Metal‐catalyzed living radical graft copolymerization of olefins initiated from the structural defects of poly(vinyl chloride)

Commercial poly(vinyl chloride) (PVC) contains allyl chloride and tertiary chloride groups as structural defects. This article reports the use of the active chloride groups from the structural defects of PVC as initiators for the metal‐catalyzed living radical graft copolymerization of PVC. The following monomers were investigated in graft copolymerization experiments: methyl methacrylate, butyl methacrylate, tert‐butyl methacrylate, butyl acrylate, methacrylonitrile, acrylonitrile, styrene, 4‐chloro‐styrene, 4‐methyl‐styrene, and isobornylmethacrylate. Cu(0)/bpy, CuCl/bpy, CuBr/bpy, Cu₂O/bpy, Cu₂S/bpy, and Cu₂Se/bpy (where bpy = 2,2′‐bipyridine) were used as catalysts. Living radical polymerizations initiated from 1‐chloro‐3‐methyl‐2‐butene, allyl bromide, and 1,4‐dichloro‐2‐butene as models for the allyl chloride structural defects and from 3‐chloro‐3‐methyl‐pentane and 1,3‐dichloro‐3‐methylbutane as models for the tertiary chloride defects were studied. Graft copolymerization experiments were accessible in solution, in a swollen state, and in bulk. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1120–1135, 2001     

Arenesulfonyl iodides: The third universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates and styrenes

The metal‐catalyzed living radical polymerization of methyl methacrylate and styrene initiated with freshly prepared p‐toluenesulfonyl iodide (TsI) and catalyzed with CuX/2,2′‐bipyridine (bpy), where X is Cl, Br, or I, and various self‐regulated copper‐based catalytic systems, such as copper/bpy, copper(I) oxide/bpy, copper(I) sulfide/bpy, copper(I) selenide/bpy, and copper(I) telluride/bpy, is reported. The exchange of C? I into C? Br and C? Cl takes place when the living radical polymerization of methyl methacrylate is catalyzed by copper(I) bromide/bpy and copper(I) chloride/bpy, respectively. Therefore, the use of the TsI initiator facilitates the synthesis, starting from a single initiator, of poly(methyl methacrylate) containing C? I, C? Br, and C? Cl chain ends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3920–3931, 2005     

Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator

Our laboratory has reported the elaboration of an iterative strategy for the synthesis of dendritic macromolecules from conventional monomers. This synthetic method involves a combination of self‐regulated metal‐catalyzed living radical polymerization initiated from arenesulfonyl chlorides and an irreversible terminator multifunctional initiator (TERMINI). The previous TERMINI, (1,1‐dimethylethyl)[[1‐[3,5‐bis(S‐phenyl‐4‐N,N′ diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane, was prepared in nine reaction steps. The replacement of the previous TERMINI with one that requires only three steps for its synthesis, diethylthiocarbamic acid S‐{3‐[1‐(tert‐butyl‐dimethyl‐silanyloxy)‐vinyl]‐5‐diethylcarbamoylsulfanyl‐phenyl} ester, and the use of the more reactive Cu₂S/2,2′‐bipyridine rather than the Cu₂O/2,2′‐bipyridine self‐regulated catalyst have generated an accelerated method for the synthesis of dendritic macromolecules. This method provides rational design strategies for the synthesis of dendritic macromolecules with different compaction by the use of a single monomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4894–4906, 2005     

In situ atom transfer radical polymerization of styrene with a tetraethylthiuram disulfide/copper bromide/2,2′‐bipyridine initiating system

The living radical polymerization of styrene in bulk was successfully performed with a tetraethylthiuram disulfide/copper bromide/2,2′‐bipyridine (bpy) initiating system. The initiator Et₂NCS₂Br and the catalyst cuprous bromide (CuBr) were produced from the reactants in the system through in situ atom transfer radical polymerization (ATRP). A plot of natural logarithm of the ratio of original monomer concentration to monomer concentration at present, ln([M]₀/[M]) versus time gave a straight line, indicating that the kinetics was first‐order. The number‐average molecular weight from gel permeation chromatography (GPC) of obtained polystyrenes did not agree well with the calculated number‐average molecular weight but did correspond to a 0.5 initiator efficiency. The polydispersity index (i.e., the weight‐average molecular weight divided by the number‐average molecular weight) of obtained polymers was as low as 1.30. The resulting polystyrene with α‐diethyldithiocarbamate and ω‐Br end groups could initiate methyl methacrylate polymerization in the presence of CuBr/bpy or cuprous chloride/bpy complex catalyst through a conventional ATRP process. The block polymer was characterized with GPC, ¹H NMR, and differential scanning calorimetry. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4001–4008, 2001     

Controlled/living polymerization of MMA promoted by heterogeneous initiation system (EPN‐X–CuX–bpy)

The polymerization of methyl methacrylate (MMA) promoted by heterogeneous initiation system (ethyl‐2‐halopropionate (EPN‐X)–CuX–2,2′‐bipyridyl (bpy), where X = Br or Cl) is studied in detail. The results show that ethyl‐2‐bromopropionate (EPN‐Br) is an efficient initiator as expected, and that CuCl–bpy, instead of CuBr–bpy, is a better catalyst for the controlled polymerization of MMA. The solvents with a high value of dielectric constant (ε) will lead to fast initiation and narrow molecular weight distribution (MWD). As a result, the controlled, living polymerization of MMA with EPN‐Br–CuCl–bpy can be got in ethyl acetate (EAc) at 100°C and in acetonitrile at 80°C. All results suggest that the initiation reaction is a controlling step in the controlled polymerization of MMA. The relationship between the UV spectra of CuCl–bpy and the performances of the polymerization in EAc or acetonitrile suggest that the formation of bis‐bpy complex, [Cubpy₂]X⁻, will lead to fast initiation and good control of the polymerization. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1255–1263, 1999     

From metal‐catalyzed radical telomerization to metal‐catalyzed radical polymerization of vinyl chloride: Toward living radical polymerization of vinyl chloride

The metal‐catalyzed radical polymerization of vinyl chloride (VC) in ortho‐dichlorobenzene initiated with various activated halides, such as α,α‐dihaloalkanes, α,α,α‐trihaloalkanes, perfloroalkyl halides, benzyl halides, pseudohalides, allyl halides, sulfonyl halides, α‐haloesters, α‐halonitriles, and imidyl halides, in the presence of Cu(0)/2,2′‐bipyridine, Fe(0)/o‐phenantroline, TiCp₂Cl₂, and other metal catalysts is reported. The formation of the monoadduct between the initiator and VC was achieved with all catalysts. However, propagation was observed only for metals in their zero oxidation state because they were able to reinitiate from geminal dihalo or allylic chloride structures. Poly(vinyl chloride) with molecular weights larger then the theoretical limit allowed by chain transfer to VC were obtained even at 130 °C. In addition, the most elemental features of a living radical polymerization, such as a linear dependence of the molecular weight and a decrease of polydispersity with conversion, were observed for the most promising systems based on iodine‐containing initiators and Cu(0), that is, I? CH₂? Ph? CH₂? I/Cu(0)/bpy (where bpy = 2,2′‐bipyridyl), at 130 °C. However, because of the formation of inactive species via chain transfer to VC and other side reactions, the observed conversions were in most cases lower than 40%. A mechanistic interpretation of the chain transfer to monomer in the presence of Cu species is proposed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3392–3418, 2001     

Catalytic effect of dimethyl sulfoxide in the Cu(0)/tris(2‐dimethylaminoethyl)amine‐catalyzed living radical polymerization of methyl methacrylate at 0–90 °C initiated with CH3CHClI as a model compound for α,ω‐di(iodo)poly(vinyl chloride) chain ends

A variety of conditions, including catalysts [CuCl, CuI, Cu₂O, and Cu(0)], ligands [2,2′‐bipyridine (bpy), tris(2‐dimethylaminoethyl)amine (Me₆‐TREN), polyethyleneimine, and hexamethyl triethylenetetramine], initiators [CH₃CHClI, CH₂I₂, CHI₃, and F(CF₂)₈I], solvents [diphenyl ether, toluene, tetrahydrofuran, dimethyl sulfoxide (DMSO), dimethylformamide, ethylene carbonate, dimethylacetamide, and cyclohexanone], and temperatures [90, 25, and 0 °C] were studied to assess previous methods for poly(methyl methacrylate)‐b‐poly(vinyl chloride)‐b‐poly(methyl methacrylate) (PMMA‐b‐PVC‐b‐PMMA) synthesis by the living radical block copolymerization of methyl methacrylate (MMA) initiated with α,ω‐di(iodo)poly(vinyl chloride). CH₃CHClI was used as a model for α,ω‐di(iodo)poly(vinyl chloride) employed as a macroinitiator in the living radical block copolymerization of MMA. Two groups of methods evolved. The first involved CuCl/bpy or Me₆‐TREN at 90 °C, whereas the second involved Cu(0)/Me₆‐TREN in DMSO at 25 or 0 °C. Related ligands were used in both methods. The highest initiator efficiency and rate of polymerization were obtained with Cu(0)/Me₆‐TREN in DMSO at 25 °C. This demonstrated that the ultrafast block copolymerization reported previously is the most efficient with respect to the rate of polymerization and precision of the PMMA‐b‐PVC‐b‐PMMA architecture. Moreover, Cu(0)/Me₆‐TREN‐catalyzed polymerization exhibits an external first order of reaction in DMSO, and so this solvent has a catalytic effect in this living radical polymerization (LRP). This polymerization can be performed between 90 and 0 °C and provides access to controlled poly(methyl methacrylate) tacticity by LRP and block copolymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1935–1947, 2005     

N‐chloro amides,lactams, carbamates,and imides. New classes of initiators for the metal‐catalyzed living radical polymerization of methacrylates

Metal‐catalyzed living radical polymerization of methyl methacrylate initiated with N‐chloro amides (N‐chloro N‐ethyl propionamide, N‐chloro benzanilide, N‐chloro methylbenzamide, and N‐chloro acetanilide), lactams (N‐chloro caprolactam and N‐chloro 2‐pyrrolidinone), carbamates or urethanes (N‐chloro ethylcarbamate or N‐chlorourethane), imides (N‐chloro phtalimide, N‐chloro succinimide, trichloroisocyanuric acid, and N‐chloro saccharin) and catalyzed with the self‐regulated catalytic system Cu₂S/2,2′‐bipyridine is reported. The initiation efficiency of these initiators is determined by their structure. Regardless of the initiator efficiency, in all cases, poly (methyl methacrylate) with narrow molecular weight distribution and functionalized chain‐ends was obtained. These new classes of initiators open new strategies for the functionalization of polymer chain‐ends and for the synthesis of complex architectures by graft copolymerization initiated from N‐chloro proteins, aliphatic, aromatic and semiaromatic polyamides, and polyurethanes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5283–5299, 2005     

Organocopper‐catalyzed living radical polymerization initiated with aromatic sulfonyl chlorides

The living radical polymerization of methyl methacrylate initiated from aromatic sulfonyl chlorides and catalyzed by the new catalytic systems CuSBu/bpy CuSPh/bpy and CuCCPh/bpy (bpy = 2,2′‐bipyridine) is described. For a target degree of polymerization of 200, lowering the ratio of catalyst to sulfonyl chloride group from 1/1 to 0.25/1 mol/mol decreases the values of the experimental rate constant of polymerization from 5.12 × 10⁻², 2.4 × 10⁻², and 1.87 × 10⁻² min⁻¹ to 1.8 × 10⁻³, 4.9 × 10⁻³, and 4.2 × 10⁻³ min⁻¹ for CuSBu, CuSPh, and CuCCPh, respectively, whereas the corresponding initiator efficiency increases from 62 to 99%. The external orders of reaction in the catalyst are 0.79 for CuSPh, 0.88 for CuCCPh, and 1.64 for CuSBu. A mechanistic interpretation that involves the in situ generation of, most likely, the real catalyst CuCl, starting from combinations of CuSBu, CuSPh, and CuCCPh and sulfonyl chloride or alkyl halide growing species, is suggested. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4353–4361, 2000     

ATRP of methyl methacrylate using a novel binol ester‐based bifunctional initiator

Novel bifunctional initiators [1,1′‐Bi‐2‐naphthol bis(2‐bromo‐2‐methylpropionate); (R)‐, (S)‐, and racemic‐] were synthesized from the esterification of 1,1′‐bi‐2‐naphthol and used as initiators in atom transfer radical polymerization (ATRP) in conjunction with N,N,N′,N′,N″‐pentamethyldiethylenetriamine (PMDETA), and copper (I) bromide or copper (I) chloride. The initiators synthesized were completely characterized by UV, FTIR, NMR, and Mass spectroscopies. A detailed investigation of the ATRP of methyl methacrylate (MMA) with the bifunctional initiators (BBiBN) along with CuBr or CuCl/PMDETA catalyst system in anisole was carried out at 30 °C. Thus, MMA polymerization is shown to proceed with first‐order kinetics, with predicted molecular weight, and narrow polydispersity indices. The ATRP of glycidyl methacrylate (GMA) and tert‐butyl acrylate (tBA) were also performed with BBiBN initiator in conjunction with CuBr/PMDETA catalyst system. The polymerization of GMA was carried out at 30 °C, but tBA was polymerized at 60 °C. Gel permeation chromatography (GPC), FTIR, NMR, UV spectroscopies, and TGA were used for the characterization of the polymers synthesized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 902–915, 2004     

High‐throughput experimentation in atom transfer radical polymerization: A general approach toward a directed design and understanding of optimal catalytic systems

High‐throughput experimentation (HTE) was successfully applied in atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) for the rapid screening and optimization of different reaction conditions. A library of 108 different reactions was designed for this purpose, which used four different initiators [ethyl 2‐bromoisobutyrate, methyl 2‐bromopropionate, (1‐bromoethyl)benzene, and p‐toluenesulfonyl chloride], five metal salts (CuBr, CuCl, CuSCN, FeBr₂, and FeCl₂), and nine ligands (2,2′‐bipyridine and its derivatives). The optimal reaction conditions for Cu(I) halide, CuSCN, and Fe(II) halide‐mediated ATRP systems with 2,2′‐bipyridine and its 4,4′‐dialkyl‐substituted derivatives as ligands were determined. Cu(I)‐mediated systems were better controlled than Fe(II)‐mediated ones under the examined conditions. A bipyridine‐type ligand with a critical length of the substituted alkyl group (i.e., 4,4′‐dihexyl 2,2′‐bipyridine) exhibited the best performance in Cu(I)‐mediated systems, and p‐toluenesulfonyl chloride and ethyl 2‐bromoisobutyrate could effectively initiate Cu(I)‐mediated ATRP of MMA, resulting in polymers with low polydispersities in most cases. Besides, Cu(I) halide‐mediated ATRP with 4,5′‐dimethyl 2,2′‐bipyridine as the ligand and p‐toluenesulfonyl chloride as the initiator proved to be better controlled than those with 4,4′‐dimethyl 2,2′‐bipyridine as the ligand, and polymers with much lower polydispersities were obtained in the former cases. This successful HTE example opens up a way to significantly accelerate the development of new catalytic systems for ATRP and to improve the understanding of structure–property relationships of the reaction systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1876–1885, 2004     

CuI and CuII salts of group VIA elements as catalysts for living radical polymerization initiated with sulfonyl chlorides

The living radical polymerization of methyl methacrylate initiated from sulfonyl chlorides and catalyzed by the new catalytic systems Cu₂Y/Bpy and CuY/Bpy, where Y is O, S, Se, or Te and Bpy is 2,2′‐bipyridine, is described. An induction time was observed in all polymerization experiments. The values of the experimental rate constants of polymerization (k_p ^exp) increased whereas the corresponding induction times decreased in the order Y = O < S < Se < Te. For the entire series of catalysts, k_p ^exp for CuY was less than k_p ^exp for Cu₂Y. A mechanistic interpretation that involves the in situ generation of the CuCl/CuCl₂ pair, starting from Cu₂Y or CuY, is provided. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3839–3843, 2000     

Catalytic effect of ionic liquids in the Cu2O/2,2′‐bipyridine catalyzed living radical polymerization of methyl methacrylate initiated with arenesulfonyl chlorides

The effect of 1‐butyl‐3‐methylimidazolium hexafluorophosphate ionic liquid on the living radical polymerization of methyl methacrylate initiated with arenesulfonyl chlorides and catalyzed by the self‐regulated Cu₂O/2,2′‐bipyridine catalyst was investigated. A dramatic acceleration of the living radical polymerization of methyl methacrylate in this ionic liquid was discovered. This accelerated living radical polymerization maintained an initiation efficiency of 100%, eliminated the induction period of this catalyst, and produced poly(methyl methacrylate) with molecular weight distribution of 1.1 and perfect bifunctional chain‐ends. The kinetic analysis of the living radical polymerization in the presence of ionic liquid demonstrated a rate constant of propagation that follows an almost first order of reaction on the ionic liquid concentration and therefore, the ionic liquid exhibits catalytic effect. The catalytic effect of the ionic liquid facilitated the reduction of the catalyst concentration from stoichiometric to catalytic and allowed the decrease of the polymerization temperature from 80 to 22 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5609–5619, 2005     

ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers

This article reports the synthesis of the block and graft copolymers using peroxygen‐containing poly(methyl methacrylate) (poly‐MMA) as a macroinitiator that was prepared from the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of bis(4,4′‐bromomethyl benzoyl peroxide) (BBP). The effects of reaction temperatures on the ATRP system were studied in detail. Kinetic studies were carried out to investigate controlled ATRP for BBP/CuBr/bpy initiating system with MMA at 40 °C and free radical polymerization of styrene (S) at 80 °C. The plots of ln ([M_o]/[M_t]) versus reaction time are linear, corresponding to first‐order kinetics. Poly‐MMA initiators were used in the bulk polymerization of S to obtain poly (MMA‐b‐S) block copolymers. Poly‐MMA initiators containing undecomposed peroygen groups were used for the graft copolymerization of polybutadiene (PBd) and natural rubber (RSS‐3) to obtain crosslinked poly (MMA‐g‐PBd) and poly(MMA‐g‐RSS‐3) graft copolymers. Swelling ratio values (q_v) of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by Fourier‐transform infrared spectroscopy (FTIR), ¹H‐nuclear magnetic resonance (¹H NMR), gel‐permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and the fractional precipitation (γ) techniques. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1364–1373, 2010     

Synthesis of end‐functionalized poly(methyl methacrylate) by ruthenium‐catalyzed living radical polymerization with functionalized initiators

A series of functionalized 2‐bromoisobutyrates and 2‐chloro‐2‐phenylacetates led to α‐end‐functionalized poly(methyl methacrylate)s in Ru(II)‐catalyzed living radical polymerization; the terminal functions included amine, hydroxyl, and amide. These initiators were effective in the presence of additives such as Al(Oi‐Pr)₃ and n‐Bu₃N. The chlorophenylacetate initiators especially coupled with the amine additive gave polymers with well‐controlled molecular weights (M_w/M_n = 1.2–1.3) and high end functionality (F_n ～ 1.0). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1937–1944, 2002     

A facile strategy for synthesis of α,α′‐heterobifunctionalized poly (ε‐caprolactones) and poly (methyl methacrylate)s containing “clickable” aldehyde and allyloxy functional groups using initiator approach

Two new initiators, namely, 4‐(4‐(2‐(4‐(allyloxy) phenyl)‐5‐hydroxypentane 2‐yl) phenoxy)benzaldehyde and 4‐(4‐(allyloxy) phenyl)‐4‐(4‐(4‐formylphenoxy) phenyl) pentyl 2‐bromo‐2‐methyl propanoate containing “clickable” hetero‐functionalities namely aldehyde and allyloxy were synthesized starting from commercially available 4,4′‐bis(4‐hydroxyphenyl) pentanoic acid. These initiators were utilized, respectively, for ring opening polymerization of ε‐caprolactone and atom transfer radical polymerization of methyl methacrylate. Well‐defined α‐aldehyde, α′‐allyloxy heterobifunctionalized poly(ε‐caprolactones) (M_n,GPC: 5900–29,000, PDI: 1.26–1.43) and poly(methyl methacrylate)s (M_n,GPC: 5300–28800, PDI: 1.19–1.25) were synthesized. The kinetic study of methyl methacrylate polymerization demonstrated controlled polymerization behavior. The presence of aldehyde and allyloxy functionality on polymers was confirmed by ¹H NMR spectroscopy. Aldehyde‐aminooxy and thiol‐ene metal‐free double click strategy was used to demonstrate reactivity of functional groups on polymers. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Quantification of ATRP initiator density on polymer latex particles by fluorescence labeling technique using copper‐catalyzed azide‐alkyne cycloaddition

We developed a novel fluorescence labeling technique for quantification of surface densities of atom transfer radical polymerization (ATRP) initiators on polymer particles. The cationic P(St‐CPEM‐C₄DMAEMA) and anionic P(St‐CPEM) polymer latex particles carrying ATRP‐initiating chlorine groups were prepared by emulsifier‐free emulsion polymerization of styrene (St), 2‐(2‐chloropropionyloxy)ethyl methacrylate (CPEM), and N‐n‐butyl‐N,N‐dimethyl‐N‐(2‐methacryloyloxy)ethylammonium bromide (C₄DMAEMA). ATRP initiators on the surface of polymer particles were converted into azide groups by sodium azide, followed by fluorescent labeling with 5‐(N,N‐dimethylamino)‐N′‐(prop‐2‐yn‐1‐yl)naphthalene‐1‐sulfonamide (Dansyl‐alkyne) by copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The reaction time required for both azidation of ATRP‐initiating groups and successive fluorescence labeling of azide groups with Dansyl‐alkyne by CuAAC were investigated in detail by FTIR and fluorescence spectral measurement, respectively. The ATRP initiator densities on the cationic P(St‐CPEM‐C₄DMAEMA) and anionic P(St‐CPEM) particle surfaces were estimated to be 0.21 and 0.15 molecules nm^?2, respectively, which gave close agreement with values previously determined by a conductometric titration method. The fluorescence labeling through click chemistry proposed herein is a versatile technique to quantify the surface ATRP initiator density both on anionic and cationic polymer particles. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4042–4051     

Polymerization of acrylamide photoinitiated by tris(2,2′‐bipyridine)ruthenium(II)–amine in aqueous solution: Effect of the amine structure

The photopolymerization of acrylamide (AA) initiated by the metallic complex tris(2,2′‐bipyridine)ruthenium(II) [Ru(bpy)₃⁺²] in the presence of aliphatic and aromatic amines as co‐initiators was investigated in aqueous solution. Aromatic amines, which are good quenchers of the emission of the metal‐to‐ligand‐charge‐transfer excited state of the complex, are more effective co‐initiators than those that do not quench the luminescence of Ru(bpy)₃⁺², such as aliphatic amines and aniline. Laser‐flash photolysis experiments show the presence of the reduced form of the complex, Ru(bpy)₃⁺¹, for all the amines investigated. For aliphatic amines, the yield of Ru(bpy)₃⁺¹ increases with temperature, and on the basis of these experiments, a metal‐centered excited state is proposed as the reactive intermediate in the reaction with these amines. The decay of the transient Ru(bpy)₃⁺¹ is faster in the presence of AA. This may be understood by an electron‐transfer process from Ru(bpy)₃⁺¹ to AA, regenerating Ru(bpy)₃⁺² and producing the radical anion of AA. It is proposed that this radical anion protonates in a fast process to give the neutral AA radical, initiating in this way the polymerization chain. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4265–4273, 2001     

Synthesis of phosphate end‐functional polymers and application to thermally latent polymeric initiators

Novel phosphates, O‐p‐(hydroxymethyl)benzyl O,O‐diethyl phosphate ( 1 ) and O‐(2‐bromoisobutyryloxymethyl)benzyl O,O‐diethyl phosphate ( 2 ) were synthesized by the reaction of diethyl phosphorochloridate with 1,4‐benzenedimethanol and the successive reaction with 2‐bromoisobutyryl bromide in the presence of triethylamine and submitted to the polymerization of ?‐caprolactone and methyl methacrylate as the initiators. They afforded phosphate end‐functional poly(?‐caprolactone) and poly(methyl methacrylate) with controlled molecular weights and polydispersity ratios by living ring‐opening polymerization and samarium‐induced polymerization. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate end‐functional polymers as the latent polymeric initiators in the presence of ZnCl₂. The polymerization of GPE did not proceed below 90 °C, but it rapidly proceeded to afford poly(GPE) above the temperature. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3832–3840, 2001     

Living radical polymerization. II. Improved atom transfer radical polymerization of acrylamide in aqueous glycerol media with a novel pentamethyldiethylenetriamine‐based soluble copper(I) complex catalyst system

An improved atom transfer radical polymerization (ATRP) of acrylamide was achieved in a glycerol/water (1:1 v/v) medium with 2‐halopropionamide initiators, CuX (X = Cl or Br) as catalysts, pentamethyldiethylenetriamine (PMDETA) as a ligand, and CuX₂ (≥20 mol % CuX) and excess alkali halide (ca. 1 mol/dm³) as additives. The first‐order kinetic plots for the disappearance of the monomer at 130 °C were linear; this was a significant improvement over the results obtained earlier with the bipyridine ligand. However, even under such improved situations, about 7 mol % of the polymer chains were estimated to be formed dead. The polydispersity index was approximately 1.5. At a lower temperature (ca. 90 °C), a lower polydispersity index (1.24) was obtained for the bromide‐based initiating system. Chain‐extension experiments proved the living nature of the polymers. The presence of both extra halide ions and the monomer was necessary to take the CuX–PMDETA complex into solution. It was suggested that the soluble Cu(I) complex was formed with one PMDETA molecule acting as a monodentate ligand and with two halide ions and one acrylamide molecule occupying the other three coordination sites. Some support for the involvement of all three ligands (X^?, PMDETA, and acrylamide) in the complex formation was obtained from ultraviolet–visible spectroscopy studies. The better ATRP with the PMDETA ligand was attributed to the better stability and lesser hydrolysis of the 1:1 Cu⁺²/PMDETA complex with respect the corresponding bipyridine complex. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2483–2494, 2004