WO2008156984A1 - Utilisation de cyclodextrines dans une synthèse de polymère à architecture contrôlée - Google Patents

Utilisation de cyclodextrines dans une synthèse de polymère à architecture contrôlée Download PDF

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WO2008156984A1
WO2008156984A1 PCT/US2008/065033 US2008065033W WO2008156984A1 WO 2008156984 A1 WO2008156984 A1 WO 2008156984A1 US 2008065033 W US2008065033 W US 2008065033W WO 2008156984 A1 WO2008156984 A1 WO 2008156984A1
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polymerization
och
radical polymerization
ether
ethylene glycol
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PCT/US2008/065033
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Manuel A. Garcia-Leiner
Florence Mehlmann
Robert K. Prud'homme
Margarita Herrera-Alonso
Lin Fu
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Arkema Inc.
Princeton University
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Publication of WO2008156984A1 publication Critical patent/WO2008156984A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Definitions

  • the invention relates to the use of macroniolecular organic compound carriers, such as cyclodextrins, in a controlled radical polymerization process in aqueous media.
  • the process can be used with a nitroxide-mediated process, atom transfer radical polymerization or similar processes to form controlled architecture homopolymer and block polymers.
  • the macromolecular organic compound carrier can also be used to form amphiphilic block copolymers in aqueous media by several different controlled-radical polymerization processes.
  • the use of a macromolecular organic compound carrier in an aqueous media controlled radical polymerization process presents a means for recycling of the macromolecular organic compound carrier and radical control agent.
  • US 5,521,266 describes a method for using macromolecular organic compound carriers - such as cyclodextrins to aid in the emulsion polymerization of monomers having very low solubility.
  • the cyclodextrins or other macromolecular organic compounds contain a hydrophobic cavity in which a monomer having very low water solubility can be complexed and hence solubilized in an aqueous medium.
  • DE 10027744 describes the synthesis of polystyrene by a TEMPO emulsifier- free controlled radical polymerization in water, using cyclodextrins.
  • Amphiphilic block copolymers have been produced by a controlled radical polymerization either neat, or in a solvent solution, as described in US Appln.No.l 1/491,342.
  • aqueous controlled-radical polymerization can be facilitated using cyclodextrins or similar macromolecular organic compound carriers for Beta-nitroxide mediated polymerization, and in the formation of amphiphilic block polymers.
  • One advantage of this process of polymerization is that the radical control agent can be easily recovered and recycled.
  • the invention relates to a process for forming a controlled architecture polymer through the polymerization of one or more ethylenically unsaturated monomers via beta-nitroxide-mediated controlled radical polymerization or atom transfer radical polymerization in the presence of a macromolecular organic compound carriers, and wherein said polymerization occurs in an aqueous media.
  • the invention also relates to amphiphilic block copolymers comprising at least one hydrophilic block and at least one hydrophobic block, wherein said amphiphilic block copolymer is fully or partially formed in an aqueous media by a controlled- radical polymerization process in the presence of one or more macromolecular organic compound carriers.
  • the invention further relates to a recycleable process for controlled radical polymerization in an aqueous media comprising: a) reacting one or more ethylenically unsaturated monomers in aqueous media in the presence of one or more macromolecular organic compound carriers by controlled radical polymerization preferably atom transfer radical polymerization (ATRP) or beta-nitroxide-mediated controlled radical polymerization to form a controlled-architecture polymer; b) removing the polymer from the aqueous medium; c) recovering or recycling the radical control agent stabilized by the macromolecular organic compound carrier; and d) re-using the radical control agent and macromolecular organic compound carrier in an additional polymerization reaction.
  • controlled radical polymerization preferably atom transfer radical polymerization (ATRP) or beta-nitroxide-mediated controlled radical polymerization to form a controlled-architecture polymer
  • ATRP atom transfer radical polymerization
  • beta-nitroxide-mediated controlled radical polymerization to form a controlled-architecture polymer
  • Figure 1 Structure for ⁇ -cyclodextrin (6-member ring) showing central hydrophobic cavity.
  • Figure 2 Semilogarithmic kinetic plot (a), and evolution of molecular weight and polydispersity (b) for the ATRP of CMA in water.
  • Figure 5 Particle size distribution of PEG-based nanoparticles suspended in an aqueous solution of m-
  • Figures 6 and 7. Particle size distributions of mPEG-b-PMMA nanoparticles suspended in an aqueous solution of m- ⁇ -cyclodextrin/MMA complex.
  • the invention relates to the use of macromolecular organic compound carriers in aqueous controlled polymerization reactions.
  • aqueous medium refers to a fluid that is primarily water. Preferably the medium contains 10 percent or more by weight of water.
  • a 100 percent water media is contemplated by the invention, hi addition to water, other solvents that are miscible with water can be present at up to 90 weight percent, including but not limited to alcohols (methanol, ethanol, isopropanol), glycols, dimethyl sulfoxide (DMSO), acetone, tetrahydrofuran, n-methylpyrrolidone, and polar carbonates, and glycol ether solvents to include:
  • Ethylene glycol monobutyl ether (2-butoxyethanol, CH 3 CH 2 CH 2 CH 2 OCH 2 CH 2 OH), a widely used solvent in paintings and surface coatings, cleaning products and inks
  • Ethylene glycol dimethyl ether (dimethoxyethane, CH 3 OCH 2 CH 2 OCH 3 ), a higher boiling alternative to diethyl ether and THF, also used as a solvent for polysaccharides, a reagent in organometallic chemistry and in some electrolytes of lithium batteries
  • Beta-nitroxide as described in beta-nitroxide mediated polymerization, is defined herein as possessing a hydrogen atom in the beta position.
  • the macromolecular organic compound carriers are used in the invention to solubilize the poorly water-soluble monomers, ligands, initiators and other low solubility components in the aqueous environment.
  • the macromolecular organic compounds are formed of a structure having a hydrophilic central cavity and a hydrophilic outer shell.
  • Macromolecular organic compounds useful as aqueous media carrier include, but are not limited to, cyclodextrin, cycloinulohexose, cycloinuloheptose, cycloinuloctose, calixarene, cavitand, and derivatives thereof.
  • One preferred class of macromolecular compounds are cyclodextrins, shown in Figure 1.
  • Cyclodextrins are a class of ring sugar molecules typically composed of 6, 7, or 8 glucosidyl residues, denoted as ⁇ , ⁇ , or ⁇ -cyclodextrins respectively. They exhibit a torus-shaped structure with a hydrophobic cavity and a hydrophilic outer side.
  • hydrophobic cavity allows them to form host-guest complexes by inclusion of hydrophobic molecules, while their polar hydrophilic shell maintains the complex soluble in water.
  • Their amphiphilic character can be used to polymerize hydrophobic monomers in aqueous solutions in the absence of surfactants.
  • the macromolecular organic compound carrier is used at a level of 0.5 mol percent to 500 mol percent, and preferably 1.0 mol percent to 250 mol percent based on the total moles of monomers
  • Controlled radical polymerization is a method to synthesize polymers with well-defined and predetermined architecture.
  • the controlled architecture can be a homopolymer having a very narrow particle size distribution, a star, comb, graft, gradient, or other structure, or a block copolymer (di-block, tri-block, etc.).
  • These processes generally combine a typical free-radical initiator along with a compound to control the polymerization process and result in polymers with specific compositions, controlled molecular weight, and narrow molecular weight distributions.
  • These free- radical initiators used may be those known in the art, including, but not limited to peroxy compounds, peroxides, hydroperoxides and azo compounds which decompose thermally to provide free radicals.
  • the initiator may also contain the control agent.
  • controlled radical polymerization techniques include, but are not limited to, atom transfer radical polymerization (ATRP), reversible addition fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), boron-mediated polymerization, and catalytic chain transfer polymerization (CCT). Descriptions and comparisons of these types of polymerizations are described in the ACS Symposium Series 768 entitled Controlled/Living Radical Polymerization: Progress in ATRP, NMP, and RAFT, edited by Krzystof Matyjaszewski, American Chemical Society, Washington, D.C., 2000.
  • amphiphilic block copolymers are water soluble, water dispersible, or generally capable of absorbing and/or transmitting water (hydrophilic block), while at least one other polymer block is water insoluble (hydrophobic block).
  • dispersible is meant the copolymer forms a stable uniform suspension (without the addition of further materials such as emulsifiers) when combined with water at 25 0 C.
  • hydrophilic or “hydrophilic polymer” as used herein is meant the polymer block segment is water soluble, water dispersible, or generally capable of absorbing and/or transmitting water.
  • the hydrophilic block could be a hydrophilic homopolymer, a random copolymer containing one or more hydrophilic monomers, or a random copolymer containing one or more hydrophilic monomers with one or more hydrophobic monomers.
  • the hydrophilic block might be formed by any technique known in the art, including step growth and condensation polymerization. One example would be to prepare the hydrophilic block by controlled radical polymerization.
  • Monomers useful in forming the hydrophilic block polymer include but are not limited to, acrylic acid, methacrylic acid, and the salts, esters, anhydrides and amides of methacrylic and acrylic acid; dicarboxylic acid anhydrides; carboxyethyl acrylate; hydrophilic derivatives of styrene; and acrylamides.
  • Specific useful monomers include, but are not limited to maleic anhydride, maleic acid, substituted maleic anhydride, mono-ester of maleic anhydride, itaconic anhydride, itaconic acid, substituted itaconic anhydride, monoester of itaconic acid, fumaric acid, fumaric anhydride, fumaric acid, substituted fumaric anhydride, monoester of fumaric acid, crotonic acid and its derivatives, acrylic acid, methacrylic acid, dimethylacrylamide, diethyl acrylamide, n-isopropylacrylamide, dimethylaminoethyl acrylate, diethylaminoethylacrylate, styrene sulfonic acid, acrylamido 2-methyl 2- propane sulfonate, vinylpyrrolidone, 2-carboxyethyl acrylate, methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate,
  • hydrophilic monomers of the invention include acrylic acid, methacrylic acid, salts of acrylic and methacrylic acid, methoxyethyl acrylate, dimethylacrlyamide, 2-carboxyethyl acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, and itaconic acid.
  • the hydrophobic polymer block can be a hydrophobic homopolymer, random copolymer containing one or more hydrophobic monomers, or a random copolymer containing one or more hydrophobic monomers with one or more hydrophilic monomers.
  • One preferred method of controlled radical polymerization in an aqueous media using a macromolecular organic compound carrier is nitroxide-mediated CRP using beta-nitroxides.
  • This type of CRP allows for the use of a larger variety of monomers in the polymer, including the use of acrylics and especially acid functional acrylics.
  • Nitroxide-mediated polymerization can be used in existing equipment at reaction times and temperature similar to other free radical polymerizations.
  • One advantage of nitroxide-mediated CRP is that the nitroxide is generally innocuous and can remain in the reaction mix, while other CRP techniques often require the removal of the control compounds from the final polymer. Furthermore, stringent purification of the reagents is not needed.
  • the mechanism for this control may be represented diagrammatically as below:
  • M with M representing a polymerizable monomer and P representing the growing polymer chain.
  • the key to the control is associated with the constants Kd eact , k ac t and k p (T. Fukuda and A. Goto, Macromolecules 1999, 32, pages 618 to 623). If the ratio kdeact/kact is too high, the polymerization is blocked, whereas when the ratio k p /kdeact is too high or when the ratio k deac /k act is too low, the polymerization is uncontrolled.
  • TEMPO and TEMPO-based alkoxyamines are not suited to the controlled polymerization of acrylics.
  • the free radical polymerization or copolymerization is carried- out under the usual conditions for the monomer or monomers under consideration, as known to those skilled in the art, with the difference being that a ⁇ -substituted stable free radical is added to the mixture.
  • a traditional free radical initiator it may be necessary to introduce a traditional free radical initiator into the polymerization mixture as will be evident to those skilled in the art.
  • Another process describes the polymerization of the monomer or monomers under consideration using a alkoxyamine obtained from beta-nitroxides of formula (I) wherein A represents a mono -or polyvalent structure and R L represents a mole weight of more than 15 and is a monovalent radical, and n > 1.
  • Another process describes the formation of polyvalent alkoxyamines of formula (I), based on the reaction of multifunctional monomers, such as, but not limited to, acrylate monomers and alkoxyamines at controlled temperatures.
  • the multifunctional alkoxyamines of formula (I), wherein n > 2 may then be utilized to synthesize linear, star, and/or branched polymeric and copolymeric materials from the monomer or monomers under consideration.
  • DEPN N-t-butyl-N-[l-diethylphosphono-(2,2,- dimethylpropyl)]nitroxide
  • the DEPN radical may be linked to an isobutyric acid radical or an ester or amide thereof.
  • a useful initiator is iBA-DEPN initiator, which has the following structure, in which SGl is the DEPN group.
  • iBA-DEPN initiator when heated separates into two free radicals, one of which initiates polymerization and one of which, the SGl nitroxide radical, reversibly terminates polymerization.
  • the SGl nitroxide radical dissociates from methacrylates above about 25 0 C and disassociates from acrylates above about 90 °C.
  • esters and amides Of CH 3 CH(SGl)CO 2 H are preferably derived from lower alkyl alcohols or amines, respectively, for example, the methyl ester, CH 3 CH(SGl)CO 2 CH 3 .
  • Polyfunctional esters for example the diester of 1 ,6-hexanediol [CH 3 CH(SGl)C ⁇ 2 ] 2 [(CH 2 ) 6 ], can also be used.
  • Difimctional initiators can be used to prepare symmetrical A-B-A block copolymers.
  • Initiators with higher functionality for example the tetraester of pentaerythritol [CH 3 CH(SGl)CO 2 CH 2 J 4 C], can be used to prepare star copolymers of the type 1(BA) n , in which I is the initiator and n is the functionality of the initiator.
  • a monofunctional alkoxyamine is used to prepare an AB block copolymer.
  • a difunctional alkoxyamine can be used to produce a triblock ABA copolymer.
  • a triblock copolymer can also be made from a monofunctional alkoxyamine by extending an AB diblock copolymer with an additional A segment (i.e., three sequential reactions of an A segment, then a B segment, then another A segment).
  • Another method for making a triblock copolymer from a monofunctional alkoxyamine is to first react the monofunctional alkoxyamine with a diacrylate (such as butanediol diacrylate) to create a difunctional alkoxyamine.
  • a diacrylate such as butanediol diacrylate
  • NMP controlled radical polymerization
  • a preferred controlled radical polymerization method is Atom Transfer Radical Polymerization (ATRP).
  • a typical polymerization protocol of this process is described below:
  • Deionized water is degassed by bubbling nitrogen or argon for a minimum of 12 hours prior to reaction.
  • Methyl methacrylate is passed through a column to eliminate the inhibitor (monomethyl ether hydroquinone).
  • methyl methacrylate To the remaining m-/J-CD/H 2 O solution is added methyl methacrylate, and as is the case for the initiator, complexation of the monomer takes place upon stirring. Copper (I) bromide and 2,2'-bipyridine are weighed and added to a clean scintillation vial, followed by water. The water-soluble metal/ligand complex is formed upon sonication.
  • the initiator solution is transferred to the flask containing the complexed monomer via cannula, and heated by immersion in an oil bath, to a temperature between 75 0 C and 90 0 C. After approximately 10 min, the metal/ligand complex solution is added to the reaction mixture via syringe. Precipitation of a polymeric product occurs shortly after, indicative of the reaction.
  • the second aliquot is added to a clean scintillation vial containing 4,4'-dinonyl-2,2'-dipyridyl and a magnetic stir bar.
  • complexation of the ligand occurs only at elevated temperatures, to form a clear solution. Once the complex has formed it is stable at room temperature.
  • copper (I) bromide To this solution is added copper (I) bromide, and the suspension is immersed in an oil bath at temperatures ranging from 75 0 C to 90 0 C. Once the solution turns clear, it is transferred via cannula to the reaction mixture comprised of the complex ed monomer and initiator.
  • an aqueous controlled radical, aqueous media polymerization system include:
  • the process of the invention provides a "green" approach to controlled radical polymerization.
  • an aqueous polymerization eliminates the need for organic solvents currently used in most controlled radical polymerizations.
  • the use of the macromolecular carrier effectively isolates the radical control agent from the polymer promoting better purification of the polymer and separation mechanisms for control agents or other substances.
  • the polymer can be removed from the aqueous media, and the control agents reused in subsequent additional polymerizations.
  • Cyclodextrins have been used for the polymerization of hydrophobic monomers in aqueous environments either through the formation of inclusion complexes, or as surface-active compounds in emulsion polymerizations.
  • the monomer is added under semicontinuous conditions to a solution of the cyclodextrin and an anionic surfactant in water, the amount of monomer greatly exceeds that of cyclodextrin (on a molar basis), and the initiators used are generally water-soluble. Examples of these approaches can be found in the literature, such as those presented by Lau on EP A0710675, Leyrer et al. on EP A0780401 and Rimmer and Tantterstall ⁇ Polymer 1990, 40, 6673-6677).
  • Tetramethylethylenediamine (TMEDA) was distilled under nitrogen. Copper (I) bromide, copper (II) bromide, 2,2'-dipyridyl (bipy), methylated-/?-cyclodextrm (m- ⁇ - CD), and o-phenanthroline were used as received.
  • EXAMPLE 1 Free-radical polymerization of MMA in aqueous media The polymerization of methyl methacrylate in aqueous solutions of m- ⁇ -CD using a common thermal initiator (K 2 S 2 Og) was studied according to the following protocol. A clean and dry round bottom flask containing a magnetic stir bar and capped with a rubber septum was charged with m- ⁇ -CD (0.2-2.0 g, 0.15-1.50 mmol) and purged with nitrogen for 1 h. Water (25 mL) was added via syringe and the solution was stirred for 20 min. K 2 S 2 O 8 (1-20 mg, 1% wt with respect to MMA) was added and allowed to dissolve with stirring for 10 min.
  • K 2 S 2 O 8 (1-20 mg, 1% wt with respect to MMA
  • the flask was immersed in an oil bath at 90 °C and nitrogen was bubbled through the solution for 15 min.
  • Methyl methacrylate (0.12-2 mL, 1.1-18.8 mmol) was added dropwise to the vigorously stirring solution (300 rpm) over 45 min.
  • the suspension was stirred for an additional 30 min and allowed to cool to room temperature.
  • the polymer was filtered (Whatman grade 4, 20-25 ⁇ m pore size), washed with water, and set to dry in a vacuum oven at 50 °C for 12 h.
  • Examples include polymerizations of H-butyl methacrylate in isopropano I/water (McDonald and Rannard, Macromolecules 2001, 34, 8600-8602), and methyl methacrylate in ethanol/water (Jewrajka et al., Macromolecules 2004, 37, 4325-4328).
  • the polymerization of methyl methacrylate in waterethanol mixtures by ATRP was carried out according to the following protocol: 2,2'-dipyridyl (bipy) (14.5 mg, 0.09 mmol) and copper (I) bromide (6.7 mg, 0.05 mmol) were transferred to a clean scintillation vial equipped with a magnetic stir bar and a septum.
  • TMEDA tetramethylethylenediamine
  • CuBr tetramethylethylenediamine
  • o-phenanthroline is poorly water-soluble in water, as reported by Burgess and Haines ( J. Chem. Eng. Data 1978, 23, 196-197). In this case, it was necessary to complex it with m- ⁇ -CO prior to metal/ligand complex formation. Once dissolved, copper bromide was added and the solution was sonicated.
  • EXAMPLE 6 ATRP ofm- ⁇ -CD/MMA complex in water. Effect oflisand inclusion in the cyclodextrin cavity.
  • EXAMPLE 8 ATRP of other monomers complexed by cyclodextrins in water. Case of cyclohexyl methacrylate (CMA)
  • CMA was polymerized following the same procedure as outlined previously for the synthesis of PMMA.
  • CMA was purified either by distillation under reduced pressure or by passage through a column packed with inhibitor-remover beads.
  • Methylated /3-cyclodextrin (m-0-CD) (5.6 g, 4.28 mmol) was added to a clean round bottom flask containing a magnetic stir bar. To this flask was added water (70 mL) and stirred vigorously to dissolve the cyclodextrin. The solution was allowed to stir overnight with bubbling argon.
  • m-/3-CD 95 mg
  • the ratio of CD/CMA chosen was based on values previously reported, where the optimum molar ratio of stable m- ⁇ -CD:CMA complexes ranged from 1.15 to 1.38.
  • the metal/ligand complex was formed in situ in the monomer solution by addition of copper (I) bromide (4.9 mg, 0.03 mmol), copper (II) bromide (3.3 mg, 0.015 mmol), and 2,2'-dipyridine (15 mg, 0.1 mmol). The solution was allowed to equilibrate at the desired reaction temperature (50-85 0 C) for 10-15 min, after which time the initiator solution was added via cannula. Reactions were stopped by exposure to air.
  • reaction temperature was also studied for the case of cyclohexyl methacrylate following the polymerization protocol described in Example 8.
  • the effect of increased temperature on this reaction was studied since it has been established that some of the side reactions for ATRP that occur in aqueous media are more pronounced at higher temperatures.
  • the results are presented in Figure 3, where an increase in temperature resulted in higher molecular weights for the same polymerization conditions.
  • PCMA synthesized under these conditions showed relatively high concentration of the complexing agent. This behavior is slightly different than that observed in MMA where the precipitate obtained upon reaction contained little to no m- ⁇ -CD. Since CMA has a higher binding constant to m- ⁇ -CD than MMA, it is believed that a considerable portion remains threaded during polymerization.
  • EXAMPLE 10 ATRP ofm- ⁇ -CD/CMA complex in water. Effect of initiator concentration Control over the molecular weight can also be achieved for cyclohexyl methacrylate. The results are presented in Figure 4 and show that the molecular weight of PCMA is sensitive to the molar ratio of monomer to initiator.
  • EXAMPLE 11 ATRP of CMA with mPEG-Br macroinititator
  • water-soluble macroinitiators for the ATRP of water-insoluble monomers can be conveniently applied towards the fabrication of micelles of amphiphilic block copolymers with controlled block lengths and, hence, particle size.
  • Synthesis of block copolymers capable of self-assemble into micelles in the reaction medium could potentially be used as effective macroinitiators for the reactions described in this invention.
  • Having control on the amphiphilic character of these copolymers can drive their self-assembly and have a direct effect on specific parameters such as the particle size. This invention provides some examples of these processes.
  • the protocol for the synthesis of the macroinitiator is described as follows: Monomethoxy poly(ethylene glycol), mPEG 5000 g/mol (5.0 g, 1.0 mmol) was weighed and added to a 500 mL clean round bottom flask containing a magnetic stir bar. Toluene (250 mL) was added and the solution was maintained under reflux overnight. mPEG was dried by azeotropic distillation of the solvent. Dichloromethane (250 mL) was then added and the solution was cooled to 0 0 C with an ice bath.
  • EXAMPLE 12 ATRP of MMA with mPEG-Br macroinititator Following the synthesis of block copolymers of poly(ethylene glycol)-£- poly(cyclohexyl methacrylate) (mPEG-6-PCMA) from a mPEG-macroinitiator described in Example 11, polymerization of MMA under the same conditions was studied. mPEG- ⁇ -PMMA micelles were synthesized to direct the self-assembly in the reaction solution into micelles and prevent precipitation of the resulting polymer. In addition in an attempt to control the particle size the MMA/macroinitiator ratio was varied.
  • a stock solution of the metal/ligand complex was prepared by dissolving copper bromide (5 mg, 0.03 mmol) and bipy (10 mg, 0.06 mmol) in water (2 mL). The amount of metal/ligand stock solution added to each of the vials was calculated based on the molecular weight of each of the polymers. Polymerization proceeded at 35 °C for 3 h. The solutions were precipitated into water, the polymer was isolated by filtration and dried in a vacuum oven.
  • Entry 1 corresponds to a polymer that was synthesized in the presence of CuBr 2 (Table 7, entry 1); entry 2 is the polymer that was synthesized in a wate ⁇ ethanol mixture. In both cases an increase in molecular weight was observed, suggesting that despite precipitation (for the reaction in pure water) the polymers retain their reactivity.

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  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne l'utilisation de supports de composé organique macromoléculaire, tels que des cyclodextrines, dans un procédé de polymérisation par voie radicalaire contrôlée dans un milieu aqueux. Le procédé peut être utilisé avec un procédé contrôlé par du nitroxyde, une polymérisation par voie radicalaire par transfert d'atome ou des procédés similaires pour former un homopolymère à architecture contrôlée et des polymères blocs. Le support de composé organique macromoléculaire peut aussi être utilisé pour former des polymères blocs amphiphiles dans un milieu aqueux par divers procédés de polymérisation par voie radicalaire contrôlée différents. En outre, l'utilisation de supports de composé organique macromoléculaire dans un procédé de polymérisation par voie radicalaire contrôlée en milieu aqueux présente un moyen de recyclage du support de composé organique macromoléculaire et de l'agent de contrôle radicalaire.
PCT/US2008/065033 2007-06-15 2008-05-29 Utilisation de cyclodextrines dans une synthèse de polymère à architecture contrôlée WO2008156984A1 (fr)

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US60/944,190 2007-06-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101914173A (zh) * 2010-08-19 2010-12-15 苏州大学 一种工业级单体的可控聚合方法
WO2024020780A1 (fr) * 2022-07-26 2024-02-01 Dic Corporation Polymère en forme d'étoile, peinture, revêtement et procédé de production d'un polymère en forme d'étoile

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910551A (en) * 1997-01-06 1999-06-08 American Dental Association Health Foundation Polymerizable cyclodextrin derivatives
US20030209686A1 (en) * 2000-02-14 2003-11-13 The Procter & Gamble Company Articles to aid the ironing of fabrics and methods of use
US7008990B2 (en) * 2000-06-16 2006-03-07 Basf Aktiengesellschaft Use of polymeric reaction product

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5910551A (en) * 1997-01-06 1999-06-08 American Dental Association Health Foundation Polymerizable cyclodextrin derivatives
US20030209686A1 (en) * 2000-02-14 2003-11-13 The Procter & Gamble Company Articles to aid the ironing of fabrics and methods of use
US7008990B2 (en) * 2000-06-16 2006-03-07 Basf Aktiengesellschaft Use of polymeric reaction product

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101914173A (zh) * 2010-08-19 2010-12-15 苏州大学 一种工业级单体的可控聚合方法
WO2024020780A1 (fr) * 2022-07-26 2024-02-01 Dic Corporation Polymère en forme d'étoile, peinture, revêtement et procédé de production d'un polymère en forme d'étoile

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