Asymmetric anionic polymerization of (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl)methyl methacrylate leading to a helical polymer

A novel racemic methacrylate, (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl)-methyl methacrylate¹ (2F4F2PyMA), was synthesized and polymerized with chiral complexes of N,N′-diphenylethylenediamine monolithium amide (DPEDA-Li) with (−)-sparteine (Sp), (2S, 3S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB), and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP) in toluene at −78°C. The monomer showed higher resistance against methanolysis compared with triphenylmethyl methacrylate (TrMA) and several other analogues. In the asymmetric anionic polymerization of 2F4F2PyMA, PMP was found to be a more effective chiral ligand than DDB and Sp and gave quantitatively an optically active polymer with nearly perfect isotacticity. Enantiomer selection was observed in the polymerization of racemic 2F4F2PyMA with the chiral lithium complexes. Chiral recognition ability of the optically active poly(2F4F2PyMA) was examined by an enantioselective adsorption experiment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2013–2019, 1998     

Preparation and characterization of optically active polymers containing pendent and terminal chiral units via atom transfer radical polymerization

Optically active homopolymers and copolymers, bearing chiral units at the side chain and end chain, were prepared via atom transfer radical polymerization (ATRP) techniques. The well‐defined optically active polymers were obtained via the ATRP of pregnenolone methacrylate (PR‐MA), β‐cholestanol acrylate (CH‐A), and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one acrylate (HPD‐A) with ethyl 2‐bromopropionate as the initiator and CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalytic system. The experimental results showed that the polymerizations of PR‐MA, CH‐A, and HPD‐A proceeded in a living fashion, providing pendent chiral group polymers with low molecular weight distributions and predetermined molecular weights that increased linearly with the monomer conversion. Furthermore, the copolymers poly(pregnenolone methacrylate)‐b‐poly[(dimethylamino)ethyl methacrylate] and poly(pregnenolone methacrylate‐co‐methyl methacrylate) were synthesized and characterized with ¹H NMR, transmission electron microscopy, and polarimetric analysis. In addition, when optically active initiators estrone 2‐bromopropionate and 20‐(hydroxymethyl)‐pregna‐1,4‐dien‐3‐one 2‐bromopropionate were used for ATRPs of methyl methacrylate and styrene, terminal optically active poly(methyl methacrylate) and polystyrene were obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1502–1513, 2006     

Editorial

Abstract

Asymmetric syntheses of optically active polymethacrylate, polyacrylate, polyacrylamide, and polyisocyanate with helical conformation and their chiral recognition abilities are described. 1-Phenyldibenzosuberyl methacrylate (PDBSMA) gave a purely onehanded-helical, optically active polymer ([α]₃₆₅ +1670 ～ +1780º) with almost perfectly isotactic structure by anionic polymerization using optically active initiators. Radical polymerizations of PDBSMA using chiral initiators, chain transfer agents, and additives also afforded optically active polymers with a prevailing onehanded helicity. Triphenylmethyl acrylate yielded an optically active, helical polymer ([α]₃₆₅ +102º) having a dyad isotacticity of 70% using an optically active anionic initiator. Although the polyacrylate demonstrated chiral recognition ability as a chiral stationary phase for HPLC, the ability was low mainly because of the low degree of one-handedness. N-(3-Chlorophenyl)-N-phenylacrylamide gave an optically active, helical polymer ([α]_365–343º) in the asymmetric anionic polymerization; the polymer had a dyad tacticity of 77%. Optically active polyisocyanates with a predominantly one-handed helical conformation were prepared in homo-and co-polymerization of optically active phenyl isocyanate derivative. These polyisocyanates showed the ability to discriminate enantiomers in solution.     

Synthesis and properties of microgel bearing a mercapto group

Vinylbenzyl S-thioacetate ( 1 ) was prepared from thioacetic acid and chloromethylstyrene. Although bulk polymerization of 1 afforded a crosslinked polymer, solution polymerization in chlorobenzene afforded a corresponding soluble polymer. The S-thioacetate group did not react during the radical polymerization of 1 . Bulk copolymerization of 1 with styrene afforded a soluble copolymer when the feed ratio of 1 was lower than 30 mol %. Soap-free emulsion copolymerization of 1 , St, divinylbenzene, and 2-hydroxyethyl methacrylate (66 : 28 : 1 : 5) was carried out in water using 2,2′-azobis (N,N′-dimethyleneisobutyramidine) dichloride as an initiator to afford uniform spherical microgel 2 , whose average diameter was 135 nm. Aminolysis of 2 with an excess amount of butylamine in the presence of sodium tetrahydridoborate followed by treatment with hydrochloric acid resulted in complete removal of the acetyl group to give a slightly distorted spherical microgel (MG-SH) bearing mercapto group. The average diameter of MG-SH was 165 nm. Trans-esterification of p-nitrophenyl acetate ( 3 ) in the presence of triethylamine was efficiently accelerated by the addition of MG-SH. The radical polymerization of methyl methacrylate (MMA) in the presence of suspended MG-SH in chlorobenzene afforded the MMA-grafted microgel. Although MG-SH is a crosslinked gel, it acts as a soluble polymer bearing mercapto group. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1443–1451, 1997     

Chiral arylnickel complexes as highly active initiators for screw‐sense selective living polymerization of 1,2‐diisocyanobenzenes

Optically active chiral organonickel complexes served as efficient chiral initiators for living aromatizing polymerization of 1,2‐diisocyanobenzene derivatives, which afford optically active helical poly(quinoxaline‐2,3‐diyl)s up to 84% s.e. (screw‐sense excess). In comparison with asymmetric polymerization with the corresponding organopalladium initiators, the nickel initiators show a much greater polymerization rate, while the selectivity remains high. The organonickel initiators can be generated in situ from nickel(0) precursors with the corresponding enantiopure (S,S)‐2‐(4,5‐diphenylimidazolin‐2‐yl)phenyl chloride, leading to the convenient synthesis of highly stereo‐controlled poly(quinoxaline‐2,3‐diyl)s. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 898–904, 2010     

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     

A novel one-pot oxidation polymerization of dithiols obtained from bifunctional five-membered cyclic dithiocarbonates with amines

One-pot oxidation polymerization of dithiols, obtained from bifunctional five-membered cyclic dithiocarbonates ( 4a and 4b ) with two equivalents of amines, was studied. The monomers 4a and 4b were synthesized by the reactions of bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether with carbon disulfide, respectively. Polydisulfides with M̄_ns 4600–20,200 were obtained quantitatively in the oxidation polymerization of the dithiols obtained in situ by the reactions of 4a with benzylamine, n-butylamine, and piperidine. On the other hand, dithiols obtained from 4b with benzylamine, afforded cyclic disulfides as well as the polydisulfide under similar conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 79–84, 1998     

Syntheses and polymerizations of novel chiral poly(acrylamide) macromonomers and their chiral recognition abilities

Chiral poly(acrylamide) macromonomers (PMB‐1, PMB‐2, PPAE‐1, and PPAE‐2) were synthesized from 2‐methacryloyloxyethyl isocyanate and prepolymers, that is, poly[(S)‐methylbenzyl acrylamide] or poly(L ‐phenylalanine ethylester acrylamide with a terminal carboxylic acid or hydroxy group. Radical homopolymerizations of poly(acrylamide) macromonomers were carried out under several conditions to obtain the corresponding optically active polymers. A strong temperature dependence on the specific optical rotation was observed for poly(PPAE‐2) in comparison with that for the corresponding prepolymer. This might have resulted from a change in the conformation caused by hydrogen bonds between polymer‐graft branches in the polymacromonomer. Radical copolymerizations of poly(acrylamide) macromonomers with styrene and methyl methacrylate were performed with azobisisobutyronitrile in tetrahydrofuran at 60 °C. Chiroptical properties of the copolymers were slightly influenced by comonomer units. Chiral stationary phases were prepared by the radical polymerization of poly(acrylamide) macromonomers in the presence of silica gel containing vinyl groups on the surface. Some racemic compounds such as menthol and mandelic acid were resolved on the chiral stationary phases for high‐performance liquid chromatography. The conformation based on hydrogen bonds between polymer‐graft branches in the polymacromonomers may play an important role in chiral discrimination. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1726–1741, 2002     

Samarium poly(oxamide) polyanions as novel polymeric initiators. One-pot syntheses of graft copolymers

Samarium poly(oxamide) polyanions, formed quantitatively in situ by the reductive coupling polymerization of aromatic diisocyanates with samarium (II) iodide/hexamethylphosphoramide (HMPA) system, were directly used as the polymeric initiators in the graft polymerization with some electrophilic monomers. The graft polymerization of ϵ-caprolactone (CL) with several polyanions derived from bifunctional isocyanates, including tolylene 2,6-diisocyanate, o-tolidine diisocyanate and diphenylmethane diisocyanate, provided the corresponding graft copolymers in one-pot, indicating that the polyanion could work as a new type of reactive polymer. Several factors such as reaction temperature and time and the amount of HMPA and CL affected the behavior of the present polymerization system, and the graft copolymer was obtained quantitatively under the appropriate conditions. The results of the graft polymerizations of tert-butyl methacrylate and methyl methacrylate with the polyanion were also presented. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1381–1387, 1997     

Samarium enolate on crosslinked polystyrene beads. II. An anionic initiator for the well‐defined synthesis of poly(allyl methacrylate) on a solid support

A samarium enolate, supported on a crosslinked polystyrene resin, successfully initiated the living anionic polymerization of allyl methacrylate (AMA) to afford the corresponding poly(AMA) with well‐controlled molecular weights. Diblock, triblock, and tetrablock copolymerizations with methyl methacrylate (MMA) were also successfully performed. The formed polymers, supported on the resin by a benzyl ester linker, were quantitatively isolated from the resin by selective cleavage of the linker with trifluoroacetic acid (TFA). Allyl ester in the side chain was not affected by this isolation step. The allyl group of the immobilized poly(AMA‐b‐MMA) on the resin was transformed into a 2,3‐dihydroxypropyl group by osmium oxidation. The resulting copolymer was isolated by TFA treatment of the resin, and it showed amphiphilicity. In both the polymerization and side‐chain modification, the formed polymers were easily washed from excess reagents only by filtration, and this demonstrated the feasibility of the automated synthesis of functional polymers based on this solid‐supported polymerization technique. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 853–860, 2003     

Synthesis,characterization, and application of helical polymers

This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.     

Synthesis and chiral recognition ability of optically active poly{N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide} with various tacticities by radical polymerization using Lewis acids

The radical polymerization of an optically active methacrylamide, N‐[(R)‐α‐methoxycarbonylbenzyl]methacrylamide, was carried out in the absence and presence of Lewis acids such as yittribium trifluoromethanesulfonate [Yb(OTf)₃] and scandium trifluoromethanesulfonate [Sc(OTf)₃]. Catalytic amounts of the Lewis acids significantly affected the stereoregularity of the obtained polymers. The polymerization with Yb(OTf)₃ in tetrahydrofuran afforded isotactic polymers (up to mm = 87%), whereas the conventional radical method without the Lewis acid produced polymers rich in syndiotacticity (up to rr = 88%). The radical polymerization in the presence of MgBr₂ proceeded in a heterotactic‐selective manner (mr = 63%). Thus, the isotactic, syndiotactic, and heterotactic poly(methacrylamide)s were synthesized by the radical processes. The chiral recognition abilities of the obtained optically active poly(methacrylamide)s were affected by the stereoregularity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3354–3360, 2003     

Synthesis of chiral micelles and nanoparticles from amino acid based monomers using RAFT polymerization

Homopolymers of ^tbutyl acrylate (P^tBuA) and a monosubstituted acrylamide (PAM) having an amino acid moiety in the side chain, N‐acryloyl‐(L )‐phenylalanine methyl ester 1 , have been synthesized by Reversible Addition‐Fragmentation Chain Transfer (RAFT) polymerization. Diblock copolymers of these homopolymers were also synthesized by chain extending P^tBuA with monomer 1 and after modification, using simple acid deprotection chemistries of the acrylate block to afford a poly (acrylic acid) block, an optically active amphiphilic diblock copolymer was isolated. The optically active amphiphilic diblock copolymers, which contain chiral amino acid moieties within the hydrophobic segment, were then self‐assembled to afford spherical micelles which were subsequently crosslinked throughout the shell layer to afford robust chiral nanoparticles. The hydrodynamic diameters (D_h) of the block copolymer micelles and nanoparticles were measured by dynamic light scattering (DLS) and the dimensions of the nanoparticles were determined using tapping‐mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3690–3702, 2008     

Stereospecific and asymmetric polymerization of 1-phenyldibenzosuberyl methacrylate with radical and anionic initiators

Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)₂ at 40°C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)-and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N′-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.     

End‐functionalized polystyrene by ATRP: A facile approach to primary amino and carboxylic acid terminal groups

Monoamino‐terminated and monocarboxylic acid‐terminated polystyrenes containing active halogenated end groups were prepared by atom transfer radical polymerization (ATRP) using the so‐called initiator method and protective group chemistry. α‐Chloropropionates were synthesized and utilized as initiators containing the tert‐butoxycarbonyl (t‐BOC)‐protected amino and the tert‐butyl (t‐Bu)‐protected carboxylic acid function, respectively. Optimum polymerization conditions were attained using CuCl/N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) as catalyst and 10 vol % n‐butanol as homogenizing agent at 110 °C. However, targeting larger quantities an alternative route was established employing 50 vol % N,N‐dimethylformamide (DMF). Subsequent hydrolysis of the ω‐tert‐butoxycarbonyl polystyrenes afforded well‐defined polymers with quantitative deprotection of the functional groups. Comparatively, thermolytic cleavage of the protective sites was studied. ¹H NMR verified the quantitative removal of the t‐BOC‐protecting groups. Furthermore, the resulting α‐amino‐ω‐chloro polystyrenes were reacted with Sanger reagent to confirm the existence of the thereby converted primary amino groups. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3845–3859, 2009     

(−)-Sparteine: The compound that most significantly influenced my research

A chiral diamine alkaloid, (−)-sparteine (Sp), has been found to be very effective as a ligand for Grignard reagents when used for the enantiomer-selective polymerization of racemic RS-1-phenylethyl methacrylate. The enantiomeric excess of the initially polymerized monomer is 93%, and at about a 60% conversion, nearly optically pure R-monomer is recovered. This enantiomer selectivity is today the highest in polymer chemistry. Triphenylmethyl methacrylate (TrMA) is a unique monomer that gives a highly isotactic polymer even during radical polymerization. When TrMA is polymerized with the Sp complex with n-butyllithium in toluene at −78 °C, an optically active, isotactic polymer [poly(triphenylmethyl methacrylate) (PTrMA)] with a one-handed helical conformation is obtained. The helical structure is maintained even at room temperature in solution. Analogous helical polymethacrylates that show various conformational changes have also been found. One-handed helical PTrMA exhibits high chiral recognition to a variety of racemates as a chiral stationary phase (CSP) for high-performance liquid chromatography. This finding has led to the development of very powerful CSPs based on polysaccharides, such as cellulose and amylose. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4480–4491, 2004     

Syntheses and radical polymerization behavior of novel optically active methacrylamides having (L)-leucine structure in the side chains

Syntheses and radical polymerizations of methacrylamides having (L)-leucine and N-methyl-(L)-leucine methyl ester structures in the side chains N-methacryloyl-(L)-leucine methyl ester (MA-L-M) and N-methyl-N-methacryloyl-(L)-leucine methyl ester (N-Me-MA-L-M) were carried out. The monomers were prepared by the reactions of methacryloyl chloride with the corresponding amino acid methyl esters. Radical polymerizations were carried out in the presence of appropriate initiators at 60°C and 120°C. MA-L-M afforded the corresponding polymer with M_ns 38,000 ∼ 372,000 in high yields, while N-Me-MA-L-M afforded a trace amount of polymer at 60°C and in a low yield even at 120°C. Both inversion and increase of absolute value of specific rotation were observed in the transformation from MA-L-M (+1.3°C) to poly(MA-L-M) (−35.7°C). Changes in the CD spectral pattern and the conformation of the leucine moiety were confirmed from the monomer to polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2681–2690, 1998     

Asymmetric cyclopolymerization of N‐tert‐butyl‐N‐allylacrylamide in the presence of β‐cyclodextrin

The radical polymerization of N‐tert‐butyl‐N‐allylacrylamide (t‐BAA) was carried out in a dimethyl sulfoxide/H₂O mixture in the presence of β‐cyclodextrin (β‐CD). The polymerization proceeded with the complete cyclization of the t‐BAA unit and yielded optically active poly(t‐BAA). The IR spectrum of the obtained polymer showed that the cyclic structure in the polymer was a five‐membered ring. The optical activity of poly(t‐BAA) increased with an increasing molar ratio of β‐CD to the t‐BAA monomer. The interaction of β‐CD with t‐BAA was confirmed by ¹H NMR and ¹³C NMR analyses of the polymerization system. It is suggested that interaction of the t‐BAA monomer with the hydrophobic cavity of β‐CD plays an important role in the asymmetric cyclopolymerization of t‐BAA. The radical copolymerization of t‐BAA with styrene (St), methyl methacrylate, ethyl methacrylate, or benzyl methacrylate (BMA) also produced optically active copolymers with a cyclic structure from the t‐BAA unit. St and BMA carrying a phenyl group were predicted to compete with t‐BAA for interaction with β‐CD in the copolymerization system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2098–2105, 2000     

Synthesis and characterization of ferrocene containing block copolymers

Narrowly dispersed diblock copolymers containing poly(methyl methacrylate) [PMMA] or poly(nonafluorohexyl methacrylate) [PF9MA] as the first block and poly(ferrocenylmethyl methacrylate) [PFMMA] as the second block, were prepared by anionic polymerization for the first time. Disordered bulk morphologies in the case of PMMA‐b‐PFMMA were observed and explained in terms of low Flory–Huggins interaction parameter (χ ≤ 0.04). In the case of PF9MA‐b‐PFMMA hexagonally packed cylinder morphology (HEX) was substantiated from TEM and SAXS observations. Furthermore, high incompatibility between PF9MA and PFMMA blocks allowed for the formation of well‐ordered ferrocene containing cylinders on silica substrate upon exposure of the thin films to a saturated solvent vapor. It was shown that the cylinder orientation, parallel or perpendicular to the surface, could easily be controlled by appropriate choice of the solvent and without the need for preliminary surface modification, for example by means of grafted brush layer. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 495–503     

Synthesis of phosphonated copolymers with tailored architecture by reversible addition‐fragmentation chain transfer polymerization (RAFT)

The synthesis by reversible addition‐fragmentation chain transfer (RAFT) polymerization of three phosphonated terpolymers with tailored architecture has been studied. A phosphonated methacrylate (MAUPHOS) was copolymerized with vinylidene chloride (VC₂) and methyl acrylate (MA) to prepare a gradient terpolymer poly(VC₂‐co‐MA‐co‐MAUPHOS). Besides, hydroxyethyl acrylate (HEA) was used as a functional monomer in RAFT polymerization to prepare a statistical poly(VC₂‐co‐MA‐co‐HEA) terpolymer and a diblock poly(VC₂‐co‐MA)‐b‐poly(HEA) terpolymer. The HEA‐containing polymers were then modified with a phosphonated epoxide to introduce the phosphonated group. The control of the polymerization was proven by kinetic studies (evolution of molecular weight vs. conversion) and by a successful block copolymerization. The architecture of the terpolymers was determined by the reactivity ratios of the monomers: terpolymerization of VC₂, MA, and HEA leading to an ideal statistical terpolymer (no composition drift) whereas terpolymerization of VC₂, MA, and the phosphonated methacrylate led to a gradient terpolymer. These terpolymers were characterized by size exclusion chromatography, ³¹P NMR and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 13–24, 2006