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Title:
UNIMOLECULAR LIGAND-INITIATOR DUAL FUNCTIONAL SYSTEMS (UMLIDFS) AND USE THEREOF
Document Type and Number:
WIPO Patent Application WO/2011/040881
Kind Code:
A1
Abstract:
This invention relates to the polymerization of vinyl monomers by atom transfer radical polymerization (ATRP) using metal salts in ppm molar quantities. It relates to the polymerization under ATRP conditions using unimolecular ligand-initiator dual functional systems (UMLIDFS) where the initiator and ligand for complexing the metal are part of the same molecule.

Inventors:
PARTHIBAN, Anbanandam (1 Pesek RoadJurong Island, Singapore 3, 62783, SG)
Application Number:
SG2010/000362
Publication Date:
April 07, 2011
Filing Date:
September 27, 2010
Export Citation:
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Assignee:
AGENCY FOR SCIENCE, TECHNOLOGY AND RESEARCH (1 Fusionopolis Way #20-10, Connexis, Singapore 2, 13863, SG)
PARTHIBAN, Anbanandam (1 Pesek RoadJurong Island, Singapore 3, 62783, SG)
International Classes:
C08F4/00; C07D211/00; C08F10/00; C08F12/08; C08F20/00; C08F20/06; C08F20/44; C08F26/06; C08F30/02; C08F36/08
Domestic Patent References:
WO2006003352A1
WO2004052944A1
WO2009122220A1
Foreign References:
US20070129239A1
Other References:
HUANG ET AL.: 'Polypeptide Diblock Copolymer: Syntheses and Properties of Poly(N-isopropyllacrylamide)-b-Polylysine' MACROMOLECULES vol. 41, 2008, pages 7041 - 7052
LEE ET AL.: 'Synthesis of Complementary Host and Guest Functionalized polymeric Building block and Their Self Assembling Behavior' MACROMOLECULES vol. 42, no. 17, 2009, pages 6483 - 6494
NIEHOFF ET AL.: 'One-Pot Procedure for the Preparation of Rod-Coil Block Copolymers via a Bifunctional Initiator' MACROMOL. SYMP, [Online] vol. 275-276, no. 1, 2009, pages 82 - 89 Retrieved from the Internet:
LOOS ET AL.: 'Construction of functional porphyrin polystyrene nano-architectures by ATRP' CHEM. COMMUN., [Online] 2005, pages 60 - 62 Retrieved from the Internet: [retrieved on 2004-12-01]
DATABASE CAS 18 October 2007 STN Database accession no. 950906-45-3
Attorney, Agent or Firm:
SCHIWECK, Wolfram (Viering, Jentschura & Partner LLPP.O. Box 1088,Rochor Road, Singapore 3, 91183, SG)
Download PDF:
Claims:
CLAIMS:

1. A compound having the general formula (I):

R-X-Y (I) wherein

R is an initiator selected from the group consisting of halogenated alkane, benzylic halide, Q!-haloester, Q!-haloketone, ohalonitrile and sulfonyl halides;

X is a linker selected from the group consisting of optionally substituted aliphatic, optionally substituted aromatic, optionally substituted hetero aromatic and optionally substituted aralkyl or is a direct bond connecting R and Y;

Y is a ligand capable of coordinating to a metal centre selected from the group consisting of aliphatic, aromatic, hetero aromatic and aralkyl.

2. The compound of claim 1, wherein R may have the following general formula (II):

(R')(R2)C(Z)-(R3)- (II), wherein R 1 and R 2 are independently selected from hydrogen, optionally substituted alkyl, and optionally substituted aryl;

Z is a halogen; and

R3 is a group which can activate the cleavage of the C-Z bond.

3. The compound of claim 2, wherein R contains at least one chlorine atom or at least one bromine atom.

4. The compound of any of claims 1 to 3, wherein R is selected from (H)2C(Br)-C(0)-, (H)2C(C1)-C(0)-, (CH3)(H)C(Br)-C(0)-, (CH3)(H)C(C1)-C(0)-, (CH3)2C(Br)-C(0)-, (CH3)2C(C1)-C(0)-, (C2H5)(H)C(Br)-C(0)-, (C2H5)(H)C(C1)-C(0)-, (C2H5)2C(Br)- C(O)-, and (C2H5)2C(C1)-C(0)-.

5. The compound of any of the preceding claims, wherein X is selected from optionally substituted -CH2-, optionally substituted -C2H5-, optionally substituted -C6H4-, and optionally substituted -C5H4N-.

6. ; The compound of any one of the preceding claims, wherein Y comprises at least one heteroatom capable of coordinating to a metal centre.

7. The compound of any one of the preceding claims, wherein Y comprises at least two heteroatoms capable of coordinating to a metal centre.

8. The compound of claim 6 or 7, wherein the heteroatom(s) is/are independently selected from nitrogen, oxygen and sulfur.

9. The compound of any of claims 6 to 8, wherein at least one or all of the heteroatoms are part of the aliphatic, alicyclic, aromatic, or heteroaromatic units and positioned in such a way that complexation occurs when treated with a metal salt.

10. The compound of any one of claims 6 to 9, wherein the heteroatom is nitrogen.

11. The compound of claim 10, wherein the nitrogen atoms is tertiary in nature.

12. The compound of claim 10, wherein all of the nitrogen atoms are tertiary in nature.

13 The compound of claim 10, wherein Y is selected

-46-

15. A polymerization composition comprising:

a) at least one compound of any one of claims 1 to 14; and

b) at least one metal salt.

16. The composition of claim 15, wherein the metal salt is selected from salts of Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Zn.

17. The composition of claim 16, wherein the metal salt is a halide.

18. The composition of any one of claims 15 to 17, wherein the metal salt is a halide of Cu in +1 oxidation state or a mixture of halides of copper in +1 and +2 oxidation states.

The composition of any one of claims 15 to 18, wherein the metal salt is CuCl, CuBr or CuBr2.

20. The composition of any one of claims 15 to 19, wherein the metal salt has a concentration in the ppm range.

21. The composition of any of claims 15 to 20 further comprising at least one kind of vinyl monomer.

22. The composition of claim 21, wherein the at least one kind of vinyl monomer is selected from the group consisting of ethylene, propylene, styrene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, butadiene, 1,7-octadiene, 1 ,4-hexadiene norbornene, acrylate, acrylic acid, methacrylate and methacrylic acid, vinyl sulphonic acid and its derivatives, vinyl phosphonic acid and its derivatives, acrylonitrile, vinyl pyridine, isobutene, maleimide, isoprene, vinylidene chloride and mixtures thereof.

23. Use of the composition of any one of claims 15 to 22 for atom transfer radical polymerization (ATRP) of at least one kind of vinyl monomer.

24. The use of claim 23, wherein the at least one kind of vinyl monomer comprises a functional group such as a carboxylic acid, a sulphonic acid or a phosphonic acid group.

25. The use of claim 23 or 24, wherein the at least one kind of vinyl monomer contains at least one carboxylic group.

26. The use of any one of claims 23 to 25 wherein the at least one kind of vinyl monomer is acrylic acid or methacrylic acid.

27. The use of any one of claims 23 to 26, wherein ATRP is carried out in solution phase using an organic solvent, a dispersed phase using water or a surfactant solution.

28. The use of any one of claims 23 to 27, wherein ATRP is carried out in the absence of solvents.

29. A polymer obtained by the use of any one of claims 23 to 28.

30. The polymer of claim 29 comprising at least one polar carboxylic acid group wherein the weight percentage of residual metal is less than 0.02%.

Description:
UNIMOLECULAR LIGAND-INITIATOR DUAL FUNCTIONAL SYSTEMS

(UMLIDFS) AND USE THEREOF

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims the benefit of priority of US provisional application "Atom transfer radical polymerization using lower amounts of metal salts and direct polymerization of acidic monomers by unimolecular ligand-initiator dual functional systems (UMLIDFS)" being filed with the US Patent and Trademark Office on September 29, 2009 and being assigned the official serial number 61/246,661. The content of this application filed on September 29, 2009 is incorporated herein in its entirety by reference for all purposes, including an incorporation of any element or part of the description, claims or drawings not contained herein and referred to in Rule 20.5(a) of the PCT, pursuant to Rule 4.18 of the PCT. FIELD OF THE INVENTION

[0002] This invention relates to the polymerization of vinyl monomers including acidic monomers like acrylic acid and methacrylic acid in the free acid form by atom transfer radical polymerization (ATRP) using metal salts in ppm molar quantities. More specifically, this invention relates to the polymerization under ATRP conditions using unimolecular ligand-initiator dual functional systems (UMLIDFS) where the initiator and ligand for complexing the metal are part of the same molecule.

BACKGROUND OF THE INVENTION [0003] Commercially available synthetic polymers are typically produced by conventional radical polymerization process which yields polymers with broad molecular weight distribution. Since radical polymerization proceeds with continuous termination reaction, it is not possible to make polymers with predetermined molecular weight and well defined micro structures like block copolymers and gradient copolymers. As a means of controlling the polymerization proceeding by free radical pathway, atom transfer radical polymerization (ATRP) was developed recently. ATRP is one of the most widely used controlled polymerization techniques in academic laboratories around the world for preparing well defined polymers with predetermined molecular weight and low polydispersity with well defined functional groups at the end of polymer chain. By virtue of its ability to make a variety of copolymers by radical means, it is more suited to make specialty polymers. Additionally, cross polymerization processes are possible by the introduction of suitable end functionalities and the overall process is free of radical initiators.

[0004] However, ATRP has not become a widely adopted industrial process due to various problems associated with the process. One of the major drawbacks associated with the process is the presence of metal impurities in the final polymer in unacceptably high quantities. This is attributed to the large quantities of metal salt viz. CuBr either alone or in conjunction with CuBr 2 employed during polymerization. The presence of residual metal impurities impacts the performance of polymers in many respects. Due to the presence of residual metal impurities the polymers appear reddish brown to green in colour. This coloration is intensified during the thermal processing of the polymer. In addition, the residual metal impurity adversely affects the toxicity of the polymer and also lowers the thermooxidative stability of the polymer. The residual metal could also affect the mechanical properties of injection molded materials.

[0005] Typically, in order to remove the residual metal impurities, the polymer solutions are passed through a column of alumina (A1 2 0 3 ). The metal impurities are adsorbed on the alumina and the polymer is separated from the resulting solution either by precipitation or by removing the solvent. Since the polymer solutions tend to be highly viscous beyond a molecular weight of 10,000 and above, passing such solutions through alumina column on an industrial scale would be costly and time consuming. Various reports have disclosed processes for removing residual metal impurities from polymers prepared by ATRP catalyzed by copper salts. These processes involve the treatment of polymer solutions with various acidic or basic adsorbents, using oxidizing or reducing agents or an extracting agent. As noted above, carrying out these post polymerization purification operations at industrial scale would be prohibitive in terms of cost for various reasons like additional machinery, enhanced production time, treatment of waste, handling highly viscous solutions, handling of inflammable liquids in large quantities, etc. In view of the aforementioned problems it is desirable to have a process which employs low quantities of metal salt during polymerization so that the quantity of residual metal used in the polymerization is equal to the metal impurity present in the purified polymer. [0006] Another significant drawback of the present ATRP process is its inability to homo ^ or copolymerize polar monomers like acrylic and mefhacrylic acids directly. Polar, carboxylic acid groups impart many characteristics to polymers such as pH responsiveness, high adhesion, high oil resistance, high heat resistance, high tensile properties and high resistance to wax removers, improved solvent resistance. As the modern trend in coating industry is to make formulations free of volatile organic components, the ability of these polymers to dissolve in aqueous medium after neutralization is an added advantage of these copolymers. Polar carboxylic acid group bearing homo- and copolymers have many applications in various industry sectors. They are used in the paper industry, in the paint industry, in detergents, in water treatment, in cement industry, in textile industry, in healthcare, in hygienic articles and leather industry. They are also used to aid the grinding of various inorganic minerals like calcium carbonate, precipitated calcium carbonate, titanium dioxide, clay and kaolin.

[0007] In the conventional free radical polymerization, substantial amounts of homopolymers of acrylic and methacrylic acids are produced during copolymerization. Because of this the copolymers are subjected to dialysis for prolonged periods to get rid of homopolymers. As for the synthesis of polymers bearing pendant carboxylic acid groups, a two step process comprising the homo- or copolymerization of t-butyl ester of acrylic acid or methacrylic acid under ATRP conditions followed by hydrolysis using a strong and highly corrosive acid like trifluoroacetic acid is necessary. An example of such a process is illustrated in FIG. 1.

[0008] These processes are atom inefficient as it involves the additional protection and deprotection steps. However, it cannot be adopted universally, especially for sterically hindered monomers such as tert-butyl methacrylate where polymerization occurs slowly. Furthermore, hydrolysis of the ester is often incomplete due to solubility problems associated with the intermediate which in turn results in partially hydrolyzed polymer. Since these acids are readily available commercially in the free acid form, using these acids without any additional conversion would be the most cost effective and efficient method of producing polymers bearing pendant carboxylic acid groups.

[0009] Additionally, the current ATRP process is energy intensive in that the reaction mixture is subjected to repeated freeze-pump-thaw cycles in order to make it completely free of air, particularly, oxygen. Such freezing and thawing cycles are not viable for an industrial scale process. [0010] At the early stages of the development of the ATRP process, efforts were concentrated predominantly in the preparation of materials of varying nature well within the limitation of the process. Many attempts were also made to overcome some of the deficiencies of the process. Among the various attempts that were made to improve the process, substantial focus was on ligand modification and on alkyl halide employed as initiator. There were also attempts to carry out the polymerization under high pressure. However, reduction in metal salt employed in the polymerization and broadening the scope of polymerization to include carboxylic acid containing monomers could not be achieved without any additional complications.

SUMMARY OF THE INVENTION

[0011] In a first aspect, the present invention provides compounds according to a unimolecular ligand-initiator dual functional system (UMLIDFS) so that an ATRP process could be carried out with low quantities of metal salt(s). These compound have the general formula R-X-Y (I), wherein R is an initiator selected from the group consisting of halogenated alkane, benzylic halide, or-haloester, a-haloketone, a-halonitrile and sulfonyl halides; X is a linker selected from the group consisting of optionally substituted aliphatic, optionally substituted aryl, optionally substituted heteroaryl and optionally substituted aralkyl or is a direct bond connecting R and Y; and Y is a ligand capable of coordinating to a metal centre selected from the group consisting of aliphatic, aryl, heteroaryl and aralkyl.

[0012] In a second aspect, the present invention provides a composition comprising a) at least one compound of the present invention; and b) at least one metal salt.

[0013] In a third aspect, the present invention provides the use of the inventive composition for atom transfer radical polymerization (ATRP) of vinyl monomers.

[0014] In a fourth aspect, the present invention provides a polymer obtained by the inventive use described in the present application.

[0015] Other objectives and advantages of the invention will become readily apparent from the following discussion.

BRIEF DESCRIPTION OF THE DRAWINGS [0016] The invention will be better understood with reference to the detailed description when considering in conjunction with the non- limiting examples and the accompanying drawings.

[0017] FIG. 1 depicts a scheme for the typical preparation of copolymers containing polar acidic groups by ATRP.

[0018] FIG. 2 depicts (a) the general structure of the UMLIDFS of the present invention wherein the ligand and the initiator are connected by the linker group into a single entity and (b) depicts a preferred embodiment of the present inventive technology.

[0019] FIG. 3 depicts the general mechanism of ATRP.

[0020] FIG. 4 depicts the homopolymers synthesized using the UMLIDFS of the present invention.

[0021] FIG. 5 depicts the copolymer of acrylic acid and n-isopropyl acrylamide (AA-b/ran-NIPAAm).

[0022] FIG. 6 depicts the copolymer of methacrylic acid and n-butyl acrylate (MAA-b/raw-nBA).

[0023] FIG. 7 depicts (a) the homopolymer of polymethacrylic acid (PMAA) and (b) the copolymer of polymethacrylic acid and polystyrene (PMAA-b/ran-PS).

[0024] FIG. 8 depicts the aqueous alkali solutions of copolymers, from left to right: (a) polystyrene-methacrylic acid (PS-MAA), (b) acrylic acid-styrene-n-butyl acrylate (AA-Sty-nBA), (c) methacrylic acid-n-butyl acrylate (MAA-nBA), (d) acrylic acid-n- isopropyl acrylamide (AA-NIPAAm), (e) acrylic acid- styrene (AA-Sty), (f) acrylic acid-n- butyl acrylate (AA-nBA), (g) acrylic acid-methacrylic acid-n-butyl acrylate (AA-MMA- nBA).

[0025] FIG. 9 depicts (a) the cross-linked alkali salt of PAA swollen in 0.9 wt % NaCl solution (Swelling ratio = 1031); (b) the cross-linked PAA swollen in NaOH solution.

[0026] FIG. 10 depicts the film developed from 2 wt% aqueous solution of copolymer PAA-b/ran-PS.

[0027] FIG. 11 depicts a GPC analysis showing the position of molecular weight for PMMA and PMMA-PI

[0028] FIG. 12 depicts the structures of nBA-MAA copolymer using dispersions ofZnAc. [0029] FIG. 13 depicts the structures of PS-MAA copolymer using dispersions of

ZnAc.

[00301 FIG. 14 depicts the structures of AA-NIPAAm copolymer using dispersions of ZnAc.

DETAILED DESCRIPTION OF THE INVENTION

[0031] In the following description non-limiting embodiments of the present invention will be explained.

[0032] In the context of the present invention, the term "comprising" means including, but not limited to, whatever follows the word "comprising". Thus, use of the term "comprising" indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present. The term "consisting of means including, and limited to, whatever follows the phrase "consisting of. Thus, the phrase "consisting of ' indicates that the listed elements are required or mandatory, and that no other elements may be present. The term "consisting essentially of means including any elements listed after the phrase, and limited to other elements that do not interfere with or contribute to the activity or action specified in the disclosure for the listed elements. Thus, the phrase "consisting essentially of indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present depending upon whether or not they affect the activity or action of the listed elements.

[0033] The object of the present invention is the provision of a unimolecular ligand-initiator dual functional system (UMLIDFS), wherein the ligand and initiator are combined into a single molecule. Whilst atom transfer radical polymerization (ATRP) typically involves four major components, i.e. a metal halide, alkyl halide, nitrogen containing ligand and a vinyl monomer, the present technology allows the homogenization of the catalyst, i.e. making the metal complex completely soluble in the reaction medium and minimizing the number of components in the reaction medium.

[0034] As shown in FIG. 2(a), the ligand and initiator are connected by a linker group to form a single entity. As ATRP involves redox cycles of the metal which is directly associated with the active and dormant states of the growing polymer chain as illustrated in FIG. 3, this bifunctional system allows the active and dormant states to proceed intramolecular ly since the ligand would be present in one end of the chain and the halide at the other end of the same polymer chain. This species during active cycle would then combine with the vinyl monomer resulting in chain extension. Thus a four component heterogeneous reaction mixture would be reduced to two component viz. the complex comprising of metal salt and ligand-initiator and the vinyl monomer, homogeneous solution by this modification.

[0035] Therefore, the present technology relates to a compound having the following generic structure:

R-X-Y (I) wherein

R is an initiator selected from the group consisting of halogenated alkane, benzylic halide, ohaloester, ohaloketone, ohalonitrile and sulfonyl halides;

X is a linker selected from the group consisting of optionally substituted aliphatic, optionally substituted aryl, optionally substituted heteroaryl and optionally substituted aralkyl or is a direct bond connecting R and Y;

Y is a ligand capable of coordinating to a metal centre selected from the group consisting of aliphatic, aryl, heteroaryl and aralkyl.

[0036] The groups R, X and Y may be independently selected as defined in the following, but are not limited to.

[0037] The term "aliphatic", alone or in combination, refers to a straight chain or branched chain hydrocarbon comprising at least one carbon atom. Aliphatics include alkyls, alkenyls, and alkynyls. In certain embodiments, aliphatics are optionally substituted. Aliphatics include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. -butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, ethynyl, butynyl, propynyl, and the like, each of which may be optionally substituted. As used herein, aliphatic is not intended to include cyclic groups.

[0038] The term "alkyl", alone or in combination, refers to a fully saturated aliphatic hydrocarbon. In certain embodiments, alkyls are optionally substituted. In certain embodiments, an alkyl may comprises 1 to 20 carbon atoms, for example 1 to 10 carbon atoms or 1 to 6 carbon atoms, wherein (whenever it appears herein in any of the definitions given below) a numerical range, such as "1 to 20" or "C 1 -C 20 ", refers to each integer in the given range, e.g. "Ci-C 20 alkyl" means that an alkyl group comprises only 1 carbon atom, or 2 carbon atoms, 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, 6 carbon atoms, 7 carbon atoms, 8 carbon atoms, 9 carbon atoms, 10 carbon atoms, 11 carbon atoms, 12 carbon atoms, 13 carbon atoms, 14 carbon atoms, 15 carbon atoms, 16 carbon atoms, 17 carbon atoms, 18 carbon atoms, 19 carbon atoms, up to and including 20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-amyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.

[0039] The term "alkenyl", alone or in combination, refers to an aliphatic hydrocarbon having one or more carbon-carbon double-bonds. In certain embodiments, alkene groups are optionally substituted. Examples of alkene groups may include, but are not limited to, ethenyl, propenyl, butenyl, 1 ,4-butadienyl, pentenyl, hexenyl, 4-methylhex- 1-enyl, 4-ethyl-2-methylhex-l-enyl and the like.

[0040] The term "alkynyl", alone or in combination, refers to an aliphatic hydrocarbon having one or more carbon-carbon triple-bonds. In certain embodiments, alkyne groups are optionally substituted. Examples of alkyne groups may include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

[0041] The term "aryl" refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom. The term "aromatic" refers to a group comprising a covalently closed planar ring having a delocalized [pi]-electron system comprising 4n+2 [7T] electrons, where n is ah integer. Aryl rings may be formed by five, six, seven, eight, nine, or more than nine carbon atoms. Aryl groups may be optionally substituted. Examples of aryl groups may include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, anthracenyl, tetralinyl, fluorenyl, indenyl, and indanyl. In certain embodiments, an aryl group may be substituted at one or more of the para, meta, and/or ortho positions. Examples of aryl groups comprising substitutions may include, but are not limited to, 3-halophenyl, 4-halophenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 3- aminophenyl, 4-aminophenyl, 3-methylphenyl, 4-methylphenyl, 3-methoxyphenyl, 4- methoxyphenyl, 4-trifluoromethoxyphenyl, 3-cyanophenyl, 4-cyanophenyl, dimethylphenyl, naphthyl, hydroxynaphthyl, hydro xymethylphenyl, (trifluoromethyl)phenyl, alkoxyphenyl, 4-morpholin-4-ylphenyl, 4-pyrrolidin-l-ylphenyl, 4-pyrazolylphenyl, 4-triazolylphenyl, and 4-(2-oxopyrrolidin-l-yl)phenyl or any of the groups shown explicitly below. [0042] The term "heteroaryl" refers to an aromatic heterocycle. Heteroaryl rings may be formed by three, four, five, six, seven, eight, nine, or more than nine atoms. Heteroaryls may be optionally substituted. Examples of heteroaryl groups may include, but are not limited to, aromatic C 3 - 8 heterocyclic groups comprising one oxygen or sulfur atom or up to four nitrogen atoms, or a combination of one oxygen or sulfur atom and up to two nitrogen atoms, and the like. In certain embodiments, heteroaryl groups may be optionally substituted. Examples of heteroaryl groups may include, but are not limited to, unsubstituted and mono- or di-substituted derivatives of furan, benzofuran, thiophene, benzothiophene, pyrrole, pyridine, indole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, imidazole, benzimidazole, pyrazole, indazole, tetrazole, quinoline, isoquinoline, pyridazine, pyrimidine, purine and pyrazine, furazan, 1,2,3-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, triazole, benzotriazole, pteridine, phenoxazole, oxadiazole, benzopyrazole, quinolizine, cinnoline, phthalazine, quinazoline, quinoxaline and the like.

[0043] The term "aralkyl" refers to a group comprising an aryl group bound to an alkyl group.

[0044] The term "linker" refers to an atom or group of atoms that link (or separate) two or more groups to (or from) one another by a desired number of atoms. For example, in certain embodiments, it may be desirable to link or separate the initiator and the ligand by one, two, three, four, five, six, or more than six atoms. In such embodiments, any atom or group of atoms may be used to link or separate those groups by the desired number of atoms. The linker of the present invention may also be a direct bond connecting R and Y.

[0045] The term "optionally substituted" refers to a group in which none, one, or more than one of the hydrogen atoms has been replaced with one or more group(s) independently selected from: alkyl, heteroalkyl, haloalkyl, heterohaloalkyl, cycloalkyl, aryl, arylalkyl, heteroaryl, nori-aromatic heterocycle, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halo, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O- thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C- carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, trihalomethanesulfonyl, and amino, including mono- and di-substituted amino groups. In one embodiment in which two or more hydrogen atoms have been substituted, the substituent groups may be linked to form a ring. [0046] In addition to the above, in one embodiment R may have the following general formula (II): (R'XR^CCZHR 3 )-, wherein in formula (II) R 1 and R 2 may be independently selected from hydrogen, optionally substituted alkyl, such as methyl, ethyl, /-propyl, «-butyl, /-butyl and tert. -butyl, and optionally substituted aryl, such as aralkyl; Z may be a halogen, such as F, CI and Br; and R 3 may be a group which can activate the cleavage of the C-Z bond, such as, but not limited to, C(O), CN, phenyl, -CONH 2 , lactone, ketone and the like.

[0047] In one embodiment R may be, but is not limited to, (H) 2 C(Br)-C(0)-, (H) 2 C(C1)-C(0)-, (CH 3 )(H)C(Br)-C(0)-, (CH 3 )(H)C(C1)-C(0)-, (CH 3 ) 2 C(Br)-C(0)-, (CH 3 ) 2 C(C1)-C(0)-, (C 2 H 5 )(H)C(Br)-C(0)-, (C 2 H 5 )(H)C(C1)-C(0)-, (C 2 H 5 ) 2 C(Br)-C(0)-, (C 2 H 5 ) 2 C(C1)-C(0)- and the like.

[0048] X is a linking atom or group which preferably covalently connects the initiating moiety R and the ligating species Y. Besides the definitions given above, in one embodiment of the invention X may be, but is not limited to, optionally substituted -CH 2 -, optionally substituted i C 2 H 5 -, optionally substituted -C 6 H 4 -, optionally substituted -C 5 H N- and the like. In one embodiment X may also be a Si-group, for example a Si chain provided that it is stable under the conditions of the present invention. In one illustrative embodiment, may be 2,4-dimethylphenyl.

[0049] Y is the ligating species of the UMLIDFS of the present invention. Besides the definitions given above, in one embodiment Y may comprise at least one heteroatom. The ligand Y is capable to coordinate to the metal centre via the at least one heteroatom so that a complex between the compound of the invention and the metal centre can be formed. In one embodiment Y may comprise at least two heteroatoms, such as at least three heteroatoms or at least four heteroatoms. The heteroatom(s) may be independently selected from nitrogen, oxygen and sulphur. In one embodiment, the heteroatom is nitrogen. In one embodiment, the ligating nitrogen atoms may be tertiary in nature. In one embodiment of

the invention Y may be, but is not limited to,

As illustrated above, the at least one heteroatom may be part of the aliphatic, alicyclic, aromatic or hetero aromatic units and positioned in such a way that complexation occurs when treated with a metal salt.

[0050] In one embodiment of the present invention, the compounds may be, but are not limited, as illustrated in FIG. 2(b) or as follows:

[0051] The present invention also encompasses a polymerization composition comprising a) at least one compound as described above, and b) at least one metal salt. Such a composition may be used in polymerization reaction of one or more independently selected vinyl monomers, such as atom transfer radical polymerization (ATRP). Thus, in one embodiment of the present invention the composition may comprise at least one kind of vinyl monomer. Suitable vinyl monomers are described in more detail below.

[0052] The metal salt used in the inventive composition may be any metal salt which may be generally used in the field of the polymerization reactions. In one embodiment of the present invention, the metal salt may be a salt of, but is not limited to, Ti, Zr, Cr, Mo, W, Mn, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Zn and the like. It is possible to use two or more metal salts, for example two or more metal salts from the same metal having different oxidation states. In one embodiment the metal of the metal salt is Cu.

[0053] The corresponding anion o f the metal salt may be selected from any anion which is generally used in the field of polymerization reactions or which is generally used in metal complexes. The anion may be, but is not limited to, a halide, N0 2 , CN, OH, S0 3 H, and the like. In ' one embodiment the anion is a halide, such as F, CI, Br or I. Examples of suitable metal salts include, but are not limited to, TiCL t , ReCl 6 , FeCl 2 , RuCl 2 , RhCl 2 , NiBr 2 , NiCl 2 , CuBr, CuCl, CuBr 2 , CuCl 2 , and the like. In one embodiment the metal salt is a halide of Cu in +1 oxidation state, such as CuBr or CuCl, or a mixture of halides of copper in +1 and +2 oxidation states.

[0054] The metal salt is typically used in an amount which is smaller than the amount generally used in polymerization chemistry. For example, the metal salt may be used in an amount of about 1 x 10 "6 mol or about 1 x 10 "5 mol. In one illustrative example the metal salt may be used in an amount of about 1/10 mg, such as 1/100 mg or 1/1000 mg. The metal salt may also be used in an amount in the ppm range.

[0055] The compounds of the invention may be used for polymerizing olefins, such as one kind of vinyl monomer or a mixture of two or more different kinds of vinyl monomers. In one aspect of the present invention, the inventive compound may thus be used for atom transfer radical polymerization (ATRP) of at least one kind of vinyl monomer. Thus, in one embodiment of the invention the polymerization is carried out using the polymerization composition.

[0056] The vinyl monomer(s) which may be polymerized in the present invention may be selected from the group of vinyl monomers generally used in the field of polymerizations. A vinyl monomer in the sense of the present invention is any organic compound that contains a vinyl group (-CH=CH 2 ) or a derivative thereof, such as a derivative of ethylene (CH 2 =CH 2 ). In one embodiment, the vinyl monomer may be a α,β- unsaturated olefin. For example, the vinyl monomer may be, but is not limited to, ethylene, propylene, styrene, C 4 -C 10 olefins, such as 1-butene, isobutene, 1-pentene, 1-hexene, 4- methyl- l÷pentene, 1 -heptene, 1-octene, 1-nonene, 1-decene, as well as diene, such as butadiene, 1,7-octadiene and 1,4-hexadiene, or cyclic olefins, such as norbornene, acrylate, acrylic acid, methacrylate, methacrylic acid, and the like and mixtures of any of such vinyl monomers. In one embodiment, the vinyl monomer may be styrene, acrylate, acrylic acid, methacrylic acid or one of its derivatives, vinyl sulphonic acid or one of its derivatives or vinyl phosphonic acid or one of its derivatives, acrylonitrile, vinyl pyridine, isobutene, maleimide, isoprene, vinylidene chloride, or any mixture of these monomers.

[0057] The term "acrylate" refers to a group of formula R a -OC(0)C(CH 2 )(H). R a may be Ci-C 20 alkyl, C 2 -Cj 2 ether, vinyl group or allyl group. Examples of acrylates include, but are not limited to, acrylate, propargyl acrylate, n-butyl acrylate (nBA), n- isopropyl acrylamide (NIPAAm), allyl acrylate, 2-allyloxyethyl acrylate, 2- propargyloxyethyl acrylate and 1 -hexenylacrylate.

[0058] The term "methacrylate" refers to a group of formula R b - OC(0)C(CH 2 )(CH 3 ). R b may be C 1 -C 20 alkyl, C 2 -d 2 ether, vinyl group or allyl group. Examples of methacrylates include, but are not limited to, di(propylene glycol) allyl ether methacrylate, propargyl methacrylate, 2-(methacryloyloxy)ethyl ester, allyl methacrylate, allyl acrylate, propargyl methacrylate and propargyl acrylate.

[0059] In one embodiment of the present invention the at least one kind of vinyl monomer may comprise one or more functional groups. Generally, any functional group may be attached to the at least one kind of vinyl monomer. Using functional groups, the final properties of the prepared polymer may be influenced in the desired manner. For example, the vinyl monomers used in the present invention may comprise a functional group such as, but not limited to, a carboxylic acid, a sulphonic acid, a phosphoric acid group or also combinations of such groups and the like.

[0060] Accordingly, with the system of the present invention both homopolymers and copolymers may be prepared. Polymers that contain only a single type of vinyl monomers are known as homopolymers, while polymers containing a mixture of different vinyl monomers are known as copolymers. As mentioned above, every combination of different vinyl monomers mentioned above may be polymerized. For example, it is possible to copolymerize acrylic acid(s) and methacrylic acid(s) directly. With the compound and the composition of the present invention it is possible to control the polymerization reaction and to control the composition and the properties of the finally obtained polymer. For example, the polymerization may be controlled by varying the ratio between monomer and initiator. In case of copolymerization, control may also be ensured by the quantities of comonomers used and by the mode of addition, such as for example sequential addition of monomers or addition of all monomers at the beginning of the reaction process.

[0061] The polymers obtained using the inventive composition may have a molecular weight in the range of about 1.000 to about 1.000.000, such as about 1.000 to about 100.000, or about 1.000 to about 10.000.

[0062] In one embodiment, the molecular weight of the polymers may be below about 10.000, such as below about 7.500 or below about 5.000 in case they are used as additives. In the context of the present invention, "additives" are those compounds/components which impart a particular property when used in combination with various other components. For example, additives may provide hydrophobic or hydrophilic propertiesor may influence viscosity or dispersing capabilities. In one embodiment, low molecular weight polymers or high molecular weight polymers may be used as additives. In one embodiment, the molecular weight of the polymers may be about 100.000 to about 900.000, such as about 100.000 to about 750.000 in case they were used as resins. In the context of the present invention, "resin" is a polymer which is used as structured material like some components of automotive or airplane parts, wind shields made up of polymers and the like.

[0063] The polymers obtained may comprise at least one polar carboxylic acid group wherein the weight percentage of residual metal is less than about 0.02%. For example, the residual metal may be present in an amount of less than about 500 ppm, such as less than about 250 ppm, less than about 100 ppm, less than about 50 ppm, less than about 10 ppm, less than about 1 ppm or even less than about 0.1 ppm.

[0064] ATRP polymerization using the compound and/or composition of the present invention may be carried out in solution phase using an organic solvent or may be conducted under a solvent-free reaction conditions. The organic solvent may be, but is not limited to, aromatic or a mixture of aromatic and aliphatic hydrocarbons, such as substituted and unsubstituted benzenes, for example toluene and the xylenes, methanol, ethanol, acetone, anisol, diphenyl ether, ethyl acetate, DMF, ethylene carbonate, supercritical carbon-di-oxide and the like. It is also advantageous to carry out this process in water or preferably in surfactant solution so that the polymers are obtained as fine powders dispersed in water or as emulsions thereby enhancing their separation and making them closer to application.

[0065] The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject-matter from the genus, regardless of whether or not the excised material is specifically recited herein.

EXAMPLES [0066] Exemplary embodiments of the present invention are described below.

(a) Preparation of 2,4-dimethyl-6-bis(2-(diethylamino)-ethyl)aminomethyl phenol (TAP)

(I)

[0067] Paraformaldehyde (0.35g, 0.0116 mol) and Ν,Ν,Ν,Ν- tetraethyldiethylenetriamine (2.48g, 0.0115 mol) were mixed together and heated at 80°C for lh. A solution of 2,4-dimethylphenol (1.41g, 0.0115 mol) in methanol (10 mL) was then added and the reaction mixture was refluxed for 24h at 80°C. Methanol was removed under vacuum. The spectroscopic characteristics of the product obtained matched with that of the reported compound [Inoue, Y. et al. Macromolecules 2003, 36, 7432-7438.] Yield: 3.25g (76.6%). GC analysis of the product indicated that the product is free from the starting materials, viz. the triamine as well as the phenol.

(b) Preparation of (II) [0068] Compound I (lg, 0.00286 mol) was dissolved in dry dichloromethane (20 mL). Triethylamine (0.726g, 0.007 mol) was added to the dichloromethane solution. This reaction solution was cooled in an ice bath. 2-Bromoisobutyl bromide (0.74g, 0.0032 mol) was then added and the bath was allowed to warm up to room temperature. The reaction mixture was stirred for a total period of 24h. The dichloromethane solution after diluting with additional dichloromethane (10 mL) was transferred to a separating funnel and washed repeatedly with deionized water. It was then dried over anhydrous MgS04 and removed in a rotavapor. Honey coloured viscous oily liquid was obtained. Yield: lg (70%).

Ή-NMR (CDC1 3 , 400 MHz): δ Η (ppm): 0.903-0.939 (12H, t, 4xCH 3 ), 2.02 (6H, s, 2xCH 3 ), 2.06 (s, CH 3 ), 2.22 (s, CH 3 ), 2.41-2.46 (q, 4xCH 2 ), 2.49-2.6 (m, 4xCH 2 ), 3.445 (s, CH 2 ), 6.84 (s, 1H), 7.12 (s, 1H). 13 C-NMR (CDC1 3 , 100 MHz) 5 C (ppm): 1 1.38 (4xCH 3 ), 15.9 (CH 3 ), 20.88 (CH 3 ), 30.99 (2xCH 3 ), 47.32 (4xCH 2 ), 51.69 (2xCH 2 ), 52.35 (CH 2 ), 53.72 (CH 2 ), 55.22 (CH 2 ), 128.34, 129.71, 130.26, 131.21, 135.6, 145.26, 169.51. m/z (ESI, positive ion): 498.26897 (Exact neutral mass: 497.2617). Example 2: Preparation of polystyrene macroinitiator (PS-MI)

[0069] To a two neck 50 mL RB flask, CuBr (O.Olg, 6.97x l0 "5 mol) and II (0.174g, 0.349 mmol) were added and dry nitrogen gas was passed through the flask. Toluene (4 mL) was added to the flask with stirring under nitrogen atmosphere followed by styrene (4 mL, 3.635g, 0.0349 mol). Dry nitrogen gas was passed through the flask for 30 minutes and then the flask was immersed in a preheated oil bath maintained at 110°C. The flask was heated with stirring overnight (16h) under nitrogen atmosphere and the contents of the flask solidified during this period. The reaction flask was cooled by removing from the oil bath. THF (15 mL) was added and the flask was sonicated for 2 minutes to dissolve the polymer. The THF solution was precipitated in hexane. The precipitated solid was then filtered and dried. Yield: 3g (78.76%). GPC (THF as eluent): M n = 14,925; M w = 19552; Polydispersity = 1.31. The n value for PS-MI may be any number from 2 to 2000, more preferably, the n value may be any number from 2 to 200. Example 3: Preparation of polystyrene (PS)

In this example, PS is prepared, wherein n may be any number from 2 to 200. a) Method 1 : Preparation of PS in the presence of tertiary amine

[0070] To a two neck 100 mL RB flask, CuBr (O.OOlg, 6.97X10 "6 mol), tri-n- propylamine (O.Olg, 6.97><10 "5 mol) and II (0.035g, 7.02x l0 "5 mol) were added and dry nitrogen gas was passed through the flask. Toluene (8 mL) followed by styrene (8 mL, 7.27g, 0.0873 mol) was added to the flask with stirring under nitrogen atmosphere. Dry nitrogen gas was passed through the flask for 30 minutes and then the flask was immersed in a preheated oil bath maintained at 1 10°C. The flask was heated with stirring for 22h and 15 minutes under nitrogen atmosphere and the contents of the flask solidified during this period. The reaction flask was cooled by removing from the oil bath. THF was added to dissolve the polymer. The THF solution was precipitated in large excess of methanol. The precipitated solid was then filtered and dried. Yield: 6.6g (90.35%). GPC (THF as eluent): M n = 60,892; M w = 124,666; Polydispersity = 2.04. b) Method 2: Preparation of PS in the absence of additional tertiary amine base

[0071] CuBr (O.OOlg, 6.9X10 "6 mol), II (0.015g, 3 10 "5 mol), styrene (8 mL, 7.27g,

0.0698 mol) and toluene (8 mL) were heated at 110°C for 20h under nitrogen atmosphere.

The contents of the flask turned highly viscous over this period. It was dissolved in THF and precipitated in large excess of methanol. The white solid precipitated was filtered, washed repeatedly with methanol and dried. Yield: 5.96g (81.81%). GPC (THF as eluent):

M n = 74,318; M w = 1 12,559; Polydispersity = 1.51. c) Method 3: Preparation of PS by a solvent free process

[0072] To a two neck 100 mL RB flask, CuBr (O.OOlg, 6.97x 10 "6 mol) and II (0.003g, ό χ ΐθ "6 mol) were added and dry nitrogen gas was passed through the flask. Styrene (10 mL, 9.09g, 0.0873 mol) was added to the flask with stirring under nitrogen atmosphere. Dry nitrogen gas was passed through the flask for 30 minutes and then the flask was immersed in a preheated oil bath maintained at 1 15°C. The flask was heated with stirring for 19h under nitrogen atmosphere and the contents of the flask solidified during this period. The reaction flask was cooled by removing from the oil bath. THF was added to dissolve the polymer. The THF solution was precipitated in methanol. The precipitated solid was then filtered and dried. Yield: 6g (66%). GPC (THF as eluent): M n = 31,805; M w = 64,352; Polydispersity = 2.02.

Example 4: Preparation of polyCmethyl methacrylate) (PMMA)

a Method 1 : Preparation of PMMA in the presence of tertiary amine-base

[0073] i) CuBr (O.Olg, 6.97x l0 "5 mol), II (0.035g, 7.02xl0 "5 mol), tri-n- propylamine (O.Olg, 6.97xl0 "5 mol), MMA (15 mL, 14.04g, 0.14 mol) and toluene (15 mL) were heated at 70°C for 21h and 30 minutes under nitrogen atmosphere. A gel like mass was obtained. It was dissolved in THF and precipitated in large excess of methanol. The white solid precipitated was filtered, washed repeatedly with methanol and dried. Yield: 13g (92.36%). GPC (THF as eluent): M n = 122,026; M w = 235,871 ; Polydispersity = 1.93.

[0074] ii) CuBr (0.005g, 3.48xl0 "5 mol), II (0.018g, 3.61 xl0 "5 mol), tri-n- propylamine (0.005g, 3.48x10 "5 mol), MMA (10 mL, 9.36g, 0.0935 mol) and acetonitrile (10 mL) were heated at 70°C for 18h under nitrogen atmosphere. The contents of the flask turned solid over this period. It was dissolved in THF and precipitated in large excess of methanol. The white solid precipitated was filtered, washed repeatedly with methanol and dried. Yield: 5g. (53.32%). GPC (THF as eluent): M n = 190,967; M w = 747,946; Polydispersity = 3.91. . b) Method 2: Preparation of PMMA in the absence of tertiary amine base

[0075] PMMA was prepared in the same way as that of PS-MI in Example 2. CuBr (0.0062g, 4.32x10 "5 mol), II (0.149g, 0.3 mmol), MMA (3.2 mL, 2.995g, 0.03 mol) and toluene (3 mL) were heated overnight (15h) at 100°C. Yield: 2.5g (79.52%). GPC (THF as eluent): M n = 16,660; M w = 23657; Polydispersity = 1.42

[0076] ii) Compound II (0.1 17g, 2.346*10^ mol) and CuBr (0.0006g, 4.1 x10^ mol) were weighed into a 50 mL two neck RB flask. Toluene (2 mL) was added with stirring under nitrogen atmosphere followed by MAA (2 mL, 2.03g, 0.0236 mol). The flask was heated at 110°C for 16h. During this period a finely powdered white solid was obtained. Yield: 2g (93.15%). 'H-NMR analysis of the solid in CD 3 OD indicated the presence of— CH 3 signals of PMAA at 1 to 1.3 ppm as a broad two sets of signals and the - CH 2 - signal at 1.8-2.2 ppm. The latter signal is also interspersed with the -CH 3 signal of residual monomer. c) Method 3: Preparation of PMMA

[0077] i) CuBr (0.0006g, 4.1 X10 "6 mol), II (O.OlOg, 2xl0 *5 mol), MMA (10 mL,

9.36g, 0.0935 mol) and toluene (10 mL) were heated at 90°C for 16h and 30 minutes under nitrogen atmosphere. The contents of the flask turned highly viscous over this period. It was dissolved in THF and precipitated in large excess of methanol. The white solid precipitated was filtered, washed repeatedly with methanol and dried. Yield: 4.96g (53%). GPC (THF as eluent): M n = 71187; M w = 96602; Polydispersity = 1.35.

[0078] ii) CuBr (O.OOlg, 6.9X10 "6 mol), II (0.01 Og, 2xl0 "5 mol), MMA (10 mL, 9.36g, 0.0935 mol) and acetone (15 mL) were heated at 60°C for 20h under nitrogen atmosphere. The viscous solution was added dropwise to a large excess of methanol. The white solid precipitated was filtered, washed repeatedly with methanol and dried. Yield: 2g (21.34%). GPC (THF as eluent): M n = 61,946; M w = 86,909; Polydispersity = 1.40.

Example 5: Preparation of block copolymer from PS-MI by ligand free protocol

[0079] CuBr (0.005g, 3.48*10 _5 mol), PS-MI (0.5g, 4.76xl0 "5 mol), MMA (5 mL, 4.68g, 0.0467 mol) and toluene (6 mL) were heated overnight (15h) at 100°C. The contents of the flask solidified over this period. It was then dissolved in THF. The final product was obtained by precipitation of the polymer solution in THF into methanol. A white solid was obtained after filtering and drying. Yield: 4.5g (86.87%). GPC (THF as eluent): M n = 45,021 ; M w = 64520; Polydispersity = 2.16. The high polydispersity may be due to the presence of dead chain ends in the PS-MI, since the conversion of monomer in the case of PS-MI is more than 95%.

Example 6: Preparation of polv(acrylic acid) macroinitiator (PAA-MI)

[0080] PAA-MI was prepared in the same way as that of PS-MI in Example 2. CuBr (0.005g, 3,48xl0 "5 mol), II (0.36g, 0.72 mmol), AA (5 mL, 5.255g, 0.0729 mol) and toluene (5 mL) were heated overnight (15h) at 110°C. The reaction mixture turned to white solid during this period. A small fraction was scrapped out of the flask and dissolved in CD3OD to determine monomer conversion. The reaction flask containing the solid was then soaked in methanol (50 mL) for two days and then the swollen polymer was transferred to a beaker. The swollen polymer was allowed to dry under ambient conditions. Yield: 4g. (71.24%). M n (NMR) = 6912. Conversion based on Ή-NMR analysis was 85.63 %. The M n (NMR) of PAA-MI was determined by comparing the integral ratio of proton signal appearing at 3.6 ppm (a-end of polymer chain) with proton signal at 2.1-2.4 ppm corresponding to C-H unit of PAA.

Example 7: Preparation of poly(acrylic acid-b-n-butyl acrylate) (PAA-b-PnBA)

[0081] CuBr (0.0042g, 2.92x10 "5 mol), PAA-MI (Example 8) (0.5g, 7,23 xlO "5 mol), nBA (3 mL, 2.682g, 0.0209 mol) and DMF (1.5 mL) were heated overnight (15h) at 110°C. The reaction mixture became highly viscous during this period. The reaction mixture was precipitated in methanol and dried. Yield: 1.5g (47.14%). The polymer composition based on 1H-NMR analysis was PAA 89 PnBA 175 . The polymer composition was estimated by comparing the integral ratio of proton signal at 2.2-2.4 ppm (CH unit of PAA) with that of -COOCH 2 signal of PnBA appearing at 4-4.2 ppm or the CH 3 unit of PnBA.

Example 8: Preparation of copolymers of acrylic acid and styrene by stepwise addition of monomers (PAA-b/ra»-PS)

[0082] Compound II (0.035g, 7.02x l0 "5 mol), CuBr (0.005g, 3.48x l 0 ~5 mol), AA (1.2 mL, 1.2612g, 0.0175 mol) and toluene (2 mL) were heated at 1 10°C for 2h after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. White solid deposited at the end of this 2h period. Styrene (2 mL, 1.818g, 0.0175 mol) and toluene (2 mL) were added via syringe into the reaction medium. The reaction mixture was heated for an additional 15h under nitrogen atmosphere and cooled. The solid mass in the reaction flask was dissolved in THF (30 mL) and precipitated in 20% HC1 (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 2.2g (70.64%). The polymer composition based on Ή-NMR analysis was PAAo. 13 PS 0 , 87-The polymer composition was estimated by comparing the integral ratio of proton signal at 2.2- 2.4 ppm (CH unit of PAA) with the aromatic proton signals of PS unit appearing at 6.4-7.3 ppm.

Example 9: Preparation of copolymers of acrylic acid and n-butyl acrylate by stepwise addition of monomers (PAA-b/raw-PnBA)

[0083] Compound II (0.035g, 7.02xl0 "5 mol), CuBr (0.005g, 3.48xl0 ~5 mol), AA (1.2 mL, 1.2612g, 0.0175 mol) and toluene (2 mL) were heated at 110°C for 2h after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. White solid deposited at the end of this 2h period. nBA (2.6 mL, 2.3244g, 0.018 mol) and toluene (2 mL) were added via syringe into the reaction medium with the continuous purge of nitrogen gas. The reaction mixture was heated for an additional 15h under nitrogen atmosphere and cooled. The solid mass in the reaction flask was dissolved in THF (30 mL) and precipitated in 20% HCl (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 2.45g (67.67%). The polymer composition based on Ή-NMR analysis was PAA 0 . 67 PnBAo.3 3 . The polymer composition was estimated by comparing the integral ratio of proton signal at 2.2-2.4 ppm (CH unit of PAA) with that of -COOCH 2 signal of PnBA appearing at 3.9-4.1 ppm or the CH 3 unit of PnBA. Example 10: Preparation of PAA containing terpolymers by stepwise addition of monomers

a) Preparation of PAA-b/ra«-PMMA-b/ran-PnB A

[0084] Compound II (0.035g, 7.02x10 "5 mol), CuBr (0.005g, 3.48x10 "5 mol), AA (1.2 mL, 1.2612g, 0.0175 mol) and toluene (2 mL) were heated at HO'C for lh after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. White solid deposited at the end of this 2h period. MMA (1.9 mL, 1.7784g, 0.018 mol) and toluene (2 mL) were added via syringe into the reaction medium. It was heated at 1 10°C for 3h. nBA (2.6 mL, 2.3244g, 0.018 mol) and toluene (2 mL) were added via syringe into the reaction medium. The reaction mixture was heated for an additional 18h and cooled. The solid mass in the reaction flask was dissolved in THF (50 mL) and precipitated in 20% HCl (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 3.3g (61.12%). The polymer composition based on Ή-NMR analysis was PnB Ao.1 5 PAA 0 . 35 PMMAo. 5 . b) Preparation of PS-b/ran-?AA-b/ran-?nBA

[0085] Compound II (0.035g, 7.02x l 0 "5 mol), CuBr (0.005g, 3.48x l0 "5 mol), styrene (2 mL, 1.818g, 0.0175 mol) and toluene (2 mL) were heated at 1 10°C for 4h after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. AA (1.2 mL, , 1.2612g, 0.0175 mol) and toluene (2 mL) were added via syringe into the reaction medium. It was heated at 1 10°C for 2h. nBA (2.5 mL, 2.235g, 0.017 mol) and toluene (2 mL) were added via syringe into the reaction medium. The reaction mixture was heated for an additional 18h under nitrogen atmosphere and cooled. The solid mass in the reaction flask was dissolved in THF (50 mL) and precipitated in 20% HC1 (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 3g (56.08%)). The polymer composition - based on Ή-NMR analysis was S 0 3 7 5 PAAo.3 7 5PnBAo. 2 5.The composition of this polymer was estimated as described above for other copolymers.

Example 1 1 : Preparation of PAA containing terpolymers by mixed monomer approach - PS-rflK-PnBA-ran-PAA [0086] Compound II (0.035g, 7.02x 10 "5 mol), CuBr (0.005g, 3.48x 10 "5 mol), styrene (4 mL, 3.636g, 0.035 mol), nBA (4.9 mL, 4.3806g, 0.034 mol), AA (1.2 mL, 1.2612g, 0.0175 mol) and toluene (10 mL) were heated at 110°C for 22h after initially purging the reaction mixture with dry nitrogen gas for 30 minutes. The reaction mixture became highly viscous during this period. The viscous mass in the reaction flask was dissolved in THF (40 mL) and precipitated in 20% HC1 (v/v). The aqueous layer was decanted off and the residue was washed repeatedly with water and dried. The dried polymer was subsequently soaked in excess of chloroform and then dried. Yield: 3.2g (34.36%). The polymer composition based on 1H-NMR analysis was composition of this polymer was estimated as described above for other copolymers.

Example 12: Preparation of polyCmethacrylic acid-ran-stVrene)

[0087] Compound II (0.056g, 1.123 x 10"* mol) and CuBr (0.0003g, 2X 10 "6 mol) were weighed into a 50 mL two neck RB flask. Toluene (2 mL) was added with stirring under nitrogen atmosphere followed by styrene (lmL, 0.909g, 8.73 x lO "3 mol) and methacrylic acid (1 mL, 1.015g, 0.0118 mol). The flask was heated at 1 10°C for 16h. During this period a pale yellow solid film was deposited at the bottom of the flask. Yield: 1.6g (81%). 'H-NMR analysis of the solid in d 7 -DMF indicated the composition of polymer as PS 0 58 PMAA 0 .4 2 . This estimation was based on the comparison between the intensity of aromatic proton signals of PS appearing at 6.9-7.7 ppm and the -CH 3 signal of PMAA appearing at 0.4-1 ppm. Example 13: Preparation of polyfmethacrylic acid-ra«-n-butyl acrylate)

[0088] Compound II (0.0585g, 1.173x10^ mol) and CuBr (O.OOlg, x l O^ mol) weighed into a 50 mL two neck RB flask. Toluene (3 mL) was added with stirring under nitrogen atmosphere followed by nBA (2mL, 1.788g, 0.014 mol) and methacrylic acid (1 mL, 1.01 g, 0.0118 mol). The flask was heated at 110°C for 16h under nitrogen atmosphere. Solid deposited at the bottom of the flask. The solid was allowed to swell in THF and the swollen mass was transferred to a beaker and dried. The solid was then soaked in CHC1 3 and dried. Yield: 2g (70%). The polymer composition was estimated to Example 14: Preparation of poly(acrylic acid-ran-n-isopropyl acrylamide)

[0089] Compound II (0.0467g, 9.36x 10 "5 mol) and CuBr (0.0006g, 4.1 xlO "6 mol) were weighed into a 50 mL two neck RB flask. Toluene (2 mL) was added with stirring under nitrogen atmosphere followed by n-isopropyl acrylamide (1.65g, 0.0146 mol) and acrylic acid (1 mL, 1.051g, 0.0146 mol). The flask was heated at 110°C for 16h under nitrogen atmosphere. Solid deposited at the bottom of the flask. The solid was allowed to swell in THF and the swollen mass was transferred to a beaker and dried. The solid was then soaked in CHC1 3 and dried. Yield: 2.6g (94.62%). The polymer composition was estimated to be PNIPAAmo. 5 PAAo. 5 .

Example 15: Crossliriked poly(acrylic acid) using diethylene glycol dimethacrylate (DEGDMA) as crosslinker

[0090] Compound II (0.0268g, 5.37x l 0 ~5 mol), DEGDMA (0.0849g, 3.5x 10^ mol) and CuBr (0.0003g, 2X 10 "6 mol) were weighed into a 50 mL two neck RB flask. Toluene (2.5 mL) was added with stirring under nitrogen atmosphere followed by AA (2mL, 2.102g, 0.0292 mol). The flask was heated at 110°C for 16h under nitrogen atmosphere. Solid deposited at the bottom of the flask. The solid was allowed to swell in methanol and the swollen mass was transferred to a beaker after decanting off methanol. The swollen solid was washed repeatedly with methanol and dried. Yield: 2.02g (91.25%). The acid showed a swelling ratio of 110 in 0.9 wt% NaCl solution. The sodium salt of the cross- linked polymer showed a swelling ratio of 1031 in 0.9 wt% NaCl solution. The polymer also swells in sodium hydroxide solution.

[0091] Pyridine-2-carboxaldehyde (PyC) (0.02321 mol), Ν,Ν,Ν',Ν'- tetraethyldiethylenetriamine (TEDETA) (0.02321 mol) were heated with stirring at 80°C for lh. A pale yellow solution liquid was obtained. 2,4-Dimethylphenol (DMP) (0.02321 mol) followed by methanol (20mL) was added to the yellow liquid. The reaction mixture was refluxed for 24h. Methanol was removed under vacuum in a rotavapor and the residue was diluted with ethyl acetate. It was then washed repeatedly with deionized water. The ethyl acetate solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. Yield: 7g (71%). Accurate mass calcd. for C 26 H 42 N 4 0: 426.33586, observed mass: 427.34431 (M+H)+.

[0092] 0.005555 mol of the above product was dissolved in dry dichloromethane (DCM) (20mL). The solution was cooled in an ice bath. 4-N,N-dimethylaminopyridine (0.00555 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.00557 mol) diluted in dry DCM (lOmL) was added slowly to solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly with deionized water. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: 1.8g (56%). FT-IR analysis showed the presence of ester carbonyl (-C=00) at 1751cm "1 . Accurate mass: 575.29783 (M+H)+.

[0093] Ethanolamine (0.03284 mol) and PyC (0.033 mol) were refluxed for 6h in ethanol (40mL). Ethanol was then removed in a rotavapor and the product was dried thoroughly in a rotavapor. The residue was dissolved in DCM and washed with satd. brine solution. The DCM solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. Yield: 3g (61%). Accurate mass calcd. for C 8 H 10 N 2 O: 150.0797, observed mass: 151.0871 (M+H)+ and 173.0689 (M+Na)+.

[0094] 0.01332 mol of the above product was dissolved in dry dichloromethane (DCM) (30mL). The solution was cooled in an ice bath. 4-N,N-dimethylaminopyridine (0.01513 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.01457 mol) diluted in dry DCM (lOmL) was added slowly to solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly with satd. brine. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: 1.7367g (44%). Accurate mass calcd. for Ci 2 H 15 BrN 2 0 2 : 298.0317, observed mass: 299.0397 (M+H)+; 323.0200 (M+Na)+.

[0095] 2-Aminoethylpyridine (0.041 mol) and 4-hydroxybenzaldehyde (0.041 mol) were refluxed for 18h in ethanol (50mL). Ethanol was then removed in a rotavapor and the product was dried thoroughly in a rotavapor. The residue was treated with diethyl ether and dried in a rotavapor. Yield: 1.7802g (19%). Accurate mass calcd. for Ci 4 H 14 N 2 0: 226.1106, observed mass: 227.1183 (M+H)+ and 249.1002 (M+Na)+.

[0096] 0.0088 mol of the above product was dissolved in dry dichloromethane (DCM) (20mL). The solution was cooled in an ice bath. 4-N,N-dimethylaminopyridine (0.0085 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.0081 mol) was added to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly, with satd. brine. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: 1.6832g (51%). Accurate mass calcd. for C 18 H 19 BrN 2 0 2 : 374.063, observed mass: 375.0700 (M+H)+; 397.0523 (M+Na)+. Example 18: Preparation of (VP

[0097] Picolylchloride hydrochloride (0.03314 mol) was stirred vigorously in tetrahydrofuran (THF) (30mL). To this mixture was added triethylamine (0.1636 mol). Ethanolamine (0.0164 mol) diluted in THF (20mL) was then added dropwise and the mixture was refluxed for three days. Filtered to remove the precipitated salt and THF was removed in a rotavapor. The residue was treated with ethyl acetate and filtered. Ethyl acetate was washed with satd. brine and dried over anhydrous MgS0 4 and removed in a rotavapor. Yield: 1.04g (26%). Accurate mass calcd. for C 14 H 17 N 3 0: 243.138, observed mass: 244.1453 (M+H)+ and 266.1273 (M+Na)+.

[0098] 0.0041 mol of the above product was dissolved in dry dichloromethane (DCM) (20mL). The solution was cooled in an ice bath. Triethylamine (0.01291 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.004 mol) was added to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly with satd. brine. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: lg (63%). Accurate mass calcd. for Ci 8 H 22 BrN 3 0 2 : 391.08954, observed mass: 392.09857 (M+H)+; 414.08082 (M+Na)+.

[0099] Paraformaldehyde (PF) (0.0465 mol), diethylenetriamine (DETA) (0.04628 mol) were heated with stirring at 80°C for lh under N 2 atm. 2,4-Dimethylphenol (DMP) (0.04625 mol) was added and heated for a further 2h and 30 minutes followed by the addition of PyC (0.09257 mol). The reaction mixture was heated as a neat liquid at 80°C for 24h. The reaction mixture was dissolved in diethyl ether. It was then washed repeatedly with satd. brine solution. The diethyl ether solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. The residue was treated with 9:1 hexane:diethyl ether mixture and dried. Yield: 15.329g (58%). Accurate mass calcd. for C25H 29 N 5 0: 415.2372, observed mass: 416.2442 (M+H)+, 438.2263 (M+Na)+.

[00100] 0.02611 mol of the above product was dissolved in dry dichloromethane (DCM) (80mL). The solution was cooled in an ice bath. 4-N,N-dimethylaminopyridine (0.02651 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.0267 mol) diluted in dry DCM (20mL) was added slowly to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly with satd. brine. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: 8.6153g (59%). FT-IR analysis showed the presence of ester carbonyl (-C=00) at 1751cm "1 . Accurate mass calcd. for C 2 9H 34 BrN 5 0 2 : 563.1896, observed mass: 564.1964 (M+H)+, 588.1768 (M+Na)+.

Examp e 20: Preparat on o

[00101] PyC (0.0557 mol), diethylenetriamine (DETA) (0.01851 mol) were heated with stirring at 80°C for lh under N 2 atm. 2,4-Dimethylphenol (DMP) (0.01855 mol) was added followed by the addition of methanol (50mL). The reaction mixture was refluxed for 24h. Methanol was removed in a rotavapor. The residue was dissolved in DCM and washed repeatedly with satd. brine solution. The DCM solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. The residue was dissolved in a minimum of DCM, treated with excess of hexane and cooled in a refrigerator overnight. The solid settled was redissolved in DCM after decanting off hexane. DCM was removed in a rotavapor. Yield: 4.72g (52%). Accurate mass calcd. for C 30 H 32 N 6 O: 492.2621, observed mass: 493.2698 (M+H)+, 515.2515 (M+Na)+. [00102] 0.00609 mol of the above product was dissolved in dry dichloromethane (DCM) (40mL). The solution was cooled in an ice bath. 4-N,N-dimethylaminopyridine (0.00655 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.0065 mol) was added to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered and washed repeatedly with satd. brine. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. Yield: 1.7416g (45%). Accurate mass calcd. for C 34 H 37 BrN 6 0 2 : 640.2161, observed mass: 643.2199 (M+H)+.

Examp e 2 : reparat on o

[00103] PF (0.02343 mol), Ν,Ν,Ν',Ν'-tetraethyldiethylenetriamine (TEDETA) (0.02322 mol) were heated with stirring at 80°C for lh. 4-Hydroxybenzyl alcohol (0.02327 mol) followed by methanol (30mL) was added. The reaction mixture was refluxed for 24h. Methanol was removed under vacuum in a rotavapor and the residue was diluted with diethyl ether. It was then washed repeatedly with satd. brine solution. The diethyl ether solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. Yield: 2.2g (27%). Accurate mass calcd. for C 20 H 37 N 3 O 2 : 351.2886, observed mass: 352.2960 (M+H)+.

[00104] 0.00613 mol of the above product was dissolved in dry dichloromethane (DCM) (25mL). The solution was cooled in an ice bath. Potassium carbonate (0.0065 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.0065 mol) added to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. The residue was washed repeatedly with diethyl ether and dried. Yield: 1.5746g (52%). FT-IR analysis showed the presence of ester carbonyl (-C=00) at 1747cm "1 . Accurate mass calcd. for C 24 H 42 BrN 3 0 3 : 499.241, observed mass: 502.2438 (M+H)+. Example 22: Preparation of

[00105] PyC (0.0385 mol), 1 -(2-hydroxyethyl)piperazine (0.0389 mol) were heated with stirring at 80°C for lh. A highly viscous mass was obtained which was diluted with methanol (20mL). DMP (0.0384 mol) followed by methanol (20mL) was added. The reaction mixture was refluxed for 24h. Methanol was removed under vacuum in a rotavapor and the residue was diluted with diethyl ether. It was then washed repeatedly with satd. brine solution. The diethyl ether solution was subsequently dried over anhydrous MgS0 4 and removed in a rotavapor. Yield: 7.0455g (53%). Accurate mass calcd. for C 20 H 27 N 3 O 2 : 341.2103, observed mass: 342.2177 (M+H)+, 364.1996 (M+Na)+.

[00106] 0.008 mol of the above product was dissolved in dry dichloromethane

(DCM) (25mL). The solution was cooled in an ice bath. Potassium carbonate (0.008 mol) was added and the solution was stirred. 2-Bromoisobutyryl bromide (BiBB) (0.0081 mol) added to the solution and the reaction mixture was allowed to warm up to room temperature overnight. The reaction mixture was filtered. After drying the DCM solution over anhydrous MgS0 4 , the organic solvent was removed in a rotavapor. The residue was washed repeatedly with diethyl ether and dried. Yield: 1.5268g (39%). FT-IR analysis showed the presence of ester carbonyl (-C=00) at 1739cm "1 . Accurate mass calcd. for C 24 H 32 BrN 3 0 3 : 489. 1627, observed mass: 490.1691 (M+H)+.

Examples 23-59:

[00107] Polymerization results are given in the following tables:

Polymerization results using (III)

Example Monomer, Reaction Reaction M n M w PD mol (no. of temp., °C medium

moles of (CuBr, g) (Conversion

initiator) / yield)

23 Styrene, 80 Toluene, 23972 . 63290 2.64

0.01745 (0.0008g) 2mL (92%) a

Polymerization results using LI (IV)-(VII), (IX), (X)

Example LI (mol) Monomer Yield, % M n M w PD

(mol)

30 a IV Styrene 1 8 4140 10904 2.63

(0.000152) (0.01745) 31 b V (9.72x10V MMA 20 2429 3060 1.25 5) (0.0187)

32 c VI(0.000114) Styrene 26 4876 5903 1.21

(0.01745)

33 d VI (8.8 l0 "5 ) MMA 63 15339 19854 1.29

(0.0187)

34 e VII MMA 98 33414 44673 1.33

(0.0001339) (0-028)

35 1 VII Styrene 92 39906 63097 1.58

(0.0001342) (0.0262)

36 g VII nBA >99% 34822 56942 1.63

(0.00015) (0.021)

37 h IX (0.00014) Styrene 20 39356 70174 1.78

(0.0262)

38' X (0.00013) MMA 10 31818 60554 1.90

(0.028)

10°C, 18h, 0.0007g of CuBr, Toluene 2 mL; b -l 10°C, 18h, 0.0006g of CuBr, Toluene 2 mL; c -l 10°C, 22h, <1/10 Λ of a mg of CuBr, Toluene 2 mL; d - 110°C, 22h, <1/10 Λ of a mg of CuBr, Toluene 2 mL; e -110°C, 22h, 0.0009g of CuBr, Toluene 3 mL; f -110°C, 18h, 0.0002g of CuBr, Toluene 3 mL; 8 -l 10°C, 18h, <l/10 th of a mg of CuBr, Toluene 3 mL; h - 110°C, 18h, 0.0002g of CuBr, Toluene 3 mL;

Combining ATRP and ring opening polymerization using (IX) and (X)

Example LI (mol) Monomer Yield, % M n M w PD

(mol)

39 a . IX (1 x10 " Styrene 51 10434 20355 1.95

4) (0.262) and

e- caprolactone

(0.262)

40 b IX (8x10 " Styrene 13 30661 57704 1.88

5) (0.0087) and L- lactide

(0.0088)

41 c X (9xl 0 "5 ) Styrene 74 13620 24235 1.78

(0.017) and

e- capro lactone

(0.017)

42 d X (9xl0 "5 ) Styrene 3 24179 41147 1.70

(0.017) and

L-lactide

(0.014)

-Step 1-LI, CuBr (< 1/10 of a mg) and Sty at 110°C for 11/2 hr under N 2 atm. Step 2-ECL and tin octoate (0.0424g) diluted with toluene (3 mL); 110°C for 24h; b -l 10°C for 22h, tin octoate (0.0161g), toluene (2 mL); c - 1 10°C for 22h, tin octoate (0.0221g), toluene (2 mL); d - 1 10°C for 22h, tin octoate (0.0253g), toluene (2 mL).

Polymerization results using (VIII)

Example LI (mol) Monomer Yield, % M n M w PD

(mol)

43 a 8.27x10 "5 Styrene 41 17550 30031 1.71

(0.01746)

44 b 7.71 x lO "5 MMA 71 22149 26801 1.21

(0.0187)

. 45 c 8.49x10 "5 nBA 97 38995 68037 1.74

(0.0279) (conversion

by Ή- NMR)

46 d 8.88x l0 "5 Styrene 59 6547 9345 1.42

(0.00873);

AA

(0.0146) 47 e 3.94x 10 s nBA 45 77600 1 16093 1.49

(0.042)

48* 3.89x l 0 "i nBA >95% 109197 201989 1.85

(0.042);

HEA

(8.88x 10^)

49* 4.17X 10 "5 nBA 97% 121251 210687 1.74

(0.042);

HEA

(9.16xl 0 )

50 g 3.94x 10 "5 nBA 93% 195789 256228 1.30

(0.042);

HEA

(1.58x 10 "

4 ); LL

(0.016)

a-90°C, 18h, <l/10 th of a mg of CuBr, Toluene 2 mL; b -80°C, 22h, <l/10 th of a mg of CuBr, Toluene 2 mL; C -90°C, 18h, <1/10 Λ of a mg of CuBr, Toluene 4 mL; d -l 10°C, 18h, <l/10 th of a mg of CuBr, Toluene 2 mL; e -100°C, 20h, 0.0002g of CuBr, Toluene 3 mL; f -110°C, 20h, <1/10 of a mg of CuBr, neat, HEA-hydroxyethyl acrylate; g -Step 1-nBA and HEA, 110°C, 20h, <1/10 of a mg of CuBr, neat, Step 2-Toluene 23 mL, LL, tin octoate (0.03g), 24h. ;

Polymerization results in surfactant solution (SS) using (III)

Example 3 LI (mol) Monomer Yield, % M n M w PD

(SS, mL) (mol)

51 5.28X 10 "5 MMA 97 40489 162624 4.02

( 8 ) (0.0187)

52 5.18x l0 "5 MMA 95 1 1 1793 362750 3.24

(20) (0.0187)

53 7.12x l0 "5 MMA 98 170464 371376 2.18

(10) (0.0187); nBA

(0.01395)

54 7.63x 10 "5 . MMA 92 88291 284031 3.21

(10) (0.0187);

nBA

(0.007);

AA

(0.0146)

55 8.87x l0 "5 MMA 90 101271 c 300948 2.97

(10mL) b (0.0187);

nBA

(0.007);

AA

(0.0146)

56 8.22x 10 "5 MMA 92 ND e ND ND

(lOmL of (0.0187);

SS) d nBA

(0.007);

AA

(0.0146

a-at 70°C for 18h; <l/10 th of a mg of CuBr; b -0.5858g of NaOH in lOmL of water, c -after treatment with 20 vol% HC1 solution; d -0.5745g of NaOH dissolved in lOmL of SS; ND- not determined; atex like sticky mass. Polymerization of MMA using (VII)

Example LI (mol) Monomer Yield, % M n M w PD

(Solvent, (mol)

mL)

57 a 0.001 0.0467 85 20702 34449 1.66

(Toluene,

3mL)

58 b 9.28 x lO "5 0.0187 85 31909 43925 1.37 (Toluene,

2mL) '

59 b 9.44x 10 "4 . 0.028 83 19639 29558 1.51

(Toluene,

3mL)

a 1 1 n"ri 1 ^1 /I ntl .,r>_. ' b η °ρ £ 1 O ΙΛ n th c

Example 60: Preparation of difunctional unit at one terminus of polymer chain

[00108] The difunctional unit represented in the form of diamine and the subsequent the scheme below:

DAPMMA

A shift in the position of molecular weight was observed as shown by the GPC analysis given below. The shift in the position of chromatogram to higher molecular weight region is on account of the increased size and rigidity of the polymer after imidization. The increase in RI response is due to the presence of more aromatic units after the reaction. Example 61 : Dispersion ' of inorganic compounds

[00109] Zn(OAc) 2 (0.2096g) was dissolved in deionized water (20mL). NaOH (1.6506g) was dissolved in deionized water (lOOmL). Copolymers of AA and MAA (approx. O. lOOg) were dissolved in aqueous NaOH solution (lOmL). To this solution (5mL) was added Zn(OAc) 2 solution (ImL). After allowing mixing under ambient conditions overnight, the aqueous solution was then cast on a glass plate and allowed to evaporate under ambient conditions. The film thus obtained was then viewed under scanning electron microscope (SEM). Depending on the copolymer, needle shaped structures to sheet like structures were obtained as shown below:

Example 62: Comparative polymerization studies

[00110] Table 1 provides comparison of the residual metal salts in the polymer by normal reported ATRP process with the ATRP carried out using UMLIDFS.

Table 1. Comparison of residual metal in the polymers prepared by normal ATRP and the ATRP carried out using UMLIDFS (use of compound (II))

of polymer obtained) x 100; MMA - methyl methacrylate; JACS - Journal of the American Chemical Society; Macromol. - Macromolecules.

[00111] FIG. 4 shows the homopolymers formed using the UMLIDFS are not colored, unlike products obtained from typical ATRP processes, indicating the low concentration of metal impurities present in the polymers formed. The copolymers of acrylic acid (AA) as well as methacrylic acid (MAA) were prepared and the appearance of the copolymers is illustrated in FIGs. 5-7- Samples shown in FIG. 7 are as prepared and collected from the reaction flask at the end of polymerization. Aqueous solutions of polymers were prepared by dissolving lOOmg of polymer in 5 mL of alkali solution, prepared by dissolving 0.08g of NaOH (one pellet) in 5 mL of water IV. These prepared solutions are illustrated in FIG. 8.

Example 63: Composition and other characteristics of specific copolymers

[00112] Table 2 shows the characteristics of copolymers of carboxylic acid bearing vinyl monomers like AA and MAA. Many vinyl monomers could be employed as comonomers to make a variety of copolymers including terpolymers. All of these acid containing copolymers are soluble in weakly basic solutions to yield aqueous solutions without any aid of volatile or non-volatile organic solvents. It is possible to obtain thin films from these aqueous solutions. It is also possible to make carboxylic acid containing cross-linked polymers. The cross-linked poly(acrylic acid) upon neutralization shows swelling tendency in 0.9 wt% NaCl solution, a prerequisite for superabsorbent polymer. These results may be viewed by keeping in mind that it is not possible to directly polymerize vinyl monomers bearing labile protons under ATRP conditions at present.

Table 2. Composition and other characteristics of copolymers of acrylic and methacrylic acids with other vinyl monomers

AA - acrylic acid; nBA - n-butyl acrylate; MAA - methacrylic acid; MMA methyl methacrylate; NIPAAm - n-isopropyl acrylamide; Sty - styrene; numbers in indicate the sequence of addition of monomers. [00113] FIG. 9 illustrates the cross-linked alkali salt of PAA swollen in 0.9 wt % NaCl solution (Swelling ratio = 1031), as well as the cross-linked PAA swollen in NaOH solution. The film shown in FIG. 10 was obtained by casting the 2 wt% aqueous alkali solution on a plate glass and allowing the water to evaporate under ambient conditions.

[00114] The invention illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising", "including", containing", etc. shall be read expansively and without limitation. Use of the term "comprising", "including" or containing" indicates that the listed element(s) is/are required or mandatory, but that other elements are optional and may or may not be present. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by exemplary embodiments and optional features, modification and variation of the inventions embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention.

[00115] The invention has been described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

[00116] Other embodiments are within the following claims. In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.