Precise synthesis of a series of poly(4-n-alkylstyrene)s and their glass transition temperatures

Matsushima, Satoru; Takano, Atsushi; Takahashi, Yoshiaki; Matsushita, Yushu

doi:10.1002/polb.24326

Cited by 9 publications

(10 citation statements)

References 35 publications

(67 reference statements)

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“…We conducted a literature search and found that most of the reported T g,∞ values fell below ∼ 500 K (Brandrup et al, 1999;Fox Jr. and Flory, 1950;Onder et al, 1972;Montserrat and Colomer, 1984;Papadopoulos et al, 2004;Matsushima et al, 2017). The Fox-Flory equation works very well for high-molarmass compounds and is also generally applicable to smaller compounds , as supported by an approximately linear dependence of T g on the inverse molar mass in Fig.…”

Section: Introductionmentioning

confidence: 86%

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

et al. 2018

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Abstract. Secondary organic aerosol (SOA) accounts for a large fraction of submicron particles in the atmosphere. SOA can occur in amorphous solid or semi-solid phase states depending on chemical composition, relative humidity (RH), and temperature. The phase transition between amorphous solid and semi-solid states occurs at the glass transition temperature (T g ). We have recently developed a method to estimate T g of pure compounds containing carbon, hydrogen, and oxygen atoms (CHO compounds) with molar mass less than 450 g mol −1 based on their molar mass and atomic O : C ratio. In this study, we refine and extend this method for CH and CHO compounds with molar mass up to ∼ 1100 g mol −1 using the number of carbon, hydrogen, and oxygen atoms. We predict viscosity from the T g -scaled Arrhenius plot of fragility (viscosity vs. T g /T ) as a function of the fragility parameter D. We compiled D values of organic compounds from the literature and found that D approaches a lower limit of ∼ 10 (±1.7) as the molar mass increases. We estimated the viscosity of α-pinene and isoprene SOA as a function of RH by accounting for the hygroscopic growth of SOA and applying the Gordon-Taylor mixing rule, reproducing previously published experimental measurements very well. Sensitivity studies were conducted to evaluate impacts of T g , D, the hygroscopicity parameter (κ), and the Gordon-Taylor constant on viscosity predictions. The viscosity of toluene SOA was predicted using the elemental composition obtained by high-resolution mass spectrometry (HRMS), resulting in a good agreement with the measured viscosity. We also estimated the viscosity of biomass burning particles using the chemical composition measured by HRMS with two different ionization techniques: electrospray ionization (ESI) and atmospheric pressure photoionization (APPI). Due to differences in detected organic compounds and signal intensity, predicted viscosities at low RH based on ESI and APPI measurements differ by 2-5 orders of magnitude. Complementary measurements of viscosity and chemical composition are desired to further constrain RH-dependent viscosity in future studies.

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Section: Introductionmentioning

confidence: 86%

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

et al. 2018

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“…Degree of polymerizations, DPs, were determined from M w s divided by molecular weights of monomers. Poly(4‐ n ‐alkylstyrene) samples were coded as PC m St_ X following the same manner adopted in the previous article, where m and X denote the number of carbon atom in n ‐alkyl side group and the molecular weight, respectively. For instance, PC1St_6 expresses poly(4‐methylstyrene) with molecular weight of 6 kg/mol.…”

Section: Methodsmentioning

confidence: 99%

“…Syntheses and characterization of all the poly(4-n-alkylstyrene)s used in the present work were already reported in a Additional Supporting Information may be found in the online version of this article. previous article, 32 and their molecular characteristics are summarized in Table 1. Polyisoprenes were also synthesized by living anionic polymerizations in benzene using sec-BuLi as an initiator at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…In the previous work, we have synthesized a series of poly(4‐ n ‐alkylstyrene)s, whose n ‐alkyl groups are methyl, ethyl, propyl, butyl, hexyl, and octyl, via living anionic polymerizations and reported and discussed their glass transition temperatures . Successively we regarded that these poly(4‐ n ‐alkylstyrene)s are suitable polymers to investigate miscibility with PI.…”

Section: Introductionmentioning

confidence: 99%

“…In the previous work, we have synthesized a series of poly(4-n-alkylstyrene)s, whose n-alkyl groups are methyl, ethyl, propyl, butyl, hexyl, and octyl, via living anionic polymerizations and reported and discussed their glass transition temperatures. 32 Successively we regarded that these poly(4n-alkylstyrene)s are suitable polymers to investigate miscibility with PI. In this article, therefore we discuss the compatibility of poly(4-n-alkylstyrene)s and 1,4-PI by observing their structures in bulk by differential scanning calorimetry (DSC) combined with optical microscopy (OM).…”

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confidence: 99%

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Alkyl side chain length dependent compatibility of poly(4‐n‐alkylstyrene)s and 1,4‐rich polyisoprene blends

Matsushima

Takano

Matsushita

2017

J Polym Sci B Polym Phys

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We investigated the compatibility of blends of 1,4‐rich polyisoprene (1,4‐PI) and poly(4‐n‐alkylstyrene)s with six kinds of n‐alkyl side groups, that is, methyl, ethyl, propyl, butyl, hexyl, and octyl focusing on carbon number of alkyl groups. Poly(4‐methylstyrene)/1,4‐PI blend was turned out to be immiscible at all temperature range adopted in this work and poly(4‐ethylstyrene)/1,4‐PI blend revealed UCST type phase behavior, while the others were found to be compatible. The phase diagrams of poly(4‐ethylstyrene)/1,4‐PI blends were obtained by optical microscopy, and the temperature dependence of the Flory‐Huggins interaction parameter χ has been estimated to be χ = −0.036 + 24/T by applying lattice theory, where T is the absolute temperature. From this relationship χ value at room temperature (298 K) was calculated to be 0.045, the value is reasonably low for miscible polymers system. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1791–1797

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DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

Bier

Six

Durand

2019

Macro Materials & Eng

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flame retardant, DOPO is also attractive because PH bond can be easily modified into PN, PO, or PC bonds, leading to improved thermal stability. [5][6][7][9][10][11][12] DOPO has been successfully used as an additive in many polymers (additive strategy) such as epoxy resins, [13,14] polyurethane, [9] acrylonitrile-butadiene-styrene copolymers, [15] polyamide, [16] and poly(methyl methacrylate) (PMMA). [17] Alternatively, DOPO-based monomers have been used to prepare matrices with chemically bound flame-retardant groups (reactive strategy) by step polymerization, like epoxy resins, [18][19][20][21] polyurethane, [22] poly(ethylene terephthalate), [23] polyamide, [24] ethylenevinyl acetate copolymer, [25] and polysulfone. [26,27] Nevertheless, to the best of our knowledge, only one study has been reported about the synthesis and application of DOPO-derived acrylate monomer for the preparation of flame resistant thermoplastic matrix by free radical polymerization. [28] More precisely, the latter monomer was first derived from acryloyl chloride with DOPO covalently linked as side group, then copoly merized with methyl methacrylate (MMA).Because of the very limited number of available studies, there is a need for new flame-retardant monomers able to react with common monomers via free radical polymerization. While bringing flame-retardant properties, these monomers should also preserve mechanical properties of final polymeric materials. The first requirement regarding mechanical properties is generally that the materials exhibit a high enough glass transition temperature (T g ) as compared to the conditions of targeted application. Indeed, when flame-retardant additives are blended with thermoplastics, they often act as plasticizers and consequently lower the T g of the final material, which may be a serious drawback. Such effect has been reported for DOPO. [17] Thus, the reactive strategy appears promising for providing efficient flame-retardant properties while limiting undesirable plasticizing effect.This work aimed at exploring a reactive strategy involving the design and the use of functional monomers with DOPO pending groups for including significant amounts of phosphorus in the material while keeping high enough T g . To that goal, DOPO was used as the precursor of the flame-retardant moiety and was covalently linked to methacrylate groups by aliphatic hydrocarbon spacers with number of carbon atoms ranging between 3 and 11 (Figure 2). Chemical structure and purity of the prepared novel phosphorus-containing methacrylic monomers were verified by combining several NMR Phosphorus-Containing MethacrylatesA two-step synthetic procedure is designed for preparing new flame-retardant methacrylic monomers containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as a substituent side group. DOPO and methacrylate moieties are linked by linear aliphatic hydrocarbon spacers (3 to 11 carbon atoms). Copolymerization with methyl methacrylate is carried out leading to copolymers containing between 2 and 10 wt% ...

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Precise synthesis of a series of poly(4-n-alkylstyrene)s and their glass transition temperatures

Cited by 9 publications

References 35 publications

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Predicting the glass transition temperature and viscosity of secondary organic material using molecular composition

Alkyl side chain length dependent compatibility of poly(4‐n‐alkylstyrene)s and 1,4‐rich polyisoprene blends

DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

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