Facile synthesis of poly(4‐hydroxy styrene) from polystyrene

Deokar, Sarika; Ghadage, R. S.; Rajan, C. R.; Ponrathnam, S.

doi:10.1002/app.13488

Cited by 9 publications

(5 citation statements)

References 11 publications

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“…We find that the simulated T g for PtBMA is between 380 and 470 K depending on tacticity, with the observed trend being similar to experimental values of PMMA polymers where the T g decreases going from syndiotactic to atactic to isotactic . We also find that the T g value for atactic PHS homopolymers is ∼450 K (within the experimental range: 410 K–470 K , ) and for atactic alternating copolymers is ∼440 K.…”

Section: Methodssupporting

confidence: 83%

Atomistic Modeling Approach for Predicting Association of Photoacid Generators in Extreme Ultraviolet Polymeric Photoresists

Prajwal,

Blackwell,

Theofanis

et al. 2023

Chem. Mater.

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This work advances a computational framework to probe the molecular inhomogeneities that occur in chemically amplified photoresists intended for ultraviolet (EUV) lithography. Atomistic molecular dynamics simulations were used to probe the effect of ionic and steric interactions on the dispersibility of photoacid generators (PAGs) in the polymer medium before EUV exposure, as poor dispersibility is a potential source of postexposure feature roughness. The PAGs studied include ionic salts containing a triphenyl sulfonium (TPS) cation with trifluoromethane (TFMeS), nonafluorobutane (NFBuS), perfluorophenyl (PFPS), and adamantyltetrafluoroethyl (ATFEtS) sulfonate anions, and a nonionic naphthalimide sulfonate PAG. The model photoresists studied are poly(tert-butyl methacrylate) (PtBMA) and poly(4-hydroxy styrene) (PHS) homopolymers and alternating copolymers thereof. The dissociation free-energy of isolated single and dimer PAGs in the different polymers indicates that PHS segments provide a better solvation environment for ionic PAGs than PtBMA segments and that the nonionic naphthalimide PAG has the highest dispersibility, while TPS-TFMeS solvates better than the bulkier TPS-NFBuS and TPS-ATFEtS salts. The dissociation free-energies were consistent with a trend of increasing PAG clustering in less polar media at high PAG concentrations (7 to 36 wt %), and of increasing dipole moments for PAGs in less polar implicit solvation media as estimated from density functional theory. Both simulations and infrared spectroscopy of the copolymer provide evidence of hydrogen bonded carbonyl groups whose prevalence diminishes upon the addition of ionic PAGs. For TPS-TFMeS loadings between 25 and 29 wt %, our analysis revealed short string-like salt clusters in PHS homopolymer, large globular clusters in PtBMA homopolymer, and a heterogeneous distribution of string-like and globular PAG aggregates in the alternating copolymer. For all PAG loadings, TPS-ATFEtS and TPS-NFBuS PAGs exhibited the highest extent of aggregation. Altogether, the advocated methodology is a potentially effective tool to rank and identify polymer and PAG chemistries with improved compatibility and mixing homogeneity.

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Section: Methodssupporting

confidence: 83%

Atomistic Modeling Approach for Predicting Association of Photoacid Generators in Extreme Ultraviolet Polymeric Photoresists

Prajwal,

Blackwell,

Theofanis

et al. 2023

Chem. Mater.

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“…The acetylation of PS-d5 (degree of deuteration ~85%) was conducted using cyclohexane (instead of the toxic and flammable carbon disulfide proposed in the literature) 16 as the solvent and acetyl chloride as the acylation agent ( Figure 1). The mono-substituted aromatic rings in the polymer side chain were acylated at the para position because of the large steric requirement of the attacking reagent.…”

Section: Synthesis Of Deuterated Poly(4-acetylstyrene) (Acps-d4)mentioning

confidence: 99%

“…The progress of acetylation in benzene and other lower mass analogues such as toluene and so on depends on catalyst, acyl component, solvent, and the ratio of the catalyst to acyl component. 16 In general, the dependence of the extent of acetylation of non-deuterated polystyrene could be easily monitored by the reduction in FT-IR peak at 700 cm -1 which is characteristic of monosubstituted benzene.…”

Section: Synthesis Of Deuterated Poly(4-acetylstyrene) (Acps-d4)mentioning

confidence: 99%

تخليق البولي المزالة (4-أسيتوكسيسترين) بواسطة تسلسل تفاعل البوليمر المماثل

M.¹

2016

المجلة العربية للعلوم و نشر الأبحاث

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This study describes a new simple method for preparing deuterated poly(4-acetoxystyrene). The new method offers cost-effective and alternative route to preparing deuterated polymers that otherwise have to be prepared from the deuterated monomers. Deuterated poly(4-acetylstyrene) (ACPS-d4) and poly(4-acetoxystyrene) (APS-d4) were synthesised from deuterated polystyrene under thermal reactions. The polystyrene-d5 (PS-d5) was acetylated using cyclohexane as solvent instead of carbon disulfide (a highly toxic and flammable solvent) and acetyl chloride as the acetylating agent. Using commercially available reagents, the acetyl group was converted to an acetoxy group by Baeyer-Villiger oxidation. The oxidation of ACPS was carried out with various agents and reaction conditions. The oxidation kinetics with peracetic acid was followed by FT-IR spectroscopy. The duterated polymers were characterised by nuclear magnetic resonance (NMR) and fourier transform infrared spectroscopy (FTIR). The optimised procedure will make future work using neutron scattering possible.

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“…Therefore, polymer-supported phenols were first generated by a based-catalysed hydrolysis reaction of acetoxy functional groups [50], followed by a treatment with tetrabutoxytitanium in chloroform at room temperature. The titanium loading of the supports were estimated to 0.8 AE 0.1 mmol g -1 .…”

Section: Grafting Of the Catalytic Species Onto The Polymer Supportmentioning

confidence: 99%

Polymer-supported titanate as catalyst for the transesterification of acrylic monomers

Alves

Riondel

Paul

et al. 2010

Comptes Rendus. Chimie

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Facile synthesis of poly(4‐hydroxy styrene) from polystyrene

Cited by 9 publications

References 11 publications

Atomistic Modeling Approach for Predicting Association of Photoacid Generators in Extreme Ultraviolet Polymeric Photoresists

Atomistic Modeling Approach for Predicting Association of Photoacid Generators in Extreme Ultraviolet Polymeric Photoresists

تخليق البولي المزالة (4-أسيتوكسيسترين) بواسطة تسلسل تفاعل البوليمر المماثل

Polymer-supported titanate as catalyst for the transesterification of acrylic monomers

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