Nanocrystalline cellulose/fluorinated polyacrylate latex via RAFT‐mediated surfactant‐free emulsion polymerization and its application as waterborne textile finishing agent

A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT‐mediated surfactant‐free emulsion polymerization, in which the nanocomposites formed a core‐shell spherical morphology. The influence of the content of NCC‐g‐(PAA‐b‐PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water–oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC‐g‐(PAA‐b‐PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC‐g‐(PAA‐b‐PHFBA) gradually increased. XPS showed that the fluorine‐containing groups well concentrated at the film–air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC‐based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305–1314     

Nitroxide‐Mediated Polymerization of Bio‐Based Farnesene with a Functionalized Methacrylate

Farnesene (Far) is a bio‐based terpene monomer that is similar in structure to commercially used dienes like butadiene and isoprene. Nitroxide‐mediated polymerization (NMP) is adept for the polymerization of dienes, but not particularly effective at controlling the polymerization of methacrylates using commercial nitroxides. In this study, Far is statistically copolymerized with a functional methacrylate, glycidyl methacrylate (GMA), by NMP using N‐succinimidyl modified commercial BlocBuilder (NHS‐BB) initiator. Reactivity ratios are determined to be r _Far = 0.54 ± 0.04 and r _GMA = 0.24 ± 0.02. The ability of the poly(Far‐stat‐GMA) chains to reinitiate for chain extension with styrene showed a clear shift in molecular weight and monomodal distribution. Copolymerizations using a new alkoxyamine, Dispolreg 007 (D7), is explored as it is shown to homopolymerize methacrylates, but not yet reported for statistical copolymerizations. Bimodal molecular weight distributions are observed when an equimolar ratio of Far and GMA is copolymerized with D7 due to slow decomposition of the initiator, but chain ends are active as shown by successful chain extension with styrene. Both NHS‐BB and D7 initiators are used to synthesize poly[Far‐b‐(GMA‐stat‐Far)] and poly(Far‐b‐GMA) diblock copolymers. While the NHS‐BB initiated polymer chains have lower dispersity, D7 exhibits more linear polymerization kinetics and maintains more active chain ends.     

Emulsion Copolymerization of Vinyl Acetate and Vinyl Silanes: Kinetics and Development of Microstructure

The batch emulsion copolymerization of vinyl acetate with different vinyl silane functional monomers (vinyl trimethoxysilane [VTMS], vinyl triethoxysilane [VTES], and vinyl silanetriol [VSTO]) is studied. The nature of the silane strongly affects the development of the microstructure and crosslinking ability of the latexes. A combination of techniques (Soxhlet extraction, centrifugation, assymetric‐flow field flow fractionation AF4/MALS/RI) shows that the factor controlling the molar mass and crosslinking density is the degree of hydrolysis of the alkoxysilane, producing higher molar masses and degrees of crosslinking when the degree of hydrolysis is high. Thus, the copolymer containing VSTO produced a very crosslinked latex, the one with VTMS produced a latex with a low degree of crosslinking in the wet state that can yield high degrees of crosslinking upon drying, and the latex with VTES do not produce significant amounts of crosslinking neither before nor after drying.     

An Improved Model for Polyether Production from 1,3‐Propanediol

A dynamic mathematical model is developed for production of Cerenol polyether from 1,3‐propanediol in a batch reactor system. The model accounts for polycondensation reactions and side reactions in the liquid phase and for mass transfer of volatile species to the vapor. Parameters are estimated using measured liquid‐phase concentrations of monomer, oligomers, water, and end groups as well as the mass and composition of condensate collected from the overhead condenser system. The proposed model uses novel probability factors to keep the model equations relatively simple while accounting for the complex influence of superacid catalyst on reaction rates. The model is a significant advance over previous Cerenol models because it better accounts for mass‐transfer rates and for the dynamic behavior of the condenser. In addition, the proposed model accounts for the inhibitory influence of water on polycondensation kinetics due to hydration of hydroxyl ends. The model equations and parameter estimates provide a substantial improvement in fit to the data, especially for long reaction times and high catalyst levels, resulting in a 97% reduction in the value of the weighted least squared objective function compared to equations and parameters from a previous model.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.     

Rare-earth metal derivatives supported by aminophenoxy ligand: Synthesis,characterization and catalytic performance in lactide polymerization

A library of rare-earth metal derivatives supported by an aminophenoxy ligand was prepared and their catalytic performance in lactide polymerization was investigated. It was found that the synthetic strategy had a profound effect on the formation of aminophenoxy rare-earth metal complexes. Amine elimination between Ln[N(SiMe₃)₂]₃(μ-Cl)Li(THF)₃ (Ln = Yb, Y) and 1 equiv. of the aminophenol [HONH] ([HONH] = ο-OCH₃-C₆H₄NHCH₂(3,5-^tBu₂-C₆H₂-2-OH)) in toluene gave the unexpected heterobimetallic bis(aminophenoxy) rare-earth metal complexes [ON]₂LnLi(THF)₂ (Ln = Yb ( 1 ), Y ( 2 )). When the reactions were carried out in THF and TMEDA, amine elimination produced the aminophenoxy rare-earth metal amide complexes {[ON]LnN(SiMe₃)₂}₂ (Ln = Yb ( 5 ), Y ( 6 )) in ca 85% isolated yields. Complexes 5 and 6 could also be obtained from salt metathesis reaction of {[ON]LnCl(THF)}₂ (Ln = Yb ( 3 ), Y ( 4 )) with NaN(SiMe₃)₂ in a 1:2 molar ratio. In addition, treatment of complexes 3 and 4 with NaOAr (Ar = &bond;C₆H₄-4-^tBu) and (SiMe₃)₂NC(NPrⁱ)₂Na in 1:4 and 1:2 molar ratios provided the corresponding aminophenoxy rare-earth metal derivatives {[ON](μ-OAr)Ln(μ-OAr)Na(THF)₂}₂ (Ln = Yb ( 7 ), Y ( 8 )) and {[ON]Ln[(ⁱPrN)₂CN(SiMe₃)₂]}₂ (Ln = Yb ( 9 ), Y ( 10 )), respectively. These complexes were fully characterized, and their molecular structures were determined using single-crystal X-ray diffraction. Polymerization experiments showed that complexes 1 , 2 , 5 , 6 , 9 and 10 were highly active for the ring-opening polymerization of l -lactide in toluene, and complex 1 promoted l -lactide polymerization in a controlled fashion. The polymerization of rac-lactide initiated by the neutral aminophenoxy rare-earth metal complexes 5 , 6 , 9 and 10 in THF afforded heterotactic polymers.     

Synthesis and formulation of self-immolative PEG-aryl azide block copolymers and click-to-release reactivity with trans-cyclooctene

Self-immolative aryl azides can react with trans-cyclooctenes (TCO), triphenylphosphines or hydrogen sulfide (H₂S) to activate prodrugs, imaging probes and drug delivery systems. To date, the synthesis of polymers containing these aryl azide self-immolative linkers and their reactivity with a strained alkene (i.e., in a bioorthogonal reaction) has not been explored. Also, due to the instability of aryl azides towards light and high temperatures, the polymerization methods compatible with aryl azides are limited. Through systematic investigation of the reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP) methods, a self-immolative PEG-aryl azide block copolymer (PEG₄₅-b-ABOC₂₈ 2 ) and a non-responsive 4-fluoroaryl block copolymer (PEG₄₅-b-FBOC₂₄ 3 ) was prepared. ATRP provided the desired polymers in a highly controlled manner, whereas the RAFT conditions led to higher levels of aryl azide polymer degradation. The ATRP derived polymers 2 and 3 were formulated into nanoparticles of approximately 200 nm diameter, and particle triggering was demonstrated by the [3+2]-cycloaddition reaction of TCO with PEG₄₅-b-ABOC₂₈ 2 in solution (pure polymer) and as a formulated nanoparticle. Preliminary in vitro cell viability studies suggested that the stimuli-responsive aryl azide polymers/nanoparticles are not cytotoxic up to 200 μg/ml concentrations.     

Polymerization-induced self-assembly of amino-acid-based nano-objects by reversible addition–fragmentation chain-transfer dispersion polymerization

A series of amino-acid-based amphiphilic diblock copolymer nano-objects having different morphologies were developed by reversible addition–fragmentation chain-transfer (RAFT) dispersion polymerization of styrene (St) in methanol. This was mediated by six different hydrophilic poly(N-acryloyl amino acid) macro-chain transfer agents (CTAs), including three carboxylic-acid-containing ones, poly(N-acryloyl-l -proline) (PAProOH), poly(N-acryloyl-4-trans-hydroxy-l -proline) (PAHypOH), and poly(N-acryloyl-l -threonine) (PAThrOH) prepared by RAFT polymerization, and their methyl ester forms, PAProOMe, PAHypOMe, and PAThrOMe. The effects of polymerization conditions on RAFT dispersion polymerization of St using a dithiocarbamate-terminated PAProOH was investigated. A systematic study of the effects of monomer conversion and concentration afforded the formation of various morphologies (i.e., spheres, worms, and vesicles). The effects of hydrogen-bonding and ionic interactions of the macro-CTAs on the assembled structures of the nano-objects were evaluated using six different macro-CTAs. Transforming the products from methanol to water via dialysis produced amino-acid-based block copolymer nano-objects, exhibiting pH-responsive morphological change, in aqueous solution.     

Effects of C3-aromatic heterocycles on 1,3,5-triaryl-2-pyrazoline sulfonium salt photoacid generators as light-emitting diode-sensitive cationic photoinitiators

Four 1,5-diphenyl-3-aromatic heterocyclyl-2-pyrazoline-based sulfonium salt photoacid generators (PAGs) with different aromatic heterocycles substituted on C3 atom and dimethyl sulfonium group on C5 atom were synthesized. These PAGs were highly photosensitive in the 365–425 nm light-emitting diode region, and the intramolecular charge transfer from the pyrazoline ring to sulfonium salts induced efficient photolysis and high Φ_H⁺. The heterocycles as well as their substituted positions significantly influenced the energy of the S₂ orbital, which was determined by the electrochemical and absorption properties of the PAGs. The raising of the S₂ orbital energy enlarged the energy gap of S₀–S₂ and S₁–S₂, resulting in blue shift of the absorption spectra and increase in the quantum yield of photoacid generation (Φ_H⁺), respectively. When the energy of excited electrons was higher than that of the S₂ orbital, the transition from S₀ to S₂ (π–π*) occurred before the C-S cleavage on S₁ and the PAGs showed high Φ_H⁺ values (0.52–0.72). The transition from S₀ to S₁ (π–σ*) occurred when the energy of electrons is lower than that of the S₂ orbital, and the PAGs showed low Φ_H⁺ value. The photopolymerization kinetics demonstrated that these PAGs were highly efficient cationic photoinitiators.     

Living ring-opening metathesis polymerization of norbornenes bay-functionalized perylene diimides

Ring-opening metathesis polymerization (ROMP)-derived poly(oxanorbornene imide)s bearing bay-linked mono - alkoxy -M1 and 1,7-di-alkoxy M2 functionalized perylene diimides (PDIs) were synthesized using Grubb's third ( G3 ) and Hoveyda-Grubbs second generation ( HG2 ) ruthenium-alkylidene metathesis initiators. The mono-alkoxy-derived PDI-based non-ladderphane polymer poly M1 displayed 67% to 77% of the trans olefin content in the polymer chain depending on the initiator used for the polymerization. When using the symmetrical 1,7-di-alkoxy-derived PDI-based polymer poly M2 having the ladderphane type-structure, this displayed a significant amount of cis and trans olefin contents in the polymer chains, irrespective of the type of initiators used for the polymerization. ROMP of both monomers M1 and M2 proceeded in a well-controlled manner with a linear dependence of molecular weight on the monomer/initiator ratio using G3 as initiator. Optical properties of the ladderphane-based poly M2 and non-ladderphane-based poly M1 were characterized in both solution and the film state. X-ray diffraction (XRD) analysis for all the polymers showed significant π-stacking in the thin film state with ordered molecular packing and closer values of d-spacing for both poly M1 and poly M2 . Film morphology examined by AFM elucidated homogenous smooth polymer surface for both polymers in general, but with some irregularities observed for poly M1 . In addition, CV analysis revealed both polymers could be good candidates as electron-accepting materials, with excellent film-forming ability, and thermal stability.