[go: up one dir, main page]

WO2002030996A2 - Amorceurs multi-fonctionnels pour la polymerisation radicalaire a transfert d'atomes - Google Patents

Amorceurs multi-fonctionnels pour la polymerisation radicalaire a transfert d'atomes Download PDF

Info

Publication number
WO2002030996A2
WO2002030996A2 PCT/US2001/032141 US0132141W WO0230996A2 WO 2002030996 A2 WO2002030996 A2 WO 2002030996A2 US 0132141 W US0132141 W US 0132141W WO 0230996 A2 WO0230996 A2 WO 0230996A2
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
initiator
meth
radical polymerization
carbon atoms
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2001/032141
Other languages
English (en)
Other versions
WO2002030996A3 (fr
Inventor
Kevin C. Olson
James B. O'dwyer
Simion Coca
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PPG Industries Ohio Inc
Original Assignee
PPG Industries Ohio Inc
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 PPG Industries Ohio Inc filed Critical PPG Industries Ohio Inc
Priority to AU2002215351A priority Critical patent/AU2002215351A1/en
Publication of WO2002030996A2 publication Critical patent/WO2002030996A2/fr
Publication of WO2002030996A3 publication Critical patent/WO2002030996A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C08F4/00—Polymerisation catalysts

Definitions

  • Catalysts that may be used in the ATRP preparation of the (co)polymer of the present invention include any transition metal compound that can participate in a redox cycle with the initiator and the growing (co)polymer chain. It is preferred that the transition metal compound not form direct metal bonds with the polymer chain.
  • heterocyclyl refers to pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl, indolyl, isoindolyl, indazolyl, benzofuryl, isobenzofuryl, benzothienyl, isobenzothienyl, chromenyl, xanthenyl, purinyl, pteridinyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phenoxathiinyl, carbazolyl, cinnolinyl, phenanthridinyl, acridinyl, 1,10-phenanthrolinyl, phenazinyl, phenoxaziny
  • Preferred heterocyclyl groups include pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl and indolyl, the most preferred heterocyclyl group being pyridyl.
  • Ri, R 2 , R 3 and R_ 4 are preferably lower alkyl, from 1 to 6 carbon atoms, and most preferably lower alkyl from 1 to 4 carbon atoms.
  • any radically polymerizable alkene containing a polar group can serve as a monomer for polymerization.
  • the preferred monomers are ethylenically unsaturated monomers include those of general formula IV:
  • the residues may each independently be residues of monomers having more than one (meth)acryloyl group, such as (meth)acrylic anhydride, diethyleneglycol bis(meth)acrylate, 4,4'- isopropylidenediphenol bis(meth)acrylate (Bisphenol A di(meth)acrylate), alkoxylated 4,4'-isopropylidenediphenol bis(meth)acrylate, trimethylolpropane tris(meth)acrylate and alkoxylated trimethylolpropane tris(meth)acrylate.
  • the terms "alkyl”, “alkenyl” and “alkynyl” refer to straight-chain or branched groups.
  • aryl also applies to the aryl groups in “aryloxy” and “aralkyl."
  • phenyl may be substituted from 1 to 5 times and naphthyl may be substituted from 1 to 7 times (preferably any aryl group, if substituted, is substituted from 1 to 3 times) with one of the above substituents.
  • aryl refers to phenyl, naphthyl, phenyl substituted from 1 to 5 times with fluorine or chlorine, and phenyl substituted from 1 to 3 times with a substituent selected from the group consisting of alkyl of from 1 to 6 carbon atoms, alkoxy of from 1 to 4 carbon atoms and phenyl.
  • aryl refers to phenyl and tolyl.
  • heterocyclyl refers to pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl, indolyl, isoindolyl, indazolyl, benzo furyl, isobenzofuryl, benzothienyl, isobenzothienyl, chromenyl, xanthenyl, purinyl, pteridinyl, quinolyl, isoquinolyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phenoxathiinyl, carbazolyl, cinnolinyl, phenanthridinyl, acridinyl, 1,10-phenanthrolinyl, phenazinyl, phen
  • Preferred heterocyclyl groups include pyridyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyranyl and indolyl, the most preferred heterocyclyl group being pyridyl.
  • those vinyl heterocycles which, when unsubstituted, contain an N— H group may be protected at that position with a conventional blocking or protecting group, such as a -C 6 alkyl group, a tris- Ci -C ⁇ 5 alkylsilyl group, an acyl group of the formula R ⁇ 3 CO (where R ⁇ 3 is alkyl of from 1 to 20 carbon atoms, in which each of the hydrogen atoms may be independently replaced by halide, preferably fluoride or chloride), alkenyl of from 2 to 20 carbon atoms (preferably vinyl), alkynyl of from 2 to 10 carbon atoms (preferably acetylenyl), phenyl which may be substituted with from 1 to 5 halogen atoms or alkyl groups of from 1 to 4 carbon atoms, or aralkyl (aryl-substituted alkyl, in which the aryl group is phenyl or substituted phenyl and the alkyl group is from 1 to 6 carbon
  • N-substituted maleimides include, but are not limited to, N-(C ⁇ -C 2 o linear or branched alkyl) maleimides, e.g., N-methyl maleimide, N-tertiary-butyl maleimide, N-octyl maleimide and N-icosane maleimide; N ⁇ (C 3 -C 8 cycloalkyl) maleimides, e.g., N- cyclohexyl maleimide; and N-(aryl) maleimides, e.g., N-phenyl maleimide, N-(C ⁇ -C 9 linear or branched alkyl substituted phenyl) maleimide, N-benzyl maleimide and N- (C ⁇ -C linear or branched alkyl substituted benzyl) maleimide.
  • N-(C ⁇ -C 2 o linear or branched alkyl) maleimides e.g., N-methyl maleimide, N
  • the oxirane functional monomer or its residue that is reacted with a carboxylic acid may be selected from, for example, glycidyl (meth)acrylate, 3,4- epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl) ethyl(meth)acrylate, allyl glycidyl ether and mixtures thereof.
  • carboxylic acids that may be reacted with the oxirane functional monomer or its residue include, but are not limited to, para-nitrobenzoic acid, hexanoic acid, 2-ethyl hexanoic acid, decanoic acid, undecanoic acid and mixtures thereof.
  • the amounts and relative proportions of the initiator, the transition metal compound and the ligand are those for which ATRP is most effectively performed.
  • the amount of initiator used can vary widely and is typically present in the reaction medium in a concentration of from 10 "4 moles / liter (M) to 3 M, for example, from 10 "3 M to 10 "1 M.
  • the molecular weight of the polymer product can be directly related to the relative concentrations of initiator and monomer(s), the molar ratio of initiator to monomer is an important factor in polymer preparation.
  • the molar ratio of initiator to monomer is typically within the range of 10 "4 : 1 to 0.5 : 1, for example, 10 "3 : 1 to 5 x 10 "2 : 1.
  • the molar ratio of transition metal compound to initiator is typically in the range of 10 "4 : 1 to 10 : 1, for example, 0.1 : 1 to 5 : 1.
  • the molar ratio of ligand to transition metal compound is typically within the range of 0.1 : 1 to 100 : 1, for example, 0.2 : 1 to 10 : 1.
  • the ATRP preparation of the (co)polymer typically is conducted at a reaction temperature within the range of 25°C to 140°C, preferably from 50°C to 100°C, and a pressure within the range of 1 to 100 atmospheres, usually at ambient pressure.
  • the atom transfer radical polymerization is typically completed in less than 24 hours, e.g., between 1 and 8 hours.
  • the ATRP transition metal catalyst and its associated ligand typically are separated or removed from the (co)polymer product prior to its use. Removal of the ATRP catalyst may be achieved using known methods, including, for example, adding a catalyst binding agent to the mixture of the (co)polymer, solvent, and catalyst, followed by filtering. Examples of suitable catalyst binding agents include, for example, alumina, silica, clay or a combination thereof. A mixture of the polymer, solvent, and ATRP catalyst may be passed through a bed of catalyst binding agent. Alternatively, the ATRP catalyst may be oxidized in situ, the oxidized residue of the catalyst being retained in the (co)polymer.
  • the initiators may include active hydrogen-containing groups to permit crosslinking of the initiator by known crosslinking methods.
  • the initiator may include other functionality, such as one or more ionic group or groups that can be converted into ionic groups, such as quaternary amine or sulfonium groups.
  • An ionic group-containing polymer prepared in such a manner can be useful as a component of an electrodepositable film-forming composition for use in preparing a coating layer on an electroconductive substrate.
  • the initiator may further contain an active group that permits grafting of other groups to the (co)polymer, such as (co)polymer chains that cannot be prepared by a controlled radical polymerization process.
  • An example of such a chain is a polyoxyalkylene chain, which may be useful in solubilizing the (co)polymer, depending upon the intended use for the (co)polymer.
  • (Co)polymers may be mixed (co)polymers produced by chain propagation in the presence of two monomers.
  • Block (co)polymers can be produced by chain propagation with a sequence of different monomers.
  • hydrophilic monomers i.e., a poly(alkylene glycol) (meth)acrylate
  • hydrophobic monomers i.e., an alkyl (meth)acrylate
  • the (co)polymer may have nonionic moieties, ionic moieties and combinations thereof, hi one embodiment of the present invention to introduce hydrophilic segments into the (co)polymer, the monomer can be selected from poly( alkylene glycol) (meth)acrylates; C ⁇ -C alkoxy poly(alkylene glycol) (meth)acrylates; hydroxyalkyl (meth)acrylates having from 2 to 4 carbon atoms in the alkyl group; N-(hydroxy C ⁇ -C alkyl) (meth)acrylamides (e.g., N-hydroxymethyl (meth)acrylamide and N-(2-hydroxyethyl) (meth)acrylamide); N,N-di-(hydroxy C ⁇ -C 4 alkyl) (meth)acrylamides (e.g., N,N-di(2-hydroxyethyl) (meth)acrylamide); carboxylic acid functional monomers; salts of carboxylic acid functional monomers; amine functional monomers; salts
  • Poly(alkylene glycol) (meth)acrylates and Cj-C 4 alkoxy poly(alkylene glycol) (meth)acrylates are prepared by known methods.
  • (meth)acrylic acid or hydroxyalkyl (meth)acrylate e.g., 2-hydroxyethyl (meth)acrylate
  • an alkyl (meth)acrylate may be transesterified with a C ⁇ -C alkoxy poly( alkylene glycol), e.g., methoxy poly(ethylene glycol).
  • poly(alkylene glycol) (meth)acrylates and C ⁇ -C 4 alkoxy poly(alkylene glycol) (meth)acrylates include, poly(ethylene glycol) (meth)acrylate and methoxy poly(ethylene glycol) (meth)acrylate, the poly(ethylene glycol) moiety of each having a molecular weight of from 100 to 800.
  • An example of a commercially available C alkoxy poly(alkylene glycol) (meth)acrylate is methoxy poly(ethylene glycol) 550 methacrylate monomer from Sartomer Company, Inc.
  • carboxylic acid functional monomers include, but are not limited to, (meth)acrylic acid, maleic acid, fumaric acid and undecylenic acid.
  • the monomer may be a residue of a precursor of a carboxylic acid functional monomer that is converted to a carboxylic acid residue after completion of the controlled radical polymerization, e.g., maleic anhydride, di(C ⁇ -C alkyl) maleates and C ⁇ -C alkyl (meth)acrylates.
  • residues of maleic anhydride can be converted to diacid residues, ester/acid residues or amide/acid residues by art-recognized reactions with water, alcohols or primary amines, respectively.
  • Residues of C ⁇ -C alkyl (meth)acrylates can be converted to (meth)acrylic acid residues by art-recognized ester hydrolyzation methods, which typically involve the concurrent removal of an alcohol, such as t-butanol by vacuum distillation.
  • Salts of carboxylic acid functional monomers include, for example, salts of (meth)acrylic acid and primary, secondary or tertiary amines, such as, butyl amine, dimethyl amine and triethyl amine.
  • Amine functional monomers include, for example, amino(C2-C alkyl) (meth)acrylates, e.g., 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate and 4-aminobutyl (meth)acrylate; N-(CpC 4 alkyl)amino(C 2 -C 4 alkyl) (meth)acrylates, e.g., N-methyl-2-aminoethyl (meth)acrylate; and N,N-di(C ⁇ -C 4 alkyl)amino(C2-C alkyl) (meth)acrylates, e.g., N,N-dimethyl-2-aminoethyl (meth)acrylate.
  • amino(C2-C alkyl) (meth)acrylates e.g., 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate and 4-aminobuty
  • the monomer may also comprise residues of salts of amine functional monomers, e.g., salts of those amine functional monomers as recited previously herein. Salts of the amine functional monomer residues may be formed by mixing a carboxylic acid, e.g., lactic acid, with the (co)polymer after completion of controlled radical polymerization.
  • the (co)polymer contains a segment that includes carboxylic acid functional monomers selected from (meth)acrylic acid, maleic anhydride, maleic acid, di(C ⁇ -C 4 alkyl) maleates, and mixtures thereof.
  • the polymer segment is a residue of amine functional monomers selected from amino(C 2 -C alkyl) (meth)acrylates, N-(C ⁇ -C 4 alkyl)amino(C 2 -C 4 alkyl) (meth)acrylates, N,N-di(C ⁇ -C alkyl)amino(C 2 -C alkyl) (meth)acrylates and mixtures thereof.
  • the (co)polymer also may contain a segment that contains cationic moieties selected from ammonium, sulphonium and phosphonium.
  • Ammonium, sulphonium and phosphonium moieties may be introduced into the graft copolymer by means known to the skilled artisan.
  • the N,N-dimethylamino moieties may be converted to ammonium moieties by mixing an acid, e.g., lactic acid, with the (co)polymer.
  • the oxirane groups may be used to introduce sulphonium or phosphonium moieties into the (co)polymer.
  • Sulphonium moieties may be introduced into the (co)polymer by reaction of the oxirane groups with thiodiethanol in the presence of an acid, such as lactic acid.
  • Reaction of the oxirane groups with a phosphine e.g., triphenyl phosphine or tributyl phosphine, in the presence of an acid, such as lactic acid, results in the introduction of phosphonium moieties into the (co)polymer.
  • a phosphine e.g., triphenyl phosphine or tributyl phosphine
  • the (co)polymer can be a block (co)polymer having one or more segments.
  • the (co)polymer may have the general formula VI:
  • each of A and B in general formula VI may represent one or more types of monomer residues, while p and s represent the average total number of A and B residues occurring per block or segment of A residues (A-block or A-segment) and B residues (B-block or B-segment), respectively, and ⁇ is the residue from the initiator and X is a halide.
  • the A- and B-blocks may each have at least one of random, block, e.g., di- block and tri-block, alternating and gradient architectures.
  • Gradient architecture refers to a sequence of different monomer residues that changes gradually in a systematic and predictable manner along the polymer backbone.
  • an A-block containing 6 residues of methyl methacrylate (MMA) and 6 residues of ethyl methacrylate (EMA), for which p is 12, may have di-block, tetra- block, alternating and gradient architectures as represented in general formulas VII, V ⁇ i, IX and X. v ⁇
  • the order in which monomer residues occur along the backbone of the (co)polymer typically is determined by the order in which the corresponding monomers are fed into the vessel in which the controlled radical polymerization is conducted.
  • the monomers that are incorporated as residues in the A- block of the graft (co)polymer are generally fed into the reaction vessel prior to those monomers that are incorporated as residues in the B-block.
  • the relative reactivities of the monomers typically determines the order in which they are incorporated into the living polymer chain.
  • Gradient sequences of monomer residues within the A- and B-blocks can be prepared by controlled radical polymerization, and, in particular, by ATRP methods by (a) varying the ratio of monomers fed to the reaction medium during the course of the polymerization, (b) using a monomer feed containing monomers having different rates of polymerization, or (c) a combination of (a) and (b).
  • (Co)polymers containing gradient architecture are described in further detail in United States Patent No. 5,807,937 at column 29, line 29 through column 31, line 35.
  • Subscripts p and s represent average numbers of residues occurring in the respective A- and B-blocks.
  • subscript s has a value of at least 1, and preferably at least 5 for general formula I.
  • subscript s has a value of typically less than 300, preferably less than 100, more preferably less than 50 and most preferably less than 20 for general formula I. The value of subscript s may range between any combination of these values, inclusive of the recited values, e.g., s may be a number from 1 to 100.
  • Subscript p may be 0, or may have a value of at least 1, and preferably at least 5.
  • Subscript p also typically has a value of less than 300, preferably less than 100, more preferably less than 50 and most preferably less than 20. The value of subscript p may range between any combination of these values, inclusive of the recited values, e.g., p may be a number from 0 to 50.
  • the (co)polymer typically has a number average molecular weight (Mn) of from 400 to 10,000, e.g., from 400 to 5,000 and most preferably from 400 to 1,500, as determined by gel permeation chromatography (GPC) using polystyrene standards.
  • Mn number average molecular weight
  • the polydispersity index, i.e., weight average molecular weight (Mw) divided by number average molecular weight (Mn), of graft portion(s) of the (co)polymer typically are less than 2.0, preferably less than 1.8 and most preferably less than 1.5.
  • ⁇ of general formula V is or is derived from the residue of the initiator used in the preparation of the (co)polymer by controlled radical polymerization, and is free of the radically transferable group of the initiator.
  • the symbol ⁇ , more specifically ⁇ - is the difunctional residue of formula XI:
  • R 1 ; R 2 , R 3 and R are ethyl.
  • the radically transferable group is a halide group, preferably a bromide group.
  • X may be the radically transferable halide groups of an ATRP initiator.
  • the halide residue may be (a) left on the (co)polymer, (b) removed, or (c) chemically converted to another moiety.
  • the radically transferable group may be removed by substitution with a nucleophilic compound, e.g., an alkali metal alkoxylate.
  • Graft-group-terminal halogens can be removed from the (co)polymer by means of a mild dehalogenation reaction.
  • the reaction is typically performed as a post-reaction after the graft (co)polymer has been formed, and in the presence of at least an ATRP catalyst.
  • the dehalogenation post-reaction is performed in the presence of both an ATRP catalyst and its associated ligand.
  • the (co)polymers of the present invention can be used as, without limitation, film-forming compositions, rheology modifiers, pigment or ink dispersants, gel matrices and molding resins.
  • the fields of use of the polymers are varied and include, without limitation, industrial uses, such as in the automotive industry, medical uses, such as in the production of novel films and matrices for use in bioengineering and tissue engineering, pharmaceutical uses, such as in the production of drug delivery matrices and chemical industry uses, such as in the preparation of gels for product separation and purification, and in chemical and biological research, such as in tailored gel matrices for reagent purification.
  • a monomeric initiator precursor having two radically transferable groups was prepared from the ingredients as enumerated in the following Table A. Table A
  • a monomeric initiator having two radically transferable groups (methylene bis-(diethyl 2-bromomalonate)) was prepared from the ingredients as enumerated in the following Table B.
  • Table B A monomeric initiator having two radically transferable groups (methylene bis-(diethyl 2-bromomalonate)) was prepared from the ingredients as enumerated in the following Table B.
  • Charge 1 was added to a 5 liter, 4-necked flask equipped with a motor driven glass stirrer, water cooled condenser, addition funnel, and a heating mantle and thermometer connected through a temperature feedback control device. With continuous stirring, Charge 2 was added to the flask over a period of 6.5 hours, during which time the contents of the flask were observed to exotherm to a temperature of 75°C. With the completion of the addition of Charge 2, the contents of the flask were stirred for an additional three hours. Upon complete reaction of the bromine marked by the disappearance of an orange color and the cooling of the contents to ambient room temperature, Charge 3 was added. The contents of the flask were transferred to a separatory funnel, the retained organic layer was dried over calcium sulfate and dichloromethane was removed by vacuum distillation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention a trait à un procédé de polymérisation radicalaire contrôlé, au cours duquel de nouveaux (co)polymères sont préparés au moyen d'amorceurs (dialkyle 2-halomalonate)-alkylène bis, tels qu'un méthylène bis-(diéthyle 2-bromomalonate). La présente invention concerne également de nouveaux produits (co)polymères du procédé.
PCT/US2001/032141 2000-10-13 2001-10-12 Amorceurs multi-fonctionnels pour la polymerisation radicalaire a transfert d'atomes Ceased WO2002030996A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002215351A AU2002215351A1 (en) 2000-10-13 2001-10-12 Multi-functional initiators for atom transfer radical polymerization

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US68701300A 2000-10-13 2000-10-13
US09/687,013 2000-10-13

Publications (2)

Publication Number Publication Date
WO2002030996A2 true WO2002030996A2 (fr) 2002-04-18
WO2002030996A3 WO2002030996A3 (fr) 2002-07-11

Family

ID=24758658

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/032141 Ceased WO2002030996A2 (fr) 2000-10-13 2001-10-12 Amorceurs multi-fonctionnels pour la polymerisation radicalaire a transfert d'atomes

Country Status (2)

Country Link
AU (1) AU2002215351A1 (fr)
WO (1) WO2002030996A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325213A4 (fr) * 2008-09-08 2011-11-02 Univ Kyoto Catalyseur pour polymérisation radicalaire vivante
WO2014062426A1 (fr) * 2012-10-16 2014-04-24 Henkel US IP LLC Polymérisation radicalaire contrôlée de monomères (méth)acryliques
CN111122557A (zh) * 2018-11-01 2020-05-08 武汉武药科技有限公司 一种测定偶氮二异丁腈自由基引发效率的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5789487A (en) * 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2325213A4 (fr) * 2008-09-08 2011-11-02 Univ Kyoto Catalyseur pour polymérisation radicalaire vivante
US8575285B2 (en) 2008-09-08 2013-11-05 Kyoto University Catalyst for living radical polymerization
WO2014062426A1 (fr) * 2012-10-16 2014-04-24 Henkel US IP LLC Polymérisation radicalaire contrôlée de monomères (méth)acryliques
US9006362B2 (en) 2012-10-16 2015-04-14 Henkel IP & Holding GmbH Controlled radical polymerization of (meth)acrylate monomers
CN111122557A (zh) * 2018-11-01 2020-05-08 武汉武药科技有限公司 一种测定偶氮二异丁腈自由基引发效率的方法
CN111122557B (zh) * 2018-11-01 2022-07-12 武汉武药科技有限公司 一种测定偶氮二异丁腈自由基引发效率的方法

Also Published As

Publication number Publication date
WO2002030996A3 (fr) 2002-07-11
AU2002215351A1 (en) 2002-04-22

Similar Documents

Publication Publication Date Title
US6590049B1 (en) Multi-functional initiators for atom transfer radical (Co)polymerization
KR100570245B1 (ko) 마이크로겔 및 그의 제조 방법
US6162882A (en) Preparation of novel homo- and copolymers using atom transfer radical polymerization
TW448189B (en) Process for the controlled radical polymerization or copolymerization of (meth)acrylic and vinyl monomers
KR100567615B1 (ko) 제어된 라디칼중합에 의한 블록중합체 합성방법
US6812291B1 (en) Method for block polymer synthesis by controlled radical polymerization from dithiocarbamate compounds
US6737486B2 (en) Polymerization process
WO2003027155A1 (fr) Copolymeres comprenant des (meth)acrylates a faible tension superficielle
JP2010520342A (ja) ポリアミン−ポリアクリレート分散剤
JP2007515538A (ja) 連鎖移動剤を使用した重合
JPWO2010140372A1 (ja) リビングラジカル重合の重合開始剤
JP2010513648A (ja) メタクリレート単位に基づくコポリマー、その調製方法及びその用途
US20030100675A1 (en) Coating compositions which contain a low surface tension (meth) acrylate containing block copolymer flow control agent
WO2002070575A2 (fr) Promoteurs d'adherence de copolymere de polyolefine acrylique halogenee
US6069205A (en) Block copolymers
US6586530B1 (en) Low surface tension (meth) acrylate containing block copolymer prepared by controlled radical polymerization
EP1776399B1 (fr) Polymeres monodisperses contenant des fractions d'acide (alkyl)acrylique, precurseurs, procedes de production de ces polymeres et leurs applications
WO2002030996A2 (fr) Amorceurs multi-fonctionnels pour la polymerisation radicalaire a transfert d'atomes
EP1085027B1 (fr) Polymere et procede de production de polymere
CN106046221B (zh) 一类可逆-休眠自由基聚合的催化剂及聚合方法
CN115746346B (zh) 具有高界面活性的混合壳型聚合物纳米粒子及其制备方法与应用
WO2003027159A2 (fr) Compositions contenant un copolymere sequence renfermant du (meth)acrylate a faible tension superficielle
KR20010041072A (ko) Ｎ-비닐 화합물로부터 중합체의 제조방법
CA1338834C (fr) Surfactifs polymeriques
JP2004067680A (ja) アルコキシアミンの合成方法およびそのラジカル重合における使用

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP