Terpolymerization kinetics of <i>N,N</i>‐dimethylaminoethyl methacrylate/alkyl methacrylate/styrene systems

Šoljić, Ivana; Jukić, Ante; Janović, Zvonimir

doi:10.1002/pen.21573

Cited by 18 publications

(18 citation statements)

References 36 publications

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“…The F–R equation represents one of the earliest attempts to linearize the copolymer composition equation :

G = r_{St} \cdot H - r_{FSt} .

…”

Section: Resultsmentioning

confidence: 99%

“…The K–T method introduces new parameters into the linearized copolymerization equation :

η = true(r_{St} + \frac{r_{FSt}}{α} true) \cdot ξ - \frac{r_{FSt}}{α},

where η and ξ are functions of the parameters G and H ,

η = \frac{G}{α + H} ξ = \frac{H}{α + H}

and α is a constant equals ( H max H min ) 1 / 2 where H max , H min are the highest and lowest values of H , respectively. The domain for the variation of ξ is between 0 and 1, whereas the domain for H is 0 and ∞.…”

Section: Resultsmentioning

confidence: 99%

“…These copolymers may be used as novel optical materials . Soljić et al presented copolymer of N , N ‐dimethylaminoethyl methacrylate and styrene with well‐defined properties, which can improve of rheological properties of lubricating mineral oils . In other work, authors surveyed sensitivity of poly(dioxolanylmethyl acrylate‐ co ‐styrene) to UV radiations and revealed that such copolymer may be used as photoresists .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

et al. 2013

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Homo‐ and copolymers of 4‐fluorostyrene (FSt) and styrene (St) were synthesized with different feed ratios using free radical bulk polymerization with azobisisobutyronitrile (AIBN) as initiator. It yielded series of (co)polymers with various amounts of included FSt, P(St‐co‐FSt) (5–50 mol%) and PFSt. The effect of the initiator concentration on the molecular weights of the homopolymers, that is, PSt and PFSt was investigated. Copolymer compositions were determined by nuclear magnetic resonance spectroscopy. The relative reactivity ratios of both comonomers were determined by applying the conventional linearization methods of Jaacks (J), Finemann–Ross (F–R), inverted Finemann–Ross (IF–R), and Kelen‐Tüdos (K–T). The reactivity ratios values of St and FSt obtained from J plot are 1.06 and 0.84, F–R plot are 1.18 and 1.06, IF–R 1.01 and 0.86, and K–T plot 1.04 and 0.88, respectively. Thermal properties of prepared (co)polymers, that is, glass transition temperature (Tg) and thermal stability, were determined from differential scanning calorimetry and thermogravimetrical measurements. The lack of significant influence of FSt comonomer content on Tg of (co)polymers was observed. Additionally, the thermal degradation kinetics of obtained PSt and PFSt was studied by thermogravimetric analysis. Kinetic parameters such as the thermal decomposition activation energy (E) and frequency factor (A) were estimated by Ozawa model [E(O) and A(O), respectively] and Kissinger model [E(K) and A(K), respectively]. The activation energy and the frequency factor of PFSt (253 kJ/mol) were higher than PSt (236 kJ/mol). The resulting activation energies estimated using the two methods were quite close. POLYM. ENG. SCI., 54:1170–1181, 2014. © 2013 Society of Plastics Engineers

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“…The F–R equation represents one of the earliest attempts to linearize the copolymer composition equation :

G = r_{St} \cdot H - r_{FSt} .

…”

Section: Resultsmentioning

confidence: 99%

“…The K–T method introduces new parameters into the linearized copolymerization equation :

η = true(r_{St} + \frac{r_{FSt}}{α} true) \cdot ξ - \frac{r_{FSt}}{α},

where η and ξ are functions of the parameters G and H ,

η = \frac{G}{α + H} ξ = \frac{H}{α + H}

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

et al. 2013

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“…Furthermore, for the ST/DPA system, the reactivity of ST is significantly higher. This leads to r ST = 2.5 relative to 1.74 for the ST/DMAEMA system …”

Section: Resultsmentioning

confidence: 99%

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Faraguna

Vidović

Jukić

2015

Polymer International

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Free radical copolymerization kinetics of 2-(diisopropylamino)ethyl methacrylate (DPA) with styrene (ST) or methyl methacrylate (MMA) was investigated and the corresponding copolymers obtained were characterized. Polymerization was performed using tert-butylperoxy-2-ethylhexanoate (0.01 mol dm −3 ) as initiator, isothermally (70 ∘ C) to low conversions (<10 wt%) in a wide range of copolymer compositions (10 mol% steps). The reactivity ratios of the monomers were calculated using linear Kelen-Tüdős (KT) and nonlinear Tidwell-Mortimer (TM) methods. The reactivity ratios for MMA/DPA were found to be r 1 = 0.99 and r 2 = 1.00 (KT), r 1 = 0.99 and r 2 = 1.03 (TM); for the ST/DPA system r 1 = 2.74, r 2 = 0.54 (KT) and r 1 = 2.48, r 2 = 0.49 (TM). It can be concluded that copolymerization of MMA with DPA is ideal while copolymerization of ST with DPA has a small but noticeable tendency for block copolymer building. The probabilities for formations of dyad and triad monomer sequences dependent on monomer compositions were calculated from the obtained reactivity ratios. The molar mass distribution, thermal stability and glass transition temperatures of synthesized copolymers were determined. Hydrophobicity of copolymers depending on the composition was determined using contact angle measurements, decreasing from hydrophobic polystyrene and poly(methyl methacrylate) to hydrophilic DPA. Copolymerization reactivity ratios are crucial for the control of copolymer structural properties and conversion heterogeneity that greatly influence the applications of copolymers as rheology modifiers of lubricating oils or in drug delivery systems.

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“…and , the distribution of occurrence probability of dyads and triads of copolymers of MMA or ST and n ‐alkyl methacrylate (DDMA + ODMA) is shown. Probabilities are calculated based on the reactivity ratios calculated by Fineman–Ross's method for the appropriate pseudo‐copolymerization systems . For the studied range of terpolymer composition, it is evident that with the increase of MMA and ST content in the copolymer the share of dyads and triads of MMA and ST increases, as well.…”

Section: Resultsmentioning

confidence: 99%

Thermal properties and side chain crystallinity of styrene and n‐alkyl methacrylate terpolymers

Karažija

Vidović

Jukić

2013

Polymer Engineering & Sci

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Differential scanning calorimetry method was used for the study of thermal properties of terpolymers of styrene (ST) or methyl methacrylate (MMA) with dodecyl methacrylate and octadecyl methacrylate. Particularly, the interdependencies of the crystallinity content and composition of terpolymers were examined. The increase of the MMA or ST content in terpolymers resulted in the increased glass transition temperatures and decrease of the ratio of crystalline relative to amorphous phase (from 10% for x MMA 5 10 mol% to 5.7% for x MMA 5 30 mol%, and from 8.5% for x ST 5 16 mol% to 4% for x ST 5 40 mol%). These kinds of copolymers are commonly used as flow improvers at low temperatures for lubricating mineral oils; therefore a direct correlation between flow behavior of polymer solutions in mineral oil (pour point) and side-chain crystallinity of copolymers was examined. Thus, by increasing the proportion of crystalline phases, i.e. the long-chain alkyl methacrylates in copolymer, the pour point of oil solutions lowers. Thus, the solution of terpolymer with crystalline phase content of 4 mol% displays the pour point of 29 C while in those with crystalline phase content higher than 7 mol% pour point lowers below 230 C. POLYM. ENG. SCI., 53:2299-2307,

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Terpolymerization kinetics of N,N‐dimethylaminoethyl methacrylate/alkyl methacrylate/styrene systems

Cited by 18 publications

References 36 publications

Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

Synthesis of polystyrene modified with fluorine atoms: Monomer reactivity ratios and thermal behavior

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Thermal properties and side chain crystallinity of styrene and n‐alkyl methacrylate terpolymers

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