WO2007025310A1 - Polymerization process with catalyst reactivation - Google Patents

Polymerization process with catalyst reactivation Download PDF

Info

Publication number
WO2007025310A1
WO2007025310A1 PCT/US2006/033792 US2006033792W WO2007025310A1 WO 2007025310 A1 WO2007025310 A1 WO 2007025310A1 US 2006033792 W US2006033792 W US 2006033792W WO 2007025310 A1 WO2007025310 A1 WO 2007025310A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerization
transition metal
polymerization process
atrp
reaction
Prior art date
Application number
PCT/US2006/033792
Other languages
English (en)
French (fr)
Inventor
Krzysztof Matyjaszewski
Wojciech Jakubowski
James Spanswick
Original Assignee
Carnegie Mellon University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carnegie Mellon University filed Critical Carnegie Mellon University
Priority to EP06813937A priority Critical patent/EP1943278B1/en
Priority to CN2006800404028A priority patent/CN101379091B/zh
Priority to DE602006017416T priority patent/DE602006017416D1/de
Priority to US11/990,841 priority patent/US7893173B2/en
Publication of WO2007025310A1 publication Critical patent/WO2007025310A1/en
Priority to US12/949,466 priority patent/US20110065875A1/en

Links

Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention is directed to an atom transfer radical polymerization process where the catalyst in the activator state, or catalytic transfer agent, is continuously regenerated.
  • CRP controlled radical polymerization
  • CRP processes typically, but not necessarily, comprise a relatively low stationary concentration of propagating chain ends in relation to dormant chain ends.
  • a dormant chain end comprises a transferable atom or group.
  • the dormant chain end may be converted to a propagating chain end by loss of the transferable atom or group to the transition metal complex in the lower oxidation state.
  • the low concentration of propagating chain ends present during the polymerization process reduces the probability of bimolecular termination reactions, leading to radical polymerization processes that behave as a "living" polymerization process.
  • the ATRP equilibrium (characterized by KATRP) most frequently involves homolytic cleavage of an alkyl (pseudo)halide bond R-X by a transition metal complex activator Mf /L which (reversibly) generates an active propagating alkyl radical R * and the corresponding higher oxidation state metal halide deactivator Mf +1 XfL in a redox reaction Scheme 1.
  • the active R" may then propagate with a vinyl monomer (M), be deactivated in this equilibrium reaction by Mt n+1 X/L, or terminate by either coupling or disproportionation with another R".
  • Mt n+1 X/L vinyl monomer
  • Such termination results in an increase in the amount of deactivator, Mt n+1 X/L, by two equivalents resulting in an increase in concentration of dormant species as a result of the persistent radical effect.
  • polymer refers to a macromolecule formed by the chemical union of monomers, typically rive or more monomers.
  • polymer includes homopolymers and copolymers including random copolymers, statistical copolymers, alternating copolymers, gradient copolymers, periodic copolymers, telechelic polymers and polymers of any topology or architecture including block copolymers, graft polymers, star polymers, bottle-brush polymers, comb polymers, branched or hyperbranched polymers, and such polymers tethered to particle surfaces or flat surfaces as well as other polymer structures.
  • ATRP is the most frequently used CRP technique with a significant commercial potential for many specialty materials including coatings, sealants, adhesives, dispersants but also materials for health and beauty products, electronics and biomedical applications.
  • the most frequently used ATRP process comprises a reversible halogen atom transfer catalyzed by redox active transition metal compounds, most frequently copper based.
  • ATRP transition metal catalysts typically comprise a transition metal complexed with a ligand.
  • radically polymerizable monomers are polymerized in the presence of a transition metal catalyst.
  • transition metal catalyst participates in a redox reaction with at least one of an ATRP initiator and a dormant polymer chain, see Scheme 1.
  • Suitable transition metal catalysts comprise a transition metal and a ligand coordinated to the transition metal.
  • the transition metal catalyst participates in a reversible redox reaction with at least one of an ATRP initiator and a dormant polymer chain.
  • Suitable transition metal catalysts comprise a transition metal and, optionally, at least one ligand coordinated to the transition metal. The activity of the transition metal catalyst depends on the composition of the transition metal and the ligand.
  • the transition metal To function as an ATRP transition metal catalyst, the transition metal must have at least two readily accessible oxidation states separated by one electron, a higher oxidation state and a lower oxidation state.
  • the reversible redox reaction results in the transition metal catalyst cycling between the higher oxidation state (the "deactivator state”) and a lower oxidation state (the “activator state”) while the polymer chains cycle between having propagating chain ends and dormant chain ends.
  • the transition metal is one of copper, iron, rhodium, nickel, cobalt, palladium, molybdenum, manganese, rhenium, or ruthenium.
  • the transition metal catalyst comprises a copper halide, and preferably the copper halide is one of Cu(I)Br or
  • Living/controlled polymerizations typically, but not necessarily, comprise a relatively low stationary concentration of polymers comprising propagating chain ends in relation to polymers having dormant chain ends.
  • the chain end comprises the transferable atom or group.
  • the dormant chain end may be converted to a propagating chain F" end by transfer of the transferable atom or group to the transition metal catalyst.
  • the description of the mechanism of an ATRP is provided for explanation and is not intended to limit the invention.
  • the disclosed mechanism is generally accepted, but different transition metal catalyst may result in different mechanisms.
  • the ligand affects the structure of the catalyst, the solubilizing effect, and 5 catalyst activity. See Catalyst Development www.chem.cmuedu/groups/maty/about/research/OS.html, hereby incorporated by reference.
  • ATRP is considered to be one of the most successful CRP and has been thoroughly described in a series of co-assigned U.S Patents and Applications, such as U. S. Patent Nos. 5,763,548; 5,807,937; 5,789,487; 5,945,491; 6,111,022; 6,121,371; 6,124,411; 6,162,882;
  • transition metal ligand combinations 20 transition metal ligand combinations and the manner in which an ATRP equilibrium can be adjusted for more or less reactive monomers.
  • Embodiments of ATRP processes provide advantages over other CRP processes, including the availability wide variety of initiators and macroinitiators, including wafers, inorganic colloids, glass, paper, and bio-active molecules including proteins, DNA, carbohydrates and many
  • 25 commercial polymers may be simply synthesized as initiators; many polymers produced by ATRP allow facile functionalization or transformation of the end groups by replacing terminal halogens with azides, amines, phosphines and other functionalities via nucleophilic substitution, radical addition or other radical combination reactions; an abundance of monomers are polymerizable by ATRP.
  • Such monomers include, but are not limited to, styrenics, (meth)acrylates, acrylonitrile,
  • ATRP acrylamides, vinyl chlorides, and other monomers.
  • Embodiments of ATRP allow the production of macromolecules with complex topology such as stars, combs and dendrimers, coupled with the ability to control composition and hence functionality in block, gradient, periodic copolymers etc. and even control polymer tacticity.
  • ATRP may be carried out in bulk, or in the presence of organic solvents or in water under homogeneous or heterogeneous conditions, in ionic liquids, and in supercritical CO 2 . .
  • transition metal catalyst in an ATRP medium may be desired.
  • Several methods have been developed to remove or reduce the amount of transition metals in the process, but these processes may add additional cost to the preparation of polymers by ATRP.
  • Such methods include performing an ATRP process with highly active catalyst that may require a lower concentration of catalyst to maintain the desired polymerization rate, for example, CuBr complexed by Me 6 TREN is ⁇ 10,000 more active than CuBr complexed by bipyridine ligands; immobilizing the catalysts on solids such as a hybrid catalyst system comprising both immobilized catalyst complexes interacting with small concentrations of soluble catalysts ( ⁇ 10-20 ppm); and several post polymerization methods developed to recover and regenerate catalysts, including separating the catalyst by filtration, adsorption, precipitation or extraction.
  • CuBr/PMDETA complex may be oxidized to Cu(II) species by exposure to air and quantitatively extracted from toluene to water, resulting, in some cases, with less than 1 ppm of catalyst remaining in the polymer.
  • concentration of catalyst in the active polymerization media while maintaining polymer reaction rate and retaining control over MW and PDI.
  • the most attractive route may be just a simple decrease of the amount of the catalyst, providing that it has a sufficient reactivity.
  • ATRP processes comprising CuBr/Me 6 TREN complexes may be carried out at room temperature with much lower concentrations of the copper based catalyst.
  • the amount of transition metal catalyst such a Cu(I) may not simply be reduced 10,000 fold. Radical termination reactions result in an increase in the concentration of the transition metal catalyst in the deactivator state and irreversible consumption of the catalyst activators.
  • the polymerization may stop if the amount of Cu(I) present in the reaction is below 10% of the initiator (as, 1 ⁇ 10% of chains are terminated).
  • the amount of terminated chains depends on the concentration of propagating radicals and rate constant of termination according to equation 1, which describes the number of terminated chains (or loss of Cu(I) activator) in an ATRP.
  • Equation 2 The ATRP rate law (Equation 2) indicates that the polymerization rate depends on the ratio of Cu(I) to X-Cu(II) concentration but does NOT depend on the absolute concentration of copper complexes. Thus, in principle, the amount of copper may be reduced without affecting polymerization rate as long as the ratio of activator to deactivator is maintained.
  • Some amount of the deactivation species (i.e. X-Cu(II)) is also needed in the system for a well-controlled polymerization because molecular weight distribution and initial molecular weight depend on the ratio of propagation and deactivation rate constants and concentration of deactivator, according to Equation 4.
  • RAFT polymerization process termination reactions are suppressed through the addition of a suitable thiocarbonylthio compound, also known as a dithioester, to an otherwise conventional free radical polymerization; i.e. there is a continuous slow generation of radicals by decomposition of a standard radical initiator in order to drive the reaction forward.
  • Control in such a RAFT process is thought to be achieved through a degenerative chain transfer mechanism in which a propagating radical reacts with the thiocarbonylthio compound to produce an intermediate radical species. This process decreases the instantaneous number of free radicals available for termination reactions that require two free radicals.
  • RAFT (co)polymerization reactions have been discussed in U. S. Patents, 6,153,705; 6,380,355; 6,642,318 and 6,855,840.
  • Polymerization processes of the present invention comprise low catalyst concentration.
  • Embodiments include a polymerization process comprising polymerizing free radically (co)polymerizable monomers in a polymerization medium comprising one or more 5 radically (co)polymerizable monomers, a transition metal catalyst complex capable of participating in a one electron redox reaction with an ATRP initiator; a free radical initiator; and an ATRP initiator; (wherein the concentration of transition metal catalyst complex in the polymerization medium is less than 100 ppm).
  • Further embodiments include a polymerization process, comprising polymerizing one or more radically (co)polymerizable monomers in the presence of at least one 10 transition metal catalyst complex; and an ATRP initiator;; and a reducing agent; wherein the transition metal catalyst complex is present at less than 10 "3 mole compared to the moles of radically transferable atoms or groups present on the ATRP initiator.
  • Figure 2 is a graph of the molecular weight and polydispersity of a polystryrene formed as a 20 function of conversion formed in the embodiment of Figure 1 ;
  • Figure 3 is a graph showing the evolution of molecular weight by GPC traces during the embodiment of the polymerization process of Figure 1 ;
  • Figure 5 is a graph of the evolution of molecular weight by GPC traces during the embodiment of the polymerization process of Figure 4;
  • Figure 6 is a graph of the GPC curves showing the presence of a small amount of terminated polymer chains which were initiated by radicals produced from thermal decomposition of AIBN at beginning of activation procedure before being overwhelmed by the bulk of the polymer prepared by CRP;
  • Figure 7 is a graph of showing the temperature dependence of the conditional stability constant of Cu 11 L ATRP catalysts with various ligands including TPMA, Me 6 TREN, and PMDETA;
  • Figure 9 is a graph of data from a Predici computer simulation of first order kinetic plot for embodiments of ICAR ATRP processes comprising styrene, various ligands including TPMA 5 PMDETA, or bpy, and 50 ppm of Cu;
  • Figure 10 is a graph of data from a Predici computer simulation of the molecular weight and polydisperisty evolution in embodiments of ICAR ATRP processes comprising styrene, various ligands including TPMA, PMDETA, or bpy, and 50 ppm of Cu;
  • Figure 11 is graph of the kinetic data from Predici computer simulations for embodiments of ICAR ATRP processes comprising styrene, various ligands including TPMA, PMDETA, or bpy, 50 ppm of Cu,and AIBN as the free radical initiator;
  • Figure 15 are graphs of the kinetic data of an embodiment of a CuCl 2 /TPMA mediated ARGET ATRP of BA, variable N 2 H 4 reducing agent.
  • [BA]o:[EtBrro]o:[CuCl 2 ]o:[TPMA]o:[N 2 H4]o 200 : 1.28 : 0.01 : 0.1 : 0.05 or 0.1;
  • [BA] 0 5.88 M; 60 0 C, 20% anisole by volume;
  • Figure 24 is graphs of the kinetic data, molecular weight and molecular weight distribution as a function of conversion for ARGET ATRP of styrene and acrylonitrile with 30
  • Figure 25 is graphs of the GPC traces for samples taken during the preparation of high molecular weight polyacrylonitrile.
  • the present invention is directed to a polymerization process that regenerate the transition metal in the activator state.
  • Embodiments could be considered to provide a new mechanism for Controlled Radical Polymerization.
  • Embodiments of the ATRP polymerization process comprise a transition metal complex catalyzed halogen transfer polymerization where the transition metal complex is continuously reactivated by reaction with radicals.
  • the radicals may be formed by the decomposition of a free radical initiator or by self initiation reactions.
  • the present invention could tie considered to be a new mechanism for continuous reactivation a transition metal complex catalyzed (pseudo)halogen transfer polymerization where the transition metal complex is continuously reactivated by reaction with formed radicals.
  • This mechanism comprises initiators for continuous activator regeneration (“ICAR”), see Scheme 2.
  • Embodiments of the present invention provide control over radical reactions that may be considered conceptually to combine aspects of ATRP and RAFT.
  • RAFT a chain transfer agent is employed to reversibly transfer a labile dithioester end group among propagating radical chains.
  • ICAR ATRP process may be considered to be similar, wherein the role ' of the dithioester transfer agent in RAFT is replaced in ICAR by the initiator or growing polymer chain end in the presence of low concentrations, ppm amounts, of an ATRP catalyst complex and there is a continuous slow generation of radicals by decomposition of a standard radical initiator in order to drive the reaction forward.
  • ATRP process over a RAFT polymerization
  • monofunctional and multifunctional ATRP initiators as disclosed in other patents and patent applications with Matyjaszewski as inventor
  • the exchange reaction in an ATRP process is WSk If with a small molecule, (Mt(II)X) 5 not with a polymeric chain end as in RAFT; and the dormant chain end can be readily modified to provide the desired tele-fiinctional groups.
  • ATRP process may comprise any radically transferable atom or group and 5 transition metal such as, for example, environmentally friendly iron complexes.
  • Embodiments of the polymerization process of the present invention are directed towards polymerizing free radically (co)polymerizable monomers in the presence of a polymerization medium comprising at least one transition metal catalyst, or precursor of the active catalytic species, at least one of a free radical initiator and a reducing agent, and an ATRP initiator
  • ATRP initiators include molecules comprising at least one radically transferable atom or group, including small molecule initiators, polymeric initiators, and polymers in the polymerization medium comprising a dormant chain end that may be reinitiated or reactivated.
  • the polymerization medium may initially comprise a free radical initiator or a reducing agent or the free radical initiator or reducing agent may be added after initiation of the polymerization. After initiation of the
  • the ATRP process comprises polymerizing free radically polymerizable monomers in a polymerization medium comprising radically polymerizable monomers, a transition metal catalyst, an ATRP initiator, a free radical initiator, wherein the
  • the polymerization medium may further comprise a solvent, or water forming either a homogeneous or heterogeneous polymerization medium.
  • the free radical initiator may be any molecule that may be induced to form free radicals, such as a molecule that forms radicals by thermal, photoiniated or other decomposition process. Free radical initiators include peroxides, azo
  • free radical initiators include acyl peroxides, acyl peroxides, benzoyl peroxides, alkyl peroxides, cumyl peroxides, tributyl peroxides, hydroperoxides, cumyl hydroperoxide, tibutyl hydroperoxide, peresters, tibutyl perbenzoate, akyl sulfonyl peroxides, dialkyl peroxydicarbonates, diperoxyketals, ketone peroxides, 2, 2' azobisisobutyronitrile ("AIBN”), 2, 2' azobis (2,4- dimethyl pertanenitrile), and 1, 1' azobis
  • the monomer of the polymerization process may also act as the free radical initiator or reducing agent in embodiments of low catalyst ATRP processes.
  • Free radical initiators decompose to form radicals at different rates based on the decomposition n > stimulus, such as temperature.
  • the free radical initiator may be soluble in the polymerization medium.
  • the free radical initiator is selected such that at the - temperature of the polymerization reaction the free radical initiator decomposes at a rate that is substantially the same as the rate of termination in the polymerization.
  • the free radical initiator forms free radicals, or the equivalent of free radicals in the reaction medium. See Table 1 for half lives of free radical initiators at various temperatures.
  • 10 b t 1 A values are for benezene or toluene solutions of the initiators.
  • the system therefore behaves essentially as a conventional RP with similar kinetics but with the ATRP initiator acting as a combination "transfer agent" - initiator present at 50 ppm or less, in some polymerization processes less than 10 ppm, Mt(II) or Mt(I) as a transfer catalyst.
  • the polymerization process comprises polymerizing free radically polymerizable monomers in a polymerization medium comprising radically polymerizable monomers, a transition metal catalyst, an ATRP initiator, and a reducing agent.
  • the polymerization medium may further comprise a solvent, or water, hi such an embodiment, the transition metal complex may be initially in the oxidatively stable higher oxidation state, such as Cu n , and reduced
  • the reducing agent may be any reducing agent capable of reducing the transition metal catalyst from a higher oxidation state to a lower oxidation state, thereby reforming the catalyst activator state.
  • reducing agents include, but are not limited to, SO 2 , sulfites,
  • the reducing agent may further be capable of complexing with the transition metal, thereby becoming a ligand.
  • the reducing agent does not produce an acid after reducing the transition metal complex from the higher oxidation state to the lower oxidation state, such as hydrazine and phenyl hydrazine.
  • the products of oxidation are either nitrogen gas or organic in nature, compared to previous exemplified ARGET systems which predominately employed metal reducing agents for the reduction process in bulk media.
  • the reducing agent may also scavenge oxidants in the polymerization medium.
  • the amount of reducing agent will be determined by the total concentration of the oxidants in the polymerization medium, if any; the amount of termination reactions in the polymerization; and the desired rate of the redox reaction.
  • the reducing agent will be present in the polymerization medium such that the molar ratio of reducing agent to ATRP initiator is less than 0.1, or in certain embodiments, less than 0.05.
  • the stability of the complexes depends very strongly upon the basicity of the ligands.
  • a ligand that is not very basic may be advantageous.
  • the basicity/nucleophilicity of the reducing agent such as N 2 H 4 and PhNHNH 2 may be an issue, particularly in the ARGET ATRP of styrene.
  • the alkyl halide chain end may react with bases resulting in both in a loss of functionality and a consumption of reducing agent.
  • the dynamics of the redox process between the Cu complexes and reducing agents (and ultimately attainable control) will likely depend upon the ligand used to form the complex with the catalyst (and value of KA TRP ) that is employed.
  • the reducing agent may be select for a particular polymerization process such that at the polymerization temperature the reducing agent reduces a sufficient quantity of transition metal catalyst in the higher oxidation state to transition metal catalyst in the lower oxidation state to substantially maintain the polymerization rate. For example, at the polymerization temperature the reducing agent reduces the additional amount of transition metal catalyst in the higher oxidation state to substantially maintain the ratio of transition metal catalyst in the higher oxidation state to transition metal catalyst in the lower oxidation state. To substantially maintain such ratio means that the ratio does not vary greater than 20% after initiation of the polymerization.
  • the concentration of the transition metal catalyst must be present in the polymerization medium and may be less than 100 ppm, less than 50 ppm, or even less than 10 ppm.
  • the reducing agents do not initiate a new polymer chain after reducing the transition metal catalyst in the higher oxidation state.
  • the atom or group transfer transition metal complex may be an efficient deactivator, i.e. efficiently donate the (X) atom or group to the growing active chain.
  • the process will be initially exemplified by the use of a very small amount of Cu, ⁇ 10 ppm complexed with a ligand that forms an active ATRP catalyst and is also an effective deactivator, such as tris[2-(dimethylamino)ethyl]amine (“Me 6 TREN”), tris[(2- pyridyl)methyl]amine (“TPMA”), and H 6 TREN.
  • ligands forming less active catalysts such as N,N, ⁇ N",N"-pentamemyldiemyleneMamine (PMDETA), 4,4'-di-(5- nonyl)-2,2'-dipyridyl (dNbpy) andN-(n-octyl)-2-pyridylmethanimine.
  • PMDETA N,N, ⁇ N",N"-pentamemyldiemyleneMamine
  • dNbpy 4,4'-di-(5- nonyl)-2,2'-dipyridyl
  • dNbpy 4,4'-di-(5- nonyl)-2,2'-dipyridyl
  • N-(n-octyl)-2-pyridylmethanimine N,N, ⁇ N",N"-pentamemyldiemyleneMamine
  • the use of low concentrations of catalyst in an ATRP reaction reduces the impact of catalyst based side reactions that limited the ability to prepare high molecular weight materials in some embodiments.
  • One possible explanation of this limitation may be that the radicals interacted with the catalyst complex.
  • the polystyryl radical may be oxidized to a cation by the Cu species, thereby limiting formation of well-defined high molecular weight polystyrenes by
  • excess ligand may be added to the polymerization. Excess ligand is present when the quantity of ligand present in the polymerization medium exceeds the amount of ligand required to complex with the transition metal to form the transition metal catalyst.
  • the amount of excess ligand, or ligand surrogate such as free amine may be as much as ten times the require amount of ligand.
  • the transition metal catalyst may complex with the monomer.
  • the ligand may complex with the monomer such as styrene with other components of the polymerization medium. For example, if tin is used as a reducing agent, sufficient ligand should be added to allow for complex formation with both the reducing agent and the transition metal of the catalyst.
  • the present invention is also directed to polymers comprising high molecular weight.
  • Embodiments include polystyrene comprising end groups typical of an ATRP process and a molecular weight of greater thatn 50,000 and polyacrylonitrile comprising end groups typical of an ATRP process and a molecular weight of greater thatn 50,000.
  • the initiator is of the formula R-X, where X is the radically transferable atom or group. After polymerization, a typical polymer formed by ATRP will have the R group on one end and the X group on the other end.
  • the definitions of R and X are defined in United States patents that are incorporated by reference.
  • the free radical initiator or the reducing agent controls the rate of polymerization by regenerating the activator catalyst complex while allowing sufficient amounts of the catalyst complex efficiently deactivates the growing chains to remain, hi such embodiments, controlled synthesis (M w /M n ⁇ 1.2) of polystyrene and poly(alkyl (meth)acrylates) can be performed with catalyst concentrations between 1 and 50 ppm. At such concentrations, catalyst removal or recycling may be unnecessary for many industrial applications, since the color of products are not significantly affected by the such low concentrations of catalysts.
  • Embodiments of the ICAR ATRP and ARGET ATRP process comprise initial use of the oxidatively stable catalyst precursors that can be prepared, stored, and shipped for use in ATRP.
  • the transition metal complex in the activator state may be generated in situ from free radical initiators, a reducing agent, an in situ formed peroxide in the case of acrylate polymerization, or a combination thereof [Acar, A. E.; Yagci, M. B.; Mathias, L. J.
  • the oxidatively stable transition metal catalyst for example Cu 11 or Fe 11 .
  • the quantity of ligand present in the polymerization medium exceeds the amount of ligand required to complex with the transition metal to form the transition metal catalyst.
  • One - si ⁇ Hed in the art would understand ' ⁇ he coordination characteristics of each transition metal complex.
  • the amount of excess ligand, or ligand surrogate such as free amine may be as much as ten times the require amount of ligand. In some polymerization processes lower amounts of ligand may lead to polymers with higher polydispersities. At reduced quantities of ligand the transition metal catalyst may complex with the monomer.
  • the ligand may complex with the monomer such as styrene with other components of the polymerization medium.
  • the monomer such as styrene
  • tin is used as a reducing agent
  • sufficient ligand should be added to allow for complex formation with both the reducing agent and the transition metal of the catalyst.
  • the present invention is also directed to polymers comprising high molecular weight.
  • Embodiments include polystyrene comprising end groups typical of an ATRP process and a molecular weight of greater thatn 50,000 and polyacrylonitrile comprising end groups typical of an ATRP process and a molecular weight of greater thatn 50,000.
  • the initiator is of the formula R-X, where X is the radically transferable atom or group. After polymerization, a typical polymer formed by ATRP will have the R group on one end and the X group on the other end.
  • the definitions of R and X are defined in United States patents that are incorporated by reference.
  • the free radical initiator or the reducing agent controls the rate of polymerization by regenerating the activator catalyst complex while allowing sufficient amounts of the catalyst complex efficiently deactivates the growing chains to remain.
  • controlled synthesis M w /M ⁇ ⁇ 1.2
  • catalyst concentrations between 1 and 50 ppm. At such concentrations, catalyst removal or recycling may be unnecessary for many industrial applications, since the color of products are not significantly affected by the such low concentrations of catalysts.
  • Embodiments of the ICAR ATRP and ARGET ATRP process comprise initial use of the oxidatively stable catalyst precursors that can be prepared, stored, and shipped for use in ATRP.
  • the transition metal complex in the activator state may be generated in situ from free radical initiators, a reducing agent, an in situ formed peroxide in the case of acrylate polymerization, or a combination thereof [Acar, A. E.; Yagci, M. B.; Mathias, L. J.
  • the free radical initiator slowly and continuously decomposes to prevent the build up of the persistent .radical, or higher oxidation state transition " metaTcbmpTex, formed by termination reactions.
  • This decomposition of the free radical initiator may be used to maintain a substantially constant rate of polymerization; i.e. keep the ratio of transition metal in the low oxidation state (activator state) to transition metal in the higher oxidation state (deactivator state) relatively constant.
  • the free radical initiator or reducing agent may be used to increase or decrease the polymerization rate.
  • the ATRP polymerization process comprises two different free radical initiators.
  • one free radical initiator may quickly activate the catalyst complex to ensure rapid initiation of the polymerization and the other may slowly act throughout the reaction to reactivate the complex, for example.
  • the self-formed free radical initiator such as present in nitroxide mediated polymerizations with styrene and TEMPO may also be used.
  • Free radical initiators may be used in coordination with reducing agents, also.
  • the following examples exemplify the broad applicability of this novel CRP. In order to obtain consistent kinetics the reagents used in most of the examples were purified however as detailed in some examples this is not a requirement and the reaction can be conducted directly with industrial grade monomers and in the presence of low concentrations of oxygen.
  • Styrene (St) Aldrich, 99%
  • raBA n-butyl acrylate
  • Me 6 TREN Tris(2-(dimethylamino)ethyl)amine
  • Ethyl 2-bromoisobutyrate (EtBrIB) (Acros, 98%), copper(II) chloride (Acros, 99%), tin(II) 2-ethylhexanoate (Sn(EH)f) (Aldrich), anisole (Aldrich, 99%) were used as received.
  • Conversion of styrene were determined using a Shimadzu GC 14-A gas chromatograph equipped with a FID detector using a J&W Scientific 30 m DB WAX Megabore column and anisole as an internal standard. Injector and detector temperatures were kept constant at 250 0 C. Analysis was carried out is ⁇ thermally " at 60 0 C for 2 min followed by an increase of temperature to 140 0 C at a heating rate of 40 °C/min and holding at 140 0 C for 2 min. Conversion was calculated by detecting the decrease of the monomer peak area relative to the peak areas of the standards.
  • Table 2 is shows typical ratio's of reagents used various ATRP processes and in a RAFT polymerization process. Table 2. Typical molar ratios of reagents used in various ATRP processes and a RAFT process
  • AGET ATRP 200 1 0.2 0.2 0.18 -
  • ARGET ATRP 200 1 ⁇ 0.01 0.1 0.1 -
  • transition metal complex is typically comprised in ARGET ATRP and ICAR ATRP processes than the other listed ATRP process. While similar reagents are used in simultaneous reverse and normal initiation ("SR&NI") ATRP as in ICAR ATRP, ICAR ATRP allows the advantage of the use of much lower concentrations of transition metal catalysts. For more description of SR&NI ATRP, see United States Patent No. 6,759,491.
  • Example 1 General procedure for Activators ReGenerated by Electron Transfer (“ARGET”) ATRP of styrene (with number average degree of polymerization (DP n ) of 200 and at 50 ppm of Cu).
  • ARGET Electron Transfer
  • Styrene (5.0 ml, 44 mmol) and anisole (1.5 ml) were added to open Schlenk flask.
  • CuCl 2 (0.29 mg, 0.22x10 '2 mmol)/Me 6 TREN (0.57 ⁇ l, 0.22x10 '2 mmol) complex in anisole (0.5 ml) was added.
  • Mixture was stirred for 10 minutes and then solution Of Sn(EH) 2 (7.0 ⁇ l, 2.2x10 "2 mmol) and Me 6 TREN (1.7 ⁇ l, 0.7x10 "2 mmol) in anisole (0.5 ml) was added.
  • Sn(EH) 2 7.0 ⁇ l, 2.2x10 "2 mmol
  • Me 6 TREN 1.7 ⁇ l, 0.7x10 "2 mmol
  • Example 3 Preparation of block copolymers: PS-PnBA and PnBA-PS An embodiment of ARGET ATRP was used for preparation of block copolymers.
  • Copolymers PS-PnBA styrene and PwBA-PS were synthesized using previously specified conditions for polymerization of styrene (WJ-03-27) and n-butyl acrylate (WJ-03-53) in the presence of reducing agent Sn(EH) 2 .
  • the conditions and results for all the reactions are presented in Table 3.
  • the polystyrene macroinitiator was prepared (WJ-03-55) by polymerization of styrene in the presence of 15 ppm of Cu.
  • WJ-03-27 a well controlled polymerization was observed demonstrating that results are reproducible.
  • WJ-03-05 200 1 0.1 0.1 0.1 500 1020 67 14000 17000 , 1.12j : i i
  • WJ-03-08 200 1 0.01 0.1 0.1 50 460 59 12300 12700 ; l. ⁇ ;
  • Figure 1 is a kinetic plot of data obtained during the ATRP polymerization process comprising polymerizing styrene in the presence of 15 ppm of a copper/Me 6 TREN catalyst and a reducing agent Sn(EH) 2 , and an ATRP initiator, EtBrIB, wherein the SN(EH) 2 corresponds to 10% of the ATRP initiator (Table 3, entry WJ-03-27).
  • Figure 1 shows that the rate of polymerization was constant with only a slight decrease after 500 minutes.
  • the molecular weight and PDl curves in Figure 2 indicates excellent control over the polymerization process.
  • Figure 3 shows smooth shift of entire molecular weight distribution towards higher molecular weights.
  • WJ-03-06 200 1 0.01 0.01 0.1 50 1000 44 9200 oligomers
  • Lewis acids may also destroy the active Cu/Me ⁇ TREN species by direct complexation with the ligand.
  • a small excess of ligand, or ligand surrogate, should be used.
  • Cu(II) species can be still regenerated to Cu(I) state by the action of a reducing agent, such as Sn(EH) 2 .
  • a reducing agent such as Sn(EH) 2 .
  • WJ-03-08 a 200 1 0.01 0.1 0.1 50 460 59 12300 12700 i;.ii
  • the amount of transition metal catalyst complex species in ATRP can be reduced down to a few ppm without losing control of polymerization, if an appropriate amount of reducing
  • Reducing agent may also be involved in atom transfer process (this would generate dual catalytic system, e.g. bimetallic catalysis), however, the sufficient amount of quickly deactivation species (i.e., X-Cu(II) ) is needed for control.
  • the concentration of reducing agent should account for [Cu(II)] sufficient amount of transition metal species to be activated, amount of air or some other radical traps present in the system, and the amount of terminated chains.
  • Sn(EH) 2 species are used as the reducing agent this concentration is ⁇ 50 ppm but depends on the particular reaction conditions.
  • the minimal amount of active ATRP catalyst also depends on the particular system, for styrene polymerization the transition metal catalyst may be to a few ppm, significantly lower than in any other reported ATRP process.
  • the examples of ARGET ATRP detailed herein demonstrate a significant improvement over traditional ATRP, since it can be carried out with drastically reduced amount of Cu species and FDA approved Sn(EH) 2 or other environmentally sound reducing agents (sugars, ascorbic acid).
  • Example 4 Development of Initiators for Continuous Activator Regeneration (ICAR) ATRP.
  • IIR Continuous Activator Regeneration
  • the polymerization medium comprises a significantly lower catalyst concentration, for example many times less than the total number of polymer chains formed in the polymerization, in order that the reaction can continue the radical initiator has to continuously generate radicals at a rate comparable to radicals consumed by termination reactions.
  • the radicals can be formed by any reaction mechanisms. Indeed, as shown below, in the case of styrene polymerization this is the mechanism that actually operates, but it was analysis of the above results that led to this unexpected recognition.
  • the relatively uncontrolled character of the polymerization could be due to too low a concentration of ligand, which allows the copper to be complexed by monomer leading to loss of active metal catalyst complex (Cu(I)/ligand), as the ligand was involved in side reactions. Consequently, in next two reactions (WJ-03-36, 37) amount of ligand was increased.
  • Styrene was polymerized in the presence of 50 and 5 ppm of Cu species respectively.
  • CuCl 2 ZMe 6 TREN was used as catalyst complex and ratio of In/Cu/ligand was 1/0.01/0.1 and 1/0.001/0.1.
  • ATRP with low catalyst concentration was performed without the presence of added reducing agent.
  • the regeneration of Cu(I) species which can be lost due to termination 0 reactions (e.g. radical coupling), was performed by generation of radicals by thermal decomposition of AEBN (polymerization at 60 0 C). In this case, radicals are produced slowly through whole reaction time and are able to reduce Cu(II) to Cu(I), so that active complex can be regenerated.
  • the conditions and results for all the reactions are presented in Table 9. 1 P
  • WJ-03-35 1 15 0.003 0.003 0.01 - 4570 0.19 3560 37200 1.40
  • WJ-03-38 15 0.003 0.1 0.01 - 7200 0.26 5200 3800 1.51 WJ-03-39 15 0.003 0.1 0.05 - 7200 0.28 5500 5100 1.44
  • WJ-03-62 1 50 0.01 0.01 0.1 2760 0.44 8700 7900 1.12
  • Cu(I) is generated at the beginning stage of the reaction and high molecular weight polymers are obtained, since there is not enough Cu(II) in the system to deactivate growing chains, (ii) Cu(I) is more soluble than Cu(II) with Me 6 TREN ligand, thus during the transfer of active complex froni preparation flask to the Schenk flask some of Cu(II) species which are not fully soluble in the transfer medium are lost. Therefore the real value of Cu species in the reaction
  • 25 medium can be different, higher when Cu(I) is used.
  • Example 6 Synthesis of a PSt-ft-PnBA block Copolymer by ICAR and ARGET ATRP.
  • a clean shift in molecular weight indicates successful chain extension of the PS- macroinitiator prepared by ICAR and formation of a block copolymer and thereby confirms the "livingness" of the macroinitiator prepared by an embodiment of ICAR ATRP. 0
  • control over molecular weight distributions in ATRP is at least in part dependent upon absolute deactivator concentration.
  • the rate constant of deactivation of a given catalyst can be calculated from equation 4.
  • the polymerization process may comprise complexes with high values of K A TRP (resulting in sufficiently high concentrations of Cu 11 in solution) and relatively fast deactivation rates, (i.e. above 10 "8 or even 0 preferably above 10 "7 ; [Tang, W., Tsarevsky, N. V. & Matyjaszewski, K.; J. Am. Chem. Soc. 128, 1598-1604.])
  • the polymerization process may comprise the catalyst that does not dissociate appreciably under the polymerization conditions.
  • the dissociation problem may be compounded by competitive complexation between the s ErSfc- l ⁇ l monomer and the ligand to the metal, as the monomer is present in very large excess compared to the catalyst in these reactions.
  • ICAR ATRP of St was first conducted at low temperature (60 0 C) where organic radicals were produced solely by the slow decomposition of azobisisobutyronitrile (AIBN) (0.1 eq vs. ethyl 2-bromoisobutyrate (EtBrIB) initiator) in the presence of 50 ppm of CuCl 2 /L complexes (entries
  • the rates of polymerization differ by less than a factor of two among reactions catalyzed by CuCl 2 complexes OfMe 6 TREN 5 TPMA, and PMDETA (entries 1-3, Table 10), suggesting KATRP may not play a significant role in determining polymerization rate.
  • control over molecular weight distribution was significantly lower in the polymerization mediated by CuC ⁇ /PMDETA. This behavior can be rationalized based on the stability of these complexes towards dissociation at high dilution.
  • the fraction of non-dissociated Cu complex can be calculated from equation (5) knowing the stability constant ( ⁇ J ) and total concentration of the complex ([CuVL]o, where j is the Cu oxidation state and L is the ligand).
  • the catalyst should have a stability constant larger than 10 8 . This should be true for both the Cu 1 and Cu 11 states of the catalyst. From this perspective, ligands such as PMDETA displaying a value of ⁇ ⁇ 10 8 at room temperature [Navon, N.; et al; Inorg. Chem. 1999, 38, 3484] are not suitable for ICAR or ARGET ATRP if narrow molecular weight distribution is desired. However this can be relaxed if broader molecular weight distribution is acceptable or even desired for certain applications.
  • thermochemistry of polyamine complexes of metal ions, including Cu 11 has been extensively studied.
  • the Predici program (version 6.3.1) was used for all kinetic modeling. It employs an adaptive Rothe methoU as a ⁇ u ⁇ e ⁇ cal sj ⁇ afegy " fo ⁇ "tin ⁇ e:3iscrifizatiori. The be followed with time. Each actual calculation took 3-5 min to complete on a personal computer. The modeling was conducted in order to obtain a clear picture of the kinetics of ICAR ATRP and determine whether the rate of polymerization in ICAR is governed by K A T RP or by the rate of AIBN decomposition. (AIBN is being used herein as an exemplary free radical initiator and it is believed that any free radical initiator can be used.
  • k & the deactivation rate constant for free radical with X-Cu" species, estimated from k ⁇ cacl for ATRP (10 "5 ⁇ 10 '8 M “1 0 s "1 ) [Matyjaszewski, K., Paik, H.-j., Zhou, P. & Diamanti, S. J. (2001) Macromolecules 34, 5125.]
  • Auand k a the rate constant for addition of radicals from EBIB (Aii) and AIBN (k ⁇ ) to styrene. Values are calculated at 60
  • Equation (7) shows how the radical concentration (and hence, the polymerization rate) under steady state conditions is primarily dependent on the AIBN decomposition rate constant, its , concentration, and the radical termination rate constant. Radical concentration should therefore not be governed by the choice of ATRP catalyst, KA TRP , or the initial concentration of Cu 11 species. This further suggests that polymerization rates can be adjusted with the choice of an appropriate free radical initiator. These predictions are in relatively good agreement with experimental observations, where apparent rates of polymerization in CuCVMe 6 TREN, TPMA and PMDETA mediated polymerizations (entries 1, 2, & 3, Table 10) are very similar.
  • the Cu catalyst formed with bpy is the least active among the three complexes in this discussion, with .KA T R P ( ⁇ 3.6X10 '9 ) and a relatively small k ⁇ (8.3x10 6 M “1 s "1 ).
  • the concentration of Cu 11 species present at quasi-steady state can be estimated from the ATRP equilibrium.
  • ICAR ATRP and ARGET processes comprise a halogen exchange process.
  • Halogen exchange processes comprise switching the radically transferable atom or group in a polymerization process to another radically transferable atom or group.
  • the catalyst employed for the second step of a block polymerization is chlorine based while that employed for the first polymerization step was bromine based.
  • the halogen on the growing chain end was converted to a chlorine soon after the macroinitiator was activated thereby, in the case of bromine to chlorine, slowing down the rate of propagation of the second polymerization to more closely to match the rate of initiation, for example. This cannot be accomplished when the ratio of catalyst to end group on the macroinitiator is significantly less than 1 : 1 and certainly not when less than 10%.
  • Another approach was a copolymerization process for either ICAR ATRP or ARGET ATRP comprising forming the second block with a different monomer, such as, for example, styrene which and in the end group on the dormant growing polymer chain predominately comprised a styrene unit then the macromolecule could be controllably reactivated.
  • An embodiment of ARGET ATRP process comprised adding acrylonitrile to the polymerization of acrylate.
  • Example 11 Expanding Range of Exemplified Reducing Agents.
  • Stability was quantitatively determined by both the value of ⁇ J and the basicity of the ligand L.
  • the stability of the complex decreases by a factor of OC L (taking into account the amount of protonation or other side reactions of L) to a new value, termed the conditional stability constant ⁇ ' * .
  • A any of the reaction components (monomer, solvent, polymer, reducing agent or the product of its oxidation, designated by A) reacts with the copper ions
  • the stability of CuVL decreases additionally by a factor of ⁇ cu taking into account these side reactions with A (characterized by stability constants ⁇ J cu J Am), according to eq (5).
  • Figure 11 illustrates the pH dependence of the stability of the Cu 11 complexes of PMDETA, Me 6 TREN, and TPMA, calculated from equation 5 (knowing the protonation constants which are available in literature) and shows that the complexes of basic ligands are very much destabilized in acidic media, especially when their stability constants in the absence of protonation (Figure 12) are relatively low (e.g., the Cu 11 complex of PMDETA).
  • Figure 12 also illustrates why PMDETA is less applicable for ARGET ATRP than the other ligands.
  • the complex of the basic Me 6 TREN is markedly more destabilized in acidic media than that of the less basic ligand TPMA. From the point of view of temperature and pH stability, TPMA appears a preferred ligand for ARGET reactions where one of the byproducts of the reducing reaction is an acid.
  • Reducing agents such as glucose were also examined.
  • the polymerization process with glucose as the reducing agent stopped after 500 minutes or so.
  • the kinetic plots and the molecular weight curves showed that each time ATRP stopped at 8-9 hours and then thermal initiated conventional radical polymerization of styrene took place, see 0 Figure 10.
  • Addition of a base can potentially extend the conversion of a polymerization with glucose as a reducing agent by diminishing the protonation of ligand and in fact triethylamine was effective, hi addition, increasing the concentration of ligand also resulted in higher conversion.
  • Another base, 1,4-di-tert-butyl-pyridine was probably to weak to affect protonation and the polymerization but the polymerization process still stopped prior to high conversion.
  • ARGET ATRP processes comprising methyl methacrylate (MMA) and styrene.
  • ARGET ATRP processes comprising MMA initiated by EtBrIB at 60 0 C resulted in observed molecular weights higher than theoretical values with M w /M n ⁇ 1.6 (entries 1 & 2, Table 12a). Better control was observed in the ARGET ATRP of MMA employing Sn(EH) 2 as a reducing agent. Polymerization of St was initiated by EtBnB at 9O 0 C (where thermal initiation should not be significant) in the presence of a 10 fold excess OfPhNHNH 2 and ligand to 50 ppm of Cu. These reactions were fairly well controlled (M w /M n ⁇ 1.3, entries 3 & 4, Figure 12a).
  • ARGET ATRP process comprising MAO as a reducing reagent
  • Anisole was used as an internal standard (10 vol.% of BA)
  • Control Run Copolymerization of styrene and acrylonitrile by ATRP (amounts entry 2 in Figure 13a).
  • a preferred ATRP catalyst possesses a low affinity for alkyl radicals and hydrogen atoms on alkyl groups in order to suppress the contribution of side reactions in the transition metal mediated polymerization.
  • copper-mediated ATRP of styrene loss of terminal 5 halogen functionality by elimination of HX results in loss of chain functionality and consequently loss of control over the reaction.
  • ARGET ATRP The main advantage of ARGET ATRP is that the system comprises continuous reactivation of a small amount of catalyst to maintain control. In most systems this means that catalyst solubility problems and purification issues are easily overcome.
  • ARGET ATRP of styrene and acrylonitrile was conducted with ethyl 2-bromoisobutyrate (EBiB) as an initiator and Me ⁇ TREN/Cu as the catalyst.
  • EBI ethyl 2-bromoisobutyrate
  • Me ⁇ TREN/Cu the catalyst.
  • Experimental conditions and properties of the SAN copolymers prepared by ARGET ATRP are shown in Figure 13b. In order to optimize the amount of copper three different concentrations of catalyst were evaluated: 10, 30 and 50 ppm versus monomer ( Figure 13b, entries 3-5). The amount of the reducing agent, Sn(EH) 2 was kept constant at 50 mol% of the initiator.
  • FIG. 17 presents the kinetic plots for the copolymerization of styrene and acrylonitrile with 30 ppm of copper versus monomer, as well as the molecular weight and polydispersities of the polymers formed in this system.
  • the kinetic plot showed a very small deviation from linear characteristics and the molecular weight was only slightly different from theoretical, a constant increase of molecular weight distribution with conversion was observed.
  • the increase in polydispersity was visible on the SEC traces with tailing to the low molecular weight species which means formation of dead chains from various termination reactions cannot be completely neglected and high monomer conversion cannot be attained with good control over polymerization under these conditions.
  • the high molecular weight SAN copolymer was obtained in a controlled radical polymerization, which leads to the conclusion that the very low concentration of catalyst used in this example significantly suppresses the side reactions of growing radicals with copper species leading to the preparation of well defined high molecular weight linear copolymers.
  • a macroinitiator was also used for the copolymerization of styrene and acrylonitrile.
  • the macroinitiator used was a poly(ethylene oxide) based macroinitiator containing a terminal 2-bromoisobutyrate group.
  • the reaction conditions are shown in Figure 13b, entry 13.
  • the linear character of the kinetic plot indicates a constant number of growing species in the reaction medium, up to 20% of monomer conversion after which the rate of monomer consumption was reduced. Slight discrepancies between theoretical molecular weight and that determined by GPC was observed only the early stage of the polymerization, due to the presence
  • reaction conditions developed using a monomfunctional initiator (EtBriBu) and PEO-macroinitiator were employed in a series of reactions with multifunctional initiators. Identical concentrations of catalyst and initiator were used in each system which should provide
  • ARGET ATRP allows a significant reduction in the amount of catalyst complex employed in the reaction and it was possible to synthesize high molecular weight polymer due to significant suppression of side reactions through reduction of the absolute concentration of the copper species in the system. Side reactions between the growing radicals and the catalyst were avoided to a significant extent.
  • the amount of copper species present in the system can be as low as 10 ppm without loss of control making this process very useful for industrial scale production.
  • Polymerization with mono-, di- and trifunctional initiators low molecular weight initiators and a macroinitiator resulted in the formation of well-defined polymers with controlled architecture. Synthesis Of SiO 2 -PSAN:
  • mini emulsion ATRP allows for compartmentalization of multifunctional initiators in the well dispersed droplets and reduces crosslinking as a consequence of low instantaneous concentration of radicals in a given droplet.
  • HEMA-TMS high molecular weight polymer suitable as a backbone for a grafting from polymerization
  • p(HEMA-TMS) RAFT very high molecular weight RAFT
  • the ratio of monomer to initiator was 10,000 to 1 and the amount of catalyst, tin and solvent were varied to find the best conditions.
  • PAN is not soluble in monomer and most organic solvents such as THF, anisole, methanol, acetone.
  • organic solvents such as THF, anisole, methanol, acetone.
  • THF trifluoride
  • anisole methanol
  • acetone a non-linear first order kinetic plot of monomer consumption
  • DMF GPC
  • AMPSA based block copolymers are desired as templating agents for the preparation of flexible conductive polymers however their preparation by standard ATRP techniques have met with a limitation on the MW of the AMPSA block.
  • the following example was run under conditions developed for the preparation OfAMPSA 27 BA 46 SAMPSA 27 in a standard ATRP reaction.
  • the conditions for this AGET ATRP are similar to those used in the 'regular' ATRP polymerization of AMPSA, with the addition of a proportion of ascorbic acid in addition to the other components.
  • the role of the added reducing agent is to reactivate any excess Cu 11 formed by termination reactions.
  • AMPSA (16.6 g) was added to a Schlenk flask, along with 8.2 g of PBA macroinitiator (MW 60,000g/mol) and degassed for 30 minutes. Degassed tributylamine (19.2 mL) and degassed DMF (48 mL) were then added, followed by stirring until the AMPSA and PBA dissolved, then another 20 minutes of degassing. Copper chloride (79.2 mg), ascorbic acid (47 mg) and bpy (87.6 mg) were added to a separate Schlenk flask, and oxygen was removed by 3 cycles of vacuum pumping and nitrogen purging.
  • TPMA has been found to be an effective ligand for AGET ATRP of NIPAAm in water when using a solvent such as 2-propanol.
  • the polymerization can be driven to >90% conversion and low polydispersity polymers can be obtained.
  • NIPAAm 200
  • Table 13a AGET ATRP of OEOMA 475 in water at 30 0 C.
  • Table 15b AGET ATRP of OEOMA 475 in water at 3O 0 C.
  • Table 15c AGET ATRP of OEOMA 475 in water at 30 0 C.
  • Sequential or gradual addition of the reducing agent therefore does allow one to control the rate of reduction and hence the ratio of Cu 1 to Cu 11 throughout the reaction and attain higher molecular weight materials.
  • the main goal of this example is to define and demonstrate a very simple procedure for grafting from flat surfaces with different monomers.
  • the initial target was to perform AGET or ARGET ATRP at room temperature in the presence of a limited amount of air in a dish (e.g. Petri dish) which can be just simply covered and insulated with parafilm.
  • a dish e.g. Petri dish
  • the polymerization did not occur even after degassing all the reagents with N 2 and adding a higher amount of reducing agent Sn(EH) 2 .
  • the next set of experiments were performed in a weighing dish, which is equipped with ground cover and is deeper than a Petri dish.
  • Solvent anisole/acetone 0.05/0.05 volume equivalents vs. M. 1.5 equivalents Of Sn(EH) 2 was added after 49.5 h.
  • Example 15 Each opening of the reactor in Example 15 resulted in addition of air, which can consume catalyst and reducing agent, however, the molecular weight of the polymer moved to higher molecular weight without any sign of tailing.
  • the polymerizations were well controlled, molecular weights were close to theoretical values and low PDI (1.28) was observed.
  • This example does show that an ATRP can be conducted from a solid flat surface and that the initial presence of a small amount of air can be compensated for by addition of excess reducing agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
PCT/US2006/033792 2005-08-26 2006-08-28 Polymerization process with catalyst reactivation WO2007025310A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP06813937A EP1943278B1 (en) 2005-08-26 2006-08-28 Polymerization process with catalyst reactivation
CN2006800404028A CN101379091B (zh) 2005-08-26 2006-08-28 在催化剂再生下的聚合方法
DE602006017416T DE602006017416D1 (de) 2005-08-26 2006-08-28 Polymerisationsverfahren mit katalysatorreaktivierung
US11/990,841 US7893173B2 (en) 2005-08-26 2006-08-28 Polymerization process with catalyst reactivation
US12/949,466 US20110065875A1 (en) 2005-08-26 2010-11-18 Polymerization process with catalyst reactivation

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US71172205P 2005-08-26 2005-08-26
US60/711,722 2005-08-26
US81481606P 2006-06-19 2006-06-19
US81484606P 2006-06-19 2006-06-19
US60/814,816 2006-06-19
US60/814,846 2006-06-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/949,466 Division US20110065875A1 (en) 2005-08-26 2010-11-18 Polymerization process with catalyst reactivation

Publications (1)

Publication Number Publication Date
WO2007025310A1 true WO2007025310A1 (en) 2007-03-01

Family

ID=37668150

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/033792 WO2007025310A1 (en) 2005-08-26 2006-08-28 Polymerization process with catalyst reactivation

Country Status (5)

Country Link
US (2) US7893173B2 (US07893173-20110222-C00005.png)
EP (1) EP1943278B1 (US07893173-20110222-C00005.png)
CN (1) CN101379091B (US07893173-20110222-C00005.png)
DE (1) DE602006017416D1 (US07893173-20110222-C00005.png)
WO (1) WO2007025310A1 (US07893173-20110222-C00005.png)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010123575A1 (en) 2009-04-23 2010-10-28 Atrp Solutions Inc Well defined stars with segmented arms
US20110082230A1 (en) * 2008-12-22 2011-04-07 Wojciech Jakubowski Control over controlled radical polymerization processes
CN101508757B (zh) * 2009-03-17 2011-05-18 南京工业大学 一种使用atrp对聚苯乙烯树脂接枝改性的方法
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
US8349410B2 (en) 2006-08-17 2013-01-08 University of Pittsburgh—of the Commonwealth System of Higher Education Modification of surfaces with polymers
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
US20140183055A1 (en) * 2010-12-17 2014-07-03 Krzysztof Matyjaszewski Electrochemically mediated atom transfer radical polymerization
US8865797B2 (en) 2007-05-23 2014-10-21 Carnegie Mellon University Hybrid particle composite structures with reduced scattering
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
US9546225B2 (en) 2008-12-22 2017-01-17 ATRP Solutions, Inc. Control over controlled radical polymerization processes
JPWO2015163383A1 (ja) * 2014-04-25 2017-04-20 国立研究開発法人産業技術総合研究所 表面改質方法、表面改質材料及び重合液
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
CN112946160A (zh) * 2021-02-09 2021-06-11 新疆大学 一种活性物质贡献率的计算方法、系统、设备及其存储介质
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes

Families Citing this family (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087819A1 (en) 2004-03-05 2005-09-22 Carnegie Mellon University Atom transfer radical polymerization process
WO2005087818A1 (en) * 2004-03-05 2005-09-22 Carnegie Mellon University Preparation of functional polymers
EP1928919B1 (en) 2005-08-23 2010-02-17 Carnegie-Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization
US9783628B2 (en) 2009-04-23 2017-10-10 ATRP Solutions, Inc. Dual-mechanism thickening agents for hydraulic fracturing fluids
WO2010123574A1 (en) 2009-04-23 2010-10-28 Atrp Solutions Inc Star macromolecules for personal and home care
WO2011075185A1 (en) 2009-12-18 2011-06-23 Oligasis Targeted drug phosphorylcholine polymer conjugates
WO2012020545A1 (ja) * 2010-08-10 2012-02-16 株式会社カネカ （メタ）アクリル系重合体の製造方法
US9587064B2 (en) 2010-12-08 2017-03-07 ATRP Solutions, Inc. Salt-tolerant star macromolecules
CN102298668B (zh) * 2011-05-30 2014-07-09 复旦大学 共聚反应中分批加料工艺条件的蒙特卡洛模拟方法
CN102289559B (zh) * 2011-05-30 2014-07-09 复旦大学 蒙特卡洛模拟预测自由基共聚体系中共聚物序列分布的方法
WO2013158183A2 (en) 2012-01-27 2013-10-24 Carnegie Mellon University Processable self-organizing nanoparticles
KR101605585B1 (ko) * 2012-06-05 2016-03-22 주식회사 엘지화학 중합체의 제조방법 및 그에 의하여 제조된 중합체
JP6294885B2 (ja) 2012-08-30 2018-03-14 エーティーアールピー ソリューションズ インコーポレイテッドＡＴＲＰ Ｓｏｌｕｔｉｏｎｓ，Ｉｎｃ． 星形高分子、星形高分子組成物および星形高分子の製造方法
US9139715B2 (en) 2012-09-14 2015-09-22 Silberline Manufacturing Co., Inc. Coating of metal pigments using phosphonic acid-based compounds
US9006362B2 (en) * 2012-10-16 2015-04-14 Henkel IP & Holding GmbH Controlled radical polymerization of (meth)acrylate monomers
CN102911304B (zh) * 2012-11-12 2014-05-07 鲁东大学 一种制备高全同立构聚丙烯腈树脂的方法
CN105263978B (zh) 2013-02-04 2018-04-17 Atrp解决方案公司 耐盐星形大分子
HUE037180T2 (hu) 2013-03-15 2018-08-28 Commonwealth Scient And Industrial Research Organization Akrilnitrilbõl származó polimer
WO2014172557A1 (en) 2013-04-18 2014-10-23 Carnegie Mellon University Functionalized polymer hybrids
CN104162450B (zh) * 2013-05-16 2016-04-13 河北科技大学 聚合物刷负载2,2,6,6-四甲基哌啶-n-氧自由基催化体系的制备方法
WO2014189610A1 (en) 2013-05-22 2014-11-27 Triblue Corporation Methods of forming a polymer layer on a polymer surface
JP6463361B2 (ja) 2013-09-08 2019-01-30 コディアック サイエンシーズ インコーポレイテッドＫｏｄｉａｋ Ｓｃｉｅｎｃｅｓ Ｉｎｃ． 第ｖｉｉｉ因子両性イオンポリマーコンジュゲート
CN103788266B (zh) * 2014-02-12 2016-03-30 中国科学院长春应用化学研究所 一种原子转移自由基聚合的方法
US9840553B2 (en) 2014-06-28 2017-12-12 Kodiak Sciences Inc. Dual PDGF/VEGF antagonists
MX2017000076A (es) 2014-07-03 2017-05-01 Atrp Solutions Inc Macromoleculas estrellas compatibles con tensoactivos.
JP6849590B2 (ja) 2014-10-17 2021-03-24 コディアック サイエンシーズ インコーポレイテッドＫｏｄｉａｋ Ｓｃｉｅｎｃｅｓ Ｉｎｃ． ブチリルコリンエステラーゼ両性イオン性ポリマーコンジュゲート
KR20180104635A (ko) 2015-12-30 2018-09-21 코디악 사이언시스 인코포레이티드 항체 및 이의 접합체
WO2017132137A1 (en) 2016-01-25 2017-08-03 Carnegie Mellon University Composite composition and modification of inorganic particles for use in composite compositions
WO2018007869A1 (en) 2016-07-02 2018-01-11 Rheomod De Mexico, S.A.P.I. De C.V. Grafted polymers
US10982266B2 (en) 2016-11-03 2021-04-20 Carnegie Mellon University Nucleic acid-polymer conjugates for bright fluorescent tags
US20190358335A1 (en) 2017-01-12 2019-11-28 Alan J. Russell Stomach acid-stable and mucin-binding protein-polymer conjugates
AU2018250695A1 (en) 2017-04-14 2019-11-07 Kodiak Sciences Inc. Complement factor D antagonist antibodies and conjugates thereof
US11857634B2 (en) 2018-04-20 2024-01-02 University of Pittsburgh—of the Commonwealth System of Higher Education Cationic amphiphilic polymers for codelivery of hydrophobic agents and nucleic acids
US11472894B2 (en) 2018-07-23 2022-10-18 Carnegie Mellon University Enzyme-assisted ATRP procedures
CN113195644B (zh) * 2018-12-19 2023-01-24 汉高股份有限及两合公司 通过原位聚合进行的对着基材的涂覆
CN109810224B (zh) * 2019-01-24 2020-06-09 中国石油大学(北京) 电子转移活化再生催化剂引发体系及成胶时间控制方法
US11667734B2 (en) 2019-02-14 2023-06-06 Drexel University Oxygen tolerant and room temperature raft through alkylborane initiation
WO2020172330A1 (en) 2019-02-20 2020-08-27 Ppg Industries Ohio, Inc. Dispersions containing graphenic carbon nanoparticles and dispersant resins
CN110498870B (zh) * 2019-07-17 2021-11-26 山东科技大学 一种利用天然材料制备pmma微球的方法
CN114786731A (zh) 2019-10-10 2022-07-22 科达制药股份有限公司 治疗眼部病症的方法
CN110922547B (zh) * 2019-12-11 2023-02-28 安徽大学 一种双锚固型嵌段共聚物及其制备方法和用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087819A1 (en) * 2004-03-05 2005-09-22 Carnegie Mellon University Atom transfer radical polymerization process

Family Cites Families (131)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US795355A (en) * 1904-12-10 1905-07-25 Julian P Lyon Jar-closure.
US3037004A (en) 1958-10-07 1962-05-29 Nat Lead Co Aqueous phase polymerization of vinyl monomers with organic cocatalysts
US3096312A (en) 1960-08-26 1963-07-02 Ronald A Henry Polymers and copolymers of 5-vinyltetrazole
US3183217A (en) 1961-03-01 1965-05-11 Exxon Research Engineering Co Copolymerization of polar with nonpolar monomers in the presence of a friedel-craftsand a free radical initator
US3350374A (en) 1963-04-30 1967-10-31 Nopco Chem Co Methods for preparing polymers of hydroxytetrazole compounds and polymers of hydrazide oxime compounds, and products
US3397186A (en) 1966-04-12 1968-08-13 American Cyanamid Co Triaminoguanidinium salts of 5-vinyl tetrazole polymers and a method for their preparation
US3862978A (en) 1967-08-24 1975-01-28 Dow Chemical Co Catalytic synthesis of organic halogen compounds from an ethylenically unsaturated compound and a halogenated organic compound
US4007165A (en) 1971-06-01 1977-02-08 Pennwalt Corporation Unsymmetrical tertiary-aliphatic azoalkanes
US3959225A (en) 1974-03-20 1976-05-25 Exxon Research And Engineering Company Thermally-staged polymer process
US3963491A (en) 1974-06-27 1976-06-15 Xerox Corporation Imaging method
US4145586A (en) 1974-11-25 1979-03-20 Swann David A Electric switches
JPS51116224A (en) 1975-04-02 1976-10-13 Toho Rayon Co Ltd A process and an apparatus for producing carbon fibers
US4374751A (en) 1980-08-08 1983-02-22 General Electric Company Polymerization initiator compositions
US4384093A (en) 1981-04-15 1983-05-17 Ashland Oil, Inc. Copolymers derived from 1,3 dioxepins and maleic anhydride or maleimides and methods
DE3486145T2 (de) 1983-07-11 1993-09-23 Commw Scient Ind Res Org Verfahren zur polymerisation und nach diesem verfahren hergestellte polymere.
US5210109A (en) 1983-11-16 1993-05-11 Dentsply Research & Development Corp. Interpenetrating polymer network compositions employing rubber-modified polymers
US5324879A (en) 1985-12-03 1994-06-28 Commonwealth Scientific And Industrial Research Organisation Oligomerization process
GB8617559D0 (en) 1986-07-18 1986-08-28 Raychem Ltd Gels
US4728706A (en) 1986-08-29 1988-03-01 E. I. Du Pont De Nemours And Company Titanium, zirconium- and hafnium containing initiators in the polymerization of acrylic monomers to "living" polymers
AU7895387A (en) 1986-09-29 1988-03-31 E.I. Du Pont De Nemours And Company Living polymers from unsaturated si, sn or ge initiators
US4806605A (en) 1987-01-27 1989-02-21 E. I. Du Pont De Nemours And Company Monomers and initiators for group transfer polymerization
US5089135A (en) 1988-01-20 1992-02-18 Mitsubishi Rayon Co., Ltd. Carbon based porous hollow fiber membrane and method for producing same
US4940648A (en) 1988-02-12 1990-07-10 Hoechst Celanese Corporation Increased sensitivity photoinitiation compositions
US4940760A (en) 1988-02-16 1990-07-10 E. I. Du Pont De Nemours And Company Group Transfer Polymerization process employing supported initiators
KR900700923A (ko) 1988-02-17 1990-08-17 야마구찌 도시아끼 포토레지스트 조성물
US5254651A (en) 1988-04-04 1993-10-19 American Cyanamid Company Room temperature curing, alternating isopropenyl-dimethylbenzylisocyanate copolymers having high isocyanate functionality
US5169914A (en) 1988-05-03 1992-12-08 Edison Polymer Innovation Corporation Uniform molecular weight polymers
CA1326322C (en) 1988-05-03 1994-01-18 Gabor Kaszas Uniform molecular weight polymers
US5331088A (en) 1988-12-19 1994-07-19 Meister John J Process for making graft copolymers from lignite and vinyl monomers
US4954416A (en) 1988-12-21 1990-09-04 Minnesota Mining And Manufacturing Company Tethered sulfonium salt photoinitiators for free radical polymerization
JP3100968B2 (ja) 1989-12-11 2000-10-23 日本ウエルディング・ロッド株式会社 グリーンボディからバインダーを除去する方法
JP2958103B2 (ja) 1989-12-12 1999-10-06 エーザイ株式会社 プラズマ照射固形製剤
CA2032581C (en) 1989-12-20 2002-03-12 Karel Ulbrich Hydrolytically degradable hydrophilic gels and the method for preparation thereof
US5102967A (en) 1989-12-27 1992-04-07 General Electric Company Process for making polysilsequioxane and polymethyl-n-hexylsilsesquioxane coating compositions and coating compositions formed thereby
US5026813A (en) 1989-12-27 1991-06-25 General Electric Company Polysilsequioxane and polymethyl-N-hexylsilsesquioxane coating compositions
JPH0759602B2 (ja) 1990-04-03 1995-06-28 日本ゼオン株式会社 重合体の製造方法
US5281681A (en) 1990-12-27 1994-01-25 Exxon Chemical Patents Inc. Photodegradable and biodegradable polyethylene
US5206303A (en) 1990-12-27 1993-04-27 Exxon Chemical Patents Inc. Entanglement-inhibited macromolecules
DE69223515T2 (de) 1991-07-15 1998-06-25 Exxon Chemical Patents Inc Lebendes karbokationisches polymerisationsverfahren
US5322912A (en) 1992-11-16 1994-06-21 Xerox Corporation Polymerization processes and toner compositions therefrom
CA2110654C (en) 1992-12-17 2006-03-21 Albert Rossi Dilute process for the polymerization of ethylene/alpha-olefin copolymer using metallocene catalyst systems
US5510212A (en) 1993-01-13 1996-04-23 Delnick; Frank M. Structural micro-porous carbon anode for rechargeable lithium ion batteries
US5405913A (en) 1993-03-22 1995-04-11 The University Of Akron Free radical copper(II)-enolate polymerization initiators
US5508353A (en) 1993-03-29 1996-04-16 Mobil Oil Corporation Comb graft polymers and their use in functional fluids
US5510307A (en) 1993-04-08 1996-04-23 Isp Investments Inc. Free radical initiator delivery system
JPH06322171A (ja) 1993-05-12 1994-11-22 Mitsui Petrochem Ind Ltd 開孔フィルムの製造方法
US5312871A (en) 1993-07-27 1994-05-17 Carnegie Mellon University Free radical polymerization process
US5466780A (en) 1994-03-30 1995-11-14 Exxon Chemical Patents Inc. Process for converting polyketones to polyesters
WO1996000654A1 (en) 1994-06-30 1996-01-11 The Deville Group, Inc. Fluoropolymer compositions and preparation and uses thereof
US5558954A (en) 1994-10-13 1996-09-24 Polystor Corporation Preparation of carbon electrodes by polymer-precipitation
US5833320A (en) 1994-11-25 1998-11-10 Yamaha Hatsudoki Kabushiki Kaisha Vehicle seat and shock-absorbing material
US5530079A (en) 1995-01-03 1996-06-25 Xerox Corporation Polymerization processes
FR2730240A1 (fr) 1995-02-07 1996-08-09 Atochem Elf Sa Stabilisation d'un polymere par un radical libre stable
US5708102A (en) 1995-03-03 1998-01-13 E. I. Du Pont De Nemours And Company Living radical polymerization of vinyl monomers
US5763548A (en) 1995-03-31 1998-06-09 Carnegie-Mellon University (Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization
US6541580B1 (en) 1995-03-31 2003-04-01 Carnegie Mellon University Atom or group transfer radical polymerization
US5656708A (en) 1995-06-05 1997-08-12 Meister; John J. Process for making graft copolymers from lignite and vinyl monomers
US5807937A (en) 1995-11-15 1998-09-15 Carnegie Mellon University Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties
US5668188A (en) 1996-01-16 1997-09-16 Sandia Corporation Process for preparing silicon carbide foam
JP3806475B2 (ja) 1996-02-08 2006-08-09 株式会社カネカ 末端に官能基を有する（メタ）アクリル系重合体の 製造方法
US5700844A (en) 1996-04-09 1997-12-23 International Business Machines Corporation Process for making a foamed polymer
US6254854B1 (en) 1996-05-24 2001-07-03 The Penn Research Foundation Porous particles for deep lung delivery
WO1997047661A1 (en) 1996-06-12 1997-12-18 University Of Warwick Polymerisation catalyst and process
EP0816385B1 (en) 1996-06-26 2002-01-30 Kaneka Corporation Process for preparing vinyl polymer
US5789487A (en) 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
TW505665B (en) 1996-08-09 2002-10-11 Du Pont Process for polymerization of olefinic monomers
FR2752237B1 (fr) 1996-08-12 1998-09-18 Atochem Elf Sa Procede de polymerisation ou copolymerisation radicalaire controlee de monomeres (meth)acryliques et vinyliques et (co)polymeres obtenus
FR2752238B1 (fr) 1996-08-12 1998-09-18 Atochem Elf Sa Procede de polymerisation ou copolymerisation radicalaire controlee de monomeres (meth)acryliques et vinyliques et (co)polymeres obtenus
US5910549A (en) 1996-08-22 1999-06-08 Carnegie-Mellon University Method for preparation of alkoxyamines from nitroxyl radicals
FR2752845B1 (fr) 1996-08-30 1998-10-30 Atochem Elf Sa Procede de (co)polymerisation radicalaire controlee de monomeres (meth)acryliques et vinyliques en presence d'un complexe de fe, ru ou os et (co)polymeres obtenus
US6191197B1 (en) 1996-09-23 2001-02-20 Bridgestone Corporation Extended polymer compostion derived from blends of elastomers and syndiotactic polystyrene
ZA978537B (en) 1996-09-23 1998-05-12 Focal Inc Polymerizable biodegradable polymers including carbonate or dioxanone linkages.
US6284850B1 (en) 1996-11-01 2001-09-04 E. I. Du Pont De Nemours And Company Polymerization of vinyl monomers
FR2755441B1 (fr) 1996-11-07 1998-12-24 Atochem Elf Sa Procede de (co)polymerisation radicalaire controlee de monomeres (meth)acryliques, vinyliques, vinylideniques et dieniques en presence d'un complexe de rh, co ou ir
FR2757865B1 (fr) 1996-12-26 1999-04-02 Atochem Elf Sa Procede de polymerisation ou copolymerisation radicalaire controlee de monomeres (meth)acryliques, vinyliques, vinylideniques et dieniques et (co)polymeres obtenus
US6126919A (en) 1997-02-07 2000-10-03 3M Innovative Properties Company Biocompatible compounds for pharmaceutical drug delivery systems
EP0864362B1 (en) 1997-03-10 2003-11-05 Japan Science and Technology Corporation Process for producing a composite structure consisting of metallic nanoparticles coated with an organic polymer
US7125938B2 (en) 1997-03-11 2006-10-24 Carnegie Mellon University Atom or group transfer radical polymerization
CN1165828A (zh) 1997-03-13 1997-11-26 华东理工大学 一种可以控制聚合反应的催化剂及应用
JP3946309B2 (ja) 1997-04-10 2007-07-18 富士フイルム株式会社 着色感光性組成物
US5886118C1 (en) 1997-04-14 2001-02-20 Univ Case Western Reserve Process for polymerizing acrylonitrile
US5910530A (en) 1997-05-19 1999-06-08 Bridgestone Corporation High damping gel derived from extending grafted elastomers and polypropylene
US5773538A (en) 1997-07-16 1998-06-30 E. I. Du Pont De Nemours And Company Process for polymerization of olefinic monomers
JP4443643B2 (ja) 1997-07-30 2010-03-31 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 表面処理剤および表面処理されたｅｐｄｍ物品
US5891971A (en) 1997-08-15 1999-04-06 Xerox Corporation Polymerization processes
DE19738913B4 (de) 1997-09-05 2004-03-18 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Blockcopolymerphasen als Template für strukturierte organisch-anorganische Hybridmaterialien
US6143848A (en) 1997-10-23 2000-11-07 The B.F.Goodrich Company End-functionalized polymers by controlled free-radical polymerization process and polymers made therefrom
BR9907687A (pt) 1998-02-09 2000-11-14 Rpc Inc Processo para o tratamento de catalisador cobalto em misturas de oxidação de hidrocarbonetos a ácidos dibásicos
US6121371A (en) * 1998-07-31 2000-09-19 Carnegie Mellon University Application of atom transfer radical polymerization to water-borne polymerization systems
AUPP337298A0 (en) 1998-05-07 1998-05-28 University Of Melbourne, The Process for microgel preparation
US5998537A (en) 1998-09-21 1999-12-07 Dow Corning Corporation Emulsions containing ultrahigh viscosity silicone polymers
GB9902564D0 (en) 1999-02-08 1999-03-24 Ici Plc Production of vinylic polymers
WO2000056795A1 (en) 1999-03-23 2000-09-28 Carnegie Mellon University Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby
JP3940546B2 (ja) 1999-06-07 2007-07-04 株式会社東芝 パターン形成方法およびパターン形成材料
DE60027309T2 (de) 1999-07-02 2006-08-31 Symyx Technologies, Inc., Santa Clara Polymerverzweigungen zur immobilisierung von molekülen auf oberflächen oder substraten, wobei die polymere wasserlösliche oder wasserdispergierbare segmente und sonden aufweisen
US6670299B1 (en) 1999-07-03 2003-12-30 Northwestern University Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts
US7049373B2 (en) 1999-08-06 2006-05-23 Carnegie Mellon University Process for preparation of graft polymers
US6288184B1 (en) 1999-09-29 2001-09-11 Sri International Hydrolytically degradable olefin copolymers
US7037992B2 (en) 1999-09-29 2006-05-02 Sri International Olefin copolymers containing hydrolytically cleavable linkages and use thereof in degradable products
US6576718B1 (en) 1999-10-05 2003-06-10 General Electric Company Powder coating of thermosetting resin(s) and poly(phenylene ethers(s))
US7064151B1 (en) 2000-04-07 2006-06-20 E. I. Du Pont De Nemours And Company Process of microgel synthesis and products produced therefrom
SE0001309D0 (sv) 2000-04-10 2000-04-10 Pharmacia & Upjohn Bv Hydrogels and methods for their production
EP1337563B1 (en) 2000-10-06 2006-12-20 Carnegie-Mellon University Polymerization process for ionic monomers
US7332550B2 (en) 2000-10-06 2008-02-19 Carnegie Mellon University Stabilization of transition metal complexes for catalysis in diverse environments
AU2002211467A1 (en) 2000-10-06 2002-04-15 Carnegie-Mellon University Preparation of nanocomposite structures by controlled polymerization
US6790919B2 (en) 2000-10-06 2004-09-14 Carnegie Mellon University Catalyst system for controlled polymerization
EP1236742A1 (en) 2001-02-28 2002-09-04 Bayer Ag Controlled free-radical polymerization products using new control agents
AU2002307151A1 (en) 2001-04-06 2002-10-21 Carnegie Mellon University A process for the preparation of nanostructured materials
DE10228228A1 (de) 2001-09-14 2003-04-03 Merck Patent Gmbh Formkörper aus Kern-Mantel-Partikeln
WO2003031480A2 (en) 2001-10-12 2003-04-17 Carnegie Mellon University Process for monomer sequence control in polymerizations
US6759491B2 (en) * 2001-10-12 2004-07-06 Carnegie Mellon University Simultaneous reverse and normal initiation of ATRP
US6672717B2 (en) 2001-11-13 2004-01-06 Xerox Corporation Ink jet printing with inks containing cationic-anionic monomer pairs
ATE421540T1 (de) 2002-02-11 2009-02-15 Rhodia Chimie Sa Verfahren zur regulierung der stabilität von emulsionen und stabilisierten emulsionen
US6784248B2 (en) 2002-02-15 2004-08-31 Ppg Industries Ohio, Inc. Thermosetting compositions containing alternating copolymers of isobutylene type monomers
US6686432B2 (en) 2002-02-15 2004-02-03 Ppg Industries Ohio, Inc. Alternating copolymers of isobutylene type monomers
US7018655B2 (en) 2002-03-18 2006-03-28 Labopharm, Inc. Amphiphilic diblock, triblock and star-block copolymers and their pharmaceutical compositions
US6828025B2 (en) 2002-05-24 2004-12-07 Mcmaster University Microencapsulation of polar liquids in copolymer shells
KR100517101B1 (ko) 2002-07-31 2005-09-27 한국과학기술연구원 이중 자극 응답성 하이드로젤 및 이의 제조 방법
WO2004014963A2 (en) 2002-08-09 2004-02-19 Carnegie Mellon University Polymers, supersoft elastomers and methods for preparing the same
US20070155926A1 (en) 2003-03-28 2007-07-05 Krzysztof Matyjaszewski Degradable polymers
US20050090632A1 (en) 2003-06-06 2005-04-28 Carnegie Mellon University Noel (co) polymers and a novel polymerization process based on atom (or group) transfer radical polymerization
DE10357679A1 (de) 2003-12-10 2005-07-07 Merck Patent Gmbh Effektfarbmittel enthaltend Kern-Mantel-Partikel
WO2005087818A1 (en) 2004-03-05 2005-09-22 Carnegie Mellon University Preparation of functional polymers
US20070106012A1 (en) 2005-02-11 2007-05-10 Krzysztof Matyjaszewski Modified carbon particles
EP1928919B1 (en) 2005-08-23 2010-02-17 Carnegie-Mellon University Atom transfer radical polymerization in microemulsion and true emulsion polymerization
WO2007059350A2 (en) 2005-11-17 2007-05-24 Carnegie Mellon University Preparation of alkoxyamines
US20090171024A1 (en) 2005-12-21 2009-07-02 Carnegie Mellon University Preparation of block copolymers
WO2008057163A2 (en) 2006-10-09 2008-05-15 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
WO2008148000A1 (en) 2007-05-23 2008-12-04 Carnegie Mellon University Atom transfer dispersion polymerization
GB2463198B (en) 2007-05-23 2013-05-22 Univ Carnegie Mellon Hybrid particle composite structures with reduced scattering
EP2257573B1 (en) 2008-03-07 2019-06-26 Carnegie Mellon University Improved controlled radical polymerization processes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087819A1 (en) * 2004-03-05 2005-09-22 Carnegie Mellon University Atom transfer radical polymerization process

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
BAUMANN, M.; ROLAND, A.-I.; SCHMIDT-NAAKE, G.; FISCHER, H, MACROMOLECULAR MATERIALS AND ENGINEERING, vol. 280/281, 2000, pages 1 - 6
HOVESTAD, N. J., MACROMOLECULES, vol. 33, 2000, pages 4048 - 4052
LAZZARI, M; CHIANTORE, O.; MENDICHI, R.; LOPEZ-QUINTELA, M. A, MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 206, 2005, pages 1382 - 1388
MATYJASZEWSKI K ET AL: "Atom transfer radical polymerization", September 2001, CHEMICAL REVIEWS, ACS,WASHINGTON, DC, US, PAGE(S) 2921-2990, ISSN: 0009-2665, XP002212148 *
MATYJASZEWSKI, K.; DAVIS, K.; PATTEN, T. E; WEI, M., TETRAHEDRON, vol. 53, 1997, pages 15321 - 15329
WANG, F.; SAYRE, L.. M., J. AM. CHEM. SOC., vol. 114, 1992, pages 248 - 255

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8349410B2 (en) 2006-08-17 2013-01-08 University of Pittsburgh—of the Commonwealth System of Higher Education Modification of surfaces with polymers
US8871831B2 (en) 2006-08-17 2014-10-28 University of Pittsburgh—of the Commonwealth System of Higher Education Modification of surfaces with polymers
US8367051B2 (en) 2006-10-09 2013-02-05 Carnegie Mellon University Preparation of functional gel particles with a dual crosslink network
US8865797B2 (en) 2007-05-23 2014-10-21 Carnegie Mellon University Hybrid particle composite structures with reduced scattering
US8252880B2 (en) 2007-05-23 2012-08-28 Carnegie Mellon University Atom transfer dispersion polymerization
US9012528B2 (en) 2008-12-22 2015-04-21 ATRP Solutions, Inc. Control over controlled radical polymerization processes
US9856331B2 (en) 2008-12-22 2018-01-02 ATRP Solutions, Inc. Control over reverse addition fragmentation transfer polymerization processes
US9546225B2 (en) 2008-12-22 2017-01-17 ATRP Solutions, Inc. Control over controlled radical polymerization processes
US8815971B2 (en) * 2008-12-22 2014-08-26 ATRP Solutions, Inc. Control over controlled radical polymerization processes
US9518136B2 (en) 2008-12-22 2016-12-13 ATRP Solutions, Inc. Control over reverse addition fragmentation transfer polymerization processes
US20110082230A1 (en) * 2008-12-22 2011-04-07 Wojciech Jakubowski Control over controlled radical polymerization processes
CN101508757B (zh) * 2009-03-17 2011-05-18 南京工业大学 一种使用atrp对聚苯乙烯树脂接枝改性的方法
US8962764B2 (en) 2009-03-27 2015-02-24 Carnegie Mellon University Preparation of functional star macromolecules
WO2010123575A1 (en) 2009-04-23 2010-10-28 Atrp Solutions Inc Well defined stars with segmented arms
WO2011075156A1 (en) * 2009-12-18 2011-06-23 ATRP Solutions, Inc. Improved control over controlled radical polymerization processes
US9644042B2 (en) 2010-12-17 2017-05-09 Carnegie Mellon University Electrochemically mediated atom transfer radical polymerization
US20140183055A1 (en) * 2010-12-17 2014-07-03 Krzysztof Matyjaszewski Electrochemically mediated atom transfer radical polymerization
US10072042B2 (en) 2011-08-22 2018-09-11 Carnegie Mellon University Atom transfer radical polymerization under biologically compatible conditions
US9533297B2 (en) 2012-02-23 2017-01-03 Carnegie Mellon University Ligands designed to provide highly active catalyst complexes
JPWO2015163383A1 (ja) * 2014-04-25 2017-04-20 国立研究開発法人産業技術総合研究所 表面改質方法、表面改質材料及び重合液
US9982070B2 (en) 2015-01-12 2018-05-29 Carnegie Mellon University Aqueous ATRP in the presence of an activator regenerator
US11174325B2 (en) 2017-01-12 2021-11-16 Carnegie Mellon University Surfactant assisted formation of a catalyst complex for emulsion atom transfer radical polymerization processes
CN112946160A (zh) * 2021-02-09 2021-06-11 新疆大学 一种活性物质贡献率的计算方法、系统、设备及其存储介质
CN112946160B (zh) * 2021-02-09 2022-10-25 新疆大学 一种活性物质贡献率的计算方法、系统、设备及其存储介质

Also Published As

Publication number Publication date
DE602006017416D1 (de) 2010-11-18
US20110065875A1 (en) 2011-03-17
EP1943278A1 (en) 2008-07-16
EP1943278B1 (en) 2010-10-06
CN101379091B (zh) 2012-05-30
US7893173B2 (en) 2011-02-22
CN101379091A (zh) 2009-03-04
US20090312505A1 (en) 2009-12-17

Similar Documents

Publication Publication Date Title
US7893173B2 (en) Polymerization process with catalyst reactivation
JP6800700B2 (ja) ラジカル重合プロセスの制御を通じた制御の改善
US11390696B2 (en) Control over controlled radical polymerization processes
Braunecker et al. Controlled/living radical polymerization: Features, developments, and perspectives
Allan et al. Organometallic mediated radical polymerization
US20090171024A1 (en) Preparation of block copolymers
Zhang et al. Controlled/“living” radical polymerization of 2-(dimethylamino) ethyl methacrylate
Bai et al. Activators generated by electron transfer for atom transfer radical polymerization: recent advances in catalyst and polymer chemistry
US7893174B2 (en) Atom transfer radical polymerization process
Hurtgen et al. Solving the problem of bis (acetylacetonato) cobalt (II)-mediated radical polymerization (CMRP) of acrylic esters
EP1928919A2 (en) Atom transfer radical polymerization in microemulsion and true emulsion polymerization
Wootthikanokkhan et al. Atom transfer radical polymerizations of (meth) acrylic monomers and isoprene
EP2325213A1 (en) Catalyst for living radical polymerization
Grishin et al. Radical-initiated controlled synthesis of homo-and copolymers based on acrylonitrile
Meng et al. Atom transfer radical polymerization of 6‐O‐methacryloyl‐1, 2; 3, 4‐di‐O‐isopropylidene‐D‐galactopyranose in solution
Kwak et al. ATRP of styrene and methyl methacrylate with less efficient catalysts and with alkyl pseudohalides as initiators/chain transfer agents
Yu et al. Controlled radical polymerization catalyzed by copper (I)–sparteine complexes
Wang et al. Low temperature effect on ATRP of styrene and substituted styrenes enabled by SaBOX ligand
Limer et al. Reverse atom transfer radical polymerisation (RATRP) of methacrylates using copper (I)/pyridinimine catalysts in conjunction with AIBN
Amass et al. N-alkyl-2-pyridinemethanimine mediated atom transfer radical polymerisation of styrene: the transition from heterogeneous to homogeneous catalysis
Ambade Controlled radical polymerization
Alipour et al. Living radical polymerization of methylmethacrylate, methylacrylate and their block copolymers with acrylonitrile by atom transfer radical polymerization
Destarac et al. The importance of the nature of initiator and solvent in atom transfer radical polymerization of methyl methacrylate catalyzed by copper (I) N‐alkyl‐2‐pyridylmethanimine complexes
Matyjaszewski 1 New catalysts for controlled/living atom transfer radical polymerization (ATRP)
Chan-Seng et al. Stable free radical polymerization of n-butyl acrylate in the presence of high-temperature initiators

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680040402.8

Country of ref document: CN

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006813937

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11990841

Country of ref document: US