Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007     

Self‐assembly of amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers

Amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers consisting of one polystyrene block and two poly(N‐isopropylacrylamide) blocks were prepared by the “arm‐first” method in which RAFT polymerization and nonconvalent ligand–metal complexation were employed. The prepared amphiphilic star‐shaped metallopolymers are able to form micelles in water. The size and distribution of the micelles were studied by dynamic light scattering and transmission electron microscopy techniques. Preliminary studies indicate that the polymer concentration and the hydrophilic poly(N‐isopropylacrylamide) block length can affect the morphologies of the formed metal‐interfaced core–shell micelles in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4204–4210, 2007     

Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

Photoinitiated curing of mono‐ and bifunctional epoxides by combination of active chain end and activated monomer cationic polymerization methods

Photoinitiated cationic polymerization of mono‐ and bifunctional epoxy monomers, namely cyclohexeneoxide (CHO), 4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexanecarboxylate (EEC), respectively by using sulphonium salts in the presence of hydroxylbutyl vinyl ether (HBVE) was studied. The real‐time FTIR spectroscopic, gel content determination, and thermal characterization studies revealed that both hydroxyl and vinyl ether functionalities of HBVE take part in the polymerization. During the polymerization, HBVE has the ability to react via both active chain end (ACE) and activated monomer mechanisms through its hydroxyl and vinyl ether functionalities, respectively. Thus, more efficient curing was observed with the addition of HBVE into EEC‐containing formulations. It was also demonstrated that HBVE is effective in facilitating the photoinduced crosslinking of monofunctional epoxy monomer, CHO in the absence of a conventional crosslinker. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4914–4920, 2007     

Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine

This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of r_EPM = 1.11 and r_MMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; r_VP = 0.005 and r_MMA = 4.7). EPyM and MMA had reactivity ratios of r_EPyM = 1.31 and r_MMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003     

Radical copolymerization of 2‐trifluoromethylacrylic monomers. II. Kinetics,monomer reactivities,and penultimate effect in their copolymerization with norbornenes and vinyl ethers

Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with ¹H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004     

Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006