Solution properties and unperturbed dimensions of stereoirregular poly(tert-butyl methacrylates)

Karandinos, Anthony; Nan, Shouyan; Mays, Jimmy W.; Hadjichristidis, Nikos

doi:10.1021/ma00008a044

Cited by 23 publications

(11 citation statements)

References 5 publications

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“…It is noteworthy that the obtained values of molecular weights (M n s) of poly(alkyl methacrylates) (PAMAs) from SEC measurement are ''apparent'' since the GPC instrument was calibrated using polystyrene standards (see column 5 of Table 1). Thus, the corrected M n values of these PAMAs were calculated following the principle of universal calibration using the available Mark-Houwink parameters in the literature, [36][37][38][39] which are provided in column 6 of Table 1. The data (entry numbers 1-3 of Table 1) also reveal that as the initial molar feed ratio of MMA to initiator increases, both the apparent and the corrected M n of the obtained PMMA increases (see columns 5 and 6 of Table 1), which is usually expected for a controlled polymerization system.…”

Section: Resultsmentioning

confidence: 99%

“…a Conditions: initiator (I) ¼ 1.02 Â 10 À4 mol; solvent ¼ 15 mL (THF); T ¼ 60 C; polymerization time ¼ 36 h. b M n (corrected) values were calculated using M n (SEC) values and applying the principle of universal calibration using the available Mark-Houwink parameters in the literature[36][37][38][39] at 30 C in THF. c Initiator efficiency (f) ¼ M n,cal /M n,SEC .…”

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confidence: 99%

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Free radical polymerization of alkyl methacrylates with N,N-dimethylanilinium p-toluenesulfonate at above ambient temperature: a quasi-living system

et al. 2010

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Free radical polymerization of alkyl methacrylates with N,N-dimethylanilinium p-toluenesulfonate at above ambient temperature: a quasi-living system

et al. 2010

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“…While the fractionation of PMMA and the poly(butyl methacrylate) samples is due to differences in chemical compositions, the fractionation of nBuMA and tBuMA is due to differences in molecular topology which affects the stiffness of the polymer chains. It has been reported that nBuMA is less rigid than tBuMA as they exhibit different characteristic ratios (C ∞ ) of 8.8 and 10.2, respectively . Furthermore, it has been shown that D T increases with increasing polymer rigidity, and from Table it can be seen that nBuMA exhibits a smaller D T value than tBuMA in THF .…”

Section: Resultsmentioning

confidence: 94%

Fractionation of Poly(butyl methacrylate) by Molecular Topology Using Multidetector Thermal Field‐Flow Fractionation

Greyling

Pasch

2015

Macromol. Rapid Commun.

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Thermal field-flow fractionation (ThFFF) is an interesting alternative to column-based fractionation being able to address different molecular parameters including size and composition. Until today it has not been shown to be able to fractionate polymers of similar molar masses and chemical compositions by molecular topology. The present study demonstrates that poly(butyl methacrylates) with identical molar masses can be fractionated by ThFFF according to the topology of the butyl group. The influence of the solvent polarity on the thermal diffusion behavior of these polymers is presented and it is shown to have a significant influence on the fractionation of poly(n-butyl methacrylate) and poly(t-butyl methacrylate). Fractionation improves with increasing solvent polarity and solvent polarity may have a greater influence on fractionation than solvent viscosity. It is found that the thermal diffusion coefficient, D(T), as well as the hydrodynamic diameter, D(h), exhibit increasing trends with increasing solvent polarity. The solvent quality has a significant influence on the fractionation. It is found that cyclohexane, being a theta solvent for poly(t-butyl methacrylate) but not for poly(n-butyl methacrylate), significantly improves the fractionation of the samples by decreasing the diffusion rate of the former but not the latter.

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“…Concerning the side-chain group dependence of the average chain dimension, it is pertinent to refer to the literature data [31][32][33] for poly (methacrylic acid) derivatives (that is, polymethacrylates). The data show that an increase in size of side-chain groups of the polymethacrylates is accompanied by an increase in the coil-limiting value C ∞ of the characteristic ratio, that is, an increase in the average chain dimension.…”

Section: Discussionmentioning

confidence: 99%

Dilute solution properties of poly(di-tert-butyl fumarate)

Awazu

Komatsubara

Osa

et al. 2016

Polym J

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The mean-square radius of gyration 〈S 2 〉 and second virial coefficient A 2 are determined from static light scattering (LS) measurements for six samples of poly(di-tert-butyl fumarate) (PDtBF) for a range of weight-average molecular weight M w from 4.35 × 10 4 to 1.73 × 10 5 in tetrahydrofuran at 30.0°C. The intrinsic viscosity [η] and translational diffusion coefficient D are also determined from viscosity and dynamic LS measurements for those samples under the same solvent conditions. From a simultaneous analysis of 〈S 2 〉 and A 2 based on the Kratky-Porod (KP) wormlike chain with excluded volume, the stiffness parameter λ − 1 and the reduced excluded-volume strength λB are determined to be 350 Å and 0.024, respectively, where we assume the shift factor M L for PDtBF to be 101 Å − 1 on the analogy of the main-chain structure of poly(diisopropyl fumarate) previously studied. For PDtBF with such a large λ − 1 , it is found that the intramolecular excluded-volume effect for 〈S 2 〉 is negligibly small in the range of M w examined. As for [η] and D, their behavior may be well explained by the corresponding KP theories using the model parameter values consistent with those determined from 〈S 2 〉 and A 2 , and the intramolecular excludedvolume effect for them can be ignored, as in the case of 〈S 2 〉.

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Solution properties and unperturbed dimensions of stereoirregular poly(tert-butyl methacrylates)

Cited by 23 publications

References 5 publications

Free radical polymerization of alkyl methacrylates with N,N-dimethylanilinium p-toluenesulfonate at above ambient temperature: a quasi-living system

Free radical polymerization of alkyl methacrylates with N,N-dimethylanilinium p-toluenesulfonate at above ambient temperature: a quasi-living system

Fractionation of Poly(butyl methacrylate) by Molecular Topology Using Multidetector Thermal Field‐Flow Fractionation

Dilute solution properties of poly(di-tert-butyl fumarate)

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