WO2000052061A1 - Utilisation d'un initiateur pour des reactions de polymerisation regulees - Google Patents

Utilisation d'un initiateur pour des reactions de polymerisation regulees Download PDF

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Publication number
WO2000052061A1
WO2000052061A1 PCT/GB2000/000695 GB0000695W WO0052061A1 WO 2000052061 A1 WO2000052061 A1 WO 2000052061A1 GB 0000695 W GB0000695 W GB 0000695W WO 0052061 A1 WO0052061 A1 WO 0052061A1
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WIPO (PCT)
Prior art keywords
group
initiator
polymerisation
reaction
independently
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PCT/GB2000/000695
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English (en)
Inventor
Jean De La Croi Habimana
Pierre Chevalier
Tristan Tapper
Original Assignee
Dow Corning Corporation
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
Priority claimed from GBGB9905121.1A external-priority patent/GB9905121D0/en
Priority claimed from GBGB9917329.6A external-priority patent/GB9917329D0/en
Application filed by Dow Corning Corporation filed Critical Dow Corning Corporation
Priority to JP2000602284A priority Critical patent/JP2002538236A/ja
Priority to AU28156/00A priority patent/AU2815600A/en
Priority to KR1020017011266A priority patent/KR20010102496A/ko
Priority to CA002363962A priority patent/CA2363962A1/fr
Priority to EP00906498A priority patent/EP1165628A1/fr
Publication of WO2000052061A1 publication Critical patent/WO2000052061A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • 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
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver

Definitions

  • the present invention relates to use of an initiator for controlled polymerisation reactions, in particular use of an initiator for controlled polymerisation of vinyl containing monomers to produce a polymer or copolymer.
  • Controlled polymerisation systems are of considerable importance in macromolecular chemistry since they allow for controlled preparation of polymers having a specific desired morphology. For example, by controlling the ratio of monomer to initiator concentration the molecular weight, molecular weight distribution, functionality, topology and/or dimensional structure of the resulting polymer can be controlled.
  • free radical polymerisation has been a commercially important process for the preparation of high molecular weight polymers .
  • a wide variety of monomers may be polymerised or copolymerised by free radical polymerisation under relatively simple conditions in bulk, solution, emulsion, suspension or dispersion.
  • a drawback of conventional free radical polymerisation is the lack of control of the morphology of the resulting polymer.
  • WO 96/30421 disclose polymerisation processes based on atom transfer radical polymerisation (ATRP) which provide for controlled radical polymerisation of styrene, (meth) acrylates, and other radically polymerisable monomers.
  • ATRP atom transfer radical polymerisation
  • the processes disclosed comprise the use of (i) an initiating system which comprises an initiator having a radically transferable atom or group, for example a 1-phenylethyl halide, alkyl 2-halopropionate, p-halomethylstyrene, or , ⁇ ' -dihaloxylene, (ii) a transition metal compound, for example Cu(I)Cl, Cu(I)Br, Ni(0), FeCl 2 , or RuCl 2 , and (iii) a C- , N- , O- , S-, or P-containing ligand which can co-ordinate with the transition metal, for example bipyridine or (alkoxy) 3 P.
  • an initiating system which comprises an initiator having a radically transferable atom or group, for example a 1-phenylethyl halide, alkyl 2-halopropionate, p-halomethylstyrene, or , ⁇ ' -dihaloxylene
  • WO 98/01480 further discloses the preparation and use of polydimethylsiloxane (PDMS) based macroinitiators; for example, benzyl chloride end groups are introduced to PDMS having silicon bonded hydrogen atoms by a platinum catalysed hydrosilylation reaction with vinylbenzylchloride .
  • PDMS polydimethylsiloxane
  • this route produces two isomers, ⁇ and ⁇ , having different activities.
  • the ⁇ isomer which represents 65% of the product is totally inactive towards initiation of controlled polymerisation reactions of vinyl monomers, and use of the ⁇ isomer results in polymers or copolymers containing unacceptably high amounts of unreacted siloxane which is difficult to remove due to slow initiation of the reaction.
  • an initiator for initiating controlled polymerisation reactions having at least one group -D-CR 8 2 X' and comprising units of the formulae (R 7 3 Si0 1/2 ) , (R 7 2 Si0 2/2 ) , (R 7 Si0 3/2 ) , and/or (Si0 4/2 ) , wherein D is a divalent straight chain or branched alkylene group containing an oxygen or nitrogen heteroatom and/or substituted by a carbonyl group, each R 8 is independently an alkyl group or a hydrogen atom, X' is a halogen atom, and each R 7 is independently a group - D-CR 8 2 X' or an optionally substituted hydrocarbon group.
  • the initiator may be a linear, branched, cyclic or resinous siloxane.
  • R 7 may be an alkyl group, (e.g. a methyl, ethyl, propyl or butyl, pentyl or hexyl group) , a substituted alkyl group, (e.g. a fluoropropyl group), an alkenyl group, (e.g. a vinyl or hexenyl group) , an aryl group (e.g. a phenyl group) , an aralkyl group (e.g. a benzyl group) or an alkaryl group (e.g. a tolyl group), and is preferably a alkyl group.
  • a substituted alkyl group e.g. a fluoropropyl group
  • an alkenyl group e.g. a vinyl or hexenyl group
  • an aryl group e.g. a phenyl group
  • an aralkyl group e.g. a benzyl
  • At least one group R 8 in each group -D- CR 8 2 X' is an alkyl group, i.e. X' is preferably a secondary or tertiary halogen atom, more preferably both groups R 8 in each group -D-CR 8 2 X' are alkyl groups, i.e. X' is more preferably a tertiary halogen atom.
  • each R 8 is a methyl group.
  • X is preferably a bromine atom.
  • Preferred examples of divalent group D include
  • R 9 is an alkyl group, for example a methyl group, or a hydrogen atom
  • each R 10 is independently a straight chain or branched alkylene group
  • r is an integer of from 1 to 4.
  • Preferred initiators used in the present invention have the formula R 7 3 SiO (SiR 7 2 0) q SiR 7 3 wherein R 7 is as defined above and q is 0 or a positive integer, for example from 10 to 100.
  • Particularly preferred initiators have the general formula (VIII) :
  • s is 0 or a positive integer, for example from 1 to 100, and t is a positive integer, for example from 1 to 10.
  • the initiator used in the present invention may be made by a method which comprises performing a condensation reaction between (i) a siloxane having at least one group R 11 and comprising units of the formulae (R 1:L 3 Si0 1/2 ) , (R ⁇ :L 2 Si0 2/2 ) , (R 1:1 Si0 3/2 ) , and/or (Si0 4/2 ) wherein at least one group R 11 is an amino-, hydroxy- or alkoxy- group, or an amino- , hydroxy- or alkoxy-substituted alkyl group and the remaining groups R 11 are each independently a group R 7 as previously defined, and (ii) a compound X'CR 8 2 -E wherein E is a group capable of participating in a condensation reaction with the amino-, hydroxy- or alkoxy- group, or an amino-, hydroxy- or alkoxy- substituted alkyl group to form a divalent straight chain or branched alkylene group containing an oxygen or nitrogen heteroatom and/or
  • the condensation reaction may be performed between an aminoalkyl substituted siloxane and an acyl halide:
  • condensation reaction may be performed between a hydroxyalkyl substituted siloxane and an acyl halide:
  • the condensation reaction may be performed at room temperature or above, for example from 50 to 100°C.
  • the initiator is used for initiating controlled polymerisation reactions, especially controlled polymerisation of vinyl containing monomers, such as those described in WO 96/30421, WO 97/18247, WO 98/01480 and Chem. Commun., 1999 99-100
  • the present initiator is capable of initiating a controlled polymerisation reaction of vinyl monomer to yield a well defined polymer or copolymer. It is more reactive than the aforementioned prior art PDMS based macroinitiators and leaves little or no unreacted siloxane remaining in the product .
  • the initiator is particularly effective for controlled polymerisation of vinyl monomers when used together with a particular catalyst composition which is solid at room temperature and comprises a transition metal or transition metal compound having on average more than one ligand co-ordinated thereto, each ligand being supported by a support via a divalent group R, wherein R is an optionally substituted C 1 -C 20 straight chain, branched, or cyclic alkylene group, arylene, alkarylene or aralkylene group .
  • the transition metal may, for example, be selected from copper, iron, ruthenium, chromium, molybdenum, tungsten, rhodium, cobalt, rhenium, nickel, manganese, vanadium, zinc, gold and silver.
  • Suitable transition metal compounds include those having the formula MY wherein M is a transition metal cation and Y is a counter anion.
  • M is preferably selected from Cu(I), Fe(II), Co (II), Ru(II) and Ni(II), and is most preferably Cu(I) .
  • Y may be, for example, Cl , Br, F, I, N0 3 , PF 6 , BF 4 , S0 4 , CN, SPh, SCN, SePh or triflate (CF 3 S0 3 ) , and is most preferably Cl or Br.
  • the catalyst composition comprises on average greater than one ligand co-ordinated with the transition metal or transition metal compound, and preferably has at least two co-ordinated ligands.
  • Suitable ligands include C- , N- , O- , P-, and S- containing ligands which can co-ordinate with the transition metal or transition metal compound.
  • WO 97/47661, WO 96/30421, WO 97/18247 and WO 98/01480 disclose many examples of suitable ligands.
  • Preferred ligands are those which contain an organodiimine group, in particular a 1, 4 -diaza-1, 3 -butadiene of formula (I),
  • each R 1 is independently a hydrogen atom, an optionally substituted C ⁇ -C ⁇ straight chain, branched, or cyclic alkyl group, aryl, alkaryl, aralkyl group or halogen atom.
  • R 1 is a hydrogen atom or an unsubstituted C 1 -C 12 alkyl group.
  • Each R 2 is independently an R 1 group, a C j ⁇ -C ao alkoxy group, N0 2 -, CN- , or a carbonyl group.
  • R 1 and R 2 groups, and R 2 and R 2 groups may form C 5 -C 8 cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclic aryl groups, for example cyclohexyl, cyclohexenyl or norbornyl groups.
  • the 2-pyridinecarbaldehyde imine compounds of formula (III) may comprise fused rings on the pyridine group.
  • a preferred organodiimine containing group is of formula (III) wherein each R 2 is a hydrogen atom.
  • Divalent group R is preferably a unsubstituted straight chain or branched alkylene group, for example a propylene group, or an aralkylene or alkarylene group, for example a benzylene or tolylene group.
  • the support may be an inorganic or organic network or polymer. Suitable inorganic networks or polymers consist of oxides of Si, Zr, Al or Ti, including mixed oxides thereof, for example a zeolite.
  • a preferred inorganic support is a siloxane polymer or network having units of the formula (R 3 3 Si0 1/2 ) a (R 3 2 Si0 2/2 ) b (R 3 Si0 3/2 ) c (Si0 4/2 ) d wherein each R 3 is independently an alkyl group, preferably a methyl group, a hydroxyl group or alkoxy group, a, J , c and d are each independently 0 or a positive integer, and a+b+c+d is an integer of at least 10.
  • the siloxane polymers and networks may be formed by polymerisation or cross-linking of silicon- containing monomers or oligomers, for example organofunctional silanes, silicas, and organocyclosiloxanes having the formula (R 4 2 SiO) e wherein R 4 is an alkyl group, for example a alkyl group, most preferably a methyl group .
  • Suitable organic network or polymer supports may comprise any organic material which will render the catalyst composition solid at room temperature and will not hinder any polymerisation reaction which the catalyst composition is to catalyse .
  • suitable organic networks or polymers include polyolefins, polyolefin halides, oxides and glycols, polymethacrylates, polyarylenes and polyesters .
  • the ligands may be physically or chemically attached to the support via divalent group R; however, chemical bonding of the ligands to the support via divalent group R is preferred.
  • catalyst compositions for catalysing controlled polymerisation reactions which are initiated according to the present invention are according to formula (VI) and (VII),
  • siloxane polymer or network has units of the formula (R 3 3 Si0 1/2 ) a (R 3 2 Si0 2/2 ) b (R 3 Si0 3/2 ) c (Si0 4/2 ) d , R 3 , a, J, c and d are as defined above and n is a positive integer.
  • the catalyst composition may be made by conventional methods known to those persons skilled in the art.
  • the molar ratios of reagents to be used to make the catalyst composition must be such that in the catalyst composition the transition metal or transition metal compound has on average more than one ligand co-ordinated thereto.
  • organodiimine containing groups which are diazabutadienes may be prepared by reaction of glyoxal with aniline derivatives:
  • X is a leaving group, for example a hydroxy or alkoxy group or a halogen atom, which diazabutadienes may then react with a suitable support material and transition metal compound to form the catalyst composition, for example :
  • n is as defined above.
  • organodiimine containing groups which are pyridine-2-carboxaldehyde imines of formula (III) above may be made by reaction of ethanolamine with pyridine-2-carboxaldehyde :
  • the pyridine-2-carboxaldehyde imine may then be reacted with a suitable support material Z and transition metal compound to form the catalyst composition, as illustrated above .
  • the catalyst composition hereinabove described in detail has an advantage over the aforementioned prior art controlled polymerisation methods in that the catalyst composition is a solid at room temperature and is thus recoverable from the polymer product and is reusable, and allows for a high degree of control over the polymerisation reaction.
  • Particularly advantageous catalyst compositions are those which are a solid at room temperature but which have a melting point at a temperature lower than the temperature at which the polymerisation reaction occurs.
  • Particularly effective polymerisation reactions may be performed in this way when the catalyst composition is a fluid in the reaction mixture at the reaction temperature and thus the transition metal compound may more easily blend into the reaction mixture to effect catalysis of the reaction.
  • the vinyl containing monomer to be polymerised may be a methacrylate, an acrylate, a styrene, methacrylonitrile or diene .
  • vinyl containing monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and other alkyl methacrylates, and the corresponding acrylates, including organofunctional methacrylates and acrylates, including glycidyl methacrylate, trimethoxysilyl propyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylaminoalkyl methacrylates, and fluoroalkyl (meth) acrylates .
  • organofunctional methacrylates and acrylates including glycidyl methacrylate, trimethoxysilyl propyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylaminoalkyl methacrylates, and fluoroalkyl (meth) acrylates .
  • the catalyst composition may be used in an amount of from 1 to 50%, preferably from 1 to 20%, more preferably from 5 to 10% by weight of the monomer.
  • a variety of polymers and copolymers can be produced by controlled polymerisation reactions initiated according to the present invention.
  • a large variety of monomers may be polymerised to afford homopolymers , random or gradient copolymers, periodic copolymers, block copolymers, functionalised polymers, hyperbranched and branched polymers, graft or comb polymers, and polysiloxane-organic copolymers.
  • Polysiloxane-organic copolymers have a number of potential applications; for example, polysiloxane- polyhydroxyalkyl acrylate block and graft copolymers are used in soft contact lens applications, polysiloxane- aminoacrylate copolymers are usable as antifoam and anti-dye transfer agents, and polysiloxane-aminoacrylate copolymers having a short aminoacrylate block are usable as textile treating agents, polyalkoxysilylalkylacrylate-polysiloxane and polyepoxyglycidylacrylate-polysiloxane copolymers are usable as additives for epoxy resins, curable powder coatings and sealants, long alkyl methacrylate or acrylate- polysiloxane copolymers are usable as surface modifiers or additives for polyolefins and polyester-polyacrylate copolymers, and the ABA methacrylate or acrylate- polysiloxan
  • Example 1 polymerisation of methylmethacrylate 5.39g (53.9mmol) of methylmethacrylate (MMA) in 11.5ml of anhydrous p-xylene was added to 0.66g of the catalyst prepared in Reference Example 2 above in a schlenk tube .
  • the mixture was deoxygenated by a single freeze-pump-thaw cycle prior to addition of 1.
  • the solution was heated at 90°C for 6 hours under N 2 and samples were taken against time for X H NMR analysis.
  • the final polymer and catalyst were separated by simple filtration on paper. The polymer was dried under vacuum to afford 3.9g of a pale yellow solid.
  • Mn number average molecular weight
  • Mn th theoretical number average molecular weight
  • 51g PDMS having -Si (CH 3 ) 2 - (CH 2 ) 2 -o- (CH 2 ) 3 CH 2 OH terminal units and a number average molecular weight of 2084 (0.049 mole of OH) and 5.43g (0.053mol) of triethylamine were placed into a 100ml flask equipped with a magnetic stirrer a condenser and an addition funnel containing 20ml of toluene. 12.37g (0.053 mole) of bromobutyratebromide was added dropwise at room temperature and the reaction was allowed to react overnight at room temperature prior to filtration of salts and evaporation of solvents. The polymer was washed with toluene and water.
  • the degree of conversion of the monomer observed by H NMR was 44%, and the Mn as measured by 1H NMR was 20,900.
  • the catalyst was extracted with p-xylene in a soxhlet for 6 hours, reusable for further polymerisations.
  • Reference Example 6 preparation of PDMS macroinitiator having pendant bromoisobutyrate groups.
  • a 500 ml 3-neck reaction flask equipped with a dropping funnel, a thermometer and a magnetic stirrer was charged with 80.5 g of dimethylethoxy end-blocked dimethylmethyl (aminopropyl) siloxane having a degree of polymerisation of 100 and containing 0.018 mole NH 2 , and 100 ml of p-xylene. After homogenisation, 3.35 ml (0.024 mole) of triethylamine was added and 5.53 g (0.024 mole) of bromo- isobutyryl bromide were injected slowly at room temperature.
  • Example 7 polymerisation of MMA
  • a 250 ml Schlenk reaction flask was charged with 2.65 g (0.76 mole) of catalyst prepared in Reference Example 7 above and 4.85 g(1.2 mmole)of the macroinitiator prepared in Reference Example 6 above.
  • the contents of the flask were vacuum dried at 80°C to remove oxygen and then covered by a nitrogen blanket. 28 g of MMA was then added under nitrogen.
  • the mixture was deoxygenated by three freeze-thaw pump cycles in liquid nitrogen.
  • the flask was then rapidly heated in an oil bath to the reaction temperature of 90°C. During the polymerisation reaction the viscosity increases and the solid particles of the catalyst remain in the polymer solution as a suspension.
  • the polymer solution is filtered, the residual monomer evaporated and the polymer analysed by X H NMR and/or by SEC to determine the average number molecular weight and the polydispersity . Based on a 100% monomer conversion and a total macroinitiator conversion, the theoretical degree of polymerisation is 233. From X H NMR calculation, the experimental degree of polymerisation is 113 after 4 hours.
  • Reference Example 9 were weighed into a Schlenk vessel and deoxygenated by exposure to a vacuum for 30 minutes. 23.6g (0.236 mole) of distilled methymethacrylate was added under nitrogen and degassed by three freeze-pump-thaw cycles. The solution was heated at 90°C for 195 minutes and samples removed. During polymerisation the solution became highly viscous, which prevented the removal of samples. After 195 minutes of polymerisation, 77% monomer conversion was measured by X H NMR.

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  • 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)
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Abstract

L'invention concerne un initiateur utilisé pour démarrer des réactions de polymérisation régulées. L'initiateur comprend des unités représentées par les formules (R73SiO), R72SIO3/2), et/ou (SiO4/2) et au moins un groupe D-CR82X, chaque R7 étant indépendamment un groupe hydrocarbure éventuellement substitué, D étant une chaîne droite bivalente ou un groupe alkylène ramifié contenant un hétératome d'oxygène ou d'azote et/ou remplacé par un groupe carbonyle, chaque R8 étant indépendamment un groupe alkyle ou un atome d'hydrogène et X1 étant un atome d'halogène. De préférence, chaque R7 est un groupe méthyle et l'initiateur comprend deux groupes -D-CR82X terminaux, R8 étant un groupe méthyle, X étant du brome et D étant un groupe CO-NR9R10 ou un groupe CO- (OR10), R9 étant un groupe alkyle ou un atome d'hydrogène et chaque R10 étant indépendamment un chaîne droite ou un groupe alkylène ramifié. L'initiateur selon l'invention est particulièrement utile pour démarrer la polymérisation régulée des monomères contenant du vinyle.
PCT/GB2000/000695 1999-03-05 2000-02-28 Utilisation d'un initiateur pour des reactions de polymerisation regulees WO2000052061A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000602284A JP2002538236A (ja) 1999-03-05 2000-02-28 制御された重合反応用開始剤の使用方法
AU28156/00A AU2815600A (en) 1999-03-05 2000-02-28 Use of an initiator for controlled polymerisation reactions
KR1020017011266A KR20010102496A (ko) 1999-03-05 2000-02-28 제어 중합 반응을 위한 개시제의 용도
CA002363962A CA2363962A1 (fr) 1999-03-05 2000-02-28 Utilisation d'un initiateur pour des reactions de polymerisation regulees
EP00906498A EP1165628A1 (fr) 1999-03-05 2000-02-28 Utilisation d'un initiateur pour des reactions de polymerisation regulees

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9905121.1A GB9905121D0 (en) 1999-03-05 1999-03-05 Initiator for controlled polymerisation reactions
GBGB9917329.6A GB9917329D0 (en) 1999-07-23 1999-07-23 Use of an initiator for controlled polymerisation reactions
GB9917329.6 1999-07-23
GB9905121.1 1999-07-23

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KR (1) KR20010102496A (fr)
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CA (1) CA2363962A1 (fr)
TW (1) TW499441B (fr)
WO (1) WO2000052061A1 (fr)

Cited By (2)

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US6858696B2 (en) * 2000-07-25 2005-02-22 Rhodia Chimie Method for synthesis of hybrid silicon and organic copolymers by controlled free radical polymerization
WO2007083097A1 (fr) * 2006-01-17 2007-07-26 Warwick Effect Polymers Ltd. Procédé de polymérisation radicalaire vivante

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GB9912077D0 (en) * 1999-05-24 1999-07-21 Unilever Plc Polysiloxane block copolymers in topical cosmetic and personal care compositions
GB9912073D0 (en) * 1999-05-24 1999-07-21 Unilever Plc Polysiloxane block copolymers in topical cosmetic and personal care compositions
JP4765356B2 (ja) * 2005-03-18 2011-09-07 Ｊｎｃ株式会社 シロキサンブロック共重合体およびその製造法
WO2010135481A1 (fr) * 2009-05-22 2010-11-25 Novartis Ag Copolymères contenant du siloxane réticulables actiniquement
JP5854303B2 (ja) * 2013-06-04 2016-02-09 Dic株式会社 重合性樹脂、活性エネルギー線硬化性組成物及び物品

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US5321108A (en) * 1993-02-12 1994-06-14 Bausch & Lomb Incorporated Fluorosilicone hydrogels
WO1998001480A1 (fr) * 1996-07-10 1998-01-15 Carnegie Mellon University Preparation de nouveaux homo- et copolymeres au moyen de la polymerisation radicalaire par transfert d'atome
EP0870774A2 (fr) * 1997-04-07 1998-10-14 Dow Corning Corporation Procédé de préparation de copolymères bloc organiques silicones
DE19838241A1 (de) * 1998-08-22 2000-02-24 Henrik Boettcher Verfahren zur chemischen Modifizierung von Feststoffoberflächen durch "lebende"/kontrollierte Radikalreaktionen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5321108A (en) * 1993-02-12 1994-06-14 Bausch & Lomb Incorporated Fluorosilicone hydrogels
WO1998001480A1 (fr) * 1996-07-10 1998-01-15 Carnegie Mellon University Preparation de nouveaux homo- et copolymeres au moyen de la polymerisation radicalaire par transfert d'atome
EP0870774A2 (fr) * 1997-04-07 1998-10-14 Dow Corning Corporation Procédé de préparation de copolymères bloc organiques silicones
DE19838241A1 (de) * 1998-08-22 2000-02-24 Henrik Boettcher Verfahren zur chemischen Modifizierung von Feststoffoberflächen durch "lebende"/kontrollierte Radikalreaktionen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6858696B2 (en) * 2000-07-25 2005-02-22 Rhodia Chimie Method for synthesis of hybrid silicon and organic copolymers by controlled free radical polymerization
WO2007083097A1 (fr) * 2006-01-17 2007-07-26 Warwick Effect Polymers Ltd. Procédé de polymérisation radicalaire vivante

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TW499441B (en) 2002-08-21
CA2363962A1 (fr) 2000-09-08
EP1165628A1 (fr) 2002-01-02
KR20010102496A (ko) 2001-11-15
JP2002538236A (ja) 2002-11-12

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