An Analysis of the Complex Participation Model for Free-Radical Copolymerization

Cais, R. E.; Farmer, R. G.; Hill, D. J. T.; O’Donnell, James H.

doi:10.1021/ma60071a009

Cited by 82 publications

(37 citation statements)

References 1 publication

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“…Also the values obtained from the ME copolymerization method deviate from the values obtained by CE co-polymerization method with HA as co-surfactant under the present study ( Table 5). The differences of the results obtained by ME and CE co-polymerizations with HA as the co-surfactant in these reaction media, and also deviations from the literature re-sults (Table 5) may be due to reasons such as temperature variation of the reaction medium [15], differences in the solubilities of monomers in aqueous phase [17,18,30], presence of the solvent HA in the reaction loci [1][2][3][4][5][6][7][8][9][10][11] and differences of the monomer partitioning in different phases of the reaction media [17,18,28].…”

Section: ] and Mayo-lewis Integration (M-l-i) [23] Methods (Figs 3 mentioning

confidence: 77%

“…The effect of solvents having different dielectric constants, solubility parameters and dipole moments have been studied in the literature [1][2][3][4]. Other possible phenomena that can lead to the dependence of reaction velocity upon the nature of the solvent are complex formation or solvation of one monomer by the solvent [5][6][7], and preferential solvation of the polymer coil by one of the monomers causing heterogeneous repartition of the monomer mixture in solution (bootstrap effect) [8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

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Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

Reddy

Thomas

Radhakrishnan

2008

Designed Monomers and Polymers

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Microemulsion (ME) and conventional emulsion (CE) co-polymerization of p-methyl styrene (pMSTY) with methyl methacrylate (MMA) are carried out at 70 • C using n-pentanol (PA) and n-hexanol (HA), respectively, as co-surfactants along with sodium lauryl sulphate (SLS) as surfactant in the reaction media, and potassium persulphate (KPS) as initiator. The co-polymers are characterized by NMR and GPC techniques. The reactivity ratios are evaluated by employing Fineman-Ross (F-R), Kelen-Tüdös (K-T) and Mayo-Lewis integration (M-L-I) methods. The K-T method yields the reactivity ratios 0.68 ± 0.02 (r pMSTY ), 0.40 ± 0.02 (r MMA ), 0.68 ± 0.02 (r pMSTY ) and 0.68 ± 0.02 (r MMA ), respectively, for the ME and CE co-polymerizations of pMSTY and MMA with PA as co-surfactant in the reaction media. The K-T method yields the reactivity ratios 1.09 ± 0.02 (r pMSTY ), 0.37 ± 0.02 (r MMA ) and 0.78 ± 0.02 (r pMSTY ) and 0.54 ± 0.02 (r MMA ), respectively, for the ME and CE co-polymerization of pMSTY and MMA with HA as co-surfactant in the reaction media.  Koninklijke Brill NV, Leiden, 2008

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Section: ] and Mayo-lewis Integration (M-l-i) [23] Methods (Figs 3 mentioning

confidence: 77%

Section: Introductionmentioning

confidence: 99%

Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

Reddy

Thomas

Radhakrishnan

2008

Designed Monomers and Polymers

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“…Comparing the double bonds of AM and styrene comonomers with poor-electron and rich-electron density, respectively, a nearby complete alternating copolymer can be formed by free radical copolymerization. The copolymerization behavior of truly alternating styrenemaleic anhydride copolymer has already been reported by many researchers [23][24][25][26]. But, the silicon-containing AM systems are still rarely seen in literature [27,28].…”

Section: Introductionmentioning

confidence: 94%

Studies of silicon-containing maleimide polymers. Part II: Synthesis and properties of poly(styrene-co-brominecontaining maleimide).

2007

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Soluble copolymers of a series of bromine-containing (N-maleimido phenoxy) silane (BMS) monomers with styrene (St) were synthesized by radical polymerization in toluene using 2,2'-azobisisobutyronitrile (AIBN) as initiator. The comonomer reactivity ratios were calculated by the conventional Fineman-Ross and Kelen-Tüdos methods and a nonlinear least-squares Tidwell-Mortimer method. The glass transition temperatures (T g 's) and thermal degradation of copolymers were determined by differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA) respectively. The introduction of silane side-chain into maleimide (MI) monomers changed the comonomer reactivity ratio with styrene from alternating to azeotropic copolymerization. The curves of T g 's versus the different compositions of the above synthesized St-BMS copolymers matched a modified T g 's equation as a increase in the effect of weight ratio on alternating-segment, and an S-shaped curve of deviation in comparison with the Fox's equation. The MIsegments within these copolymers exhibited a good compatibility and, the flame retardancy of polystyrene could be enhanced via the introduction of Si/Brcontaining maleimide.

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“…[10][11][12][13] This was mainly due to the electron-withdrawing effect of silane side chains to inhibit the carbonyl pairs withdrawing electron effect of double bond within maleimide. Besides, the polarity of styrenes was also affected by their deactivators.…”

Section: Copolymerization and Copolymer Propertiesmentioning

confidence: 99%

“…The copolymerization behavior of truly alternating styrene-maleic anhydride copolymer has already been reported by many researches. [10][11][12][13] But, the silicon-containing AM systems are still rarely seen in literature.…”

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confidence: 99%

Studies of Novel Copolymers for Deep-UV Photoresists. I. Synthesis and Properties of Poly(Styrene-co-Silicon-containing maleimide)

Shu

2006

Polym J

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ABSTRACT:Soluble copolymers of trimethyl (4-(N-maleimido) phenoxy) silane (TMMS) with styrene-series monomers were synthesized by radical polymerization in toluene at 70 C using 2, 2 0 -azobisisobutyronitrile (AIBN)as initiator. The comonomer reactivity ratios were calculated by the conventional Fineman-Ross and Kelen-Tüdos methods and a nonlinear least-squares Tidwell-Mortimer method. The glass transition temperatures (T g s) and thermal degradation of copolymers were determined by differential scanning calorimetric (DSC) and thermo-gravimetric analysis (TGA) methods, respectively. The comonomer reactivity ratio of TMMS with styrene was changed from a alternating to middle type between alternating and ideal copolymerization for the side-chain of TMMS and the deactivators of styrene. The curves of T g s versus the different compositions of the above synthesized styrene-maleimide copolymers matched the modified Johnston's equation as increasing the affect of weight ratio on alternating-segment, and exhibited an S-shaped curve of deviation in comparison with the Fox's equation. The maleimide-segments and styrene-segments within these copolymers were completely compatible and the thermal stability and flame retardancy of polystyrene could be enhanced simultaneously via the introduction of silicon-containing maleimide.

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An Analysis of the Complex Participation Model for Free-Radical Copolymerization

Cited by 82 publications

References 1 publication

Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

Studies of silicon-containing maleimide polymers. Part II: Synthesis and properties of poly(styrene-co-brominecontaining maleimide).

Studies of Novel Copolymers for Deep-UV Photoresists. I. Synthesis and Properties of Poly(Styrene-co-Silicon-containing maleimide)

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