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EP1165629A1 - Composition catalytique et procede de fabrication d'un polymere ou d'un copolymere - Google Patents

Composition catalytique et procede de fabrication d'un polymere ou d'un copolymere

Info

Publication number
EP1165629A1
EP1165629A1 EP00906513A EP00906513A EP1165629A1 EP 1165629 A1 EP1165629 A1 EP 1165629A1 EP 00906513 A EP00906513 A EP 00906513A EP 00906513 A EP00906513 A EP 00906513A EP 1165629 A1 EP1165629 A1 EP 1165629A1
Authority
EP
European Patent Office
Prior art keywords
group
catalyst composition
formula
composition according
transition metal
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.)
Withdrawn
Application number
EP00906513A
Other languages
German (de)
English (en)
Inventor
Jean De La Croi Habimana
Pierre Chevalier
Tristan Tapper
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.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
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 GBGB9905084.1A external-priority patent/GB9905084D0/en
Priority claimed from GBGB9917390.8A external-priority patent/GB9917390D0/en
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of EP1165629A1 publication Critical patent/EP1165629A1/fr
Withdrawn legal-status Critical Current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
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • 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
    • C08F4/00—Polymerisation catalysts
    • 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 a catalyst composition and a method for making a polymer or copolymer, in particular a catalyst composition and method for making a polymer or copolymer by controlled polymerisation of vinyl containing monomers .
  • 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. Processes for controlled radical polymerisation have been proposed.
  • WO 96/30421, WO 97/18247 and WO 98/01480 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 or transition metal compound, for example Cu(I)Cl, Cu(I)Br, Ni(0), FeCl 2 , or RuCl 2 , and (iii) a C- , N- , 0-, 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 ⁇ , ⁇ ' -dihaloxy
  • a 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 ⁇ C ⁇ 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-, 0-, 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.- jn straight chain, branched, or cyclic alkyl group, aryl, alkaryl, aralkyl group or halogen atom.
  • R 1 is a hydrogen atom or an unsubstituted C j. -C 12 alkyl group.
  • Each R 2 is independently an R 1 group, a C 1 -C 20 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 3 -C 8 cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclic aryl groups, for example cyclohexyl, cyclohexenyl or norborneyl 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 C -C & 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, b, 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 gylcols, 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 of the first aspect of the present invention are according to formula (VI) and (VII) ,
  • a catalyst composition which is solid at room temperature and comprises a Cu(I) compound having coordinated thereto two pyridine-2-carboxaldehyde imine ligands, each of which ligands is supported by either 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 R 3 , a, £>, c and d are as defined above or a polystyrene polymer or network.
  • a catalyst composition of the first aspect of the present invention 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 : wherein 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 and transition metal compound to form the catalyst composition, as illustrated above .
  • a catalyst composition according to the first aspect of the present invention has particular utility in methods for making polymers or copolymers by catalysing controlled polymerisation of vinyl containing monomers.
  • a method of making a polymer or copolymer by controlled polymerisation which method comprises polymerising a vinyl containing monomer in the presence of an initiator and a catalyst according to the first aspect of the present invention.
  • a catalyst composition of the first aspect of the present invention used in a method of the second aspect 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 also 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 as 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 catalyst can be recovered from the reaction mixture .
  • the vinyl containing monomer 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 .
  • the initiator used in a method of the second aspect of the present invention may be any conventional initiator suitable for use with a catalyst composition of the first aspect of the present invention in controlled polymerisation reactions.
  • examples of such initiators include 1-phenylethyl chloride and bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, esters of a 2-halo-C 1 -C 6 -carboxylic acid, for example 2-chloro or 2-bromopropionic acid and 2-chloro or 2-bromoisobutyric acid, 1-phenylethylchloride and bromide, methyl and ethyl 2-chloropropionate, methyl and ethyl 2-bromopropionate, ethyl 2-isobutyrate, ⁇ , ' -dichloro and ⁇ , ⁇ ' -dibromoxylene and hexakis ( -bromomethyl) benzene
  • a preferred initiator for use in a method of the second aspect of the present invention has at least one group -D-CR 8 2 X' and comprises 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 preferred initiator may be a linear, branched, cyclic or resinous siloxane.
  • R 7 may be an alkyl group, (e.g. a methyl, ethyl, propyl 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 C ⁇ -C,; 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 benzy
  • 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.
  • divalent group D examples 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
  • Preferred initiators used in the method of the second aspect of 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 g 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 preferred initiator used in the method of the second aspect of the present invention may be made by a method which comprises performing a condensation reaction between (i) a siloxane having at least one group Rll and comprising units of the formulae (R xl 3 Si0 1/2 ) , (R ⁇ :l 2 Si0 2/2 ) , (R 11 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
  • 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.
  • a method of the second aspect of the present invention may be performed at a variety of temperatures, for example from room temperature to 200°C, in particular between room temperature and 130°C, most preferably between 80 and 100°C.
  • a method of the second aspect may be performed in the presence or absence of a solvent.
  • Suitable solvents include water, protic and non-protic solvents including propionitrile, hexane, heptane, dimethoxyethane, diethoxyethane, tetrahydrofuran, ethylacetate, diethylether, N,N-dimethylformamide, anisole, acetonitrile, diphenylether, methylisobutyrate, butan-2-one, toluene and xylene, with toluene and xylene being preferred.
  • propionitrile hexane, heptane, dimethoxyethane, diethoxyethane, tetrahydrofuran, ethylacetate, diethylether, N,N-dimethylformamide, anisole, acetonitrile, diphenylether, methylisobutyrate, butan-2-one, toluene and xylene, with toluene and xylene being
  • the method may take place under an inert atmosphere, for example under argon or nitrogen.
  • 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 method of the second aspect of the present invention may be used to produce a variety of polymers and copolymers.
  • 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-polys
  • Example 1 preparation of first solid supported copper catalyst
  • Mn 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.
  • Example 6 polymerisation of MMA using recycled catalyst 30g (0.3mol) of MMA in 30ml of anhydrous p-xylene was added to 2.3g of the catalyst collected from Example 7 above (previously extracted with p-xylene for 6 hours in a soxhlet) in a 100ml schlenk tube.
  • the mixture was deoxygenated by a single freeze-pump-thaw cycle and heated at 90°C prior to addition of 3g of the macroinitiator prepared in Example 6 above. The reaction was continued for 44 hours at 90°C. Samples were taken against time for X H NMR analysis. During polymerisation the solution becomes very viscous but remains clear and the catalyst remains visible in the polymer solution. After polymerisation the solid catalyst was filtered out.
  • Table 3 show an excellent correlation between theoretical and experimental molecular weight and hence controlled polymerisation.
  • a 2000 ml 3 -neck reaction flask equipped with a dropping funnel, a thermometer and a reflux condenser was charged with 246 g (1.37 mole) of aminopropyltrimethoxy- silane and 300 ml of p-xylene. Then, 75 g (4.16 mole) of water was added over 60 minutes whilst distilling off methanol . After methanol removal, p-xylene is stripped off under reduced pressure to yield a white brittle solid. 84 g of the solid and 300 ml of p-xylene were then charged into a 1000 ml reaction flask and 70 g (1.0 mole) of 2-pyridine carboxyaldehyde was added slowly with cooling.
  • Example 11 polymerisation of MMA
  • a 250 ml Schlenk reaction flask was charged with 2.65 g (0.76 mole) of catalyst prepared in Example 10 above and 4.85 g(1.2 mmole)of the macroinitiator prepared in Reference Example 3 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 1 H NMR calculation, the experimental degree of polymerisation is 113 after 4 hours.

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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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne une composition catalytique solide à température ambiante, qui contient un métal de transition ou un composé de métal de transition ayant en moyenne plus d'un ligand lié à ce dernier, chaque ligand étant fixé à un support via un groupe divalent R, où R est une chaîne droite C1-C20 éventuellement substituée, un groupe alkylène ramifié ou cyclique, un arylène, un alkarylène ou un groupe aralkylène. M est de préférence Cu(I), Y est Cl ou Br, chaque ligand contient un groupe organodiimine, p. ex. 1,4-diaza-1,3-butadiène, 2,2'-bipyridine, pyridine-2-carboxaldéhyde imine, oxazolidone ou un groupe quinoline carbaldéhyde, et le support est un polymère ou un réseau organique ou siloxane. L'invention concerne également un procédé de fabrication d'un polymère ou d'un co-polymère par polymérisation contrôlée. Le procédé consiste à polymériser un vinyle contenant un monomère en présence d'un initiateur et d'une composition catalytique obtenue selon la présente invention.
EP00906513A 1999-03-05 2000-02-29 Composition catalytique et procede de fabrication d'un polymere ou d'un copolymere Withdrawn EP1165629A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9905084 1999-03-05
GBGB9905084.1A GB9905084D0 (en) 1999-03-05 1999-03-05 Catalyst composition and method for makiong a polymer or copolymer
GBGB9917390.8A GB9917390D0 (en) 1999-07-23 1999-07-23 Catalyst composition and method for making a polymer or copolymer
GB9917390 1999-07-23
PCT/GB2000/000712 WO2000053643A1 (fr) 1999-03-05 2000-02-29 Composition catalytique et procede de fabrication d'un polymere ou d'un copolymere

Publications (1)

Publication Number Publication Date
EP1165629A1 true EP1165629A1 (fr) 2002-01-02

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EP00906513A Withdrawn EP1165629A1 (fr) 1999-03-05 2000-02-29 Composition catalytique et procede de fabrication d'un polymere ou d'un copolymere

Country Status (6)

Country Link
EP (1) EP1165629A1 (fr)
JP (1) JP2002539280A (fr)
KR (1) KR20010112306A (fr)
AU (1) AU2817200A (fr)
CA (1) CA2365637A1 (fr)
WO (1) WO2000053643A1 (fr)

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Publication number Priority date Publication date Assignee Title
GB9912073D0 (en) * 1999-05-24 1999-07-21 Unilever Plc Polysiloxane block copolymers in topical cosmetic and personal care compositions
GB9912077D0 (en) * 1999-05-24 1999-07-21 Unilever Plc Polysiloxane block copolymers in topical cosmetic and personal care compositions
JP2008050399A (ja) * 2006-08-22 2008-03-06 Mitsui Chemicals Inc ４−メチル−１−ペンテン系重合体セグメントからなる重合体、フィルムまたはシート
US10294332B2 (en) * 2014-12-30 2019-05-21 Momentive Performance Materials Inc. Functionalized siloxane materials
CN120173243B (zh) * 2025-05-22 2025-08-05 中国计量大学 一种基于配位键的低温自修复聚硅氧烷材料及其制备方法与应用

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US6310149B1 (en) * 1996-06-12 2001-10-30 University Of Warwick Polymerization catalyst and process
JPH11514012A (ja) * 1996-07-23 1999-11-30 サイミックス・テクノロジーズ 有機金属化合物及び触媒の組み合わせ合成並びに分析
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GB9708487D0 (en) * 1997-04-25 1997-06-18 Bp Chem Int Ltd Novel catalysts for olefin polymerisation
GB9725455D0 (en) * 1997-12-02 1998-01-28 Univ Warwick Supported polymerisation catalyst

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Also Published As

Publication number Publication date
KR20010112306A (ko) 2001-12-20
AU2817200A (en) 2000-09-28
WO2000053643A1 (fr) 2000-09-14
CA2365637A1 (fr) 2000-09-14
JP2002539280A (ja) 2002-11-19

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