic mechanism and chemical structure of catalyst. We suggested that evaluation of catalytic activity can be used for selection of catalyst system in bio-based copolymerization of polycarbonate.

The Kinetics of Radical Copolymerization of Styrene with Alkyl Methacrylate in a CSTR (연속반응기에서 스티렌과 메타크릴산 알킬의 라디칼 공중합 반응속도론)

  • Kim, Nam Seok;Seul, Soo Duk;Cheong, Young Eon;Park, Keun Ho;Choi, Jong jueng
    • Applied Chemistry for Engineering
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    • v.10 no.5
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    • pp.796-803
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    • 1999
  • Solution copolymerization of styrene(St.) with methyl methacrylate(MMA), ethyl methacrylate(EMA) and n-butyl methacrylate(BMA) was carried out with benzoylperoxide(BPO) as an initiator in toluene at $80^{\circ}C$ in a continuous stirred tank reactor. Reaction volume and residence time were 0.6 liters and 3hours, respectively. The monomer reactivity ratios, $r_1(St.)$ and $r_2(RMA)$ determined by both the Kelen-Tudos method and the Fineman-Ross method were $r_1(St.)=0.60(0.61),\;r_2(MMA)=0.59(0.60);\;r_1(St.)=0.65(0.62),\;r_2(EMA)=0.55(0.52);\;r_1(St.)=0.75(0.67),\;r_2(BMA)=0.63(0.56)$. The cross-termination factor $\Phi$ of the copolymer over the entire St. compositions ranged from 0.26 to 0.96. The $\Phi$ factors of St.-RMA copolymer were increased with increasing St. content. The simulated conversions and copolymerization rates were compared with the experimental results. The average time to reach dynamic steady-state was three times and half of the residence time.

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Synthesis and characterization of silicone-containing polyamideimide and its gas separation

  • 이용범;심진기;이영무
    • Proceedings of the Membrane Society of Korea Conference
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    • 1997.10a
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    • pp.83-84
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    • 1997
  • 1. INTRODUCTION : Polyimides containing siloxane moiety(poly(imide siloxane), or polysiloxaneimide) have been synthesized because of their some merits over polyimide itseft. Polyimides have excellent thermal and mechanical properties but their poor solubility and processibility in their fullly imidized form give disadvantages in applications. Incorporation of siloxane units make it possible to increase solubility and processibility, and also impart impact resistance, low moisture uptake, low dielectric constant, thermo-oxidative resistance, good adhesion properties to substrate and etc.. Incorporation methods of siloxane groups into the polyimide was mainly copolymerization or terpolymerization between oligomeric dimethylsiloxane and aromatic dianhydride. A few methods of introducing siloxane units in functional groups of polyimide was reported. In our laboratory poly(amideimide siloxane) and poly(imide siloxane) were prepared and the study about their thermal kinetics was performed. In separation membrane area, polysiloxaneimides was utilized in pervaporation and gas separation. Polyimides in gas separation show high selectivity and very low permeability, and introduction of siloxane segments increase permeability with low decrease in selectivity. We aimed to introduce silicone segments into poly(amic acid) state and synthesize polymer partially imidized, and also show the gas separation characteristics of the synthesized polymer.

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Modified Carrageenan. 6. Crosslinked Graft Copolymer of Methacrylic Acid and kappa-Carrageenan as a Novel Superabsorbent Hydrogel with Low Salt- and High pH-Sensitivity

  • Pourjavadi A.;Harzandi A. M.;Hosseinzadeh H.
    • Macromolecular Research
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    • v.13 no.6
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    • pp.483-490
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    • 2005
  • A novel, polysaccharide-based, superabsorbent hydrogel was synthesized through crosslinking graft copolymerization of methacrylic acid (MAA) onto kappa-carrageenan ($_{k}C$), using ammonium persulfate (APS) as a free radical initiator in the presence of methylenebisacrylamide (MBA) as a crosslinker. A proposed mechanism for $_{k}C$­g-polymethacrylic acid ($_{k}C$-g-PMAA) formation was suggested and the hydrogel structure was confirmed using FTIR spectroscopy. The effect of grafting variables, including MBA, MAA, and APS concentration, was systematically optimized to achieve a hydrogel with the maximum possible swelling capacity. The swelling kinetics in distilled water and various salt solutions were preliminarily investigated. Absorbency in aqueous salt solutions of lithium chloride, sodium chloride, potassium chloride, calcium chloride, and aluminum chloride indicated that the swelling capacity decreased with increased ionic strength of the swelling medium. This behavior can be attributed to the charge screening effect for monovalent cations, as well as ionic crosslinking for multivalent cations. The swelling of super absorbing hydrogels was measured in solutions with pH ranging from 1 to 13. In addition, the pH reversibility and on-off switching behavior, at pH levels of 3.0 and 8.0, give the synthesized hydrogels great potential as an excellent candidate for the controlled delivery of bioactive agents.

Partially Hydrolyzed Crosslinked Alginate-graft-Polymethacrylamide as a Novel Biopolymer-Based Superabsorbent Hydrogel Having pH - Responsive Properties

  • Pourjavadi A.;Amini-Fazi M. S.;Hosseinzadeh H.
    • Macromolecular Research
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    • v.13 no.1
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    • pp.45-53
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    • 2005
  • In this study, a series of highly swelling hydrogels based on sodium alginate (NaAlg) and polymethacryl­amide (PMAM) was prepared through free radical polymerization. The graft copolymerization reaction was performed in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator and N,N'-methylenebis­acrylamide (MBA) as a crosslinker. The crosslinked graft copolymer, alginate-graft-polymethacrylamide (Alg-g­PMAM), was then partially hydrolyzed by NaOH solution to yield a hydrogel, hydrolyzed alginate-graft-poly­methacrylamide (H-Alg-g-PMAM). During alkaline hydrolysis, the carboxamide groups of Alg-g-PMAM were converted into hydrophilic carboxylate anions. Either the Alg-g-PMAM or the H-Alg-g-PMAM was characterized by FTIR spectroscopy. The effects of the grafting variables (i.e., concentration of MBA, MAM, and APS) and the alkaline hydrolysis conditions (i.e., NaOH concentration, hydrolysis time, and temperature) were optimized systematically to achieve a hydrogel having the maximum swelling capacity. Measurements of the absorbency in various aqueous salt solutions indicated that the swelling capacity decreased upon increasing the ionic strength of the swelling medium. This behavior could be attributed to a charge screening effect for monovalent cations, as well as ionic cross-linking for multivalent cations. Because of the high swelling capacity in salt solutions, however, the hydrogels might be considered as anti-salt superabsorbents. The swelling behavior of the superabsorbing hydrogels was also measured in solutions having values of pH ranging from 1 to 13. Furthermore, the pH reversibility and on/off switching behavior, measured at pH 2.0 and 8.0, suggested that the synthesized hydrogels were excellent candidates for the controlled delivery of bioactive agents. Finally, we performed preliminary investigations of the swelling kinetics of the synthesized hydrogels at various particle sizes.