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6 protocols using styrene st

1

Preparation of Polymeric Nanoparticles

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Styrene (St) (Pure ≥ 99%, Sigma-Aldrich, St. Louis, MO, USA) and methyl methacrylate (MMA) (99%, Sigma-Aldrich) were purified by passing through a column pack with neutral and basic aluminum oxide (Purum, Fluka, Honeywell, NC, USA). Acrylic acid (AA) (ACS reagent, Sigma-Aldrich) was distilled before use. Divinyl benzene (DVB) (Technical grade 80%, Fluka), poly (vinyl alcohol) (PVA) (Mw = 58000–124,000, Sigma-Aldrich), potassium persulfate (KPS) (ACS 99%, Fluka), potassium hydroxide (KOH) (85%, Sigma-Aldrich), oleic acid (OA) (Pharma grade, Panreac, ITW, Glenview, IL, USA), hexadecane (HD) (99%, Sigma-Aldrich), sodium dodecyl sulfate (SDS) (98.5% GC, Sigma-Aldrich), and zinc acetate dehydrate (Zn (CH3COO)2·2H2O) (98%, Sigma-Aldrich) were used as received. Ethanol (95%, RCI Labscan, Bangkok, Thailand), cyclohexane (≥99.8%, Sigma-Aldrich), and deionized (DI) water were applied throughout the work.
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2

Purification and Functionalization of Monomers

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Styrene (ST) (Sigma-Aldrich, St. Louis, MO, USA) has been purified through vacuum distillation. 2-Hydroxyethyl methacrylate (HEMA) (Sigma-Aldrich, St. Louis, MO, USA) and glycidyl methacrylate (GMA) (Merck, Darmstadt, Germany) have been purified by passing over short columns of activated basic alumina. Potassium persulfate (K2S2O8) (KPS) (Merck, Darmstadt, Germany) has been recrystallized from an ethanol/water mixture and then vacuum-dried. β-cyclodextrin (BCD-OH) (≥95.0%, Wacker Chemie, Munich, Germany) was vacuum-dried before use for 24 h. p-Toluene sulfonyl chloride (Ts-Cl) (reagent grade, ≥98%, Merck, Darmstadt, Germany), sodium hydroxide (reagent grade, ≥98%, pellets (anhydrous), (Sigma-Aldrich, St. Louis, MO, USA), 1,4-Diaminobutane (99%, Sigma-Aldrich, St. Louis, MO, USA), acetone (for analysis, >99%, Chemical Company Iasi), dimethyl sulfoxide (DMSO) (Aldrich-anhydrous, Darmstadt, Germany), pyridine (Aldrich, Darmstadt, Germany), glucose (Aldrich anhydrous, Darmstadt, Germany), phenol (Merck, Darmstadt, Germany), sulfuric acid (Sigma-Aldrich, St. Louis, MO, USA), bisphenol A (Merck, Darmstadt, Germany), ethanol (Chimopar, Bucuresti, România) were used as received.
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3

Polyhydroxybutyrate (PHB) Functionalization

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Polyhydroxybutyrate (PHB), marketed under the code FE-113, with a melt flow index (MFI) of 30 g/10 min (2.16 kg/190 °C—ASTM D-1238) and Mw = 340 kg/mol, is produced by PHB Industrial SA (Brazil). Maleic anhydride (MA) with 95% purity was used as a functional group in the form of flakes, manufactured by Sigma Aldrich. Dicumyl peroxide (DCP) was used as a free radical initiator in powder form with 98% purity and manufactured by Sigma Aldrich. Styrene (St) was used as a comonomer with 99% purity and was manufactured by Sigma Aldrich. Tin(II) 2-ethylhexanoate (Sn(Oct)2) was used as a catalyst with 99% purity and manufactured by Sigma Aldrich.
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4

Monomer Purification and Initiator Synthesis

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Styrene (St) (99.3% purity) and methyl methacrylate (MMA) (99.8 wt% purity) supplied by Sigma Aldrich company were distilled under reduced pressure. AIBN (Aldrich, 98% purity) was purified several times by recrystallization in methanol. The ruthenium complex was synthesized using the literature procedure.[24 (link)]
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5

Atom Transfer Radical Polymerization of Styrene and t-Butyl Acrylate

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Styrene (St) (Sigma, Aldrich, 99 %) and t-butyl acrylate (tBA) (Sigma-Aldrich, 98 %) were distilled under reduced pressure over calcium hydride prior to use. Copper (I) bromide (CuBr) (Sigma-Aldrich, 98%), 2,2'-bipyridyl (bipy) (Sigma-Aldrich, 99 %), N,N,N',N'',N'',pentamethyldiethylenetriamine (PMDETA) (Sigma-Aldrich, 99 %), phenylethyl bromide (PhEBr) (Sigma-Aldrich, 97 %), and other solvents were used as received. The diblock copolymers were prepared by atom-transfer radical polymerization (ATRP) in two steps following previously reported procedures [39] .
Polystyrene filaments were purchased from Impresoras 3D (ESUN HIPS). According to the supplier contains around 85 wt% of PS, 10 wt% acrylonitrile and 5 wt% butadiene. High molecular weight polystyrene (Aldrich, Mw =2.50•10 5 g/mol) was used as polymeric matrix. Chloroform (CHCl3) was purchased from Scharlau.
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6

Synthesis of Polystyrene-b-Poly(Acrylic Acid) Diblock Copolymers

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The monomers, t-butyl acrylate (tBA) (Sigma-Aldrich, 98 %) and styrene (St) (Sigma, Aldrich, 99 %), required purification by first dried over calcium hydride and distilled using vacuum techniques. The following list of compounds were used as received: 2,2'-bipyridyl (bipy) (Sigma-Aldrich, 99 %), phenylethyl bromide (PhEBr) (Sigma-Aldrich, 97 %), N,N,N',N'',N'',pentamethyldiethylenetriamine (PMDETA) (Sigma-Aldrich, 99 %), Copper (I) bromide (CuBr) (Sigma-Aldrich, 98%) and other solvents. Coupling reactions were carried out using N-Hydroxysuccinimide (NHS) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (Sigma-Aldrich -USA). The polystyrene-b-poly(acrylic acid) diblock copolymers were prepared following the procedures already reported by our group [39] .
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