GB2339202A - Hyperbranched hybrid block copolymers - Google Patents

Description

2339202 NOVEL HYBRID BLOCK COPOLYMERS

Field of Invention

The invention pertains to novel hybrid block copolymers obtained using pre-formed and purified hyperbranched polymers or copolymers as macro initiators.

Backaround of Invention

Linear and star shaped block copolymers constitute very important classes of polymeric materials and are widely used in a variety of applications. For instance, a block copolymer comprised of a central elastomer block and two outer plastic ones may behave as a thermoplastic elastomer. Linear and radial styrene-b butadiene-b-styrene block copolymers commercialized by Shell under the trade name Kraton TM and Phillips as Solprene T11, respectively, are examples of synthetic thermoplastic elastomers. Also, if a block copolymer is comprised of hydrophilic and hydrophobic segments, it can be used as emulsifier, surfactant, and dispersant.

Indeed, a block copolymer composed of hydrophilic and hydrophobic segments was found effective as a paint dispersant and was marketed under the trade name DispersymerTm by ICI. Block copolymers have also been widely used in various imaging applications such as in the formulation of inks ( Ma, S-H., et al, US patent 5,085,698 (1992)) and toners (Georges, M.K. et al, US patent 5,549, 998 (1996)). Other selected examples of the applications of block copolymers include charge mosaic membranes, adhesives, and polymer blend components.

Efforts have also been recently devoted to exploring novel polymeric materials based on dendritic and hyperbranched macromolecules. Tomalia et al., e.g., (US patent 4,507,466 (1985); US patent 4,558,120 (1985)) disclose that a variety of amines can be added to methyl acrylate and the products subsequently amidated with cc,co-diaminoalkanes to give well controlled starburst dendrimers or "cascade products". There has been much subsequent interest in the synthesis of dendrimers (Newkome, et al J Org. Chem. 50, 2003 (1985); Hawker, et al.

Macromolecules 23, 4726 (1990); Jansen, et al. Science, 266, 1226 (1994)), and such dendrimers have found use in a number of applications including, solubilization, catalysis, biological recognition, redox assemblies, and irreversible molecular encapsulation. Since these regularly branched deridnimers are prepared through lengthy multistep syntheses processes, their availability has been limited to polymers prepared from a small group of monomers. Hyperbranched polymers made by condensation reactions have also been suggested (Kim, et al., J. Am.

Chem. Soc. 112, 4592 (1990); Hawker et al., ibid. 113, 4583 (1991)). Again, such condensation polymers are limited in terms of composition by the synthesis process.

The synthesis of hyperbranched polymer via living, chain polymerization process of vinyl monomers has also been recently disclosed. Synthesis of hyperbranched homopolymer via living chain polymerization process of vinyl monomers is disclosed by Frechet et al (Frechet, et al. Science, 269, 1080 (1995), US patent 5,587,441, and US patent 5,587,446, the disclosures of which are incorporated by reference herein in their entireties). In the synthesis of hyperbranched polymer via living chain polymerization process of vinyl monomers, an "AB" type monomer is used as described in the above cited Frechet et al. references. The AB vinyl monomer is a polymerizable initiator molecule, which contains a second reactive group B in addition to a reactive vinyl group A, which group B is activated by an external event to produce an activated polymerizable initiator molecule A13. Not all AB molecules need to be activated to AB during the polymerization process, since both activated groups A and B can add to any available A group, and any B group that remains inactivated may become activated later as a consequence of an exchange process. Since AB monomer is fully responsible for a hyperbranching macromolecule, we refer to it as a hyperbranching monomer or branching monomer. For example, the hyperbranched polystyrene derivative can be made through living, cationic polymerization of 3-(I-chloroethyl)-ethenylbenzene in the presence of certain catalysts. Specific details as to hyperbranching AB type monomers are set forth in the above referenced documents, the disclosures of which are incorporated by reference herein in their entireties.

Based on alternative approaches, hyperbranched polymers have also been obtained by radical polymerization processes. Hyperbranched polystyrene and poly methacrylate derivatives, e.g., were obtained by stable radical polymerization (Hawker, et al. J. Am. Chem. Soc. 113, 4583, (1991)) and group transfer polymerization (Simon, et al Polym. Prep. (ACS, Polym. Chem. Div.) 38(l) 498 (1997)), respectively. Using atom transfer radical polymerization (ATRP), Gaynor, et al synthesized hyperbranched poly(chloromethyl. styrene) (PCS) and hyperbranched poly acrylate (Gaynor, et al Polym. Prep. 38 (1), 496 (1997)).

ATR-P is a recently developed living / controlled radical polymerization process (Wang, et al. J. Am. Chem. Soc., 117, 5614 (1995)).

Hyperbranched random copolymers can also be made by similar processes, using branching monomer(s) and other branching monomer(s) or nonbranchins, monomer(s). Frechet et al. US patent 5,663,260, e.g., discloses a hyperbranched copolymer comprising branching AB monomer and non-branching C monomer.

I -D ATRP of chl.oromethyl styrene and styrene has yielded a hyperbranched poly (CS co-styrene) random copolymer (Gaynor, et al Macromolecules, 29, 1079 (1996)).

Frechet et al. U.S. Patent 5,635,571 discloses A,,,CB type of branching macromonomers with A and B being functional groups and C being a segment with possible pending oligomeric ethylene oxide side chain. The polymerization, lo i.e., condensation reaction between n numbers of A group and B group, yielded a hyperbranched polymer with pending oligomeric ethylene oxide side chain, Synthesis of hybrid dendritic / linear block copolymers has also been recently developed. Using the single focal point reactive group of a convergent dendron as a macroinitiator, e.g., hybrid linear-dendritic block copolymers were made through subsequent living radical polymerization with second monomer (Frechet, Polym. Prep. (ACS, Polym. Chem. Div.), 38(l), 756, 1997). Using a divergent methodology, Chapman et al. have prepared "hydraamphiphile" copolymers where a hydrophobic dendron is attached to a hydrophilic poly (ethylene oxide) chain (Chapman, T.M. et al. J. Am. Chem. Soc. 116, 11195 (1994)). A similar approach was used by Van Hest et al. to grow surface suitably end-functionalized low molecular weight linear polystyrenes prepared by anionic means (Chem. Eur. J. 2, 1616 (1996)). These reported hybrid block copolymers, however, contain only one block linear chain per one hybrid macromolecule.

Synthesis of star-like polymers with hyperbranched cores is mentioned by Frechet et al. in US patent 5,587,441. As disclosed therein, sequential addition of more monomers to living hyperbranched polymers may yield larger hyperbranched structures or star-like polymer with hyperbranched cores. Such a subsequent chain extension, however, only applies to monomers that can be polymerized with the same polymerization mechanism and/or the same catalyst system as the one used in preparation of the living hyperbranched polymer core segment. Moreover, residual branching monomer often contaminates the final living hyperbranched polymers and a subsequent chain extension may result in uncontrolled branched polymerization.

None of the prior art reports using pre-formed and purified hyperbranched polymers as macro-initiators to initiate the polymerization of other monomers, and none of the prior art discloses hyperbranched / multi-linear hybrid copolymers, or hyperbranched / multi-graft hybrid copolymers, obtained from a pre-formed and purified hyperbranched polymer macro-initiator.

Summary of the Invention

In accordance with one embodiment of the invention, a process for the preparation of a hybrid block copolymer is disclosed comprising: preparing a purified macro-initiator comprising a hyperbranched polymer segment with multiple functionalized end group initiating sites; and using the purified macro initiator to copolymerize a solution of monomers or macromonomers to form a hybri"d hyperbranched block copolymer.

In accordance with specific embodiments of the invention, it has have discovered that using a pre-formed and purified hyperbranched polymer or copolymer with multi-focal point reactive groups, which is made through a living polymerization of branching monomers or branching monomers with other monomers including macromonomers, as a macro-initiator for subsequent polymerization with monomer or monomers including macromonomer(s) yields hybrid hyperbranched block copolymers comprising a hyperbranched polymer segment and multiple pendant linear or graft polymer units.

The hyperbranched segment may comprise any kind of polymer segment with hyperbranched architecture, and the functionalized end groups may comprise any kind of conventional polymerization initiating site. The macroinitiator may be used to polymerize any kind of monomers or macromonomers to form pendant block polymer segments with linear or grafting / comb architectures. The resultant hybrid polymers may be converted to other polymers by post modifications for specific applications. Also, some functional groups may be introduced into the chain backbone or the ends of the chain.

The hybrid hyperbranched block copolymers obtained in accordance with the invention are particularly advantageous in that they enable polymer structures comprising components exhibiting different properties (e.g., hydrophilic and hydrophobic segments) while maintaining relatively low intrinsic viscosities compared to non-hyperbranched linear block and graft copolymers of similar chemical compositions.

Brief description of preferred embodiments

This invention involves two steps. The first step is to produce a multi end functional hyperbranched polymer or copolymer by means of known living or controlled polymerization methods. The second one is to use such a preformed and purified multi end-functional hyperbranched polymer or copolymer as a macro-initiator to copolymerize monomer or monomers or macromonomer or macromonomers via certain polymerization process to produce hybrid hyperbranched block copolymers.

Macro-initiators employed in accordance with the invention comprise a hyperbranched polymer segment with multiple functionalized end groups. The hyperbranched segment may comprise any kind of polymer segment with hyperbranched architecture. Examples of hyperbranched architectures include but are not limited to: hyperbranched homopolymer, hyperbranched random copolymer, and hyperbranched-graft copolymer, such as disclosed in USSN 09/105,765 and its corresponding UK patent application.

A wide variety of known polymerization methods can be used to produce the hyperbranched architecture of the macro-initiators used in accordance with the invention. In accordance with preferred embodiments, the hyperbranched segment of the macro-initiators are obtained through a living / controlled polymerization of one or several special monomer(s), which are referred to as branching monomer, with or without additional non- branching monomers or macromonomer. Possible polymerization techniques include but are not limited to: stable radical polymerization, atom transfer radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, group transfer polymerization, ring opening polymerization, and condensation polymerization. In accordance with preferred embodiments, the hyperbranched segments are obtained through a radical polymerization process, such as stable radical polymerization and atom transfer radical polymerization (ATRP).

In accordance with particularly preferred embodiments of the invention, hyperbranched macro-initiator segments are obtained based on an ATRP process such as disclosed in World Patent Application Publication WO 96/30421, the disclosure of which is incorporated by reference herein in its entirety. In such

ATRP process, one or more radically polymerizable monomers are polymerized in the presence of an initiator having a radically transferable atom or group, a transition metal compound and a ligand to form a (co)polymer, the transition metal compound having a formula M,"X',, and the ligand being any N-, 0- P-, or S- containing compound which can coordinate in a a-bond or any carbon- containing compound which can coordinate in a 7r-bond to the transition metal, such that direct (i.e., covalent) bonds between the transition metal and growing 1 0 polymer radicals are not formed. Such process provides a high degree of control over the polymerization process, and allows for the formation of various polymers and copolymers with more uniform properties.

A wide variety of polymerizable branching monomers which can undergo chain polymerization for use in accordance with the invention are available commercially, or such monomers may be synthesized through conventional reactions. These branching monomers generally comprise a chain polymerizable group, such as a vinyl group, and a separate reactive site which can be activated thermally or in the presence of polymerization catalysts with the formation of initiating species, or branching species. Polymerizable branching monomers may be selected, e.g., from: styrenes; conjugated dienes; acrylates; amine, carboxyl, aldehyde, alkyl, cyano and hydroxyl substituted acrylic acids and acrylic acid esters; acrylamides; methacrylamides; acrylic acids; methacrylic acids; acroleins; dimethaminoethylacrylates; dimethaminoethyl methacrylates; maleic acids; and maleic anhydrides compounds, where such compounds also comprise a substituent providing a separate reactive site. The separate reactive site for the branching monomers may be provided by a substituent comprising a halogen atom (e.g., Cl, Br, or 1, preferably CI or Br) in atom transfer radical polymerization and living cationic polymerization, TENTO (2,2,6,6-tetramethyl- I -piperidinyloxy, free radical) and its derivatives in stable radical polymerization, and S and Se containing groups in atom transfer radical polymerization and related processes, substituted silicon in group transfer polymerization, metal atoms in living amonic polymerization, and tert-alkyl ammonium in metal- free anionic polymerization. The branching monomer itself may additionally comprise an oligomeric or polymeric unit containing repeating groups (e.g., about 5 to 100 repeating groups), which can be a homopolymer or random copolymer or block copolymer unit or other types of polymeric unit including dendritic and branched polymeric units.

Specific examples of polymerizable branching, monomers which may be used in accordance with the invention include but are not limited to: m-vinyl benzylchloride, p-vinyl benzylchloride, m/p-vinyl benzylchloride, trichloroethyl acrylate, trichloroethyl methacrylate, a-chloroacrynitn'le, a-chloroacrylate, achloroacrylic acid, a-bromomaleic anhydride, achloromaleic anhydride, 2-(2chloropropionyloxy)ethyl acrylate, 2-(2bromopropionyloxy)ethyl acrylate, 2-(2chloropropionyloxy)ethyl methacrylate, and 2-(2-bromopropionyloxy)ethyl methacrylate.

Macro-initiators used to produce hybrid block copolymers in accordance with the invention comprise at least 2 functionalized end group initiating sites for block polymerization, preferably from 2 to 500,000 and more preferably from 10 to 1,000 functionalized end group initiating sites for block polymerization. The multiple functionalized end groups of the macro-initiators used in accordance with the invention may comprise any kind of conventional polymerization initiating site. Most conveniently, such initiatin- site may be provided by the separate reactive site of the branching monomer(s) used in preparing the hyperbranched segment of the macro-initiator. In such instance, the hyperbranched polymers that are used as macro-initiators can be obtained by a one-pot polymerization process. Alternatively, the macro-initiators may be obtained by reacting pre-formed living, hyperbranched polymers with additional compounds to introduce other types of conventional initiating sites at the ends of the formed hyperbranched polymers.

The macro-initiators used in accordance with the invention are isolated and purified after their formation and prior to formation of the hybrid block copolymer. Purified macro-initiators used in accordance with the invention contain less than I wt% of residual monomer based upon the weight of the formed hyperbranched macro-initiator, preferably less than 0. 1 wt% and more preferably less than 0.01 wt%. Such purification levels may be achieved by combinations of conventional polymer purification techniques, such as precipitation, filtration, solvent extraction, and dialysis. They often can be stored for extended periods of time after formation and purification and be re- used; however, a loss in activity of some initiating sites during the storage may occur.

The macro-initiator may be used to polymerize any kind of monomers or macromonomers to form pendant block polymer segments with linear or graftim, comb architectures. A wide variety of known polymerization methods can be used to produce the hybrid copolymers. Such methods include, but are not limited to: radical polymerization, telomerization, atom transfer radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, group transfer polymerization, ring opening polymerization, and condensation polymerization. Any polymerization technology can be used to prepare hybrid block copolymers. Examples include but are not limited to: solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, and polymerization in C02.

A wide variety of monomer and macromonomers for synthesizing hybrid block copolymers in accordance with the invention are available commercially or can be synthesized by well-known organic reactions. These monomers and macromonomers can comprise any polymerizable groups which can be initiated by the functionalized end group initiating sites of the macro-initiator to undergo polymerization. Examples of polymerizable groups include but not limited to vinyls in anionic, cationic, radical, and group transfer polymerizations; and clyclics in ring, opening polymerizations.

In accordance with one specific embodiment, a solution of conventional relatively small monomers (e.g., non-macromonomers) may be copolymerized with a purified macro-initiator to form a hybrid hyperbranched multilinear block copolymer. Useful monomers include but not limited to: styrenes (including, e.C' styrene sulfonic acid), dienes, acrylics, methacrylics, acrylamides, methacrylamides, olefins, cyclic ethers, oxazolines, vinyl acetate, vinyl chloride, vinyl ethers, F-containing monomers, and Si-containing monomers.

In accordance with a second embodiment, a solution of macromonomers may be copolymerized with a purified macro-initiator to form a hybrid hyperbranched multi-graft block copolymer. Useful macromonomers include compounds comprising a polymerizable group as mentioned above and a oligomeric or polymeric unit containing at least two repeating groups (preferably about 5 to 100 repeating groups), which can be a homopolymer or random copolymer or block copolymer or other types of polymer including dendritic and branched polymer. Examples of oligomeric or polymeric units which may be included in macromonomers include but not are limited to: polystyrenes, polyolefines, polydienes, polymethacylates, polyacrylates, polyvinyl ethers, polysiloxanes, polylactones, polylactames, poly oxazolines, polyvinyl acetate, Fcontaining polymers, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polypeptide, polyurethane, poly(phenylene oxide)s, poly(ether sulfones), polyesters, polycarbonate, polyetherketone, poly THF, and polyvinyl acetate. The methods to make macromonomers involve initiating methods, end-capping methods, chain transfer methods, and post-modification methods.

Specific examples of macromonomers which may be used in the formation of hybrid hyperbranched multi-graft block copolymers in accordance with the invention include: (poly(dimethylsiloxane)) monomethacrylate; (poly(ethylene glycol)) monomethacrylate; (poly(ethylene glycol)) monoethylether monomethacrylate; (poly(propylene glycol)) monomethacrylate; (poly(propylene glycol)) monoacrylate; (poly(ethylene glycol)) monoacrylate; (poly(ethylene glycol)) styrene; (poly(dimethylsiloxane)) styrene; (poly(dimethylsiloxane) acrylate); (poly(styrene)) methacrylate; (poly(styrene)) vinyl acetate; (poly(methyl methacrylate)) styrene; (poly (methyl methacrylate)) methacrylate; (poly(vinyl 5 acetate)) styrene; (poly(vinyl acetate)) methacrylate; (poly(isobutylene)) methacrylate; (poly(tetrahydrofuran)) methacrylate; (poly(tetrahydrofuran)) acrylate; and (poly(amide)) styrene. In general, macromonomers for use in accordance with the invention will have molecular weights of at least about 150 and more preferably at least about 300.

The materials made in the present invention may be useful in the formulation of inks, toners, cosmetics, surfactants, dispersants, surface modifiers, rheology modifiers, mechanical property modifiers, polymer blend components, additives for coating and plastics, paints, lubricants, foams, adhesives, complexing and chelating agents, catalysts, components of medical imaging systems, carriers for gene transfection, resist or imaging materials, membrane materials for separation, hydrogels and contact lenses materials or components, cross- linidng agents, molding materials, electrostatic carriers, solid electrodes, water- and oilrepellents, antistatic agents, light harvesting materials, environment sensitive (e.g., temperature, pH, concentration, ionic strength, etc.) smart materials, binders, controlled release agents and additives for drugs or biological applications, photographic useful materials and components, emulsifiers, elastomers, plastics, thermoplastic elastomers, and others.

The following examples are illustrative of synthesis of novel hybrid block copolymers.

Example 1. Preparation of hyperbranched poly (p-chlorinemethyl styrene) macro-initiator. Commercial p-chlorinemethyl styrene (50 g), CuCl (0.715 g), and 2,2' dipyridyl (1.56 g), diphenyl ether (50 ml), all from Aldrich, were mixed in a reaction flask. The mixture was purged with dry nitrogen gas for about 15 minutes and then heated at 120 to 130'C for 19.5 hours. The resulting solid was first dissolved in THF and then precipitated in cool methanol / water (50150 v/v) mixture. Such precipitation process was repeated twice. The hyperbranched polymer was recovered by filtering through a glass filter and residual unreacted monomer was then extracted by methonol over 48 hours. The resulting purified polymer was then dnied under vacuum at 60 C for 18 hours with 88% yield.

Analysis of polymer by GPC gave weight average molecular weight (Mn) of 9000, and molecular weight distribution (the ratio of weight average molecular weight to number average molecular weight, Mw/Mn) of 6.4. 'H NMR analysis indicated that there was no unreacted p-chlorinemethyl styrene in the final 5 polymer.

Example 2. Preparation of hybrid hyperbranched poly (p-chlorinemethyl styrene) -b-linear poly (2-methyl 2-oxazoline)n block copolymer. In a glovedry box, the polymer prepared in example I (10 g), 2-methyl 2oxazoline (50 g), sodium iodide (10 g), and anhydrous dimethylformamia (200 ml), all from Aldrich, were charged to a reaction vessel equipped with a magnetic stirring bar and a stopper. The solution was then heated at 80'C for 42 hours. The resulting hyperbranched multi-linear-block copolymer was recovered from precipitation from ether with 100% yield. The final polymer is water soluble. The number average molecular weight (Mn) was calculated based on 'H NMR and Mn of hyperbranched poly (p-chlorinemethyl styrene), with being 8400. Molecular weight distribution (Mw / Mn) of block copolymer from GPC in DMF is 3.0.

Example 3. Preparation of hybrid hyperbranched poly (p-chlorinemethyl styrene) -b-linear poly (methyl acrylate)n block copolymer. The polymer prepared in example 1 (10 g), methyl acrylate (30 g), CuCl (2.6 g), 2,2'dipyridyl (4.0 g), and toluene (20 g), all from Aldrich, were charged to a reaction vessel equipped with a magnetic stirring bar and a condensor. The solution was then heated at 1 10'C for I hour. The resulting hyperbranched multi-linear-block copolymer was recovered from precipitation from methanol. The number average molecular weight (Mn) and number average molecular weight (Mn) were 8700 and 36000 from GPC measurement, respectively. The methyl acrylate content in copolymer is 65 mol% based on'H NMR analysis.

Example 4. Preparation of hybrid hyperbranched poly (p-chlorinemethyl styrene) -b-linear poly (acrylic acid)n block copolymer. The hyperbranched multi-linear-block copolymer prepared in example 3 (9 50% NaOH (10.4 a and 40 ml deionized water were added to a round bottom flask equipped with a magnetic stirring bar and a condensor. The solution was then refluxed for 64 hours. The heterogeneous solution slowly became homogeneous during the heatln<),. The resulting water soluble block copolymer was recovered by means of ID filtration. It was then dialysized and freeze-dried. The yield is ca. 85%. The hydrolysis degree of methyl acrylate in copolymer is greater than 98% based on 'H NMR analysis in D,O.

Example 5. Preparation of hybrid hyperbranched (p-chlorinemethyl styrene)b- (comb poly(ethylene glycol) ethyl ether monomethacrylate)n block copolymer. Commercial (poly(ethylene glycol)) ethyl ether monomethacrylate from Polyscience Inc. (8 g), CuCl (0.715 g, Aldrich), and 2,2' dipyridyl (1.56 g, Aldrich), and 2 g of hyperbranched (pchlorinemethyl styrene) prepared in example 1, were mixed in a reaction flask. The mixture was purged with dry nitrogen gas for about 15 minutes and then heated at 90 to 110 ' C for 5 hours and 25 minutes. The resulting hyperbranched multi- graft block copolymer was first dissolved in TBF and then precipitated in heptane. The copolymer was recovered by filtering through a glass filter and dried under vacuum at 60 C for 18 hrs with 83% yield. Analysis of the copolymer by GPC gave weight average molecular weight (Mw) of 77600, and molecular weight distribution (Mw/Mn) of :D 7.1.

Claims (25)

WHAT IS CLAIMED IS:

1. A process for the preparation of a hybrid block copolymer comprising: preparing a purified macro-initiator comprising a hyperbranched polymer segment with multiple functionalized end group initiating sites; and using the purified macro-initiator to copolymerize a solution of monomers or macromonomers to form a hybrid hyperbranched block copolymer,

2. The process of claim 1, wherein the purified macro-initiator is formed lo by reacting hyperbranching monomers to form a hyperbranched polymer and removing residual unreacted monomer.

3. The process of claim 2, wherein the purified macro-initiator is formed by reacting hyperbranching monomers and non-branching monomers or macromonomers to form a hyperbranched copolymer and removing residual unreacted monomers.

4. The process of claim 2 or 3, wherein the branching monomer comprises a styrene; conjugated diene; acrylate; amine, carboxyl, aldehyde, alkyl, cyano or hydroxyl substituted acrylic acid or acrylic acid ester; acrylamide; methacrylamide; acrylic acid; methacrylic acid; acrolein; dimethaminoethylacrylate; dimethamino ethyl methacrylate; maleic acid; or maleic anhydride compound which also comprises a substituent providing a separate reactive site.

5. The process of claim 4, wherein the separate reactive site is provided by a substituent comprising a halogen atom and the branching monomer is polymerized by atom transfer radical polymerization.

6. The process of claim 2 or 3, wherein the branching monomer comprises m-vinyl benzylchloride, p-vinyl benzylchloride, m/p-vinyl benzy1chloride, trichloroethyl acrylate, trichloroethyl methacrylate, a-chloroacrynitn'le, a chloroacrylate, a-chloroacrytic acid, a-bromomaleic anhydride, achloromaleic anhydride, 2-(2-chloropropionyloxy) ethyl acrylate, 2-(2bromopropionyloxy)ethyl acrylate, 2-(2-chloropropionyloxy)ethyl methacrylate, or 2-(2 bromoproplonyloxy)ethyl methacrylate.

7. The process of any one of claims 1-6, wherein the macro-initiator used to produce the block copolymer comprises from 2 to 500,000 functionalized end group initiating sites for block polymerization.

8. The process of any one of claims 1-6, wherein the macro-initiator used to produce the block copolymer comprises from 10 to 1,000 functionalized end group initiating sites for block polymerization.

9. The process of any one of claims 1-8, wherein the initiating sites are Z formed in situ during formation of the hyperbranched polymer segment architecture.

10. The process of any one of claims 1-8, wherein the initiating sites are formed by post-modification after formation of the hyperbranched polymer segment architecture.

11. The process of any one of claims 1-10, wherein a solution of monomers is copolymerized with the purified macro-initiator to form a hyperbranched block-multi-linear block copolymer.

12. The process of claim 11, wherein the macro-initiator used to produce the block copolymer comprises from 2 to 500,000 functionalized end group initiating sites for block polymerization.

13. The process of any one claims 1-10, wherein a solution of macromonomers is copolymerized with the purified macro-initiator to form a hyperbranched block-multi -graft block copolymer.

14. The process of claim 13, wherein the macro-initiator used to produce the block copolymer comprises from 2 to 500,000 ftinctionalized end group initiating sites for block polymerization.

15. A hybrid hyperbranched block copolymer comprising a hyperbranched C.

polymer segment and multiple pendant linear or graft block polymer units obtained by preparinc, a purified macro-initiator comprising a hyperbranched polymer segment with multiple functionalized end group initiating sites, and using the purified macro-initiator to copolymerize a solution of monomers or macromonomers.

16. A copolymer accordin- to claim 15, wherein the purified macroinitiator is formed by reacting hyperbranching monomers to form a hyperbranched polymer and removing residual unreacted monomer.

1

17. A copolymer according, to claim 16, wherein the branching monomer io comprises a styrene; conjugated diene; acrylate; amine, carboxyl, aldehyde, alkyl, cyano or hydroxyl substituted acrylic acid or acrylic acid ester; acrylamide; methacrylamide; acrylic acid; methacrylic acid; acrolem; dimethaminoethylacrylate; dimethamino ethyl methacrylate; maleic acid; or maleic anhydride compound which also comprises a substituent providing a separate reactive site,

18. A copolymer according to any one of claims 15-17, comprising from 2 1 to 500,000 pendant linear or graft block polymer units.

19. A copolymer accordin- to claim 18, comprisina from 10 to 1,000 1. pendant linear or graft block polymeric units.

20. A copolymer according to any one of claims 15-17, comprising multiple pendant linear block polymer units.

21. A copolymer according to claim 20, wherein the hyperbranched polymer segment comprises poly(chloromethyl styrene) and the multiple pendant linear block polymer units comprise linear poly(2-methyl-2-oxazoline) polymer units.

22. A copolymer according to claim 20, wherein the hyperbranched 0 polymer segment comprises poly(chloromethyl styrene) and the multiple pendant linear block polymer units comprise linear poly(methyl acrylate) polymer units.

23. A copolymer according to claim 20, wherein the hyperbranched polymer segment comprises poly(chloromethyl styrene) and the multiple pendant linear block polymer units comprise linear poly(acrylic acid) polymer units.

24. A copolymer according to any one of claims 15-17, comprising multiple pendant graft block polymer units.

25. A copolymer according to claim 24, wherein the hyperbranched polymer segment comprises poly(chloromethyl styrene) and the multiple graft block polymer units comprise comb-poly(poly(ethylene glycol) ethyl ether monomethacrylate) polymer units.