GB2338958A

GB2338958A - Hyperbranched-graft hybrid copolymers from vinyl branching monomers and vinyl macromonomers

Info

Publication number: GB2338958A
Application number: GB9914156A
Authority: GB
Inventors: Jin-Shan Wang
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1998-06-26
Filing date: 1999-06-18
Publication date: 2000-01-12
Also published as: GB9914156D0

Description

2338958 HYPERBRANCHED-GRAFT HYBRID COPOLYMERS FROM VINYL BRANCHING

MONOMERS AND VINYL MACROMONOMERS

Field of Invention

The invention pertains to hyperbranched-graft hybrid copolymers obtained from living / controlled radical copolymerization of vinyl branching monomers and vinyl macromonomers.

Background of Invention

Branched polymers and copolymers have attracted considerable attention over the past decades, since many advanced materials with new or improved properties can be obtained therefrom. Use of macromonomers, or macromers, in hornopolymerization and copolymerization processes afford a controlled pathway to synthesize of various comb / grafting branched (co)polymers. Macromonomers are relatively large molecular weight species which themselves contain oligomeric or polymeric sements, and which may be polymerized either alone or with conventional small molecule monomers, as described, e.g., by Milkovich in US patents 3,786,116, 3,842,050, 3,842,057, 3,842,058, 3,842,059, 3,862,098, 3,862,101, 3,862,102, and 3,862,267. The industry applications of these well controlled grafting / comb copolymers include surface modification, membrane materials for gas separation, hydrogels and contact lenses, dispersion agents or emulsifiers, and many others (Yamashita, Chemistry and Industry of Macromonomers, Huthig & Wepf, 1993).

In addition to relatively simple comb / graft copolymers, 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 ap 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 dendrimers are prepared through lengthy multistep syntheses processes, their availability has been limited 2 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 5 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 AB. 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-(l-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 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. (A CS, 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. _3) 8 (1), 496 (1997)).

3 ATRP is a recently developed living, / controlled radical polymerization process (Wang, et al. J. Am. Chem. S oc., 117, 5 614 (1995)).

Hyperbranched random copolymers can also be made by similar processes, using branching monomer(s) and other branching monomer(s) or nonbranching monomer(s). Frechet et al. US patent 5,663,260, e.g., discloses a hyperbranched copolymer comprising branching AB monomer and non-branching C vinyl ether monomer comprising a polyethyleneoxide side chain. Such vinyl ether macromonomers, however, can only be cationically polymerized, and accordingly can only be copolymerized with monomers with similar reactivity. ATRP of chloromethyl 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 fanctional groups and C being a segment with possible pending oligomeric ethylene oxide side chain. The polymerization, i.e., condensation reaction between n numbers of A group and B group, yielded a hyperbranched polymer with pending oligomeric ethylene oxide side chain.

None of the prior art discloses a process for polymerization of branching monomer(s) and macromonomer(s) which may be applied for a wide variety of monomers in order to provide novel hyperbranched random and hyperbranched gradient copolymers with hyperbranched backbone and controlled amounts of linear polymer chains which are randomly or gradually distributed along the hyperbranched backbone. Such a process is accordingly desired.

Summary of the Invention

In accordance with one embodiment of the invention, a process for the preparation of a hyperbranched-graft hybrid copolymer is disclosed comprising radically copolymerizing a solution comprising at least one type of branching vinyl monomer and at least one type of non-branching vinyl macromonomer.

It has been discovered that using vinyl macromonomers and vinyl branching monomers, living or controlled radical polymerization affords hyperbranched-graft copolymers with a hyperbranched backbone and pendent linear chains introduced by the macromonomer units. The radical polymerization process offers the advantage of being applicable to polymerization of a wide C variety of commercially important monomers, many of which cannot be polymerized by other processes, and of being generally performable in bulk, in 4 solution, in suspension or in an emulsion, in contrast to other polymerization processes.

The present invention enables a variety of copolymers to be produced, and provides resultant hyperbranched-graft copolymers with the following advantageous features: 1) such hyperbranched-graft hybrid macromolecules contain not only a hyperbranched backbone but also certain amount of distinct branch chains; 2) such hyperbranched copolymers may contain distinct branch chains which are not made by chain polymerization; 3) phase separation may take place between the distinct branch chain phase and the hyperbranched backbone in either bulk state or solution. Thus, hyperbranched-graft copolymers can be designed in accordance with the invention for various end uses, many of which are impossible for other polymers including previously disclosed hyperbranched random copolymers.

Brief description of preferred embodiments

This invention involves a living / controlled radical polymerization of one or several special vinyl monomer(s), which are referred to as branching monomer, with a vinyl macromonomer or several vinyl macromonomers. Various known radical polymerization processes may be used in the process of the invention, including stable radical polymerization and atom transfer radical polymerization (ATRP). In accordance with preferred embodiments of the invention, hyperbranched-graft copolymers are obtained based on an ATRP process such as disclosed in World Patent Application Publication WO 96/3 042 1, 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 t 0 C, 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 polymer radicals are not formed. Such process provides a high degree of control over the polymerization process, and allows for the formation of various copolymers with more uniform properties.

A wide variety of radically 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 radically polymerizable vinyl group and a separate reactive site which can be activated thermally or in the presence of radical polymerization catalysts with the formation of initiating species, or branching species. Radically 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 may be provided by a substituent comprising a halogen atom (e.g., Cl, Br, or I, preferably Cl or Br) in atom transfer radical polymerization, TEWO (2,2,6,6-tetramethyl-l-piperidinyloxy, free radical) and its derivatives in stable radical polymerization, and S and Se containing groups in atom transfer radical 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 radically polymerizable branching monomers which may be used in accordance with the invention include but are not limited to: mvinyl benzylchloride, p-vinyl benzy1chloride, m/p-vinyl benzylchloride, trichloroethyl acrylate, tn"chloroethyl methacrylate, a-chloroacrynitrile, a- chloroacrylate, a-chloroacrylic acid, a-bromomaleic anhydride, achloromaleic anhydride, 2-(2-chloropropionyloxy)ethyl acrylate, 2-(2bromopropionyloxy)ethyl acrylate, 2-(2-chloropropionyloxy) ethyl methacrylate, and 2-(2bromopropionyloxy)ethyl methacrylate.

A wide variety of vinyl non-branching macromonomers which can undergo chain polymerization and which may be copolymerized with branching monomers in accordance with the invention are available commercially or can be synthesized by conventional reactions. Useful macromonomers include compounds comprising a polymerizable vinyl group 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 6 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, 5 polylactones, polylactames, poly oxazolines, polyvinyl acetate, F-containing polymers, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polypeptide, polyurethane, poly(phenylene oxide)s, poly(ether sulfones), polyesters, polycarbonate, polyetherketone, poly THF, and polyvinyl acetate. Polymerizable vinyl groups may be provided by the same compounds as described above for the branching monomers, with the exception that the non- branching macromonomer co-monomers employed in accordance with the invention do not comprise a substituent providing a separate reactive site. The methods to make macromonomers involve initiating methods, end- capping methods, chain transfer methods, and post-modification methods.

Specific examples of non-branching macromonomers which may be used 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 acetate)) styrene; (poly(vinyl acetate)) methacrylate; (poly(isobutylene)) methacrylate; (poly(tetrahydrofuran)) methacrylate; (poly(tetrahydrofuran)) acrylate; and (poly(amide)) styrene.

In general, macromoners for use in accordance with the invention will have molecular weights of at least about 150 and more preferably at least about 300.

Any polymerization technology can be used to prepare the hyperbranchedgraft hybrid copolymers in the present invention. Examples include but are not limited to solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, and polymerization in CO,.

In the present invention, the polymerization can be initiated by three different methods: 1) using branching monomer as an initiator; 2) using additional chain polymerization initiator; or 3) a combination of I and 2. Examples of added 7 initiators include but are not limited to: organic halides in atom transfer radical polymerization as described in World Patent Application Publication WO 96/3042 1, and conventional radical initiators such as AIBN and BPO in stable radical polymerization.

The hyperbranched-graft copolymers of the present invention can be end capped or modified with any functional agents to produce multi-functional hyperbranched-graft copolymers. The original and modified hyperbranchedgraft copolymers can also be used as macro-initiators to undergo various polymerization with other monomers to form more complex hyperbranched polymers, as disclosed USSN 09/105,767, and its corresponding UK patent application.

The branching monomers and macromonomers can be added as mixtures or added separately. The specific polymer structures and thus their properties can be obtained by controlling the following experimental conditions:

1. Addition methods. For example, copolymerization of a mixture of branching monomer(s) and macromonomer(s) may lead to hyperbranched-graft copolymers with random sequence distribution of branching monomer(s) and macromonomer(s) along the hyperbranched backbone, whereas copolymerization of branching monomer(s) gradually added with macromonomer(s) or verseversa may give rise to hyperbranched-graft copolymers with gradient sequence distribution of branching monomer(s) and macromonomer(s) along the hyperbranched backbone.

2. Ratio of branching monomers and macromonomers.

3. Temperature.

4. Solvent.

Also, structure factors of branching monomers and macromonomers play a role in producing specific copolymers. The specific polymer structure and their properties may further be modified by using additional vinyl monomers together with branching monomers and macromonomers.

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- linking 8 acrents, molding materials, electrostatic carriers, solid electrodes, water- and oil repellents, 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 inventive polymers 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 linear graft copolymers of similar molecular structure.

The process of the invention allows the formation of a variety of copolymers with controlled structures which may not be easily obtained by prior art processes.

The following examples are illustrative of synthesis of hyperbranched graft hybrid copolymers in accordance with the invention.

Example 1

Radical Copolymerization of mixture of PDMS-MA and 4-chloromethyl styrene.

The chloromethyl styrene (CS) (6 g), poly (dimethylsiloxane monomethacrylate) (PDMS-MA) with average number molecular weight of 10000 (4 g), CuCl (97%, 0.2 g), and 2,2'dipyridyl (98%, 0.3 g), all from Aldrich, were mixed in a 100 ml flask equipped with a magnetic stir bar. After purging the heterogeneous mixture with ultra-pure nitrogen gas for 15 minutes, the flask was closed and heated at 110 to 120'C for about 6 hours. At room temperature, about 100 ml TFIF was added to the flask and insoluble salt was then removed by means of filtration. Copolymer was precipitated in ca. 1 liter water/methanol mixture (50150, v/v). 1H NMR analysis: conversion: 90% CS and 93% PDMS-NIA; composition in copolymer:

3 9% PDMS and 6 1 %CS. GPC analysis (in THF): Mn: 1675 0 (universal calibration), Mw (weight average molecular weight): 216000 (universal calibration), Mw: 207000 (light scattering), viscosity: 0.153 (dL/g).

Example 2

Radical Copolymerization of mixture of PHEMA-5 and CS. The commercial CS (8 g, Aldrich), poly ((ethylene glycol) monomethacrylate) (HENIA-5, Bimax.

Inc.) (2 g), CuCl (97%, 0.1 g, Aldrich), and 2,2'dipyridyl (98%, 0.2 g, Aldrich), were mixed in a 100 ml flask equipped with a magnetic stir bar. After purging the 9 heterogeneous mixture with ultra-pure nitrogen gas for 15 minutes, the flask was closed and heated at around 120'C for about 4 hours and 45 minutes. 1H NMR analysis of the raw solution in CDC1, indicated that 80% CS and 84% HEMA- 5 were incorporated into copolymer, respectively. At room temperature, about 100 ml THF was added to the flask and then copolymer was precipitated in ca. I liter heptane. Polymer was dried at 70 C in a vacuum oven overnight. NMR analysis of copolymer composition: 44% of HEMA-5 and 55% of CS. GPC analysis results (in DMF): Mn: 3140 (universal calibration), and Mw: 88000 (universal calibration), and viscosity: 0.779 (dL/g).

Example 3

Radical Copolymerization of mixture of PEGE-MA and CS. The commercial CS (2 g, Aldrich), poly ((ethylene glycol) monoethylether monomethacrylate) (PEGE-NIA, Polysciences Inc.) (8 g) with average number molecular weight of 400, CuCl (97%, 0.1 g, Aldrich), and 2,2'dipyridyl (98%, 0.2 g, Aldrich), were mixed in a 100 ml flask equipped with a magnetic stir bar. The polymerization process and the purification of the resultant copolymer are similar to the one in example 2. NNM analysis of copolymer composition: PEGE: 90%, and CS: 10%.

GPC analysis results (in DMF): Mn: 3140 (universal calibration), Mw: 88000 (universal calibration), and viscosity: 0.89 (dL/g).

Example 4

Radical Copolymerization of PEGE-MA added to CS polymerization solution. The commercial CS (10 g, Aldrich), CuC1 (97%, 0.2 g, Aldrich), and 2,2'dipyridyl (98%, 0.4 g, Aldrich), were mixed in a 250 ml flask equipped with a magnetic stir bar. As soon as CS polymerization started at 120 C, 10 g poly ((ethylene glycol) monoethylether monomethacrylate) (PEGE-MA, Polysciences Inc.) with average number molecular weight of 400 was drop-wisely added to the CS polymerization system over a I hour period. After PEGE-MA monomer was completely added, polymerization continued another 4 hours. The purification of the resultant aradient copolymer is similar to the one in example 2. N1MR analysis of copolymer composition: PEGE: 3 1 %, and CS: 69%. GPC analysis results (in DMF): Mn: 3480 (universal calibration), Mw: 19900 (universal calibration), and viscosity: 0.055(dL/a).

Example 5

Radical Copolymerization of CS added to PEGE-NLk polymerization solution. The commercial 10 g poly ((ethylene glycol) monoethylether monomethacrylate) (PEGE-NIA, Polysciences Inc.) with average number molecular weight of 400, 1 -phenyl ethyl chloride (0. 1 g, Aldrich), CuCl (97%, 0.2 g, Aldrich), and 2,2'dipyridyl (98%, 0.4 g, Aldrich), were mixed in a 250 ml flask equipped with a magnetic stir bar. After PEGE-MA polymerization was initiated I-phenyl ethyl chloride at 120'C polymerized at the same temperature for about minutes, CS (10 a,, Aldrich) was drop-wisely added to the PEGE-MA polymerization system over a I hour period. After CS monomer was completely added, polymerization continued another 4 hours. The purification of the resultant gradient copolymer is similar to the one in example 2. NMR analysis of copolymer composition: PEGE: 25%, and CS: 75%. GPC analysis results (in DMF): Mn: 4540 (universal calibration), Mw: 40400 (universal calibration), and viscosity: 0.081 (dL/,-).

Claims

WHAT IS CLAIMED IS:

1. A process for the preparation of a hyperbranched-graft hybrid copolymer comprising radically copolymerizing a solution comprising at least one type of radically polymerizable non-branching vinyl macromonomer and at least one type of radically polymerizable branching vinyl monomer which comprises a radically polymerizable vinyl group and a separate reactive site which can be activated thernially or in the presence of radical polymerization catalysts with the formation of initiating or branching, species which may add to a vinyl group of 10 another branching monomer or a macromonomer.

2. The process of claim 1, 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; 15 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.

3. The process of claim 2, wherein the separate reactive site is provided by a substituent comprising a halogen atom and the branching monomer and macromonomer are copolymerized by atom transfer radical polymerization.

4. The process of claim 2, wherein the branching monomer comprises m vinyl benzylchloride, p-vinyl benzylchloride, mfp-vinyl benzylchloride, trichloroethyl acrylate, trichloroethyl methacrylate, a-chloroacrynitrile, a chloroacrylate, a-chloroacrylic acid, a-bromomaleic anhydride, achloromaleic anhydride, 2-(2-chloropropionyloxy)ethyl acrylate, 2-(2bromopropionyloxy)ethyl acrylate, 2-(2-chloroprop ionyloxy) ethyl methacrylate, or 2-(2 bromopropionyloxy)ethyl methacryIate.

5. The process of any one of claims 1-4, wherein the macromonomer comprises a polyrnerizable vinyl group and a oligomeric or polymeric unit containing at least two repeating groups.

12

6. The process of claim 5, wherein the oligomeric or polymeric unit of the macromonomer comprises about 5 to 100 repeating groups.

7. The process of claim 6, wherein the oligomeric or polymeric unit of the macromonomer comprises a polystyrene, polyolefine, polydiene, polymethacylate, polyacrylate, polyvinyl ether, polysiloxane, polylactone, polylactame, poly oxazoline, polyvinyl acetate, F-containing polymer, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polypeptide, polyurethane, poly(phenylene oxide), poly(ether sulfone), polyester, polycarbonate, polyetherketone, poly TBF, or polyvinyl acetate.

8. The process of claim 5, wherein the oligomeric or polymeric unit of the macromonomer is linear or branched or hyperbranched.

9. The process of claim 5, wherein the oligomeric or polymeric unit of the macromonomer is random or block or gradient or tapered in terms of sequence distribution.

10. The process of any one of claims 1-4, wherein the non-branching macrornonomer comprises (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 acetate)) styrene, (poly(vinyl acetate)) methacrylate, (poly(isobutylene)) methacrylate, (poly(tetrahydrofuran)) methacrylate, (poly(tetrahydrofuran)) acrylate, or (poly(amide)) styrene.

11. The process of any one of claims 1-10, wherein the macromonomer has a molecular weight of at least about 150.

12. The process of any one of claims 1-10, wherein the macromonomer has a molecular weight of at least about 300.

13 13. The process of any one of claims 1-12, wherein the branching monomer is also an initiator.

14. The process of any one of claims 1-12, wherein an extra initiator is 5 present during polymerization.

15. The process of any one of claims 1-14, wherein monomers are added as a mixture during polymerization.

I

16. The process of any one of claims 1-14, wherein monomers are added separately during polymerization.

17. A hyperbranched-graft hybrid copolymer produced from copolymerization of branching monomer and non-branching macromonomer by radical polymerization processes.

18. A polymer of claim 17 wherein the polymer has functionalized chain ends.

19. A polymer of claim 17 wherein the polymer has functionalized grafting chains.

20. A polymer of any one of claims 17-19 wherein the distribution of branching monomer and macromonomer in the copolymer is random.

2 1. A polymer of any one of claims 17-19 wherein the distribution of branching monomer and macromonomer in the copolymer is tapered or gradient.

1

22. A polymer of claim 17, wherein the branching monomer comprises m vinyl benzylchloride, p-vinyl benzy1chloride, m/p-vinyl benzy1chloride, trichloroethyl acrylate, trichloroethyl methacrylate, a-chloroacrynitrile, a chloroacrylate, a-chloroacrylic acid, a-bromomaleic anhydride, achloromaleic anhydride, 2-(2-chloropropionyloxy)ethyl acrylate, 2 -(2-bromopropionylo xy) ethyl acrylate, 2-(2-chloropropionyloxy)ethyl methacrylate, or 2-(2 bromopropionyloxy)ethyl methacrylate and the non-branching macromonomer comprises (poly(dimethylsiloxane)) monomethacrylate, (poly(ethylene glycol)) 14 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), 5 (poly(styrene)) methacrylate, (poly(styrene)) vinyl acetate, (poly(methyl methacrylate)) styrene, (poly (methyl methacrylate)) methacrylate, (poly(vinyl acetate)) styrene, (poly(vinyl acetate)) methacrylate, (poly(isobutylene)) methacrylate, (poly(tetrahydrofuran)) methacrylate, (poly(tetrahydrofuran)) acrylate, or (poly(amide)) styrene. 10

23. A polymer of claim 17, wherein the branching monomer comprises chloromethyl styrene and the non-branching macromonomer comprises (poly(ethylene glycol)) monomethacrylate.

24. A polymer of claim 17, wherein the branching monomer comprises chloromethyl styrene and the non-branching macromonomer comprises (poly(ethylene glycol)) monoethylether monomethacrylate.

25. A polymer of claim 17, wherein the branching monomer comprises 20 chloromethyl styrene and the non-branching macromonomer comprises (poly(dimethylsiloxane)) monomethacrylate.