Orthogonally functionalizable copolymers based on a novel reactive carbonate monomer

A novel N‐hydroxy succinimide‐based carbonate monomer that allows direct synthesis of polymers incorporating a reactive carbonate group in the side chain was synthesized. This new monomer was copolymerized with methyl methacrylate and poly(ethylene glycol) methylether methacrylate using free‐radical polymerization to obtain organo‐ and water‐soluble reactive copolymers. Copolymerization of the activated carbonate monomer with an azide‐containing monomer and N‐hydroxy succinimide‐containing activated ester monomer provided orthogonally functionalizable copolymers. The pendant reactive carbonate groups of the copolymers were functionalized with amines to obtain carbamates. Polymers capable of orthogonal functionalization could be selectively functionalized as desired using subsequent 1,3‐dipolar cycloaddition or amidation reactions. The novel monomer and the copolymers were characterized by ¹H‐NMR, ¹³C‐NMR, and infrared spectroscopy. The efficient stepwise orthogonal functionalization of the copolymers were examined via ¹H‐NMR spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Block copolymers based on 2‐vinyl‐4,4‐dimethyl‐5‐oxazolone by RAFT polymerization: Experimental and computational studies

The ability of 2‐vinyl‐4,4‐dimethyl‐5‐oxazolone (VDM), a highly reactive functional monomer, to produce block copolymers by reversible addition fragmentation chain transfer (RAFT) sequential polymerization with methyl acrylate (MA), styrene (S), and methyl methacrylate (MMA) was investigated using cumyl dithiobenzoate (CDB) and 2‐cyanoisopropyl dithiobenzoate (CPDB) as chain transfer agents. The results show that PS‐b‐PVDM and PMA‐b‐PVDM well‐defined block copolymers can be prepared either by polymerization of VDM from PS‐ and PMA‐macroCTAs, respectively, or polymerization of S and MA from a PVDM‐macroCTA. In contrast, PMMA‐b‐PVDM block copolymers with controlled molecular weight and low polydispersity can only be obtained by using PMMA as the macroCTA. Ab initio calculations confirm the experimental studies. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Latices of poly(fluoroalkyl mathacrylate)‐b‐poly(butyl methacrylate) copolymers prepared via reversible addition–fragmentation chain transfer polymerization

Poly(fluoroalkyl mathacrylate)‐block‐poly(butyl methacrylate) diblock copolymer latices were synthesized by a two‐step process. In the first step, a homopolymer end‐capped with a dithiobenzoyl group [poly(fluoroalkyl mathacrylate) (PFAMA) or poly(butyl methacrylate) (PBMA)] was prepared in bulk via reversible addition–fragmentation chain transfer (RAFT) polymerization with 2‐cyanoprop‐2‐yl dithiobenzoate as a RAFT agent. In the second step, the homopolymer chain‐transfer agent (macro‐CTA) was dissolved in the second monomer, mixed with a water phase containing a surfactant, and then ultrasonicated to form a miniemulsion. Subsequently, the RAFT‐mediated miniemulsion polymerization of the second monomer (butyl methacrylate or fluoroalkyl mathacrylate) was carried out in the presence of the first block macro‐CTA. The influence of the polymerization sequence of the two kinds of monomers on the colloidal stability and molecular weight distribution was investigated. Gel permeation chromatography analyses and particle size results indicated that using the PFAMA macro‐CTA as the first block was better than using the PBMA RAFT agent with respect to the colloidal stability and the narrow molecular weight distribution of the F‐copolymer latices. The F‐copolymers were characterized with ¹H NMR, ¹⁹F NMR, and Fourier transform infrared spectroscopy. Comparing the contact angle of a water droplet on a thin film formed by the fluorinated copolymer with that of PBMA, we found that for the diblock copolymers containing a fluorinated block, the surface energy decreased greatly, and the hydrophobicity increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 471–484, 2007     

Systematic parallel investigation of RAFT polymerizations for eight different (meth)acrylates: A basis for the designed synthesis of block and random copolymers

Poly(acrylate)s as well as poly(methacrylate)s were successfully synthesized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerizations using 2‐cyano‐2‐butyl dithiobenzoate (CBDB) as RAFT‐agent. Four different ratios of RAFT to initiator were screened for four acrylates and four methacrylates using automated parallel synthesizer robots. The reactions were monitored by gel permeation chromatography (GPC) and gas chromatography (GC). The knowledge obtained during this screening was used for the designed synthesis of block and random copolymers containing a water‐ and a non water‐soluble monomer. The results obtained from GPC analysis together with ¹H NMR spectroscopy demonstrate the possibility to design and prepare well‐defined block and random copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3831–3839, 2005     

Synthesis and characterization of well‐defined diblock and triblock copolymers of poly(N‐isopropylacrylamide) and poly(ethylene oxide)

Well‐defined diblock and triblock copolymers composed of poly(N‐isopropylacrylamide) (PNIPAM) and poly(ethylene oxide) (PEO) were successfully synthesized through the reversible addition–fragmentation chain transfer polymerization of N‐isopropylacrylamide (NIPAM) with PEO capped with one or two dithiobenzoyl groups as a macrotransfer agent. ¹H NMR, Fourier transform infrared, and gel permeation chromatography instruments were used to characterize the block copolymers obtained. The results showed that the diblock and triblock copolymers had well‐defined structures and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.2), and the molecular weight of the PNIPAM block in the diblock and triblock copolymers could be controlled by the initial molar ratio of NIPAM to dithiobenzoate‐terminated PEO and the NIPAM conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4873–4881, 2004     

End group transformations of RAFT‐generated polymers with bismaleimides: Functional telechelics and modular block copolymers

End group activation of polymers prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization was accomplished by conversion of thiocarbonylthio end groups to thiols and subsequent reaction with excess of a bismaleimide. Poly(N‐isopropylacrylamide) (PNIPAM) was prepared by RAFT, and subsequent aminolysis led to sulfhydryl‐terminated polymers that reacted with an excess of 1,8‐bismaleimidodiethyleneglycol to yield maleimido‐terminated macromolecules. The maleimido end groups allowed near‐quantitative coupling with model low molecular weight thiols or dienes by Michael addition or Diels‐Alder reactions, respectively. Reaction of maleimide‐activated PNIPAM with another thiol‐terminated polymer proved an efficient means of preparing block copolymers by a modular coupling approach. Successful end group functionalization of the well‐defined polymers was confirmed by combination of UV–vis, FTIR, and NMR spectroscopy and gel permeation chromatography. The general strategy proved to be versatile for the preparation of functional telechelics and modular block copolymers from RAFT‐generated (co)polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5093–5100, 2008     

Styrene‐vinyl pyridine diblock copolymers: Achieving high molecular weights by the combination of anionic and reversible addition–fragmentation chain transfer polymerizations

Anionic and reversible addition–fragmentation chain transfer (RAFT) polymerizations were combined for the preparation of high molecular weight (MW) amphiphilic diblock copolymers based on the hydrophobic styrene (Sty) and the more polar 2‐vinyl pyridine (2VPy) or 4‐vinyl pyridine (4VPy). In particular, four amphiphilic Sty‐VPy diblock copolymers with MWs up to 271,000 g mol^–1 were prepared. For the polymer synthesis, first, living anionic polymerization of Sty using sec‐butyl‐lithium as initiator in tetrahydrofuran at ?70 °C, followed by termination with ethylene oxide were employed for the preparation of OH‐functionalized homopolyStys. Subsequently, a modification of the OH‐terminal group was performed by the attachment of a 4‐cyanopentanoic acid dithiobenzoate chain transfer agent (CTA) group, giving a polySty macroRAFT CTA, which was extended with 2VPy or 4VPy units using RAFT polymerization. Thus, the prepared diblock copolymers comprised a first block which was near‐monodisperse in size, and a second more heterogeneous block. All diblock copolymers were characterized in terms of their MWs and compositions by gel permeation chromatography and ¹H NMR spectroscopy, respectively, giving results close to the theoretically expected values. Films cast from chloroform solutions of the diblock copolymers were investigated in terms of their bulk morphologies using transmission electron microscopy, which indicated that the minority block consistently formed the discontinuous microphase, spherical or cylindrical. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of comb‐shaped poly(methyl methacrylate)‐b‐poly(polytetrahydrofuran acrylate) under 60Co γ‐ray irradiation

Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under ⁶⁰Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under ⁶⁰Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]₀/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by ¹H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002     

Bioconjugation of D‐glucuronic acid sodium salt to well‐defined primary amine‐containing homopolymers and block copolymers

The synthesis of well‐defined carboxylic acid‐functionalized glycopolymers prepared via one‐step postpolymerization modification of poly(N‐[3‐aminopropyl] methacrylamide) (PAPMA), a water‐soluble primary amine methacrylamide, in aqueous medium is demonstrated. PAPMA was first polymerized via aqueous reversible addition‐fragmentation chain transfer polymerization in aqueous buffer using 4‐cyanopentanoic acid dithiobenzoate as the chain transfer agent and 4,4′‐azobis(4‐cyanovaleric acid) (V‐501) as the initiator at 70 °C. The resulting well‐defined PAPMA was then conjugated with D ‐glucuronic acid sodium salt through reductive amination in alkaline medium (pH 8.5) at 45 °C. The successful bioconjugation was proven through proton (¹H) and carbon (¹³C) nuclear magnetic resonance spectroscopy and matrix‐assisted laser desorption/ionization time of flight mass spectrometry analysis, which indicated near quantitative conversion. A similar bioconjugation reaction was conducted with poly(2‐aminoethyl methacrylate) (PAEMA) and poly(2‐aminoethyl methacrylate‐b‐poly(N‐[2‐hydroxypropyl]methacrylamide) (PAEMA‐b‐PHPMA). For the PAEMA homopolymers and block copolymers, however, lower conversion was obtained, most likely because of degradation reactions of PAEMA in alkaline medium. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3052–3061, 2010     

Synthesis and characterization of well‐defined block and statistical copolymers based on lauryl methacrylate and 2‐(acetoacetoxy)ethyl methacrylate using RAFT‐controlled radical polymerization

Four well‐defined diblock copolymers and one statistical copolymer based on lauryl methacrylate (LauMA) and 2‐(acetoacetoxy)ethyl methacrylate (AEMA) were prepared using reversible addition‐fragmentation chain transfer (RAFT) polymerization. The polymers were characterized in terms of molecular weights, polydispersity indices (ranging between 1.12 and 1.23) and compositions by size exclusion chromatography and ¹H NMR spectroscopy, respectively. The preparation of the block copolymers was accomplished following a two‐step methodology: First, well‐defined LauMA homopolymers were prepared by RAFT using cumyl dithiobenzoate as the chain transfer agent (CTA). Kinetic studies revealed that the polymerization of LauMA followed first‐order kinetics demonstrating the “livingness” of the RAFT process. The pLauMAs were subsequently used as macro‐CTA for the polymerization of AEMA. The glass transition (T_g) and decomposition temperatures (ranging between 200 and 300 °C) of the copolymers were determined using differential scanning calorimetry and thermal gravimetric analysis, respectively. The T_gs of the LauMA homopolymers were found to be around ?53 °C. Block copolymers exhibited two T_gs suggesting microphase separation in the bulk whereas the statistical copolymer presented a single T_g as expected. Furthermore, the micellization behavior of pLauMA‐b‐pAEMA block copolymers was investigated in n‐hexane, a selective solvent for the LauMA block, using dynamic light scattering. pLauMA‐b‐pAEMA block copolymers formed spherical micelles in dilute hexane solutions with hydrodynamic diameters ranging between 30 and 50 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5442–5451, 2008     

A facile route to ureidopyrimidinone‐functionalized polymers via RAFT

Three new ureidopyrimidinone(UPy)‐functionalized chain‐transfer agents (CTAs) have been synthesized for use in reversible addition‐fragmentation chain transfer (RAFT) polymerization. These UPy‐CTAs are able to polymerize a wide variety of vinyl monomers to yield UPy‐functionalized polymers, including homopolymers, block copolymers, and amphiphilic block copolymers. These polymers have been characterized via ¹H and ¹³C NMR spectroscopy, gel permeation chromatography (GPC), UV/visible spectroscopy and differential scanning calorimetry (DSC) to demonstrate end‐group fidelity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

One‐step synthesis of block‐graft copolymers via simultaneous reversible‐addition fragmentation chain transfer and ring‐opening polymerization using a novel macroinitiator

One‐step synthesis of block‐graft copolymers by reversible addition‐fragmentation chain transfer (RAFT) and ring‐opening polymerization (ROP) by using a novel initiator was reported. Block‐graft copolymers were synthesized in one‐step by simultaneous RAFT polymerization of n‐butylmethacrylate (nBMA) and ROP of ε‐caprolacton (CL) in the presence of a novel macroinitiator (RAFT‐ROP agent). For this purpose, first epichlorohydrin (EPCH) was polymerized by using H₂SO₄ via cationic ring‐opening mechanism. And then a novel RAFT‐ROP agent was synthesized by the reaction of potassium ethyl xanthogenate and polyepichlorohydrin (poly‐EPCH). By using the RAFT‐ROP agent, poly[CL‐b‐EPCH‐b‐CL‐(g‐nBMA)] block‐graft copolymers were synthesized. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the one‐step polymerization reaction were evaluated. The block lengths of the block‐graft copolymers were calculated by using ¹H‐nuclear magnetic resonance (¹H NMR) spectrum. The block length could be adjusted by varying the monomer and initiator concentrations. The characterization of the products was achieved using ¹H NMR, Fourier‐transform infrared spectroscopy, gel‐permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and fractional precipitation (γ) techniques. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2651–2659     

Block copolymers of dodecafluoroheptyl methacrylate and butyl methacrylate by RAFT miniemulsion polymerization

Reversible addition‐fragmentation chain transfer (RAFT) miniemulsion polymerization of butyl methacrylate (BMA) and dodecafluoroheptyl methacrylate (DFMA) was carried out with 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) as chain transfer agent (CTA). Concentration effects of RAFT agent and initiator on kinetics and molecular weight were investigated. No obvious red oil layer (phase's separation) and coagulation was observed in the first stage of homopolymerization of BMA. The polymer molecular weights increased linearly with the monomer conversion with polydispersities lower than 1.2. At 75 °C, the monomer conversion could achieve above 96% in 3 h with [momomer]:[RAFT]:[KPS] = 620:4:1 (mole ratio). The results showed excellent controlled/living polymerization characteristics and a very fast polymerization rate. Furthermore, the synthesis of poly(BMA‐b‐DFMA) diblock copolymers with a regular structure (PDI < 1.30, PMMA calibration) was performed by adding the monomer of DFMA at the end of the RAFT miniemulsion polymerization of BMA. The success of diblock copolymerization was showed by the molecular weight curves shifting toward higher molar mass, recorded by gel permeation chromatography before and after block copolymerization. Compositions of block copolymers were further confirmed by ¹H NMR, FTIR, and DSC analysis. The copolymers exhibited a phase‐separated morphology and possessed distinct glass transition temperatures associated with fluoropolymer PDFMA and PBMA domains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1585–1594, 2007     

A minimal amount of acrylonitrile turns the nitroxide‐mediated polymerization of methyl methacrylate into an almost ideal controlled/living system

Nitroxide‐mediated controlled/living free‐radical polymerization of methyl methacrylate initiated by the SG1‐based alkoxyamine BlocBuilder was successfully performed in bulk at 80–99 °C with the help of a very small amount of acrylonitrile (AN, 2.2–8.8 mol %) as a comonomer. Well‐defined PMMA‐rich P(MMA‐co‐AN) copolymers were prepared with the number‐average molar mass, M_n, in the 6.1–32 kg mol^?1 range and polydispersity indexes as low as 1.24. Incorporation of AN in the copolymers was demonstrated by ¹H and ¹³C NMR spectroscopy, and its effect on the chain thermal properties was evaluated by DSC and TGA analyses. Investigation of chain‐end functionalization by an alkoxyamine group was performed by means of ³¹P NMR spectroscopy and chain extensions from a P(MMA‐co‐AN)‐SG1 macroinitiator. It demonstrated the very high proportion of SG1‐terminated polymer chains, which opened the door to block copolymer synthesis with a high quality of control. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 34–47, 2010     

One‐step synthesis of hyperbranched polyethylene macroinitiator and its block copolymers with methyl methacrylate or styrene via ATRP

Block copolymers of hyperbranched polyethylene (PE) and linear polystyrene (PS) or poly(methyl methacrylate) (PMMA) were synthesized via atom transfer radical polymerization (ATRP) with hyperbranched PE macroinitiators. The PE macroinitiators were synthesized through a “living” polymerization of ethylene catalyzed with a Pd‐diimine catalyst and end‐capped with 4‐chloromethyl styrene as a chain quenching agent in one step. The macroinitiator and block copolymer samples were characterized by gel permeation chromatography, ¹H and ¹³C NMR, and differential scanning calorimetry. The hyperbranched PE chains had narrow molecular weight distribution and contained a single terminal benzyl chloride per chain. Both hyperbranched PE and linear PS or PMMA blocks had well‐controlled molecular weights. Slow initiation was observed in ATRP because of steric effect of hyperbranched structures, resulting in slightly broad polydispersity index in the block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3024–3032, 2010     

Reversible addition–fragmentation transfer polymerization of p‐nitrophenyl acrylate and synthesis of diblock copolymers poly(p‐nitrophenyl acrylate)‐b‐polystyrene

Poly(p‐nitrophenyl acrylate)s (PNPAs) with different molecular mass and narrow polydispersity were successfully synthesized for the first time by reversible addition–fragmentation transfer (RAFT) polymerization with azobisisobutyronitrile (AIBN) as an initiator and [1‐(ethoxy carbonyl) prop‐1‐yl dithiobenzoate] as the chain‐transfer agent. Although the molecular mass of PNPAs can be controlled by the molar ratio of NPA to RAFT agent and the conversion, a trace of homo‐PNPA was found, especially at the early stage of polymerization. The dithiobenzoyl‐terminated PNPA obtained was used as a macro chain‐transfer agent in the successive RAFT block copolymerization of styrene (St) with AIBN as the initiator. After purification by two washings with cyclohexane and nitromethane to remove homo‐PSt and homo‐PNPA, the pure diblock copolymers, PNPA‐b‐PSt's, with narrow molecular weight distribution were obtained. The structural analysis of polymerization products by ¹H NMR and GPC verified the formation of diblock copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4862–4872, 2004     

Controlled synthesis of fluorinated copolymers with pendant sulfonates

Novel, fluorinated copolymers with different architectures bearing sulfopropyl groups were synthesized in a three‐step procedure. The first step involved atom transfer radical polymerization (ATRP) of aromatic fluorinated monomers followed by two modification reactions performed on the polymer chain: demethylation and sulfopropylation. As a result two types of fluorinated copolymers were obtained. The first one was synthesized by ATRP of 2,3,5,6‐tetrafluoro‐4‐methoxystyrene (TFMS). After the modification steps copolymers with randomly distributed sulfopropyl groups along the backbone were obtained. The second type of copolymers has diblock architecture with one of the blocks being sulfopropylated. They were synthesized via ATRP of 2,3,4,5,6‐pentafluorostyrene (FS) initiated by a PTFMS‐macroinitiator followed by demethylation and sulfopropylation of the TFMS‐block. The copolymers were characterized by size‐exclusion chromatography, FTIR, and ¹H NMR spectroscopy. Their thermal properties were investigated by differential scanning calorimetry and thermal gravimetric analyses. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7827–7834, 2008     

Narrow disperse polymers using amine functionalized dithiobenzoate RAFT agent and easy removal of thiocarbonyl end group from the resultant polymers

A novel amine functionalized RAFT agent, 2‐cyanoprop‐2‐yl(4‐N,N‐dimethylaminophenyl) dithiobenzoate has been synthesized and used to control the polymerization of vinyl monomers. This dithiobenzoate RAFT agent, although air sensitive, controlled the polymerization of MMA and St very well in an inert atmosphere and the polymerization results obtained were marginally better than using the most popular 2‐cyanoprop‐2‐yl dithiobenzoate RAFT agent. The living nature of these polymerizations was confirmed by kinetics study and chain extension reactions to yield narrow disperse di‐block copolymers. Most importantly, use of this novel RAFT agent simplified the removal procedure of the color causing end thiocarbonyl group from the RAFT derived polymers and thereby leading to polymers with improved appearance. The removal of end group from the polymer was confirmed by ¹H NMR and UV‐vis spectroscopic techniques. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Facilitating polymer conjugation via combination of RAFT polymerization and activated ester chemistry

The synthesis of block copolymers via polymer conjugation of well‐defined building blocks offers excellent control over the structures obtained, but often several coupling strategies need to be explored to find an efficient one depending on the building blocks. To facilitate the synthesis of polymers with adjustable functional end‐groups for polymer conjugation, we report on the combination of activated ester chemistry with RAFT polymerization using a chain transfer agent (CTA) with a pentafluorophenyl ester (PFP‐CTA), which allows for flexible functionalization of either the CTA prior to polymerization or the obtained polymer after polymerization. Different polymethacrylates, namely PMMA, P(t‐BuMA) and PDEGMEMA, were synthesized with an alkyne‐CTA obtained from the aminolysis of the PFP‐CTA with propargylamine, and the successful incorporation of the alkyne moiety could be shown via ¹H and ¹³C NMR spectroscopy and MALDI TOF MS. Further, the reactive α‐end‐groups of polymers synthesized using the unmodified PFP‐CTA could be converted into azide and alkyne end‐groups after polymerization, and the high functionalization efficiencies could be demonstrated via successful coupling of the resulting polymers via CuAAC. Thus, the PFP‐CTA allows for high combinatory flexibility in polymer synthesis facilitating polymer conjugation as useful method for the synthesis of block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Well‐defined epoxide‐containing styrenic polymers and their functionalization with alcohols

Polymers containing electrophilic moieties, such as activated esters, epoxides, and alkyl halides, can be readily modified with a variety of nucleophiles to produce useful functional materials. The modification of epoxide‐containing polymers with amines and other strong nucleophiles is well‐documented, but there are no reports on the modification of such polymers with alcohols. Using phenyloxirane and glycidyl butyrate as low molecular weight model compounds, it was determined that the acid‐catalyzed ring‐opening of aryl‐substituted epoxides by alcohols to form β‐hydroxy ether products was significantly more efficient than that of alkyl‐substituted epoxides. An aryl epoxide‐type styrenic monomer, 4‐vinylphenyloxirane (4VPO), was synthesized in high yield using an improved procedure and then polymerized in a controlled manner under reversible addition‐fragmentation chain‐transfer (RAFT) polymerization conditions. A successful chain extension with styrene proved the high degree of chain‐end functionalization of the poly4VPO‐based macro chain transfer agent. Poly4VPO was modified with a library of alcohols and phenols, some of which contained reactive functionalities, e.g., azide, alkyne, allyl, etc., using either CBr₄ (in PhCN at 90 °C for 2–3 days) or BF₃ (in CH₂Cl₂ at ambient temperature over 30 min) as the catalyst. The resulting β‐hydroxy ether‐functionalized homopolymers were characterized using size exclusion chromatography, ¹H NMR and IR spectroscopy, and thermal gravimetric analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1132–1144