Indian Patents
Title of Invention

LIVING RADICAL POLYMERIZATION OF ACTIVATED AND NONACTIVATED MONOMERS CONTAINING ELECTRON-WITHDRAWING SIDE GROUPS
Abstract The invention concerns a method of polymerizing an alkene monomer to produce a polymer using a catalyst that is Cu(O), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof, an initiator, and a component comprising a solvent and optional nitrogen-containing ligand, where the combination of the component and monomer is capable of diproportionating Cu(I)X into Cu(O) and Cu(II)X; where X is Cl, Br, or I.
Full Text LIVING RADICAL POLYMERIZATION OF ACTIVATED AND NONACTIVATED
MONOMERS CONTAINING ELECTRON-WITHDRAWING SIDE GROUPS
RELATED APPLICATIONS
[0001] This application claims benefit to U.S. Patent Application No. 60/835,580 filed
August 4,2006, which is incorporated herein in its entirety.
FIELD OF THE INVENTION
[0002] The invention concerns polymerization of alkenes such as acrylates,
acrylamides, styrenes and other vinyl containing aromatic groups, methacrylates, vinyl halides,
halogenated acrylates, vinyl aldehydes, halogenated olefins and any other activated and
nonactivated monomers containing electron withdrawing substituents.
BACKGROUND OF THE INVENTION
[0003] Conventional metal-catalyzed organic radical reactions and living radical
polymerizations (LRP) performed in nonpolar solvents, including atom-transfer radical
polymerization (ATRP), proceed by an inner-sphere electron-transfer mechanism that require
high activation energies. There is a need in the art for processes that can be performed at lower
activation energies and, thus, lower temperatures.

SUMMARY OF THE INVENTION
[0004] In some embodiments, the invention concerns a method of polymerizing an
alkene monomer to produce a polymer, the method comprising contacting said monomer with:
a catalyst that is Cu(0), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof;
an initiator that is one or more of sulfonyl halides, nitrogen halides or compounds of the
formula R-X, R'C(=O)OR" or R'-CN, where X is a halogen and R is C1-C6 alky, R' is a
halogen-substituted C1-C6 alkyl, and R" is a C1-C6 alkyl; and
a component comprising a solvent and optional nitrogen-containing ligand, where the
combination of the component and monomer is capable of diproportionating Cu(I)X into Cu(0)
and Cu(n)X'2 where X' is Cl, Br, or I. It should be understood that any combination of
monomer, solvent and optional ligand that diproportionates Cu(I)X into Cu(0) and Cu(II)X2 will
work in the methods of the instant invention.
[0005] In some preferred embodiments, the polymerization occurs in the presence of a
nitrogen-containing ligand.
[0006] Some preferred solvents include water, alcohol, natural or synthetic polymeric
alcohols, dipolar aprotic solvents, ethylene carbonate, propylene carbonate, ionic liquid, or a
mixture thereof.
[0007] While other ligands such as dendrimeric polyamides and polyamines are
suitable for the instant methods, preferred nitrogen containing ligand include one or more of
those of the formula:


[0008] In some embodiments, the initiator is one or more of chloroform, bromoform,
idoform, carbon tetrachloride, carbon tetrabromide, mono-, di- and trihalo-acetates and any other
initiator that is suitable for the conventional metal catalyzed living radical polymerization
including ATRP and compounds of the formula:

[0009] Suitable alkene monomer include acrylates, halogenated acrylates,
methylacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, vinyl sulfones,
vinyl ketones, vinyl sulfoxides, vinyl aldehydes, styrenes, and any other activated and
nonactivated monomers containing electron withdrawing substituents.
These monomers may be substituted. In some embodiments, the monomers optionally contain
functional groups that assist in the disproportionation of Cu(I)X into Cu(0) and Cu(II)X2,
Functional groups include amide, sulfoxide, carbonate, or onium.
[0010] Halogen-substituted alkenes include vinyl chloride, vinylidene chloride, vinyl
fluoride, vinylidene fluoride, trifhioroethylene, trifiuotochloroethylene or tetrafhioroethylene,
hexafluoropropylene and fluorinated vinyl ethers.
[0011] In some embodiments, the methods may be advantageously practiced at about
35°C or below, 25°C or below, or 20°C or below. In other embodiments, the reaction can be
carried out at any higher temperature with a lower amount of catalyst
[0012] Suitable initiators include halogen containing compounds. Examples of
initiators include chloroform, bromofonn, iodoform, carbon tetrachloride, carbon tetrabromide,

hexahalogenated ethane ,mono-di and trihaloacetates, acetophenones, halogenated amides and
polyamides such as nylons, halogenated urcthanes and polyurethane including their block
copolymers such as Lycra®, halogenated imides, acetone, and any other initiators shown to work
with conventional metal catalyzed living radical polymerization including ATRP and compounds
of the formula:

[0013] Any combination of solvent or mixture of solvent and ligand that
disproportionate Cu(I)X into Cu(0) and Cu(II)X2 are suitable for use in the instant methods. In
some embodiments, the solvent can be used also in only small amount since it can provide a
catalytic effect. See, for example, Figure 3. Thus, the solvent can act, not only as a solvent, but
as a catalyst for the reaction. Furthermore, additional solvents, which may or may not provide a
catalytic effect, can optionally be used in the reaction.
[0014] In certain embodiments, the solvent is a dipolar aprotic solvent. Preferred
dipolar aprotic solvents include DMSO, DMAc, NMP, or DMF.
[0015] The amount of catalyst used in the instant invention is from about 100% to
about 0.01%, based on moles, of the initiator. At low levels of catalyst the polymer can be used
without further purification to remove the catalyst residues.
[0016] m some embodiments, the method further comprises isolating the polymer.
Depending on the end use requirements and me amount of catalyst residue in the polymer, the
polymer may be used without the need for further purification (when low levels of catalyst are
used, for example).

[0017] In certain embodiments, the polymer produced by the processes described
herein have a number average molecular weight of at least 500. In yet other embodiments, the
polymer has a number average molecular weight of at least 106.
[0018] A telechelic polymer is a polymer carrying functionalized endgroups. Such
polymers are within the scope of the instant methods. Telechelic polymers can be used, for
example in the synthesis of block co-polymers. In some embodiments, the polymers of the
instant invention are telechelic polymers containing active balides. These telechelic polymers
can be used as initiators for the synthesis of block copolymers or can be subsequently
functionalized at the halidc chain ends via conventional organic reactions to create other
telechelic polymers. In some embodiments, the chain end concerns functionalization of a halide.
Such polymers can be reacted by conventional means to produce a block copolymer.
[0019] In some embodiments, the polymers can be functionalized by other useful
moieties. For example, the moiety may be a drug or pharmaceutical composition, such as FDA
approved pharmaceuticals, are useful moieties.
[0020] Pharmaceuticals can also be incorporated by polymerization of drug carrying
monomers and of reagents supported on monomers including monomelic solvents and FDA
approved monomers.
[0021] The invention also concerns synthesis of dendrimers and hyperbranched
polymers. Dendrimer are molecules have a tree-like or generational structure. A high level of
synthetic control is needed in the production of these compositions. This control is achieved by
step-wise reactions which create the molecule one layer at a time. The core of the dendrimer is
a multifunctional molecule and further multifunctional molecules are used to create additional
branch sites. Dendrimer can be made by divergent synthesis and convergent synthesis methods.
Divergent synthesis assembles the molecule from the core to the periphery. Convergent
synthesis assembles the molecule from the outside to termination at the core.
[0022] In one preferred embodiment, the invention concerns a method of polymerizing
an alkene monomer to produce a polymer having a number average molecular weight of at least
106, the method comprising contacting said monomer with:
Cu(0), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof;
a nitrogen-containing ligand;
an initiator that is one or more of sulfonyl halides, nitrogen halides or compounds of the
formula R-X, R'C(=O)OR' or R'-CN, where X is a halogen and R is C1-C6 alky, R' is a
halogen-substituted C1-C6 alkyl, and R" is a C1-C6 alkyk and

a solvent that is water, any alcohol or compound containing more than one OH groups
including polysaccharides polymers and monomers, dipolar aprotic solvent, ethylene carbonate,
propylene carbonate, or a mixture thereof,
wherein the solvent and nitrogen-containing ligand are capable of diproportionating
Cu(I)X into Cu(0) and Cu(II)X2 where X is F, Cl, Br or I where the diproportionation has an
equilibrium constant of at least 10s favoring the Cu(0) and Cu(II)X2 species.
[0023] The invention also concerns the products made by the processes described
herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] Figure 1. UV-VIS spectra of a) CuBr2 (0.01 mmol/mL) and CuBr (0.01
mmol/mL) in DMSO (both CuBr2 and CuBr are soluble in DMSO without ligand), b)
CuBr2/M6TREN (0.01mmol/ml) and CuBr/M6Tren (0.01 mmol/ml) in DMSO, c) UV-VIS
spectra of CuCl2/bpy, 1/3 (0.005mmol/mL) and CuCl/bpy, 1/3 (0.005 mmol/mL) in DMSO; at
25 °C, 12h; at 70 °C, 12 h, d) CuBr2/N-n-propyl-2-pyridylmeuianimine, 1/2 (0.01 mmol/ml
solution) and CuBr/ N-n-propyl-2- pyridylmethanimine (0.005 mmol/mL) in DMSO; at 25 °C,
12h and at 70 °C, 12h.
[0025] Figure 2. Kinetic plots for the Cu(0) mediated living radical polymerization of
methyl acrylate (MA) at 25 °C in DMSO, initiated with methyl 2-bromopropionate (MB?) using
Mes-TREN as a ligand (conditions: MA = 2 mL, DMSO = 1 mL, [MA]0 = 7.4 mol/L, and
[MA]o/[MBP]o = 222).
[0026] Figure 3. Determination of the external order of reaction in Cu(0), CuBr2 and
DMSO for the Cu(0)/Me6-TREN-catalyzed polymerization of methyl acrylate (MA) in DMSO at
25 °C initiated with methyl 2-bromopropionate (MBP). [MA]/[MBP] = 200/1; a) In kp app vs In
[Cu(0)], ratio [Cu(0)]/[MA] was varied from 0.01 to 1 at an equal ratio of [Cu(0)]/[ Me6-TREN]
(MA = 2 mL, DMSO = 1 mL, [MA]o = 7.4 mol/L); b) kp app vs [DMSO], DMSO was varied from
0.2 to 0.8 mL at 1.8 mL of MA. ([MA]/[MBP]/[Me6-TRENMCu(0)] = 200/1/0.4/0.4); c) kp app vs
-In [CuBr2], ratio of [CuBr2]/Cu(0)] was varied from 0.1 to 2, (Me6-TREN] was equal to sum of
[Cu(0)] and [CuBr2]. ([MA]/[MBP]/[Cu(0)] = 200/1/0.4).
[0027] Figure 4. Kinetic plots for the Cu(0) mediated living radical polymerization of
MA initiated with methyl 2-bromopropionate (MBP) at 25 °C in DMSO using Me6-TREN as a
ligand (conditions: a to b) MA =2.5 mL, DMSO - 2.5 mL, [MA]0 = 5.55 mol/L, and
[MA]o/[MBP]0 = 11,000; c to d) MA = 5 mL, DMSO = 2.5 mL, [MA]0 = 7.4 mol/L, and

[MA]0/[MBP]0 = 11,000; e to f) MA = 2 mL, DMSO =4mL, [MA]0 = 3.7 mol/L, and
[MA]0/[MBP]0 = 22,200).
[0028] Figure 5. Kinetic plots for the Cu(0) mediated living radical polymerization of
MA initiated from: CHCl3, CHCBr3, CHI3 using Me6-TREN as a ligand (conditions: a to b) MA
= 1 mL, DMSO- 1 mL, [MA]0 - 5.55 mol/L, and [MA]0/[CHCl3]0 = 222; c to d) MA -1 mL,
DMSO = 1 mL, [MA]0 - 5.55 mol/L, and EMA]0/[CHBr3]0= 222; and e to f)MA = 2mL,
DMSO = 1 mL, [MA]0 = 7.4 mol/L, and [MA]0/[CHI3]0 =222).
[0029] Figure 6. Kinetic plots for the Cu(0) mediated living radical polymerization of
MA initiated from CHBr3 using Me6-TREN as a ligand (conditions: MA = 2 mL, DMSO = 4.
mL, [MA]0 = 3.7 mol/L; a to b) [MA]0/[CHBr3]0 = 11,100; c to d) [MA]0/[CHBr3]0 = 22,200; e
to f) [MA]0/[CHCl3]0 = 18,000).
[0030] Figure 7. Kinetic plots for the living radical polymerization of MA initiated
wimatob)(8BrPr)5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52,53,S4,55,56-octakis-(2-
bromopropionyloxy) calyx[8]arene (conditions: MA = 1 mL, DMSO = 0.5 mL, [MA]0 = 7.4
mol/L, and [MA]0/[8BrPr]0 = 11,100); c to d) (4BrPr) pentaerythritol tetrakis(2-
bromopropionate) (conditions: MA = 2.5 mL, DMSO = 2.5 mL, [MA]0 = 5.55 mol/L, and
[MA]0/[4BrPr]0 = 11,100) using Me6-TREN as a ligand.
[0031] Figure 8. Kinetic plots for the Cu(0) mediated living radical polymerization of
MA initiated from CHBr3 using TREN as a ligand (conditions: a to b) MA = 2 mL, DMSO = 1
mL, [MA]0 = 7.4 mol/L, and [MA]0/CHBr3]0 = 222; c to d) MA = 2 mL, DMSO - 2 mL, [MA]0
= 5.55 mol/L, and [MA]0/[CHBr3]0 = 11,100).
[0032] Figure 9. Kinetic plots for the Cu(0) mediated living radical polymerization of
MMA initiated with: a to b) 2,2-dichloroacetophenone (DCAP) (conditions: MMA = 1 mL,
DMSO = 0.5 mL), [MMA]0 = 6.2 mol/L, and [MMA]0/[DCAP]0 = 200) using PMDETA as a
ligand; c) to d) phenoxybenzene-4,4'-disulfonylchloride (PDSC) (conditions: MMA = 1 mL,
DMSO = 0.5 mL, [MMA]0 = 6.2 mol/L, and [MMA]0/[PDSC]0 = 200) using bpy as a ligand.
[0033) Figure 10. Kinetic plots for the Cu(0) mediated living radical polymerization of
VC initiated with CHBr3 using TREN as a ligand (conditions: VC = 2.2 g, DMSO = 2 mL, [VC]0
= 8.8 mol/L, and [VC]0/[CHBr3]0= 350).
[0034] Figure 11. Kinetic plots for the living radical polymerization of VC initiated
with CHBr3 using TREN as a ligand (conditions: VC = 2.2 g, DMSO = 2 mL, [VC]0 = 8.8
mol/L, and [VC]0/[CHBr3]0 = 350). * Cu(0) catalyst was used as a wire wrapped into the
magnetic stirring bar.

[0035) Figure 12. HSQC spectrum in CD2Cl2 of polyvinylchloride containing a
combination of dibromomethyl and bromochloromethyl chain ends in addition to allyl and
chloromethyl structural defects (MnGPC = 9,000, Mw/Mn = 1.8, Conv. = 80 %). The sample was
obtained by the Cu(0)/TREN/CuBr2 catalyzed SET-LRP of VC in DMSO initiated with CHBr3
at 25 °C. Polymerization conditions were as follows: [VC]/[CHBr3]/[Cu(0)]/[TREN]/[CuBr2] =
-70/1/0.25/-0.3/0.025, DMSO = 4.0 mL, VC = 1.8 g, [VC]0 = 5.0 mol/L.
DISCUSSION OF THE INVENTION
[0036] In some embodiments, the invention concerns a method of polymerizing an
alkene monomer to produce a polymer, the method comprising contacting said monomer with a
catalyst that is Cu(O), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof; an initiator, and a
component comprising a solvent and optional nitrogen-containing ligand, where the combination
of the component and monomer is capable of diproportionating Cu(I)X into Cu(0) and Cu(II)X2
where X is Cl, Br, or I. Any combination of suitable monomer, solvent and optional ligand that
diproportionates Cu(I)X into Cu(0) and Cu(II)X2 are suitable for use in the methods of the
instant invention.
[0037] "Cu(0)" refeis to copper in the zero oxidation state. "Cu(I)" and "Cu(II)" refer
to copper in the +1 and +2 oxidation states respectively.
[0038] Solvents useful in the methods of the instant invention include water, alcohol,
dipolar aptotic solvent, ethylene carbonate propylene carbonate, ionic liquid, or mixtures thereof.
Alcohols include small molecule alcohols and polymeric alcohols. These alcohols may contain
one or multiple hydroxyl groups. Suitable alcohols include C1-C12 alcohols that may be linear or
branched. In some embodiments, preferred alcohols include C1-C6 alcohols. Suitable alcohols
include methanol, ethanol, propanol, isopropanol, butanol, and tert-butanol, glycerine,
carbohydrates such as monosaccharides, disaccharides, oligosaccharides and polysaccharides and
any other natural and synthetic polymers containing OH groups. Dipolar aprotic solvents include
dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO), N-
methylpyrrolidone (NMP). Polymeric solvent are also suitable.
[0039] As used herein "ionic liquid" refeis to a salt having a cation and an anion where
the salt is a liquid at ambient or near ambient temperatures. In some embodiments, the material
has a melting point, or melting range, below about 100 °C. tonic liquids may comprise two or
more different salts. In some embodiments, the ionic liquid can be hydrated or solvated.
Examples of ionic liquids include aluminum(III) chloride in combination with an imidazolium

halide, or imidazoliurn containing non-nucleophilic anions such as tetrafluoroborate or
hexafluoroantimonate , or hexafluorophosphate, a pyridinium or a phosphonium halide,
tctrafluoroboratee, or hexafluoroantimonate or hexafluorophosphate. The compositions include
1-ethyl-3-meihylimidazoliuni chloride, N-butylpyridinium chloride and tetrabutylphosphonium
chloride. Aa example of a known ionic liquid system is a mixture of 1-ethyl-3-
methylirnidazolium chloride and aluminium(III) chloride or 1-ethyl-3-methylimidazolium
hexafluorophosphate or tetrafluoroborate.
[0040] A wide variety of nitrogen-containing ligands are suitable for use in the instant
invention. These compounds include primary, secondary, and tertiary alkyl amines, as well as
aromatic amines, linear and branched polyethylene inline), dendritic polyamines and
polyamides. Suitable nitrogen-containing ligands include the compounds of the following
structures.

[0041] A wide variety of initiators are suitable for use in the instant invention.
Halogenated compounds are particularly suited for use in the invention. These initiators include
compounds of the formula R-X or R'C(=O)OR" where X is a halogen and R is C1-C6 alky, R' is
a C1-C6 alkyl substituted with one or more halogen atoms, and R" is a C1-C6 alkyl. Suitable

initiators include chloroform, bromoform, idoform, carbon tetrachloride, carbon tetrabromide
and compounds of the formula:

In some preferred embodiments, the initiator is an alkyl, sulfonyl, or nitrogen halide. The
nitrogen halide can be also a halogenated nylon, peptide or protein. Alternatively a polymer
containing active halide groups such as the structural defects of polyvinyl chloride), the
chloromethyl group of poly(chloromethyl styrene) of other polymers and copolymers can also
be used as initiators.
[0042] Initiators shown to work in conventional metal catalyzed living metal
polymerizations will also work with the instant methods. Such compositions are well known by
those skilled in the art. See, for example, Percee, V.; Popov, A. V.; Ramirez-Castillo, E.;
Monteiro, M.; Barboiu, B.; Weichold, O.; Asandei, A. D.; Mitchell, C. M. J. Am. Chem. Soc.
2002, 124, 4940-4941; Percec, V.; Popov, A.V.; Ramirez-Castillo, E.; Weichold, O. J. Polym.
Sci. Part A: Polym. Chem. 2003,41,3283-3299; Percee, V.; Kim, H.-J.; Barboiu, B.
Macromolecules 1997, 30, 6702-6705; V. Percee, C. Grigoras, J. Polym. Sci.:Part A: Polym.
Chem, 2005, 43, 5282-5299; and V. Percee, B. Barboiu, T. K. Bera, M. van der Sluis, R.B.
Grubbs, J.M.J. Frechet, J. Polym. Sci. :Part A: Polym. Chem. 2000,38,4776-4791; Kamigaito,
M.; Ando, T.; Sawamoto, M. Cherm. Rev. 2001,101,3689-3746; Matyjaszewski, K.; Xia, J.
Chem. Rev. 2001, 101, 2921-2990.

[0043] In some embodiments, when the term "halide" is used herein, preferred halides
include Cl, Br, F, or I.
[0044] Metal-catalyzed living radical polymerization (LRP) initiated with alkyl
sulfonyL and N-halides has been accomplished in organic and aqueous media as well as in ionic
liquids, mostly for activated monomers such as styrene, acrylates, methacrylates, and
acryionitrile. Polymers with complex architecture, such as dendritic macromolecules, have also
been synthesized by metal catalyzed LRP (Percec, V.; Barboiu, B.; Grigoras, C; Bera, T.K. J.
Am. Chem. Soc. 2003, 125,6503-6516.).
[0045] Metal-catalyzed LRP is considered to proceed via an inner-sphere redox process
in which a low oxidation state metal complex acts as a catalyst, mediating a fast exchange
between radicals and their dormant alkyl halide species. The equilibrium between active and
dormant species is shifted toward the dormant species via an excess of high oxidation state
catalyst generated by a small extent of bimolecular radical dimerization during the initial stages
of the polymerization. This concept is known as internal suppression of fast reactions or
persisten radical effect (PRE). The inner-sphere radical process is called atom-transfer-radical-
addition (ATRA). The corresponding radical polymerization was therefore, named atom-
transfer-radical-polymerization (ATRP). Non-activated monomers that generate stable alkyl
halide dormant species such as vinyl acetate, vinyl chloride, and ethylene do not and are not
expected to polymerize by the current generation of ATRP catalysts. Of specific interest is vinyl
chloride (VC) because it cannot be polymerized via any living mechanism. Recently, the metal-
catalyzed LRP of VC initiated by CHI3 and mediated via a competition between outer-sphere
single-electron-transfer (SET) and degenerative chain transfer (DT) mechanisms (SET-DTLRP)
was reported.
[0046] The polymerization processes of the present invention proceed at 25 °C in H2O
and uses as catalyst Cu(0) and/or "nascent" Cu(0) generated in situ via the disproportionation of
various Cu(I) precursors. In this polymerization, Cu(0) species act as electron-donors, and the
initiator and dormant propagating species as electron-acceptors. The Cu(I) species generated
during the formation of radicals disproportionate spontaneously into extremely reactive nascent
Cu(II) and Cu(0) species that mediate the initiation and the reversible termination. This
disproportionation generates, via a self-regulated mechanism, in situ, the Cu(II) species that, in
the case of VC, would not be accessible via a conventional PRE mechanism since the radical
polymerization of VC is dominated by chain transfer to monomer rather than bimolecular
termination. By this mechanism, the inactive Cu(I) species are spontaneously consumed and the
catalytically active Cu(0) species are continuously produced. Here we report that, under suitable

conditions, the DT part of the SET-DTLRP can be eliminated and the newly elaborated LRP
becomes SET-LRP. This polymerization process takes place in H2O, protic, dipolar aptotic, and
other polar solvents that in presence of N-ligand were discovered to disproportionate Cu(I) into
Cu(0) and Cu(II), and in addition, favor a SET process. SET-LRP occurs under very mild
reaction conditions, at room temperature and below, uses a catalytic rather than a stoichiometric
amount of catalyst, and although proceeds ultrafast, generates polymers with unprecedenuy high
molecular weight. SET-LRP is general and applies to both nonactivated and activated monomers
containing electron-withdrawing groups, such as vinyl chloride and other halogenated
monomers, acrylates, and methacrytates. It also applies to organic reactions and tolerates a
diversity of functional groups.
Selecting Catalysts.
[0047] A schematic mechanism for SET-LRP is shown in Scheme 1.

[0048] The initiation (activation) step (kact) is mediated by a SET from the electron-
donor (Cu(0) or other species) to the electron-acceptor (alkyl halide, sulfonyl halide, or N-halide
initiator). Subsequently, the Cu(I) generated in this step disproportionates instantaneously into
Cu(II) and Cu(0) species. The disproportionation of Cu(I) in H2O can proceed in the presence of
chelating compounds with an equilibrium constant of 106. Cu(I) disproportionates spontaneously
in H2O in the presence of tris(2-aminoethyl)amine (TREN) and poly(etnylene imine) (PEI). The
very reactive "nascent" Cu(II) species generated from the disproportionation reaction provide the
reversible deactivation (kdeacr) of the radicals into dormant alkyl halide species. Cu(0) promotes

the reactivation of the dormant species. Both processes occur via a SET mechanism. In order to
assess the electron-donating character of Cu(0) and other Cu(I) species, their EHOMO were
calculated. Table 1 reports the EHOMO in electron volts (ev) for Cu(0), CuCl, CuBr, CuL Cu20,
Cu2S, Cu2Se, and Cu2Te. Cu(0) is known to be an efficient single-electron-donor agent. In
addition, Cu20, Cu2S, Cu2Se, and Cu2Te have been investigated since they were developed in
our laboratory as the most efficient self-regulated catalysts for LRP initiated with sulfonyl
halides and N-halides in nonpolar, and polar solvents, in ionic liquids, and for SET-DTLRP of
VC in H2O. Their mechanism of catalysis is, however, not known for any of the previously
reported LRP reactions. CuCl, CuBr, and CuI were studied because, in the reaction mechanism
outlined in Scheme 1, depending on the structure of the initiator, they are believed to be
transient, inactive species. The results are shown in Table 1.

[00491 The most efficient electron-donor SET catalysts are Cu2Te followed by Cu2Se,
Cu(0), Cu2S and Cu2O. CuI, CuBr, and specifically CuCl are very poor electron donors although
they are catalysts of choice for ATRA and ATRP. Since the lifetime of Cu(I)X is very short in
comparison with that of Cu(0) and Cu(II)X2 species, during reaction conditions that favor
disproportionation of Cu(I) into Cu(II) and Cu(0), the SET catalytic activity of Cu(I)X halides
can be neglected. Therefore, Cu2Te, Cu2Se, Cu(0), Cu2S, and Cu2O are expected to provide the
best catalysts for the SET-LRP.

Selecting Llgands and Solvents.
[0050] A UV spectroscopy study was performed to assess the activity of various
solvents, in addition to H2O, and ligands for the dispropoitionation of Cu(I) into Cu(II) and
Cu(0). Representative examples of UV experiments are shown in Figure 1.
[0051] Deaerated solutions containing solvent, ligand, and Cu(I)X or Cu(II)X2 were
prepared and their UV spectra were recorded immediately. The Cu(II)X2 solution was used as a
standard to assess the dispropoitionation of Cu(I)X. Figure 1a shows that, in the absence of a
ligand, CuBr does not disproportionate in DMSO. However, complete and instantaneous
disproportionation of CuBr into CuBr2 and Cu(0) occurs in the presence of tris(2-
dimethylaminoethyl)arnine (Me6-TREN) in DMSO (Figure lb). When Me6-TREN was replaced
with 2,2'-bipyridine (bpy), disproportionation of CuCl was also observed in DMSO, but it was
not as fast as in the presence of Me6-TREN in DMSO (Figure 1c). However, N-n-propyl-2-
pyridyl-methanimine in DMSO does not disproportionate CuBr (Figure 1d). Me6TREN, TREN,
PEL bpy, N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), and many other N-ligands
that bind Cu(II) species disproportionate Cu(I)X into Cu(B)X2 and Cu(0) not only in H2O, but
also in protic solvents (MeOH, EtOH, ethylene glycol, diethylene glycol, triethylene glycol, 2-
(2ethoxyethoxy)ethanol, tetraethylene glycol, glycerine, phenol), dipolar aprotic solvents
(DMSO, DMF, DMAc, NMP, etc.), ionic liquids and ethylene carbonate, but not in CH3CN.
Therefore, any combination of catalyst, ligand, and solvent that was discovered here to favor
disproportionation of Cu0) into Cu(0) and Cu(H) is expected to be efficient in mediating SET-
LRP.
Selecting Initiators.
[0052] The inner-sphere atom transfer mechanism is known to show a strong
dependence of the metal catalyzed kact, on the nature of the halogen from the structure of R-X. In
two independent series of experiments the ratio, kact, (R-Br)/kact, (R-Cl) was in the range of 103 to
9x 104. However, in the case of the outer-sphere mechanism, kact has a much smaller dependence
on the nature of the halogen from R-X. For example the ratio, k.acr (R-I)/kact (R-Br) ~ kact (R-
Br)/kact, (R-Cl) ~ 1 to 10. Based on these data, it is expected that the range of initiators available
for the case of metal mediated SETLRP must be much broader man that for the case of metal
mediated inner-sphere process. Alkyl halides, sulfonyl halides, and N-halides containing Cl, Br,
and I as the halide must be efficient in the case of SETLRP. In the case of metal-catalyzed inner-
sphere ATRP iodine-containing initiators undergo a competition between inner-sphere and
degenerative transfer.

SET-LRP of Acrylates Initiated with Methyl-2-Bromopropionate (MBP) and 2-
bramopropionitrile (BPN) and Catalyzed with Cu(0)/Me6-TREN in DMSO.
[00531 Cu(0)/bpy catalyzed LRP of methacrylates initiated with sulfonyl halides in
nonpolar solvents at high temperatures was reported from our laboratory and was shown to be
accelerated by many additives including ethylene glycol. Mixtures of Cu(0)/Cu(II)X2 or even
Cu(0) alone were used to catalyze the LRP initiated with alkyl halides at high temperature in
bulk and in nonpolar solvents. It was concluded that Cu(0) increases the rate of reaction since it
reduces Cu(II)X2 to Cu(I)X, the latter being considered the catalyst Cu(0) alone was shown to
provide poor control of molecular weight and molecular weight distribution since the Cu(I)X
species generated cannot react with radicals to produce the dormant alkyl halides.
[0054] Figure 2 shows examples of LRP of methyl acrylate (MA) catalyzed by
MBP/Cu(0)/Me6-TREN carried out at 25 °C in DMSO. Complete conversions are obtained in
less than 50 min for [MBP]0/[Cu(0)]0 = 1/1 (mole/mole) (Figure 2a, b). The reaction time is
similar when [MBP]0/[Cu(0)]0 — 1/0.1 (mole/mole) (Figure 1c, d) and even when some excess of
CuBr2 is added (Figure 2e, f). In all cases, kinetic plots show internal first order of reaction in
monomer and growing species, and the resulting poly(methyl acrylate) (PMA) has low molecular
weight distribution. The amount of catalyst used is decreased from 100% versus initiator to
10% and even to 1%. Below 10% catalyst the reaction mixture is colorless.
[0055] Kinetic experiments, used according to the procedure reported previously,
provided the external orders of reaction of the polymerization in [Cu(0)], [DMSO], and [CuBr2]
(Figure 3). As expected for the mechanism illustrated in Scheme 1, a complex, less than one,
order of reaction in [Cu(0)] is observed. The orders of reaction in [DMSO] and [CuBr2] are
about one. This demonstrates the expected catalytic effect of DMSO in mis reaction and the
capability of performing the LRP in the presence of a high concentration of CuBr2 at a
reasonable high rate. These data provide instructions on how to control the rate of
polymerization. For example, the amount of DMSO used in these experiments can be less than
the amount of monomer and therefore, the reaction mixture can only be diluted with solvent.
Under these conditions only small amount of DMSO is required to mediate this polymerization.

Synthesis of Ultrahigh Molecular Weight PMA by Cu(0)/Me6-TREN Catalyzed LRP
Initiated with MBP.
[0056] The simplest test of the efficiency of a living polymerization is to assess its
ability to synthesize polymers with ultrahigh molecular weight i. e., with number average
molecular weight (Mn) larger than 106. Previously the highest molecular weight linear polymers
synthesized by LRP metal-catalyzed technique were Mn = 300,000 for poly(n-
butylmethacrylate), Mn =367,000 for polymethylmethacrylate), Mn = 554,000 for
poly(methylacrylate), and Mn-823,000 for poly(tertbutylacrylate).
[0057] Figure 4 shows representative examples of kinetic experiments in which
[MA]0/[MBP]0 = 11,000 (Figure 4a, b, c, d) and 22,200 (Figure 4 e, f). PMA with Mn = 690,000
(Mw/Mn = 1.10), 950,000 (Mw/Mn = 1.12), and respectively 1,420,000 CMw/Mn = 1.15) and
narrow molecular weight distributions were obtained in 3 h, 6 h, and respectively 10 h. The
much higher molecular weight polymers obtained by SET-LRP suggests much less termination
at much higher rate than in previous metal-catalyzed LRP performed in molar media. These are
remarkable results considering that the reaction conditions used were not optimized. Radical
polymerizations and LRP of acrylates are known to be accompanied by intramolecular chain
transfer to polymer and therefore, to produce branched polyacrylates when the reaction is
performed at high temperatures. The analysis of the HMQC and HMBC spectra of linear poly(n-
butylacrylate) made at 25 °C revealed that branching in this sample is less than 1%. A linear
PMA, free of branching, was obtained in the polymerization executed at 25 °C.
CHCl3, CHBr3, and CHI3 as Bifunctional Initiators for the LRP of MA
[0058] Catalyzed by Cu(0), Cu2Te, CuzSe, Cu2S, Cu2O/Me6-TREN in DMSO. The
simplest difunctional initiators for the synthesis of α,ω-difunctional telechetic polyacrylates are
CHCl3, CHBr3, and CHI3. Figure 5 shows kinetic experiments for all initiators and Cu(0)/Me6-
TREN catalyst. Only CHCl3 requires a small amount of CuCl2 additive to control the LRP. The
most important message provided by this figure is that regardless of the structure of the
haloform, the apparent rate constant of propagation (kp) does not depend strongly on the
structure of the halogen. Although this is a complex rate constant, its trend resembles mat
observed in other SET mediated processes and differs from that seen in ATRA and ATRP.

Synthesis of Ultrahigh Molecular Weight PMA by Cu(0)/Me6-TREN Catalyzed LRP
Initiated with Haloforms.
[0059] The bifunctional initiators CHBr3 and CHCl3 were used to demonstrate the
synthesis of ultrahigh molecular weight PMA (Figure 6). The bifunctional haloform initiators
CHBr3 and CHCl3 were also tested for the synthesis of ultrahigh molecular weight linear PMA.
The results of selected kinetic experiments using these initiators are presented in the Figure 6.
[0060] PMMA with Mn up to 1,400,000 and narrow molecular weight distribution are
easily accessible in reasonable reaction time. CHCl3 initiator gives the best results when a small
amount of CuCl2 additive was used to regulate the polymerization. The nature of the haloform
does not change significantly the kinetic parameters (including kpapp) of these polymerizations
under similar reaction conditions. This observation was also valid (wide supra) when various
haloforms were employed for the synthesis of low molecular weight PMA (Figure S). The use of
these easily available and inexpensive solvents as bifunctional initiators for the synthesis of
ultrahigh molecular weight PMA might be attractive from industrial point of view and for the
synthesis of ABA block copolymers that are not accessible with monofunctional initiators such
as MBP.
Synthesis of Ultrahigh Molecular Weight 8- and 4-Arm Star PMA.
[0061 ] The Cu(0) based catalytic system was also utilized for the synthesis of 4- and 8-
arm star PMA. The bromopropionate based 4armed (4BrPr derived from pentaerithritol) and 8-
armed (8BrPr derived from 4-tert-butyl calyx[8]arene) initiators were used in these experiments.
Representative kinetic plots of LRP of MA initiated with 4BrPr and 8BrPr star shape initiators
are shown in the Figure 7.
[0062] In all experiments, the monomer conversion reaches up to 90%. The plots of
ln[MA]0/[MA] as a function of time and that of experimental versus theoretical Mn increase
linearly. The Mw/Mn values remain very low throughout the polymerization. These results
indicate the living nature of these polymerizations and the absence of star-star coupling as well
as other side reactions. It is remarkable that both 4- and 8- arm star PMA with Mn up to
1,000,000 can be obtained in a living manner at room temperature in a relatively short time. The
decreased catalyst concentration (Figure 7a and 7b) as well as the use of a small amount of
CuBr2 as additive (Figure 7c and 7d) provides an excellent control over polymerization yielding
high molecular weight 4- and 8-arm PMA with low molecular weight distribution. Reports on
the synthesis of multi arm star polyacrylates and polymetacrylates using the same 4BrPrRef and
8BrPrRef and other multifunctional initiators under inner-sphere metal-catalyzed conditions are

available. All previous synthetic procedures required high polymerization temperatures, long
reaction times and were performed in nonpolar solvents.
LRP of MA Initiated with Haloforms and Catalyzed by Cu(0), Cu2O, Cu2S, Cu2Se,
Cu2Te/TREN in DMSO.
[0063] The simplest and the least expensive ligands that can be used in this LRP are TREN and
PEL They were previously used in the LRP of VC in H2O together with the same catalysts.
Figure 8 provides several examples of kinetics that demonstrate the very fast synthesis of
different medium molecular weight (Figure 8 a, b) and very high molecular weight PMA (Figure
8 b, c). This polymerization can be carried out in the presence or absence of CuX2 (Figure 8).
Catalysis by Cu2O, Cu2S, Cu2Se, and Cu2Te/TREN in DMSO was demonstrated by the kinetic
experiments. The resulting PMA contains two functional chain ends with different reactivity.
This suggests new strategies for the synthesis of multifunctional block copolymers and other
complex architectures.
LRP of MMA Initiated with 2,2-Dichloroacetophenone (DCAP) and Phenoxybenzene-4,4'-
Disulfonylchloride (PDSC) Catalyzed by Cu(0)/PMDETA and bpy in Dipolar Aprotic
Solvents.
[0064] Two examples of unoptimized kinetic experiments are presented in Figure 9.
The first one is initiated with DCAP and catalyzed by Cu(0)/PMDETA in Supporting Scheme
SS2) and catalyzed with Cu(0)/bpy in NMP. Both experiments were performed at 25 °C. Since
sulfonyl halides are known to undergo side reactions in the presence of DMSO and of aliphatic
N-containing ligands, the classic bpy ligand employed previously with sulfonyl halide initiators
was used. These two examples demonstrate a dramatic acceleration by comparison with related
experiments carried out in nonpolar solvents.
LRP of VC Initiated with CHBr3 and Catalyzed with Cu(0), Cu2O, Cu2S, Cu2Se,
Cu2Te/TREN in DMSO.
[0065] Previously, we have reported the SET-DT-LRP of VC initiated with CHI3 in
H2O at 25 °C catalyzed by the same catalytic systems. However, since CHI3 is a good chain
transfer agent and the polymerization mixture was heterogeneous, a two stage kinetic process
leading to a limited VC conversion was observed. In addition, CHBr3 would be a less reactive,
more stable and less expensive initiator for the polymerization of VC. Since reactivity studies on
MA have demonstrated little difference between the nature of X from the structure of R-X and its

kact, we decided to investigate reaction conditions for the polymerization of VC initiated with
CHBr3. Using Me6-TREN as a ligand in conjunction with Cu(0) mediates the polymerization of
VC only to low conversion. However, the replacement of Me6-TREN with TREN in DMSO
provided a rewarding result. Figure 10 presents selected experiments catalyzed with different
concentrations of Cu(0)/TREN and DMSO.
[0066] Without optimization, we can see that about 90% VC conversion can be reached
in a very short period of time. The molar ratio [CHBr3]0/[Cu(0)]0 can be reduced from 1/1
(Figure 10 a, b) to 1/0.5 (Figure 10 c, d) and to 1/0.1 (Figure 10 e, f) with higher rates than
previously reported with CHI3. Since the amount of DMSO used in these polymerizations is very
small, at the end of the polymerization the reaction mixture contains the white solid PVC
plasticized with some DMSO. Therefore, purification of PVC requires only washing with 1120
or MeOH. The limited amount ofCu(0) powder required to mediate this polymerization suggests
that Cu(0) wire is sufficient to promote it. Indeed, Figure 11 a,b demonstrates this concept
(compare Figure 10 c,d with Figure 11 a,b). Higher molecular weight PVC can be obtained with
higher [VC]0/[CHBr3]0 ratios in the presence of Cu(0), Cu2Te, Cu2Se, Cu2S, and Cu2O. The
resulting α,ω-dibromo (PVC) can be used as initiator for the synthesis of blockcopolymers and
other complex architectures.
Mechanistic Considerations.
[0067] The experimental observation that in situ formed Cu(I)X undergo spontaneous
disproportionation under the polymerization conditions and that most of these polymerizations
do not require externally added deactivator such Cu(II)X2 demonstrates that the active catalyst is
the nascent Cu(0) molecular species (Scheme 1). When Cu2Te, Cu2Se, Cu2S and CuzO are used
as catalysts they are the initial electron-donor catalysts. The rawer interesting question is: by
what mechanism are the radicals formed under these conditions? Several experimental
observations as well as literature data help to elaborate the most probable mechanistic hypothesis
for the activation of the dormant species. On the one hand the kpapp during LRP of MA strongly
depends on the concentration of DMSO used in the polymerization mixture (Figure 3b).
Increasing DMSO concentration leads to faster polymerization while maintaining the good
control over molecular weight and molecular weight distribution. If the radicals would be formed
through an inner-sphere homo lytic atom-transfer process, like in the case of ATRA and ATRP
than the polymerization rate and hence the kpapp would have to exhibit very little dependence on
the polarity of the reaction medium. This is because the rate of reactions where radical
intermediates are involved is not strongly dependent on the polarity of the medium. In principle

the opposite effect should be observed: polymerization rate must decrease when me monomer,
catalyst and initiator concentration decrease. This observation is an indication that the formation
of radicals is occurring via a different mechanism. One option is that ionic intermediates are
involved in the rate-limiting step of the radical formation. In this case the rate of radical
generation must dependent strongly on the polarity of the reaction medium and mis indeed was
observed experimentally (Figure 3b). The radicals are most likely generated through the
decomposition of radical-anion intermediates that are initially formed via the SET reaction
between Cu(0) species and the halogen containing substrates such as initiator and halogen
terminated polymeric chain end. These considerations are supported by literature data that show
that dipolar aprotic as well as protic solvents facilitate fast SET reactions between electron-donor
including Cu(0) and various halogen containing compounds (including haloforms and
tetrahalomethanes).
[0068] A series of Quantum Chemical calculations were also performed on model
systems to verify which path best describes the experimental observations that the nature of the
halogen does not affect the rate of polymerization of MA when Cu(0) catalyst is used under
similar conditions. The results of these calculations are shown in Scheme 2.

Scheme 2. Relative C-X bond dissociation energies in methyl 2-halopropionates:
homolytic bond dissociation (top diagram) and formation and decomposition of anion-radicals
formed by set process (bottom diagram) calculated using: (U)B3LYP/6-31+G*//(U)B3LYP/6-

31+G* (for Cl and Br Case) or (U)B3LYP/LACVP+*// (U)B3LYP/LACVP+* (for I Case)
methods.
[0069] The homolytic C-X bond dissociation energy (BDE) in the initiators MCP (X =
Cl), MBP (X = Br), and MIP (X = I) species appears to strongly depend on the nature of the
halogen and usually increases in the following order Cl > Br > I (Scheme 2, top diagram). The
calculated BDE are in good agreement with previously calculated values obtained for the same
methyl 2- halopropionate systems. The C-X bond dissociation energy depends very little on the
nature of the halogen (X) if it is occurring through the decomposition of me radical-anion formed
via a SET process (Scheme 2, bottom diagram). The generalized catalytic cycle of SET-LRP is
depicted in the Scheme 3.

Scheme 3. Proposed catalytic cycle of SET-LRP mediated by Cu(0) species in polar
media.
[0070] The reaction starts with SET reaction between Cu(0) species and the halogen
containing substrate (initiator on halogen terminated polymeric chain end). Any polar solvent
including DMSO facilitates the decrease of interaction between anion (X-) and electrophilic
radical (R) from the radical-anion pair. The radical anion cluster and Cu/L+ countercation must
be in close proximity in the so called caged ion-pair thus further facilitating decomposition of
radical-anion into the radical and the anion (X-). The reaction between radical and deactivator
CuX2/Ligand in polar media is a more complex process. One of the possible mechanisms may
involve the transfer of the halide anion X- from the deactivator to the propagating macroradical
R', leading to a similar ion-cage composed of radical anion [R—X]- and CuX/L+
countercation. The mechanism depicted in the Scheme 3 is simplified in a way to understand the
main chemical events, which might be involved in this catalytic process. The goal of this report
is not to provide a complete mechanistic investigation of the SET-LRP process mediated by
nascent Cu(0) species, but rather to develop the SET-LRP synthetic method and to compare it

with that based on the inner-sphere process. More experimental and theoretical studies are
necessary to elucidate the hypothetic mechanism outlined in Scheme 3. Investigations in this
direction are in progress and will be reported in due time.
[0071] Nevertheless, the SET-LRP reported here, together with its mechanistic
hypothesis, explains numerous literature examples in which an acceleration of the Cu(I)X-
catalyzed LRP was observed in H2O, alcohols, ethylene glycol, DMSO, DMF, and ionic
liquids.
Examples
1. Materials
[0072] Methyl 2-bromopropionate (MBP) (98%), 2-bromopropionitrile (BPN) (97%),
2,2-dichloroacetophenone (DCAP) (99%), bromoform (98%), chloroform (99%), N,N,N',N',N'-
pentamethyldiethylenetriamine (PMDETA) (99%), tris(2-ammoemyl)amine (TREN) (96%),
polyethyleneimine (PEI, linear, Mn ca 423, b.p. 250 °C), dimethylsulfoxide (DMSO) (99%),
N,Ndimethylformamide (DMF) (99%), l-methyl-2-pyrrolidone (NMP) (95%), ethylene
carbonate (98%), phenol (99+%), CuCl (98+%), Cul (98%), and Cu(0) powder (99%) were
purchased from Aldrich and used as received. Iodoform (99+%), CuBr (98%), CuBr2 (99+%),
ethylene glycol (99+%), diethylene glycol (99%), triethylene glycol (99%), tetraethylene glycol
(99.5%), 2-(2-ethoxyethoxy)ethanol (98+%), N,N-dimethylacetamide (DMAC) (99%), and
glycerol (99+%) were purchased from Acros and used as received. Cu2O, Cu2S (99.5%), Cu2Se
(99.5%), and Cu2Te (99.5%) were purchased from Alfa Aesar and used as received. Methanol
(CH3OH) (ACS grade), acetonitrile (CH3CN) (HPLC grade), and tetrahydrofuran (THF) (HPLC
grade) were purchased from Fisher and used as received. CuCl2 (98+%) was purchased from
Fluka and used as received. 2,2'-Bipyridine (bpy) (99+%) was purchased from Lancaster and
used as received. Ethanol (ACS grade) was purchased from Pharmco-AAPCR and used
as received.
[0073] Methylacrylate (MA) (99%), methyl methacrylate (MMA) (99%), n-butyl
acrylate (nBA) (99%), and tert-butyl acrylate (tBA) (99%) were purchased from Acros
Organics. In order to remove the inhibitor, the monomers were passed through a basic Al2O3
chromatographic column (flash) just before use. Vinyl chloride (VC) (99%) was purchased from
Aldrich.
[0074] Hexamethylated tris(2-aminoemyl)amine (Me6-TREN) was synthesized as
described in the literature (Ciampolini, M.; Nardi, N. Inorg. Chem. 1966, 5, 41-44). The
difunctional initiator phenoxybenzene-4,4'-disulfonylchloride (PDSC) was synthesized

according to a literature procedure (Percec, V.; Kim, H.-J.; Barboiu, B. Macromolecules 1997,
30,6702-6705). The 4-arm star multi-functional initiator pentaerythritol tetraltis(2-
bromopropionate) (4BrPr) was synthesized according to the literature (Matyjaszewski, K.;
Miller, P. J.; Pyun, J.; Kickelbick, G.; Diamanti, S. Macromolecules 1999, 32,6526-6535). Also
synthesized according to a literature procedure was the 8-arm star initiator
5,11,17,23,29,35,41,47-octa-tert-butyl-49,50,51,52,53,54,55,56-octakis-(2-
bromopropionyloxy)calyx[8]arcne (8BrPr) (Angot, S.; Murthy, K. S.; Taton, D.; Gnanou, Y.
Macromolecules 2000, 33, 7261-7274). The ligand N -n -propyl-2-pyridyl-rnethanimine was
synthesized via a procedure from the literature (Haddleton, D. M.; Jasieczek, C. B.; Hannon, M.
J.; Shooter, A. J. Macromolecules 1997, 30, 2190-2193). N-chloro-2-pyrrotidinone (NCP) was
synthesized according to a literature procedure (Curini, M.; Epirano, F.; Marcotullino, M. C;
Rosati, O.; Tsadjout, A. Synlett2000, 813-814).
2. Techniques
[0075] 500 MHz 1H-NMR spectra were recorded on a Broker DRX500 machine at 20
°C in CDCl3 or THF-d8, with or without tetramethylsilane (TMS) as an internal standard. Gel
permeation chromatographic (GPC) analyses of the polymer samples were done on a Perkin-
Elmer Series 10 high performance liquid chromatograph, equipped with an LC-100 column oven
(40 oC), a Nelson Analytical 900 Series integrator data station, a Perkin-Elmer 785A UV-VIS
detector (254 nm), a Varian star 4090 refractive index (RI) detector and two AM gel (500 Å, 5
µm and 104 Å, 5 µm for low molecular weight samples) or three AM gel (500 Å, 10 µm; 104 Å,
5 µm; and 105 Å, 10 µm for high molecular weight samples) columns. THF (Fisher, HPLC
grade) was used as eluent at a flow rate of 1 mL/min. The number (Mn) and weight average
(Mw) molecular weights of the PMA and PMMA samples were determined with PMMA
standards purchased from American Polymer Standards. The Mn and Mw of the PVC samples
were determined with polystyrene (PS) standards purchased from American Polymer Standards
or Pressure Chemical. The molecular weight values for PVC were corrected with Universal
Calibration with the following Mark-Houwink parameters for PVC: K = 1.50x10-2 mL/g and a =
0.77.6 The UWIS spectra were recorded on a Shimadzu UV-1601 spectrophotometer.
3. UV Spectroscopic Analyses of Cu(I)X Disproportionation
|0076] Typical UV-VIS Spectroscopic Analysis of CuX/Ligand and CuX2/Ligand
Complexes in Different Solvents. CuBr (2.3 mg, 0.01 mmol) or CuBr2 (2.3 mg, 0.01 mmol) was
placed in a quartz UV-VIS cell (1 mm path length) and purged with argon. To the cell was added

3 mL of a deoxygenated stock solution of Me6-TREN in DMSO (0.76 mg/mL, 0.0033
mmol/mL). The cell was sealed under argon via a rubber septum with a screw cap. After
vigorous shaking, the cell was placed in the UV-VIS spectrometer for measurement. In the case
of the CuBr/Me6-TREN complex, the UV-VIS spectra were taken after approximately 10 rain to
allow the Cu(0) obtained by disproportionation to precipitate in the bottom of the quartz cell. The
absorbance was recorded in the 200 - 1100 nm range.
4. Synthesis
A. Typical Procedure for Cu(0) Catalyzed LRP of MA.
[0077] The MA monomer (2 mL, 22.2 mmol), DMSO (1 mL), methyl 2-
bromopropionate initiator (16.7 mg, 0.1 mmol), Me6-TREN (23 mg, 0.1 mmol), and Cu(0)
powder (6.3 mg, 0.1 mmol) were added to a 25 mL Schlenk tube in the following order: Cu(0),
MA, ligand, DMSO, initiator. The Schlenk tube containing the reaction mixture was then frozen
in a dry ice/acetone bath at —78 °C and deoxygenated with three consecutive standard freeze-
pump-thaw cycles. Subsequently, the Schlenk tube with the reaction mixture was placed in an oil
bath (25 ±0.1 oC) with stirring. The side arm of the Schlenk tube was purged with argon and the
polymerization reaction was sampled with an airtight syringe. The monomer conversion was
determined by 1H-NMR spectroscopy, whereas the Mn and Mw/Mn values were determined by
GPC withPMMA standards (conversion: 98 % (50 min), Mn GPC = 19,100, Mw/Mn = 1.21).
B. Typical Procedure for Cu(0) Catalyzed LRP of MMA.
[0078] The monomer (MMA) (2 mL, 18.8 mmol), DMSO (1 mL), initiator (DCAP)
(19.0 mg, 0.1 mmol), Cu(0) powder (6.3 mg, 0.1 mmol), and PMDETA ligand (17 mg, 0.1
mmol) were added to a 25 mL Schlenk tube in the following order Cu(0), monomer, ligand,
DMSO, initiator. The Schlenk tube was frozen in dry ice/acetone bath at -78 °C and
deoxygenated with three standard freeze-pump-thaw cycles. After the final thaw, the Schlenk
tube with containing the reaction mixture was placed in an oil bath (25 ± 0.1 °C) and stirred. The
side arm of the Schlenk tube was purged with argon and the polymerization reaction was
periodically sampled with an airtight syringe. The monomer conversion was determined by 1H-
NMR spectroscopy and the Mn and Mw/Mn values were determined by GPC with PMMA
standards (conversion: 84 % (300 min), Mn GPC = 20,000, Mw/Mn = 1.19).

C. Typical Procedure for Cu(0) Catalyzed LRP of VC
[0079] In a typical experiment, a 50 mL Ace Glass 8648 #15 Ace-thred pressure tube
equipped with bushing and a plunger valve was charged with 2 mL of a previously degassed
stock solution of CHBr3 in DMSO (126 mg, 0.5 mmol CHBr3 in 10 mL DMSO). Cu(0) (6.3 mg,
0.1 mmol) and TREN (14.2 mg, 0.1 mmol) were then added to the tube. The rube was filled with
argon, closed, and frozen in acetone/dry ice bath at -78 oC. Then, precondensed VC
(approximately 3 mL, 43 mmol) was added to the tube. The tube was closed and degassed
through the plunger valve by applying vacuum and then filling the tube with argon 5 times. The
valve was closed and the tube with reaction mixture was stirred in a water bath at 25 ± 0.1 °C.
After appropriate reaction time, the tube was removed from the water bath and opened slowly to
allow any unreacted VC to evaporate. The conversion of VC was determined gravimetrically.
The reaction mixture was diluted with a small amount of THF (3 mL) and the mixture was
slowly poured into MeOH (150 - 200 mL) with stirring. An aliquot from the reaction mixture
was further diluted with THF and filtered through a 0.5 urn membrane filter. The filtrate was
analyzed by GPC. The kinetic data was accumulated from individual experiments since sampling
of the reaction was not possible (conversion: 85 % (180 min), MnGPC = 31,600, Mw/Mn =
1.53)..
D. Typical Procedure for Synthesis of Low Molecular Weight PMA.
[0080] In a typical polymerization experiment, catalyst Cu(0) (0.63 mg- 0.01 mmol) (or
0.01 mmol of any Cu2X compound, where X = O, S, Se or Te), monomer MA (2mL, 22.2
mmol), DMSO additive (1mL), M6Tren Ligand (2.3 mg, 001 mmol) where charged in a 25 mL
schlenk tube. The initiator CHBR3 (25.2 mg, 0.1mmol) was added last to the polymerization
mixture. The Schlenk tube was closed and the places in a dry ice/acetone bath (78 oC) in order to
freeze the reaction mixture. The polymerization mixture was degassed through freeze-thaw-
freeze cycles, filled with Ar gas and placed in an oil bath (25 ± 0.1 oC). The reaction mixture
becomes slightly greenish after approximately 10-15 min. The polymerization stopped in 50 min.
after reaction started. The Schlenk tube was opened and small aliquot of the polynwrizarion
mixture was dissolved in CDCl3 and the conversion of MA was measured by 1H NMR. Another
part of the aliquot from the reaction mixture was diluted with THF, filtered through 0.5-µm
membrane filter and the molecular weight of the PMA was analyzed by GPC against PMMA
standards. Conversion of MA 92 % (90 min). MnGPC= 17,800, Mw/Mn = 1.18. The rest of the
reaction mixture was dissolved in 10 mL THF and the PMA was precipitated (gummy mass) in
120 mL Methanol under stirring. The methanol was removed by decantation and the resulting

gummy mass was washed again with MeOH to remove residual monomer and additive (2 X 50
mL). Methanol was removed again by decantation and the final colorless PMA polymer was
dried under vacuum until constant weight was reached. Note: it is remarkable that regardless the
catalyst used the resulting PMA is colorless product after precipitation in MeOH.
E. Typical Procedure for Synthesis of Ultrahigh Molecalar Weight PMA.
[0081] In a typical experiment, MA monomer (2 mL, 22.2mmol), DMSO additive (1.6
mL) where charged in a 25 mL schlenk tube. Because of very high DP used ([MA]0/[MPB]0
11,100) it was only possible to add catalyst (Cu(0)), ligand (MgTren) and initiator (MPB) to the
polymerization mixture using the stock solution/suspension. The Cu(0) catalyst (6.3 mg,
0.1mmol) and the M6Tren ligand (23 mg., 0.1 mmol) were putted in degassed 10 mL DMSO.
The vial containing above mixture were shaken intensively and 0.2 mL of these stock suspension
containing Cu (0) catalyst (0.126 mg., 0.002 mmol) and M6Tren ligand (0.46 mg., 0.002 mmol)
were taken out and added to a polymerization mixture. The stock solution of the initiator (MPB)
was introduced in a similar manner. The, initiator MPB (25.2 mg, 0.1 mmol) was dissolved in 10
mL degassed DMSO and 0.2 mL of this solution containing MPB initiator (0.5 mg., 0.0019
mmol) was added to the polymerization mixture. The schlenk tube was closed and the
polymerization mixture was degassed using standard freeze-taw-freeze cycles. The shclenk tube
was backfilled with Ar gas and places in an oil bath (25 ±0.1 °C). The reaction was stopped in
550 min. The reaction mixture remained colorless even at the end of the reaction. The conversion
and Mn and Mw/Mn were determined in a similar manner as descried previously. Conversion of
MA 96 % (550min), MnGPC= 935,000, Mw/Mn = 1.17. the rest of the polymerization mixture
was dissolved in 50 mL THF and the PMA was isolated in a similar manner as described in
previous section.
F. Typical Procedure for Synthesis of 4 armed star PMA.
[0082] In a typical polymerization experiment, Cu(0) (6.3 mg. 0.1 mmol), MA (1 mL,
11.1 mmol), DMSO (0.5 mL), and Me6-TREN (2.3 mg, 0.1 mmol) were charged in a 25 mL
Schlenk tube. The initiator 4BrPr (16.9 mg, 0.025 mmol) was added to the polymerization
mixture last. The Schlenk tube was closed and placed in a dry ice/acetone bath (-78 °C) in order
to freeze the reaction mixture. The polymerization mixture was degassed through freeze-pump-
thaw cycles, filled with Ar gas and placed in an oil bath (25 ± 0.1 oC). The reaction mixture
becomes greenish after approximately 10 min. The polymerization completed in 35 min. The
Schlenk tube was opened, a small aliquot of the polymerization mixture was dissolved in CDCl3,

and the conversion of MA was measured by 1H NMR. Another aliquot from the reaction
mixture was diluted with THF, filtered through a 0.5-µm membrane filter, and the molecular
weight of the PMA was analyzed by GPC against PMMA standards. Typical results were as
follows: conversion of MA=97% (35 min), MnGPC= 39,300, Mw/Mn = 1.21. The remainder of
the reaction mixture was dissolved in 10 mL THF and the resultant 4-armed PMA was
precipitated (gummy mass) in 120 mL methanol with stirring. The methanol was removed by
decantation and the gummy mass was washed again with MeOH to remove residual monomer
and DMSO (2 x 50 mL). Methanol was removed again by decantation and the final colorless
PMA was dried under vacuum until constant weight was reached. Note: it is remarkable that,
regardless of the catalyst, the resulting 4-armed star PMA is colorless after precipitation in
MeOH.
G. Typical Procedure for Synthesis of PMMA.
[0083] In a typical polymerization experiment, Cu(0) (6.3 mg. 0.1 mmol), MMA (2
mL, 18.8 mmol), DMSO (1 mL) and PMDETA (17 mg, 0.1 mmol) were charged in a 25 mL
Schlenk tube. The initiator DCAP (18.9 mg, 0.1 mmol) was added to the polymerization mixture
last. The Schlenk tube was closed and then placed in a dry ice/acetone bath (-78 °C). The
polymerization mixture was degassed through three freeze-pump-thaw cycles, filled with Ar gas,
and placed in an oil bath (25 + 0.1 °C). The polymerization was stopped after 330 min. The
Schlenk tube was opened and a small aliquot of the polymerization mixture was dissolved in
CDCl3. The conversion of MMA was measured by 1H NMR. Another aliquot from the reaction
mixture was diluted with THF, filtered through a 0.5-um membrane filter, and the molecular
weight of the PMMA was analyzed by GPC against PMMA standards. Typical results were as
follows: conversion of MMA=83% (330 min), MnGPC= 20,000, Mw/Mn =1.19. The rest of
mixture was dissolved in 10 mL THF and the PMMA was precipitated (white powder) in 120
mL methanol with stirring. The mixture was filtered and the resulting PMMA was washed with
MeOH (50 mL), distilled water (50 mL), and again with MeOH (50 mL), and then dried under
vacuum until a constant weight was obtained. The resulting PMMA is a white powder. No
green color associated with Cu(II) species is visually detectable.
5. Quantum Chemical Calculations
[0084] All of the calculations were performed on a PC using Spartan' 04 Quantum
Mechanics Program: (PC/ X 86). The geometry optimizations were performed using B3LYP
functional. The 6-31+G* was used for all C, H, O, Cl, Br, S, and Se atoms. Since I and Te atoms

are not included in the standard 6-31+G* basis set, they were described with the LACVP+* basis
set. The systems containing unpaired electrons were optimized with the spin unrestricted
formalism. The spin contamination was found to be negligible in these cases, since the value of
operator was always found to cluster around 0.75.
[0085] The most stable conformation of MCP, MBP, MIP and corresponding free
radicals has been reported to have the value of the central C-O-C(O)-C dihedral angle close to
180o.9 The conformational analysis of MCP, MBP, MIP neutral molecules, corresponding
radicals and radical anions performed at PM3 level indeed revealed that the most stable
conformations of the above species have a central C-O-C(O)-C dihedral angle close to 180o. The
geometries of these species were preliminary optimized at the PM3 level, followed by HF-DFT
optimization at (U)B3LYP/6-31+G* or (U)B3LYP/LACVP+* level of theory. The C-X (X = Cl,
Br, I) hemolytic bond dissociation energies (BDE) for MCP, MBP, and MIP were calculated
using the formula: BDE = [Eabs(radical) + Eabs(atom)] -Eabs(neutral molecule). Radical-anions
were optimized as follows: Neutral Molecule + 1 electron (charge = -1, spin multiplicity = 2).
The C-X- bond heterolytic dissociation energy in radical anions were calculated using the
formula: E = [Eabs(radical) + Eabs(X-)] -Eabs(neutral molecule). The homolytic BDE, the energy
for radical-anion formation and energy of the radical-anion decomposition into radicals and
anion (X-) were recalculated in kcal/mol (1 hartree = 627.509 kcal/mol).
[0086] All geometry optimizations were performed without symmetry constraints (C1
symmetry) in order to ensure that the resultant geometry is not a local minimum. The frequency
calculations were performed to verify mat the optimized structures were the energy minima on
the potential energy surface (no imaginary frequency). The absolute energies of the calculated
species are reported without corrections for zero point vibrational energy. The energy of
EHOMO for Cu(0), Cu20, Cu2S, Cu2Se, Cu2Te, CuCl, CuBr and CuI were calculated at
(U)HF/6-31+G* (or (U)HF/LACVP+* for I and Te case) level on the (U)B3LYP/6-31+G* (or
(U)B3LYP/LACVP+* for I and Te case) optimized geometries (except Cu(0)).
[0087] A list of HF-DFT optimized geometries (Cartesian Coordinates) and absolute
energies (in a u.) for all calculated species follow.











6. Chain End Analysis of Pory(methyl)acrylates (PMA) Synthesized by Cu(0)-Mediated
SET-LRP of MA Initiated with Haloforms.
[0088] The 1H NMR (500 MHz) spectra of PMA prepared by SET-LRP of MA
initiated with haloform initiators (CHX3, X = Cl, Br, I) and catalyzed either by Cu(0)/Me6-TREN
or Cu(0)/TREN (with or without CuX2 deactivator) reveal the signals of the protons of the main-
chain (methyne and methylene) are present in the region 1.31 - 2.52 ppm. The signal of OCH3
side group appears at 3.60 ppm. Of special interest are the signals associated with the -CH2-
CHXC(O)OMe (X = Cl, Br, and I) chain ends and the initiator fragments -CHX2 and -CHX- (X
- Cl, Br, I). It is interesting to note that, in the case of CHCl3 and CHBr3 initiated SET-LRP of
MA, the resulting polymers contain only -CHCl2 and -CHBr2 (signals at 5.65 and 5.60 ppm,
correspondingly) fragments from the haloform initiators. The signals from the protons attached
to the -HC-Cl and -HC-Br chain ends (-CH2-CHXC(O)OMe end groups) are observed at 4.19
and 4.15 ppm, correspondingly. The integral ratio of-CHX and -CH2-CHXC(O)OMe (X = Cl,
Br) signals is 1:1 and is the same for PMA samples isolated at low and high conversion of MA.
The latter observation demonstrates that CHCl3 and CHBr3 compounds act as monofunctional
initiators in these polymerizations. The comparison of the 1H NMR spectra of PMA obtained
using two different catalysts (Cu(0)/Me6-TREN and Cu(0)/TREN/CuBr2) demonstrates that these
two catalysts give the same chain end functionality in the resulting PMA.
[0089] In the case of CHI3 initiator, the structure and chain end functionality of the
PMA is a function of the conversion of MA. At low conversion, the PMA obtained is mostly

growing in one direction (the signal at 4.97 ppm belongs to the-initiator fragment -CHI2 and the
signal at 4.32 ppm is attributed to the terminal methyne proton -CH2-CHIC(O)OMe). The ratio
of the integral of the signals observed at 4.32 and 4.97 ppm is 1:1 for the PMA polymers
obtained at low conversion of MA. However, at high conversion, the intensity of-CHI2 signal
(4.97 ppm) decreases by comparison with the -CHrCHIC(O)OMe group methyne signal. This
means that, during polymerization, the PMA starts to grow in two directions. Unfortunately the
signal of-CHI- proton, which should appear at around 2.1-2.2 ppm, is hidden inside the PMA
main-chain proton signals. The 'H NMR spectra of the PMA obtained during SET-LRP of MA
. initiated with CHI3 and catalyzed by Cu(0)/Me6-TREN or Cu(0)/TREN catalyst are almost
identical, thus demonstrating that the chain end functionality of the resulting PMA does not
depend on the catalyst structure.
[0090] 1H NMR (500 MHz) spectra of poly-t-BuA (Figure 12) obtained during LRP of
t-BuA initiated with the monofunctional MPB initiator and catalyzed by Cu(0)/Me6-TREN
catalyst in DMF show signals at 1.08 -1.13 ppm belonging to the CH3- group from MPB
initiator (adjacent to the -CH group). The signal at 3.62 ppm belongs to the OMe group from the
MPB initiator. The multiplet in 4.04 -4.10 ppm region belongs to the terminal -CH2-
CHBrC(O)O-t-Bu methyne proton signal. In all cases the NMR and GPC determined molecular
weights are in good agreement, which further supports the correctness of the assignment of the
1H NMR spectra of PMA obtained from SET-LRP of MA initiated with haloforms.
7. Structural Analysis of Poly(t-butyl acrylate) and Poly(n-buryl acrylate).
[0091] Structural Analysis of Poly(t-butyl acrylate) and Poly(n-buryl acrylate)by g
HSQC and g HMBC. g-HSQC and g-HMBC NMR spectra of low molecular weight poly(t-butyl
acrylate) and poly(n-butyl acrylate) recorded on a 600 MHz NMR spectrometer show the
detailed microstructure of these two polymers. gHSQC spectra of both samples show multiple
resolved resonances in ΔH = 1 -3 - 2.0 ppm and δC = 34.0 - 38.0 ppm range for main chain CH2
groups. Resonances from tetrad configurational structure (i.e. mmm, mrm, mmr, rarr, rrr, rmr)
are well resolved along with many CH2 resonances from terminal groups. These resonance
patterns are consistent with a higher syndiotactic content of the poly(t-butyl acrylate) and highly
atactic nature of poly(n-butyl acrylate). This result is also weD complemented by the splitting
pattern of main chain CH resonances: δH = 2.1 - 2.4 ppm and δC = 40.0 - 43.0 ppm. Previous
NMR studies of these classes of polymers show that branches formed by intra- and
intermolecular chain transfer reactions result in the formation of quaternary carbons at the
branching point. A quaternary carbon at the branching point would show resonance in the 47.0 -

48.5 ppm region in the 13C NMR spectrum. However, in these samples, we failed to detect any
quaternary carbons in this region from the g-HMBC NMR spectrum. Also, the g-HMBC would
show two bond correlations to protons of the CH2 and CH groups from the branched quaternary
carbon. Failure to detect any such correlations (along with any detectable signal in 13C NMR
spectrum) indicates the very low probability of a chain transfer reaction during this
polymerization process. This result confirms that the polymers obtained at room temperature are
mostly linear chains and, even if there are branched structures, they exist in such a small
concentration that they are undetectable by multi-dimensional NMR spectroscopy.

What is Claimed:
1. A method of polymerizing an alkene monomer to produce a polymer, the method
comprising contacting said monomer with:
a catalyst that is Cu(0), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof;
an initiator that is one or more of sulfonyl halides, nitrogen halides or compounds of the
formula R-X, R'C(=O)OR", or R'-CN, where X is a halogen - and R is C1-C6 alky, R' is a
halogen-substituted C1-C6 alkyl, and R" is a C1-C6 alkyl; and
a component comprising a solvent and optional nitrogen-containing ligand, where the
combination of the component and monomer is capable of diproportionating Cu(I)X into Cu(0)
and Cu(II)X2 where X is Cl, Br, or I.
2. The method of claim 1 wherein the polymerizing occurs in the presence of a nitrogen-
containing ligand.
3. The method of claim 1 wherein the solvent is water, alcohol, dipolar aprotic solvent,
ethylene carbonate, propylene carbonate, ionic liquid, or a mixture thereof.
4. The method of claim 2 wherein the nitrogen containing ligand comprises at least one
compound of the formula:


5. The method of claim I wherein the alkene monomer comprises one of more of acrylates,
methylacrylates, halogen-substituted alkenes, acrylamides, methacrylamides, and styrene,
wherein said monomers optionally contain functional groups that assist in the.disproportionation
of Cu(I)X into Cu(0) and Cu(II)X2 .
6. The method of claim 5 wherein the substituent group is amide, sulfoxide, carbonate, or
onium.
7. The method of claim 1 wherein the alkene monomer is an acrylate.
8. The method of claim 1 wherein the alkene monomer is a methylacrylate.
9 The method of claim 1 wherein the alkene monomer comprises one or more halogen-
substituted alkenes that are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene
fluoride, or tetrafluoroethylene, trifluorochloroethylene.
10. The method of claim 1 wherein the alkene monomer is an acrylamide.
11. The method of claim 1 wherein the alkene monomer is a methylacrylate.
12. The method of claim 1 wherein the alkene monomer is styrene.
13. The method of claim 1 wherein said contacting occurs at about 25°C or below.
14. The method of claim 1 wherein the initiator is one or more of chloroform, bromoform,
idoform, carbon tetrachloride, carbon tetrabromide and compounds of the formula:


15. The method of claim 1 wherein the solvent is a dipolar aprotic solvent.
16. The method of claim 1 wherein the solvent is DMSO or DMF.
17. The method of claim 1 wherein the solvent is DMSO.
18. The method of claim 1 where the amount of catalyst is about 100% to about 0.1%, based
on moles, of the initiator.
19. The method of claim 1 further comprising isolating the polymer without the need for
further purification.
20. The method of claim 1 wherein the polymer has a molecular weight of at least 500.
21. The method of claim 1 wherein the polymer has a molecular weight of at least 105.
22. The method of claim 1 further comprising functionalizing at least one terminal end of the
polymer.

23. The method of claim 22 wherein the polymer is functionalized by a drug moiety.
24. The method of claim 1 wherein the alkene monomer comprises a drug moiety.
25. A method of polymerizing an alkene monomer to produce a polymer having a number
average molecular weight of at least 106, the method comprising contacting said monomer with:
Cu(0), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof;
a nitrogen-containing ligand;
an initiator that is one or more of sulfonyl halides, nitrogen halides or compounds of the
formula R-X, R'C(=O)OR", or R'-CN, where X is a halogen and R is C1-C6 alky, R' is a
halogen-substituted C1-C6 alkyl, and R" is a C1-C6 alkyl; and
a solvent that is water, alcohol, dipolar aprotic solvent, ethylene carbonate, propylene
carbonate, or a mixture thereof;
wherein the solvent and nitrogen-containing ligand are capable of diproportionating
Cu(I)X into Cu(0) and Cu(II)X2 where X is Cl, Br, I where the diproportionation has an
equilibrium constant of at least 106 favoring the Cu(0) and Cu(II)X2 species.
26. The product of the process of claim 1.
27. The product of the process of claim 21.
28. A dendrimer made by the method comprising the method of claim 1.
29. The method of claim 1, wherein the catalyst comprises solid copper.
30. The method of claim 29, wherein said solid copper is copper wire.
31. The method of claim 29, wherein the alkene monomer comprises at least one of methyl
acrylate, methyl methacrylate, and vinyl chloride.
32. The method of claim 29, wherein the initiator is bromoform or methyl 2-propionate
33. The method of claim 29, wherein the ligand is tris[2-(dimentylamino)ethyl]amine.

The invention concerns a method of polymerizing
an alkene monomer to produce a polymer using a
catalyst that is Cu(O), Cu2Te, CuSe, Cu2S, Cu2O, or a combination thereof, an initiator, and a component comprising a solvent and optional nitrogen-containing ligand, where the
combination of the component and monomer is capable of diproportionating Cu(I)X into Cu(O) and Cu(II)X; where X is Cl, Br, or I.

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Patent Number 272041
Indian Patent Application Number 843/KOLNP/2009
PG Journal Number 12/2016
Publication Date 18-Mar-2016
Grant Date 15-Mar-2016
Date of Filing 04-Mar-2009
Name of Patentee THE TRUSTEES OF THE UNIVERSITY OF PENNSYLVANIA
Applicant Address 3160 CHESTNUT STREET, SUITE 200, PHILADELPHIA, PA
Inventors:
# Inventor's Name Inventor's Address
1 PERCEC, VIRGIL 2026 DELANCEY PLACE, PHILADELPHIA, PA 19103-6510
PCT International Classification Number c08f 4/611
PCT International Application Number PCT/US2007/017396
PCT International Filing date 2007-08-03
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/835,580 2006-08-04 U.S.A.