SUPPORTED POLYMERISATION CATALYST

Abstract: The invention relates to supported ligands and catalysts for use in the polymerisation of olefinically unsaturated monomers such as vinylic monomers, comprising the use of a compound attached to support, the compound being capable of complexing with a transitional metal. Preferably the compound capable of complexing with a transition metal is a diimine such as a 1,4-diaza-1,3-butadiene, a 2-pyridinecarbaldehyde imine, an oxazolidone or a quinoline carbaldehyde. Preferably the catalysts are used in conjunction with an initiator comprising a homolytically clevable bond with a halogen atom. The application also discloses processes for attaching ligands to supports, and processes for using the catalysts disclosed in the application.

Description: SUPPORTED POLYMERISATION CATALYST The present invention relates to immobilised supported polymerisation catalysts for atom transfer polymerisation of olefinically unsaturated monomers in which molecular weight control is achieved by the presence of certain transition metal, especially copper, complexes. It is desirable to be able to produce high molecular weight polymers with a low molecular weight distribution by catalysed addition polymerisation, in particular of vinylic monomers. Hitherto this has been achieved by polymerising via ionic processes typically in the presence of organometallics such as aikyl lithium's which are sensitive as regards reaction with water and other protic species. As such monomers containing functional groups are not readily polymerised. The use of ionic systems also precludes the use of solvents which contain protic groups and/or impurities resulting in very stringent reaction conditions and reagent purity being employed. More recently atom transfer polymerisation based on the combination of a transition metal halide and aikyl halide have been utilised. For example Matyjasewski (Macromoiecuies ( 1995), vol 28, pages 7901 -7910 and WO96/30421 ) has described the use of CuX (where X=C1, Br) in conjunction with bipyridine and an aikyl halide to give polymers of narrow molecular weight distribution and controlled molecular weight. This system suffers from the disadvantage that the copper catalyst is partially soluble in the system and thus a mixture of homogeneous and heterogeneous polymerisation ensues. The level of catalyst which is active in solution is thus difficult to determine. The catalyst residues which are soluble in the reaction medium prove difficult to remove from the product. Percec (Macromolecules, ( 1995), vol. 28, page 1995) has extended Matyjasewski's work by utilising arenesulphonyi chlorides to replace aikyl chlorides, again this results in a mixture of homogeneous and heterogeneous polymerisation and catalyst residues are difficult to remove from the product. Sawamoto (Macromolecules, ( 1995), vol. 28, page 1721 and Macromolecules, ( 1997), vol. 30, page 2244) has also utilised a ruthenium based system for similar polymerisation of methacrylates. This system requires activation of monomer by an aluminium alkyi in order to achieve the best results, itself sensitive to reaction with protic species which is an inherent disadvantage. These systems have been described as proceeding via a free radical mechanism which suffers from the problem that the rate of termination is > 0 due to normal radical-radical combination and disproportionation reactions. The inventors have found that the use of diimines such as l ,4-diaza- l,3-butadienes and 2-pyridinecarbaldehyde imines may be used in place of bipyridines. These ligands offer the advantage of homogeneous polymerisation and thus the level of active catalyst can be accurately controlled and only one polymerisation process ensues. This class of ligand also enables the control of the relative stability of the transition metal valencies, for example, Cu(I) and Cu(Il), by altering ancillary substituents and thus gives control over the nature of the products through control over the appropriate chemical equilibrium. Such a system is tolerant to trace impurities, trace levels of 0 2 and functional monomers, and may even be conducted in aqueous media. This system is the subject of copending patent application number PCT/GB97/01 587. A further advantage of this system is that the presence of free-radical inhibitors traditionally used to inhibit polymerisation of commercial monomers in storage, such as 2, 6-di-tert-butyl-4-methylphenol (topanol), increases the rate of reaction of the invention. This means that lengthy purification of commercial monomers to remove such radical inhibitors is not required. Furthermore, this indicates that the system is not a free-radical process. This is contrary to Matajaszewski and Sawamoto who show free-radical based systems. A difficulty identified by the inventors for the commercialisation of the radical polymerisation system of Matajazewski and Sawamoto, and the diimine-based system described above is that high levels of catalysts is required for acceptable rates of polymerisation. This means that catalyst is relatively expensive as it is not recycled/reused and it must be removed by lengthy procedures to prevent contamination of the final product and to keep production costs down. The inventors have therefore identified a process for attaching the catalyst to supports which allows the catalyst to be easily recovered and produces products with substantially less contamination than previously described systems. Such supported catalysts were expected by the inventors to clump together since each metal ion can coordinate with two-ligands, each of which is attached to a support. This would reduce the effectiveness of such supported systems. However, this has not been observed by the inventors. Furthermore, the metal ion is tightly bound to the ligands and does not leach off into the surrounding solution or product, allowing it to be reused. A first aspect of the invention provides a supported ligand for use in catalysts for polymerisation of olefinically unsaturated monomers, especially vinylic monomers, said ligand being one or more compounds attached to a support. Such a ligand has general formula: S(D) „ FORMULA 1 where: S is the support, D is a compound attached to the support, said compound being capable of complexing with a transition metal. n is an integer of one or more. Preferably, the support is inorganic, such as silica, especially silica gel. Alternatively the support may be organic, especially an organic polymer, especially a cross-linked organic polymer, such as poly(styrene-w-divinyibenzone). Preferably the support is in the form of beads. This latter form is particularly advantageous because it has a high surface area which allows the attachment of a large number of compounds, whilst presenting a large surface area to the medium to be catalysed. The compound (D) may be adsorbed onto the support or covalently attached to the support. Preferably the compound is an organic compound comprising Schiff base, amine, hydroxyi, phosphine or diimine capable of complexing with a transition metal ion. Each Schiff base, amine, hydroxyi, phosphine or diimine is preferably separated from the support by a branched or straight aikyl chain, especially a chain containing 1 to 20 carbon atoms. The chain may comprise one or more aromatic groups as part of the aikyl chain. One preferred ligand is the use of a support attached to two or more alkyl-amines, such as aminopropyl-, aminobutyl-, aminopentyl-, aminohexyi-, aminoheptyl- or aminooctyl- functionalised support. The amine groups are capable of forming a complex with one or more transition metal ions. Especially preferred compounds are diimines. Preferably one of the nitrogens of the diimine is not part of an aromatic ring. Preferably the diimine is a l,4-diaza-l,3-butadiene R4 Formula 2 a 2-pyridinecarbaIdehyde imine R10 Formula 3 an Oxazolidone Formula 4 or a Quinoiine Carbaldehyde Formula 5 where R,, R 2/ R 10 , R π , R 12 and R, 3 may be varied independently and R,, R 2/ R I0/ Rπ, R12 and R 13 may be H, straight chain, branched chain or cyclic saturated aikyl, hydroxyalkyl, carboxyalkyl, aryl (such as phenyl or phenyl substituted where substitution is as described for R 4 to R 9 ), CH 2 Ar (where Ar = aryl or substituted aryl) or a halogen. Preferably R,, R 2 , R 10; R„, R 12 and R, 3 may be a C, to C 20 aikyl, hydroxyalkyl or carboxyalkyl, in particular G to C 4 aikyl, especially methyl or ethyl, n-propylisopropyi, n-butyl, sec-butyl, tert-butyl, cyclohexyl, 2-ethylhexyI, octyl decyl or lauryl. R,, R 2 , Rio, Rπ, R12 and R, 3 may especially be methyl. R 3 to R 9 may independently be selected from the group described for R,, R , Rio, Ri i, R12 and Rπ or additionally OQ-l2n + i (where n is an integer from 1 to 20), N0 2 , CN or 0 = CR (where R = aikyl, benzyl PhCH 2 or a substituted benzyl, preferably a G to C 20 aikyl, especially a G to C 4 aikyl). Furthermore, the compounds may exhibit a chiral centre α to one of the nitrogen groups. This allows the possibility for polymers having different stereochemistry structures to be produced. Compounds of general Formula 3 may comprise one or more fused rings on the pyridine group. One or more adjacent Ri and R 3 , R 3 and R , R and R 2 , R ]0 and R 9 , Re and R 9 , Re and R 7 , R 7 and Rό, Rό and R 5 groups may be C 5 to Q cycloalkyl, cycloalkenyl, polycydoaikyl, polycydoalkenyi or cyclicaryl, such as cyclohexyl, cyclohexenyl or norborneyl. The diimine compounds are preferably covalently attached to the support via positions RI , R2, R9, RI O, R1 1 , R12 or RI 3. They may be attached via a linkage group, such as a schiff base to the support. Preferred diimines include: Formula 6 Formula 7 Formula 10 Formula 11 Formula 12 Formula 13 Formula 14 Formula 15 Formula 16 Formula 17 Formula 24 Formula 25 Formula Formula Formula 28 CSOH Formula 29 where: * indicates a chiral centre RI 4 = Hydrogen, G to Go branched chain aikyl, carboxy- or hydroxy- G to Go aikyl. The ligands, according to the first aspect of the invention may be used to form a catalyst for the addition polymerization of olefinically unsaturated monomers by using them in conjunction with; a) a compound of formula 30 MY where M is a transition metal in a low valency state or a transition metal in a low valency state co-ordinated to at least one co-ordinating non-charged ligand and Y is a monovalent or polyvalent counterion; and b)an initiator compound comprising a homolytically cleavable bond with a halogen atom. Homolytically cleavable means a bond which breaks without integral charge formation on either atom by homolytic fission. Conventionally this produces a radical on the compound and a halogen atom radical. For example: However, the increase in the rate of reaction observed by the inventors with free-radical inhibitors indicates that true free-radicals are not necessarily formed using the catalysts of the invention. It is believed that this possibly occurs in a concerted fashion whereby the monomer is inserted into the bond without formation of a discrete free radical species in the system. That is during propagation this results in the formation at a new carbon-carbon bond and a new carbon-halogen bond without free-radical formation. The mechanism possibly involves bridging halogen atoms such as: where: ML is a transition metal-diimine complex. A "free-radical" is defined as an atom or group of atoms having an unpaired valence electron and which is a separate entity without other interactions. Transition metals may have different valencies, for example Fe(II) and Fe(IIl), Cu(I) and Cu(II), a low valency state is the lower of the commonly occurring valencies, i.e. Fe(II) or Cu(l). Hence M in Formula 30 is preferably Cu(I), Fe(II), Co(II), Ru(II) or Ni(II), most preferably Cu(I). Preferably the co-ordinating ligand is (CH 3 CN) 4 .Y may be chosen from CI, Br, F, I, NOj, PF 6 , BF 4 , S0 4 , CN, SPh, SCN, SePh or triflate (CF 3 SOj). Copper (I) triflate may be, which may be in the form of a commercially available benzene complex (CF 3 Sθ3Cu) 2 .GH . The especially preferred compound used is CuBr. Preferably the second component (b) is selected from: RX Formula 31 Formula 32 Formula 33 Formula 34 Form ula 35 Formula 36 Formula 37 Formula 38 Formula 39 Formula 40 Formula 41 where R is independently selectable and is seleαed from straight, branched or cyclic aikyl, hydrogen, substituted aikyl, hydroxyalkyl, carboxyalkyl or substituted benzyl. Preferably the or each alkyi, hydroxyalkyl or carboxyalkyl contains 1 to 20, especially 1 to 5 carbon atoms. X is a halide, especially I, Br, F or Q. The second component (b) may especially be seleαed from Formulae 43 to 52: Formula 42 where: X = Br, I or Cl, preferably Br R' = -H, -(CH 2 ) P R" (where m is a whole number, preferably p - 1 to 20, more preferably 1 to 10, most preferably 1 to 5, R" = H, oH, CooH, halide, NH 2 , SOj, CoX - where x is Br, 1 or C) or: Formula 43 R l n = -COOH, -COX (where X Is Br, I, F or CI), -OH, -NH 2 or -S0 3 H, especially 2-hydroxyethyI-2'-methyI-2' bromopropionate. Formula 44 Formula 45 Especially preferred examples of Formula 45 are: Formula 46A Formula 46B Br may be used instead at CI in Formulae 46A and 46B. Formula 47 Formula 48F Formula 49 Formula 50 Formula 51 Formula 52 and Formula 53 The careful selection of functional aikyl halides allows the production of terminally functioπalised polymers. For example, the seleαion of a hydroxy containing alkyi bromide allows the production of α-hydroxy terminal polymers. This can be achieved without the need of protecting group chemistry. The transition metai may be precoordinated to the ligand covalentiy attached to its support. Accordingly a second aspeα of the invention provides a catalyst for use in the addition polymerisation of olefinically unsaturated monomers, especially vinyl monomers comprising a compound of general formula: Formula 52 [(SD) c M] d+ A where: M = a transition metal in a low valency state or a transition metal co-ordinated to at least one co-ordinating non-charged ligand. S = a support, D = a compound attached to the support, the compound being capable of complexing with a transition metal, d = an integer of 1 or 2, c = an integer of 1 or 2, A = a mono oilent or divalent counter ion, such as CI, Br, F, I, N0 3 , PF 6 , BFα, S0 4 , C , SPh. Preferably M is as defined for Formula 30 above. S may be as defined for Formula 1. D may be adsorbed or covalentiy attached to the support. D may be a compound as described earlier for the first aspeα of the invention. D may have one of the nitrogens as not part of a diimine ring. D may be a diimine according to Formulae 2-29 as previously defined. Preferably the catalyst is used with an initiator comprising a homolytically cleavable bond with a halogen atom, as previously defined. Preferred initiators are those defined in the first aspeα of the invention according to Formulae 31 to 53. A third aspect of the invention provides a process for the production of compound such as diimine covalentiy attached to supports, according to the first or second aspects of the invention. The invention provides a process for producing a ligand for use in the catalysis of addition polymerisation of olefinically unsaturated monomers, especially vinylic monomers, comprising the steps of: (a) providing a primary amine functionaiised support; (b) providing a ligand precusor comprising an aldehyde group or ketone group; and (c) reacting the primary amine functionaiised support with the ligand precursor to form a di i mine compound covalentiy attached to the support. The primary amine of the functionaiised support reacts with the aldehyde group or ketone group to form a Schiff base. Accordingly the diimine may be produced by providing a ligand precursor with an aldehyde or ketone group replacing one of the imine groups of the final produα, the reaction with the primary amine producing the second iimine group. This is shown in the reaction scheme below which shows the reaction of a support functionaiised with a primary amine with 2-pyridine carbaidehyde to form a diimine attached to the support according to the first aspect of the invention. This can then be mixed with copper bromide or copper chloride to form a catalyst according to the second aspect of the invention. Scheme 1 Alternatively an aldehyde or a ketone group may be provided separately on a diimine ligand precusor. Such a suitable precursor is shown in Formula 53 This allows t he diimine to be decoupled from the support to allow controlled polymerisation. Alternatively the following reaction scheme may be followed: where x = an integer of 1 to 20 The primary amine group may alternatively be provided on the ligand precursor and reaαed with a ketone or aldehyde funαionalised support. The suppor t material may be functionaiised inorganic material, such as silica, especially silica gel. Alternatively functionaiised organic support, especially a functionaiised cross-linked polymeric support, such as poiy(styrene-w-divinyibenzene) may be used. Such supports are preferably usually used for adsorbing compounds or in chromatography. Preferably t he reaction to form the Schiff base occurs at room tempera t ure. Preferably t he functionaiised support is an aminopropyi functional silica and the ligand precursor is 2-pyridine carbaldehyde. The supported ligands and supported catalysts of the invention may be used in batch reactions or in continous reactions to polymerise olefinically unsaturated monomers. In the latter case, the supported catalyst or ligand may be packed into columns and the reaction mixture passed through. The supported ligand or supported catalyst may be conveniently removed from a reaction mixture by for example filtration, precipitation or centrifugation. Alternatively the support may be magnetised beads and the catalyst is removed by means of a magnet. The invention also provides the use of the catalyst according to the first or second aspect of the invention in the addition polymerisation of one or more olefinically unsaturated monomers and the polymerised products of such processes. The components may be used together in any order. The inventors have unexpectedly found that the catalyst will work at a wide variety of temperatures, including room temperature and as low as - 15°C Accordingly, preferably the catalyst is used at a temperature of -20 ° C to 200 ° C, especially -20°C to 150 ° C, 20°C to 130oC, more preferably 90°C The olefinically unsaturated monomer may be a methacrylic, an acrylate, a styrene, methacryionitriie or a diene such as butadiene. Examples of olefiπicaiiy unsaturated monomers that may be poiymerised include methyl methacrylate, vinyiacetate, vinyl chloride acyionitonile, methacyiamide, acrylamide, ethyl methacrylate, propyi methacrylate (ail isomers), butyl methacrylate (all isomers), and other aikyl methacrylates; corresponding acrylates; also functionaiised methacryiates and acrylates including giyddyl methacrylate, trimethoxysilyi propyi methacrylate, ally! methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylaminoalkyl methacrylates; fluoroaikyl (meth) acrylates; methacryiic acid, acrylic acid; fumaric add (and esters), itaconic acid (and esters), maieic anhydride; styrene, α-methyi styrene; vinyl halides such as vinyi chloride and vinyl fluoride; acrylonitriie, methacrylonitrile; vinylidene halides of formula CH2 - C(Hal) 2 where each halogen is independently CI or F; optionally substituted butadienes of the formula CH 2 ~- C(R' 5 ) C(R 15 ) = CH 2 where R 1S is independently H, CI to CIO aikyl, α, or F; suiphonic adds or derivatives thereof of formula CH2 = CHSO∑OM wherein M is Na, , Li, N(R I6 ) 4 where each R 16 is independentiy H or C- to C 1 Q aikyl, D is COZ, ON, N(R 16 ) 2 or SO∑OZ and Z Is H, Li, Na, or N(R I6 ) 4 ; acrylamide or derivatives thereof of formula CH 2 = CHCON(R 16 ) 2 and methacryiamide or derivative thereof of formula CH2 = C(CHj)CON(R l6 )2. Mixtures of such monomers may be used. Preferably, the monomers are commercially available and may comprise a free-radical inhibitor such as 2, 6-di-tert-butyl-4-methylpenol or methoxypienol. Preferably the co-catalysts are used in the ratios 0.01 to 1000 D : MY, preferably 0.1 to 10, and compound MY : initiator 0.0001 to 1000, preferably 0.1 to 10 , where the degree of polymerisation is controlled by the ratio of monomer to (b) (expressed as rnoiar ratios). Preferably the components of the catalyst of the second aspect of the invention are added at a ratio M:initiator of 3: 1 to 1 : 100. Preferably the amount of diimine : metal used in the systems is between 1000: 1 and 1 : 1 , especially, 100: 1 and 1 : 1 , preferably 5: 1 to 1 : 1 , more preferably 3: 1 to 1 : 1. The ratio of RX:Copper is 1000: 1 to 1 : 1 , especially 100: 1 to 1 : 1. The reaction may take place with or without the presence of a solvent. Suitable solvents in which the catalyst, monomer and polymer product are sufficiently soluble for reactions to occur include water, protic and non-protic solvents including propionitrile, hexane, heptane, dimethoxyethane, diethoxyethane, tetrahydrofuran, ethylacetate, diethylether, N,N-dimethylformamide, anisole, acetonitrile, diphenyiether, methylisobutyrate, butan-2-one, toluene and xylene. Especially preferred solvents are xylene and toluene, preferably the solvents are used at at least 1 % by weight, more preferably at least 10% by weight. Preferably the concentration of monomer in the solvents is 100% to 1 %, preferably 100% to 5%. The reaction may be undertaken under an inert atmosphere such as nitrogen or argon. The reaction may be carried out in suspension, emulsion, mini-emulsion or in a dispersion. Statistical copoiymers may be produced using the catalysts according to the invention. Such copolymers may use 2 or more monomers in a range of ca.O- 100% by weight of each of the monomers used. Block copolymers may also be prepared by sequential addition of monomers to the reaction catalyst. Telechelic poiymers, may be produced using caialysts of the invention. For example, a functional initiator such as Formula 21 may be used with transformation of the w-Br group to a functional group such as -OH or -C0 2 H via use of a suitable reactant such as sodium azide. Comb and graft copoiymers may be produced using the caialysts of the invention to ailow, for example, polymers having functional side chains to be produced, by use of suitable reagents. Embodiments of the invention will now be described by way of example and with reference to the following figure: Figure 1 show the polymerisation of methyimethacryiate for four monomer additions to supported catalyst which has been coileαed at the end of each previous polymerisation reaction. Figure 2 shows infrared spectra for the stepwise synthesis of pyridyl ligand onto cross-linked polystyrene beads. Figure 3 shows kinetic reproducibility of silica supported atom transfer polymerisation from experiments carried out with diffeerent silica supported ligands synthesised at different times. Figure 4 shows recycling experiments carried out with support S4 using the same conditions: [MMA] : [Cu] : [Si-lig] : [E2 BI] = 100 : 1 : 3 : 1 Figure 5 shows reinitiation of PMMA. Experimental Reagents: Methyl methacrylate (Aldrich, 99%) was purified by passing through a column of activated basic alumina to remove inhibitor. Copper(I) bromide (Aldrich, 98%) was purified according to the method of Keller St Wycoff. Toluene (Fisons, 99.8%) was dried over sodium. Ethyl-bromoisobutyrate (Aldrich, 98%), 2-pyridene carboxaldehyde, 3-aminipropyl-functionaiised silica gel (Aldrich, 9% functionaiised), silica gel (Merck), and iethyi ether (BDH, 98%) were used as received. Ref: Keller, R.N.; Wycoff, H.D. Inorg. Svnth. 2.1 ( 1946) Characterisation: Conversion was measured by gravimetry, and molecular weight distributions were measured using size exclusion chromatography (SEC) on a system equipped with a guard column, a mixed E column (Polymer Laboratories) and a refractive index detector, using tetrahydrofuran at 1 mL.min " ' as an eluent. Poly(MMA) standards in the range ( 10 ° - 200 g.mol " ' ) were used to calibrate the SEC SiO 7 , supported catalyst - covalentiy bound Schiff bases Example 1 : 2-pyridine carboxaidehyde (0.714 g, 6.67 x 10 '3 mol) was added to 3-aminopropylfunctionalised silica gel (3.00 g, 3.15 x 10 '3 mol of active NH 2 ) dispersed in diethyi ether (50 mL) and stirred for 1 hr. The diethyi ether was removed and the ligand functionaiised silica gel washed with two aliquots of diethyi ether (50 mL), and dried under vacuum. The ligand functionaiised silica gel was added to a Schlenk flask and purged with nitrogen. To this, a solution of toluene (30g), MMA ( l Og) and ethyl 2-bromoisobutyrate (0.138g) that was degassed by three freeze-pump-thaw cycles, was added. This was followed by the addition of copper(I) bromide (0.144g). The addition copper(I) bromide results in the SiO 2 supported catalyst. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90oC to commence reaction. Samples were taken periodically for conversion and molecular weight analysis. After approximately 20 hr the mixture was cooled to room temperature and the SiO 2 supported catalyst allowed to settle. The polymer solution was removed via cannuia, and the SiO 2 supported catalyst washed with two aliquots of toluene (50mL). To this, another solution of toluene, MMA and ethyl 2-bromoisobutyrate was added (concentrations as per previous solution) and the mixture placed in oil bath at 90oC. This procedure was repeated for two more monomer additions, demonstrating that the SiO 2 supported catalyst could be used at least four times for conssecutive reactions. The results are shown in table 1 and figure 1. PoMstrvene-w-divinvibenzene) supported catalvst-covaltentlv bound Schiff base Example 2: 2-pyridine carboxaidehyde (0.5 g, 6.67 x 10 "3 ) was added to aminofunαioπaiised cross-linked poiystryene beads ( 1.30g) dispersed in tetrahydrofuran (50mL) and stirred for 1 hr. The tetrahydrofuran was removed and the ligand functionaiised poiystryene beads washed with two aliquots of tetrahydrofuran (50mL) and dried under vacuum. The iigand functionaiised poiystryene was added to a Schlenk flask and purges with nitrogen. To this, a solution of toluene ( 12g), MMA (4.0g) and ethyl 2-bromoisobutyrate (0.075g), that was degassed by three freeze-pump-thaw cycles, was added. This was followed by the addition of copper(l) bromide (0.057g). The addition copper(I) bromide produced the polystyrene supported catalyst. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90oC to commence reaction. Samples were taken periodically for conversion and molecular weight analysis. After approximately 20 hr the mixture was cooled to room temperature and the polystyrene supported catalyst allowed to settle. The polymer solution was removed via cannuia. The results are shown in table 1 and figure 2. SiO ■ > adsorbed catalyst Example 3: A solution of toluene (21 g), MMA (7.1 g), ethyl 2-bromoisobutyrate (0.1 39g) and N- n octyi pyridylmethanimine (0.465g) that was degassed by three freeze-pump-thaw cycles, was added to Schlenk flask containing siiica gel (3.0g). To this, copper(l) bromide (0.095g) was added. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90oC to commence reaction. Samples were taken periodically for conversion and molecular weight analysis. After approximately 20 hr the mixture was cooled to room temperature and the SiO 2 adsorbed catalyst allowed to settle. The polymer solution was removed via cannula. The results are shown in table 1. SiO 7 adsorbed catalyst (ID- Non covalentiy bound on amino functionaiised silica Example 4: A solution of toluene (21 g), MMA (7.1 ), ethyl 2-bromoisobutyrate (0.1 39g) and N- n octyl pyridylmethanmine (0.465g) that was degassed by three freeze-pump-thaw cycles was added to Schlenk flask containing 3-aminopropyI-functionaiised silica gel (3.0g). To this, copper(I) bromide (0.095g) was added. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90oC to commence reaction. Samples were taken periodically for conversion and molecular weight analysis. After approximately 20 hr the mixture was cooled to room temperature and the SiO 2 adsorbed catalyst allowed to settle. The polymer solution was removed via cannula. The results are shown in table 1. Table 1 : .Molecular weight and conversion reaults far examples I - 4. Examine πme /hr Conversion V „ PDI 1A 1.33 0.458 21400 45800 2.14 IB :o 0.980 21000 45600 2.18 1C 26 - . - - ID :s 0.380 13600 40400 2.97 IE 30.5 0.726 18600 44600 2.39 IF 45 0.976 18700 46300 2.48 1G 49 25 - . - 1H 51.75 0.149 25000 46100 1.85 11 70 0.942 24800 49600 2.00 U "7.25 - . • • IK -7.33 0.031 21200 38500 1.81 1L 78.75 0.085 18300 37300 103 1M 92.5 0.760 11200 32200 2.87 2A 1 0.388 9030 17600 1.95 2B 2.33 0.681 1 1500 18900 1.64 2C .58 0.876 12800 21300 1.67 2D 17.92 0.986 13300 22600 1.70 A 1 0.446 3950 15000 1.67 B 2.33 0.666 10600 17000 1.61 ;c 3.58 0.753 10200 15200 1.50 3D 17.92 0 817 10600 15800 1.50 4A 1 0 702 11400 20200 1.76 4B 2.33 0.891 5970 19700 3.31 4C 3.58 0.906 1 1800 21100 1.79 4D 17.92 0 922 1 1300 20800 1.84 Time i mm ι Conversion Vtn Mw PDi 5A 120 59 8600 15400 1.78 5B 300 33 9700 15600 1.61 5C 1380 96 H300 19200 1.70 Example 5: Ru(PPh ) CI on 3-aminopropyl-fuπctionalised silica gel 0.14g Ru(PPh 3 ) 3 CI 2 ( 1.461 x 10 4 mol) together with 0.558 g (5.84 x l O -4 mol) 3-aminopropyl-funαionaiised silica gel ( - 9% functionaiised; - 1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum-argon cycles. To this mbcture was added 1.5 mi degassed MMA ( 1.395 x 10 "2 mol) and 5 mi degassed xylene and the mixture heated to 96oC and stirred. The polymerisation reaction was initiated by the addition of ethyl-2-bromoisobutyrate, 0.021 ml ( 1.430 x 10 mol), and the timer was started. Samples were removed at regular intervals and the percentage conversion and molecular weight of the produα polymer determined (conversions were by ' H NMD . Example 6: RuCI T on 3-aminooropyl-fuπctioπalised silica gel 0.095 g RuCI 3 (4.65 x 10 + mol) together with 1.86 g ( 1.395 x 10 3 mol) 3-aminopropyI-π j nctionalised silica gel ( ~ 9% functionaiised; ~ 1.05 mmol NH ; /gram) was added to a schlenk and subjeαed to three vacuum/argon cycles. To this mbcture was added 5 ml degassed MMA (4.65 x 10 " 2 mol) and 15 ml degassed xylene and the mbcture heated to 90oC and stirred. The polymerisation reaction was initiated by the addition of ethyl 2-bromoisobutyrate, 0.069 mi (4.65 x 10 "* mol), and the timer was started. Time (mm) Conversion o/„ Mn Mw PDi 6A 120 6.9 209000 336000 1.61 6B 300 15.1 192000 341000 1.775 όC 1380 74.2 84700 225000 2.65 Example 7: RhCl (H ■> O) i on 3-aminoDropyl-funαionalised silica gel 0.122 g RhCl 3 (H z O) 3 (4.65 x 10 moi) together with 1.86 g ( 1.395 x 10 ' mol) 3-aminpropyI-funαionaiised silica gel ( - 9% funαionaiised; - 1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum.argon cycles. To this mixture was added 5 mi degassed MMA (4.65 x 10 "2 mol) and 1 5 mi degassed xylene and the mbcture heated to 90oC and stirred. The polymerisation reaction was initiated by the addition of ethyI-2-bromoisobutyrate, 0.069 mi (4.65 x 10 "4 moi), and the timer was started. Time (min) Conversion Mn Mw PDi 7A 120 6.1 93600 314000 3.35 7B 300 21.5 17900 320000 1.78 7C 1380 68.7 89100 243000 2.72 Example 8: AgfCF T CO A on 3-aminoDroDγl-ftιnαionalised silica gel 0.1 Og Ag(CF 3 CO 2 ) (4.65 x 10 mol) together with 1.86g ( 1.395 x 10 "3 mol) 3-aminoproply-functionalised silica gel ( - 9% functionaiised; ~ 1.05 mmoi NH 2 /gram) was added to a schlenk and subjected to three vacuum/argon cycles. To this mbcture was added 5 ml degassed MMA (4.65 x 10 '2 moi) and 15 mi degassed xylene and the mixture heated to 90oC and stirred. The polymerisation reaction was initiated by the addition of ethyl 2-bromoisobutyrate, 0.069 mi (4.65 x 10 "4 mol) and the timer was started. Time ( in) Conversion Mn Mw PDi 8A 120 2.6 61200 226000 3.68 8B 300 13.4 149000 324000 2.18 8C 1380 41.8 148000 299000 2.01 The precursor shown in Formula 53 may be produced by reaαing 2-pyridine carbaldehyde with an α-aminocarboxyllc acid, such as 8-amino caprylic acid, followed by mild reduction or byoupling of the parent acid through an amide link. It is envisaged that the use of amino acids will allow the incorporation of asymetry into the system. SYNTHESIS OF POLYSTYRENE SUPPORT The pyridyl route Scheme The pyridyl route to ligand functionaiised polystyrene support Step 1 A Step 2 Table Comparison of synthesis techniques and characterisation of polystyrene supports synthesised via the pyridyl route. n° type Stepl Stepl Step2 n ligand/g by n Cu/g by % retention parti part2 NMR (% vs ICP between ICP ** *** th) (% vs theory) and NMR PS1 PS 1 1 1 1.75 x lO- 3 1.38 x lO- 3 98.5 (55.7) (63.5) PS2 PS 2.32 x 10- 3 5.82 x 10- 33.4 (71) (26.8) PS3 PS 3.09 x lO- 3 ? (98.5) PS4 PSm 1.27 x lO- 3 ? (40.4) PS5 PSp 2.84 x 10- 3 ? (90.7) PS6 PSp 2.77 x 10e- 3 1.39 x lO- 3 87.8 (88.6) (80.6) PS7 PSp 2.94 x 10- 3 1.44 x lO" 3 69.9 (94) (66.9) ' Stepl-partl : 1=DMF, 50°C; 2=DMF, 110°C '* Stepl-part2 : 1=DMF, RT; 2=EtOH, 80°C; 3=DMF, 90°C *** Step2 : l=Et2O, RT; 2=Toluene, 130°C, soxhlet; 3=Toluene, RT Analysis of support Table. Infrared peak assignments for polystyrene supported ligands synthesised following the pyridyl route Support type functional groups 1R peak assignment (cm- 1 ) A chloromethylated CH2-CI 1250 B Phthalimido C=O 1710, 1770 functions C amino functions NH2 1630, 3200 D ligand functions C=N 1490, 1600, 1650 Figure 2 shows infrared spectra for the stepwise synthesis of the pyridyl ligand onto cross-linked polystyrene beads. Typical procedure for the synthesis of support PS5, PS6 and PS7 Stepl-Partl : Phthalimidomethylated cross-linked polystyrene beads (B) To a stirred suspension of cross-linked chloromethylated beads (3 g, 12 mmol) in DMF (100 ml) was added potassium phthalimide (11.19g, 60.4 mmol) and the reaction mixture was heated at 110°C for 7h. After cooling, toluene (100 ml) was added and the reaction mixture was filtrated then washed with water (100 ml), methanol (100 ml) and diethyi ether (100 ml). The solid was dried under vacuum at RT for one day, then at 60°C overnight in a vacoven. Product : white solid (4.15 g). IR absorption: 1710, 1770 cm-1 (v C=O). Elemental analysis: 80.64 %C, 5.85 %H, 3.49 %N (theoretical; 81.43 %C, 5.82 %H, 3.88 %N). Stepl-Part2 : Aminomethylated cross-linked polystyrene beads (C) To a stirred suspension of phthalimide derivative (4.07g, 16.3 mmol) in ethanol (150 ml) was added hydrazine monohydrate (4.6 ml, 0.147 mol). The reaction mixture was heated at 80°C for 3h then cooled to room temperature and left overnight (careful, once the hydrazine has been added, you need enough solvent to compensate the swelling of the beads). Then the reaction mixture was filtered and die solid washed with water (100 ml), methanol (50 ml) and diethyi etiier (50 ml). The solid was dried under vacuum at RT for one day, then at 60°C overnight in a vacoven. Product : white solid (3.24 g). IR absorption: 1650, 1600. 1490 cm-1 (v N-H?). Elemental analysis: 76.61 %C, 6.56 %H. 8.48 %N (theoretical; 85.7 %C, 8.22 %H, 6.06 %N). Step2 : Pyridiniminemethylated cross-linked polystyrene beads (D) To a suspension of amino derivated support C (1.94 g, 7.74 mmol NH2) in toluene (50 ml) was added pyridine carbaldehyde (1.661 g, 15.3 mmol). The mixture was heated under reflux (130°C) in a soxhlet extractor in which the thimble contained 3 A molecular sieves. The support was removed by filtration and washed successively with THF (50 ml), methanol (50 ml) and diethyi ether (50 ml) to give, after drying under reduced pressure at RT and 60°C overnight to constant weight, an orange solid (2.18 g). IR absorption: 1650, 1600, 1490 cm-1 (v C=N). Elemental analysis: 81.06 %C, 6.5 %H, 8.05 %N (theoretical; 84.36 %C, 6.88 %H, 8.75 %N). The (di)amine route Scheme Example of cross-linked polystyrene beads functionalisation with ethylene diamine Scheme. The different cross-linked polystyrene beads supported ligand obtained from the (di)amine route. Table. Summary of cross-linked polystyrene supports synthesised following the (di)amine route. Suppor Suppoπ code Amine used Amine n ligand g by t functionalisation NMR reaction (% vs th) E PS-EDA-lig ethylene diamine DAI 2.75 e- 3 (99.7) F PS-DETA-lig diethylene triamine DAI 4.02 e- 3 (99.5) G PS-TAEA-lig tris(2-aminoethyl)am DA3 2.63 e- 3 ine (70.8) H PS-HE DA- hexamethylenediami DA2 lig ne Procedure for synthesis of PS supports following the (di)amine route Synthesis DAI : (supports E & F) A suspension of chloromethylated cross-linked polystyrene beads (3g, 4 mmol of Cl/g resin. 12 mmol) was shaken in round bottom flask with 15 ml amine during one day at room temperature. The polymer was filtered and successively rinsed two times with 10% triethylamine in dimethylformamide, once witii DMF, four times with 10% EON in tetrahydrofuran. three times with THF and three times with methanol. The solid was then dried under vacuum at RT then at 80°C in the vacoven to constant weight. Synthesis DA2 : (support H) Same as DAI but the amine is mix with 100 ml DMF in order to solubilised it. Synthesis DA3 : (support G) A suspension of chloromethylated cross-linked polystyrene beads (3g, 4 mmol of Cl/g resin. 12 mmol) in DMF (100 ml) was shaken in round bottom flask with tris(2-aminoethyl)amine (5 ml. 33.4 mmol) for 6h at 65°C under N2 atmosphere. After cooling to room temperature, the resin was filtered and washed successively with two times with 10% triethylamine in dimethylformamide, once with DMF, four times with 10% Et3N in tetrahydrofuran, three times with THF and tiiree times with methanol. The solid was then dried under vacuum at RT tiien at 80°C in the vacoven to constant weight. The amino-hexanol route of pyridine carbaldehyde. leading to the spaced supported ligand. Scheme. Two different ways to the synthesis of hexanoxy supported ligand HO Table. Functionalisation of supports synthesised following the amino-hexanol route Support n ligand/g by NMR n Cu g by ICP % retention between (% vs th) (% vs theory) ICP and NMR Kl 2.13 x 10- 3 1.43 x 10- 3 87.6 (90) (80.5) K2 2.16 x lO- 3 1.12 x lO- 3 68 (91) (63.1) L ? 9.25 x 10- 4 ? (52.1) Procedure for synthesis of polystyrene supports via the amino-hexanol route N- n hexanehydroxy-2-pyridine methanimine (2) : 6-phthalimido-l-h.exanol (5) : A solution of 6-amino-l-hexanol (7.54 g, 62.4 mmol) in 15 ml THF was added to a stirred slurry of N-(ethoxycarbonyl)phthaiimide (14.08 g, 63 mmol) in 50 ml THF at 0°C (ice-water bath) with a pressure equalising funnel. After 5 minutes , the bath was removed and the mixture stirred overnight at ambient temperature. After removal of the solvent under reduce pressure, the compound was distillated (0.4 Torr) to give ethyl carbamate. The residue was put through a crystallisation procedure from a solution of toluene (25 ml) and hexane (10 ml) but the product stayed oily. The cristallisation started with scratching the product with spatula to give a light brown solid (13.9 g, 90 % yield). Η NMR: δ =7.81, 7.71 (m, 4H); 3.61 (m, 4H); 2.3 (s, 1H); 1.68, 1.39 (overlapping multiplets, 8H). Elemental analysis: 67.8 %C, 6.9 %H, 5.7 %N (theoretical; 68 %C, 6.93 %H, 5.66 %N). Route A : Phthalimidohexanoxy methylated cross-linked polystyrene beads (I) : To a slurry of potassium hydride (0.81 g, 33.7 mmol) and tetrahydrofuran (100 ml) was added, with stirring, a solution of 6-phthalimido-l-hexanol (5) (5.92 g, 23.9 mmol), dibenzo-18-crown-6 (200 mg, 0.56 mmol) and hexamethylphosphoric triamide (10 ml). After 1 hour at ambient temperature, a slurry of chloromethylated polystyrene beads (3 g, 12 mequiv. CI) in tetrahydrofuran (50 ml) was added. The reaction mixture was stirred and heated under reflux for 48 hours. The polymer was separated by filtration and washed successively with solutions of tetrahydrofuran ethanol (1/1), tetrahydrofuran/methanol (1/1) and then with diediyl ether. The polymer was dried under redure pressure to constant weight to give a white solid (4.36 g, - 60 %). IR absorption: 1710,1770 cm-1 (v C=O),1075 cm-1 (v C-O-C) Route A : Aminohexanoxy methylated cross-linked polystyrene beads (J) : Same procedure as for support C. Route A : Pyridiniminehexanoxy methylated cross-linked polystyrene beads (K) : Same procedure as for support D. IR absorption: 1650 cm-1 (v C=N). Route B : Pyridiniminehexanoxy methylated cross-linked polystyrene beads (L) : Same procedure as for support I, replacing phthalimido-hexanol (5) by N- n hexanehydroxy-2-pyridine methanimine (2). IR absorption: 1650 cm-1 (v C=N). Synthesis of silica support Scheme. Two different silica supports synthesised by direct condensation of pyridine carbaldehyde onto the primary supported amine. Suppoπs S 1 to S4 were found to be bright orange solids, although S5 was light yellow and S6 beige. Supports SI to S5 were easily complexing copper bromide in methanol (black colour of the support). It took time to notice a change of colour for S6, when trying to complex CuBr. Table Comparison of synthesis routes and characterisation of silica supported ligands. Silica support Step2 « n iigand/g by NMR n Cu g by ICP % retention (% vs th) (% vs theory) between ICP and NMR SI 2* 1.04 e- 3 7.08 e- 4 84 (>100) (84) S2 2 1.15 e- 3 7.92 e- 4 93.8 (>100) (93.8) S3 2 1.16e- 3 ? ? (>100) S4 2 1.16 e- 3 7.22 x lO" 4 85.6 (>100) (85.6) S5 3 9.88 e-* ? ? (MOO) S6 1 ? ? ? » Step2 : l=Et2O, RT; 2=Toluene, 130°C, soxhlet; 3=Toluene, RT * Step2 method 2 : Typically mixture of 3 -aminopropyi silica gel (15 g, 15.75 mmol) in toluene (150 ml) with pyridine carbaldehyde (3.6g, 33 mmol). SILICA SUPPORTED ATOM TRANSFER POLYMERISATION In a typical SSATP reaction, CuBr (0.134 g, 9.34 x 10" 4 mol) and the support (x grams , depending on the experimentally calculated loading of ligand onto the support; [Sι-lιg]:[Cu] = n: l, where [Si-lig] is the concentration of ligand anchored to the silica support and n = 1, 2, 3, 4) were placed in a predried Schlenk flask which was evacuated and then flushed with nitrogen three times. Deoxygenated toluene (20 ml, 66% v/v) and deoxygenated methyl methacrylate (10 mL, 9.36 x 10" 2 mol) were added and the suspension stirred. The flask was heated in a thermostatted oil bath at 90 °C and when the temperature had equilibrated ethyl-2-bromoisobutyrate (0.137 mL, 9.34 x 10-* mol. [MMA]0:[In]0= 100:1) was added. Samples (1-2 ml) were taken periodically after initiator was added. Conversions were calculated by gravimetry heating sample to constant weight overnight at 90°C under vacuum. The polymer was then diluted in THF and passed through basic aluminium oxide in order to remove the copper catalyst which has gone into solution. Table Silica Suppoπed Atom Transfer Polymerisations of MMA in toluene Type" Support* [lig]/[Cu] Time Conv. Mnth- Mn(SEC) PDI (min) (%) (g/mol) (gmol) ATP / 2 60 15 1500 3430 1.14 360 80 8010 9050 1.11 SiNH2 < 1 60 13 1300 ? ? 300 34 3400 182800 2.1 SiNH2 2 60 19 1900 ? ? 300 52 5200 146300 1.94 SSATP SI 1 60 27 2700 19700 1.63 360 67 6700 18500 1.8 SSATP S2 1 60 33 3300 12250 1.59 360 75 7510 15950 1.56 SSATP S2 2 60 48 4800 12200 1.6 360 98 9810 14900 1.68 SSATP S2bis 1 30 29 2900 12300 1.65 300 76 7610 18200 1.64 SSATP S3 2 30 35 3500 12800 1.68 250 86 8610 15500 1.71 SSATP S4 2 30 36 3600 12800 1.68 260 91 9110 16350 1.78 SSATP S5 2 30 30 3000 18900 2.1 300 91 9110 16500 2.1 SSATP S6 ? 60 40 4000 50850 2.5 240 74 7410 50800 2.4 ° further data are available in annex c 3 -aminopropyi silica gel; here [lig] is equal to the concentration of amine functions on the silica support. Mn(th) = ([MMMA]0/[I]0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. Figure 3 shows kinetic reproducibility of silica supported atom transfer polymerisation from experiments carried out with different silica supported ligands synthesised at different times. Recycling experiments Recycling experiments, using the same support, have also been carried out. Here, we present the results obtained when support S4 was used (some recycling experiments with support S2 are also available in § VI.3.2). A first polymerisation was carried out using 3 equivalents of silica supported ligand in reference to copper ([MMA]:[Cu]:[Si-lig S4]:[E2BI] = 100:1:3:1), then the solution medium was removed from the Schlenk tube with a syringe. The support, still carrying the transition metal catalyst, was washed three times with degassed toluene introduced and removed from the tube by syringe. The support was then dried under vacuum. During all this procedure, the support stayed in the schlenk tube and was kept under nitrogen in order to avoid any deactivation by contact with air. The washed support was then reused for a new polymerisation by introducing into the schlenk tube, in the following order : 20 ml of toluene, 10 ml of MMA and 0.137 ml of E2BI (same condition as before : [MMA] :[Cu]: [Si-lig] :[E2BI] = 100:1:3:1). Three recycling polymerisations were experimented with the same support. Figure 4 shows recycling experiments carried out with support S4 using the same conditions; [MMA] :[Cu]: [Si-lig] :[E2BI] = 100:1:3:1 Each recycling experiment shows a decrease of the kinetic rate of polymerisation for MMA. However, recyclings 2 and 3 have the same kinetic behaviour. It seems that the catalyst activity is affected after each polymerisation. Probably, the amount of active species is reduce during the time of the experiment and the time of the washing of the support. This degradation finds a limit after a certain time or a certain number of recycling. The polydispersities still remain the same (around 1.7), even after several use of the support. Table. Recycling experiments carried out with support S4 for the polymerisation of MMA by silica supported atom transfer polvmerisation; [MMA]:[Cu]:[Si-lig]:[E2BI] = 100:1 :3:1 Experiment" Time Conversion Mnth Mn(SEC) PDI (min) (%) (gmol) (g/mol) First polym. 30 41 4100 11600 1.76 180 90 9010 13800 1.8 Recycling 1 130 43 4300 13900 1.75 330 81 8110 16850 1.69 Recycling 2 130 8 800 360 57 5700 17100 1.69 Recycling 3 130 8 800 ? ? 310 43 4300 17200 1.7 Influence of initiator and solvent on silica supported atom transfer polymerisation of M A Table. Influence of initiator and solvent on silica supported atom transfer polymerisation of MMA Support [lig]/[Cu] Initiator* Solvent Conv.% Mnth' Mn(SEC) HUT (6h) (g/mol) (g mol) SI 1 E2BI Toluene 67 6 500 18 500 1.79 SI 1 DPB Toluene 25 2500 8300 1.74 SI 1 TS Toluene 38 3800 9200 1.74 SI 1 E2BI Anisole 60 6000 14250 1.68 SI 1 E2BI Phe2O 84 8410 17580 1.71 * E2BI : ethyl-2-bromoisobutyrate; DPB : 1,1,1-diphenyi methyl bromide; TS : tosyl bromide c Mn(th) = ([MMMA]0/[I]0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. RUTHENIUM SUPPORTED ATOM TRANSFER POLYMERISATION Typical polymerisation procedure In a typical reaction, for example [In]:[Ru]:[SiNH2] = 1:1:2, the ruthenium RuC12(PPh3)3 (-0.45 g, 4.69 x 10" 4 mol) and the support (-0.90 g, 9.49 x 10-*) are introduced in a schlenk tube and subjected to three vacuum/nitrogen cycles. Deoxygenated toluene (15 ml, 75% v/v) and deoxygenated methyl methacrylate (5 ml, 4.67 x lO -2 mol) were added and the suspension stirred. The flask was heated in a thermostatted oil bath at 90 °C and when the temperature had equilibrated ethyl-2-bromoisobutyrate (0.069 mL, 4.69 x \0 mol, [MMA]0:[In]0= 100:1) was added. Samples (1-2 ml) were taken approximately 15, 30, 60, 120, 180, 240 and 300 minutes after initiator was added. Conversions were calculated by gravimetry heating sample to constant weight overnight at 90 °C under vacuum. The polymer was then diluted in THF and passed through basic aluminium oxide in order to remove the ruthenium catalyst which has gone into solution. Table. Molar ratios of components used in Silica supported-Ruthenium mediated-ATP Experiment (MMA) [E2BI] [RuC12fPPh3)3] [support]* 1 100 2 1 4 2 100 1 1 4 3 100 0.5 1 4 4 100 2 8 5 100 0.5 2 6 100 1 8 7 100 1 2 8 100 0.5 silica b 9 100 0.5 A1203 « 10 d 100 2 1 4 a concentration of NH2 on 3-aminopropyl functionaiised silica gel b silica gel c basic alumina d reused the catalyst from experiment 1 Table. Results for silica supported-ruthenium mediated-ATP (SS-Ru-ATP) Experiment t (min) Conversion Mnth Mn PDI (%) (gmol) (gmol) 1 30 34 1700 5040 1.82 180 90 4550 6780 1.56 2 30 40 4000 6750 1.76 180 93 9260 10700 1.5 30 35 7040 10300 1.74 240 91 18200 21500 1.49 4 30 46 4600 6530 1.56 180 98 9810 11250 1.54 5 30 23 2330 6420 1.97 180 78 7770 10500 1.55 6 30 39 3900 8000 3.1 120 88 8850 11300 2.22 7 30 26 2600 5280 1.50 180 75 7510 8380 1.47 8 45 18 1800 5780 1.51 240 42 4220 7850 1.67 9 45 22 2200 5850 1.59 180 40 4000 7240 1.57 10 30 25 1250 4930 2.14 240 88 4400 6770 1.73 Reinitiation Experiments In order to confirm the living character of this polymerisation, reinitiations from previously synthesised PMMA (made by silica supported-ruthenium mediated-ATP : SS-Ru-ATP) have been carried out. Two types of macroinitiators PMMAl and PMMA2 have been synthesised following the conditions from experiments 4 and 7 respectively. They have been used for initiation of MMA and BzMA by SS-Ru-ATP, keeping the same catalyst and support quantities. Table , molar ratios of components used in silica supported-ruthenium mediated-ATP reinitiation experiments Experiment Macroinitiator' Monomer 2 [RuCI2(PPh3)3] [support]* (|In|) (IMl) 11 PMMAl MMA 2 8 (0.317) (100) 12 PMMAl BzMA 2 8 (0.317) (63) 13 PMMA2 MMA 1 2 (0.338) (100) 14 PMMA2 BzMA 1 2 (0.338) (63) concentration of NH2 on 3 -aminopropyi functionaiised silica gel Table. Data for SS-Ru-ATP macroinitiation experiments using different monomers Experimen Mass Time Conv % Mnth Mnexp PDI - targeted (min) 2 nd pol° (g mol) (g mol) 11 41600 0 0 10083 1.37 30 30 20162 15230 1.57 285 85 36736 31013 2.62 12 45040 0 0 10083 1.37 30 60 30548 23262 1.60 180 95 43297 37105 1.88 13 39080 0 0 9465 1.26 30 30 18079 14282 1.37 330 95 37147 29369 1.48 14 42280 0 0 9465 1.26 30 55 27113 18132 1.35 200 90 39535 26969 1.35 POLYSTYRENE SUPPORTED ATOM TRANSFER POLYMERISATION Typical polymerisation procedure In a typical PS-SATP reaction, CuBr (0.134 g, 9.34 x lO" mol) and the support (x grams, depending on the experimentally calculated loading of ligand onto the support; [PS-lig]:[Cu] = n:l, where [PS-lig] is the concentration of ligand anchored to the polystyrene support and n = 1, 2, 3, 4, etc..) were placed in a predried Schlenk flask which was evacuated and then flushed with nitrogen three times. Deoxygenated toluene (20 ml, 66% v/v) and deoxygenated methyl methacrylate (10 mL. 9.36 x 10" 2 mol) were added and the suspension stirred. The flask was heated in a thermostatted oil bath at 90 °C and when the temperature had equilibrated ethyl-2-bromoisobutyrate (0.137 mL, 9.34 x 10" 4 mol, [MMA]0:[In]0= 100:1) was added. Samples (1-2 ml) were taken periodically after initiator was added. Conversions were calculated by gravimetry heating sample to constant weight overnight at 90°C under vacuum. The polymer was then diluted in THF and passed through basic aluminium oxide in order to remove the copper catalyst which has gone into solution. Table. Polystyrene Supported Atom Transfer Polymerisations of MMA in toluene Type Support [lig]/[Cu]* Time Conv. Mnth c Mn(SEC PDI (min) (%) (g mol) ) (g/mol) ATP 60 15 1 500 3 430 1.14 360 80 8 010 9 050 1.11 PS-SAT PS2 1.25 33 29.6 2 960 14020 1.55 P 83 47.2 4720 14760 1.62 120 55.6 5560 16510 1.51 185 66.3 6630 16520 1.56 245 72.2 7230 15500 1.66 300 77.5 7760 15590 1.66 363 83.6 8370 16230 1.62 PS-SAT PS4 35 25.6 2600 8125 1.47 P 310 84 8400 11150 1.63 PS-SAT PS6 1.25 30 25.1 2510 7530 1.45 P 61 36.7 3670 8670 1.54 120 49.4 4940 10215 1.51 180 60.1 6010 11140 1.53 240 68.6 6860 11740 1.51 300 75.2 7530 11670 1.56 PS-SAT PS6 bis 1.25 32 25.1 2 510 6 950 1.41 P 60 35.5 3550 8170 1.41 147 55.1 5510 9880 1.41 196 62.6 6260 10590 1.41 240 67.5 6750 10710 1.43 300 73.5 7360 11370 1.42 PS-SAT PS7 31 20.9 2100 8320 1.42 P 300 53.3 5300 12050 1.45 PS-SAT PS7 31 28.5 2800 7580 1.39 P 300 70 7010 11890 1.39 * Here [lig] is equal to the concentration of ligand functions on the polystyrene support. c Mn(th) = ([MMMA]0/[I]0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. Effect of the amount of polystyrene supported ligand Table. Effect of the amount of polystyrene support on polystyrene supported atom transfer polymerisations of MMA in toluene Su PP° rt [Hg]/[Cu]* Time Conv. M Ϋ^ Mn(SEC) PDF (min) (%) (g/mol) (g/mol) PS7 31 20.9 2090 8320 1.42 60 28.0 2800 8790 1.48 123 38.5 3850 10510 1.44 186 45.2 4520 11190 1.45 253 50.4 5040 12550 1.39 300 53.3 5330 12050 1.45 PS7 31 28.5 2850 7580 1.39 60 35.7 3570 8110 1.43 123 50.8 5080 9970 1.39 186 59.8 5980 11130 1.36 251 63.4 6340 11070 1.4 300 70.0 7010 11890 1.39 PS7 31 34.9 3490 7870 1.43 60 45.5 4550 9630 1.42 123 60.9 6090 11390 1.44 186 69.5 6950 12140 1.48 252 78.9 7900 12940 1.48 300 82.7 8280 13450 1.48 PS7 31 37.8 3780 85900 1.55 60 51.0 5100 9700 1.63 123 69.7 6970 11120 1.68 186 81.1 8120 12230 1.66 252 87.2 8730 13510 1.59 300 89.2 8930 13650 1.59 * Here [lig] is equal to the concentration of ligand functions on the polystyrene support. c Mn(th) = ([MMMA]0/[I]0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. The (di)amine route Table. Experimental data for the PS-SATP of MMA mediated by copper catalyst complexed by different supports synthesised following the (di)amine route Support name [Lig]0/[Cu] time Conv. Mn Mn PDI 0 (min) (%) (th)» (SEC) (SEC) E PS-EDA-lig -3 29 34.0 3 400 7 020 2.43 241 96.0 9 610 13 900 2.09 G PS-TAEA-li 2.9 36 36.6 3 660 12 375 2.06 g 312 95.2 9 530 15 890 1.95 H PS-HEMDA- 2 30 25.8 2 580 16 050 1.78 li 180 74.7 7480 16250 1.77 292 93.5 9360 16150 1.8 FI PS-DETA-li ~5 36 44.1 4410 10440 2.61 g 67 62.3 6230 11570 2.31 131 83.1 8320 12950 2.15 188 92.7 9280 14120 2.08 250 99.1 9920 17110 1.79 F2 PS-DETA-li -5 29 38.6 3 860 9 200 2.02 g 62 62.0 6200 11080 1.92 126 82.2 8230 13250 1.86 181 90.9 9100 14340 1.86 241 96.6 9670 14640 1.89 b Mn(th) = ([MMMA]0/[Tj0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. The amino-hexanol route Table. Experimental data for the PS-SATP of MMA mediated by copper catalyst complexed by different supports synthesised following the amino-hexanol route Support name [Lig]0/[Cu] time Conv. Mn (th)* Mn PDI . 0 (min) (%) (SEC) (SEC) PS7 PS-lig 2 31 28.5 2850 7580 1.39 60 35.7 3570 8110 1.43 123 50.8 5080 9970 1.39 186 59.8 5980 11130 1.36 251 63.4 6340 11070 1.4 300 70.0 7010 11890 1.39 Kl PS-AHO- 30 27.1 2 710 13 880 1.81 ig 64 42.4 4240 14540 1.78 119 58.9 5890 15670 1.75 180 70.6 7070 15870 1.76 244 79.8 7990 18040 1.6 292 85.6 8570 18250 1.63 K2 PS-AHO-1 30 26.8 2 680 10 370 1.6 ig 64 44.0 4400 12660 1.53 119 61.0 6100 14730 1.53 180 72.9 7300 16230 1.48 244 82.5 8260 16660 1.51 292 87.4 8750 18080 1.46 PS-AHO-1 2 30 12.9 1 290 26 130 1.8 ig 64 19.1 1910 26950 1.81 119 27.3 2730 29210 1.79 180 33.9 3390 29390 1.83 244 38.1 3810 30750 1.78 292 42.9 4290 29920 1.84 b Mn(th) = ([MMMA]0/[I]0 x MWMMA) x conversion, where MWMMA is the molecular weight of methyl methacrylate and [MMMA]0/[I]0 is the initial concentration ratio of MMA to initiator. REINITIATION EXPERIMENTS In a typical reinitiation experiment, CuBr (0.134 g, 9.34 x 10" 4 mol) and the macroinitiator (x grams, depending on the experimental molecular weight obtained from SEC and assuming that PDI = 1, [macroinitiator] :[Cu] = 0.182:1) were placed in a predried Schlenk flask which was evacuated and then flushed wim nitrogen three times. Deoxygenated toluene (30 ml, 75% v/v) and deoxygenated methyl methacrylate (10 mL, 9.36 x 10" 2 mol, [MMA]0:[Cu]0=100:l) or deoxygenated benzyl methacrylate (10 ml, 5.92 x 10" 2 mol, [BzMA]0:[Cu]0=63.22:l) were added and the suspension stirred until all the macroinitiator is dissolved. The flask is then submitted to three Freeze-Pump-Thaw cycles (FPT). When the temperature had equilibrated to room temperature, N- n pentyl-2-pyridine methanimine ligand (1) (0.36 ml, 1.87 x lO -3 moi, [Lig]0:[Cu]0=2:l) is added by syringe and the flask is heated straightforward in a thermostatted oil bath at 90 °C. Samples (1-2 ml) were taken periodically using syringes after the start of the heating. Conversions were calculated by gravimetry heating sample to constant weight overnight at 90°C under vacuum. The polymer was then diluted in THF and passed through basic aluminium oxide in order to remove the copper catalyst which has gone into solution. Table, molar ratios of components used in reinitiation experiments *** Experimeπ Macroinitiator 4 [In] Monomer pentyl [CuBr] t 2 ligand [MMA] [Lig] 1 PM A (A) 0.182 100 2 1 2 PMMA (S) 0.182 100 2 1 3 PMMA (P) 0.182 100 2 1 4 PMMA (L) 0.182 100 2 1 a PMMA (A) synthesised following conditions [MMA]: [CuBr]: [lig] :[E2BI] = 100:1:2:1 PMMA (S) svnthesised following conditions [MMA]: [CuBr]: [Si-lig S4]:[E2BI] = 100:1:1:1 PMMA (P) synthesised following conditions [MMA]:[CuBr]:[PS-lig PS6]:[E2BI] = 100:1:1:1 PMMA (L) synthesised following conditions [MMA]: [CuBr]: [Si-lig S4]:[E2BI] = 100:1:2:1 These results are shown in Figure 5. Table. Data for macroinitiation experiments using different monomers Experiment Macroinit. Time Conv % Mnth Mnexp PDI (min) 2 nd pol° (gmol) (gmol) 1 PMMA 0 0 7616 1.19 (A) 34 10.5 13374 12546 1.17 63 15.1 15898 14760 1.21 130 22.1 19749 19230 1.25 61%~3h 186 26.9 22419 22270 1.3 244 30.6 24419 25210 1.31 278 32.5 25507 27570 1.29 2 PMMA(S) 0 0 16575 1.46 33 10.4 22293 17130 1.28 62 15.1 24873 22510 1.39 129 22.2 28761 29540 1.25 2h 185 26.7 31244 31330 1.27 241 30.5 33366 34640 1.25 278 32.7 34534 35810 1.25 3 PMMA (P) 0 0 13105 1.25 33 12.1 19773 18770 1.17 62 17.1 22493 20510 1.19 129 23.2 25853 23940 1.20 185 28.2 28608 26300 1.20 241 31.8 30617 28440 1.21 278 32.8 31143 29150 1.22 4 PMMA (L) 0 0 6896 1.46 33 10.9 12862 12250 1.19 62 15.7 15508 14340 1.19 129 23.3 19704 18250 1.18 185 27.3 21901 20480 1.19 69% 2h 241 30.8 23812 16130 1.19 278 33.3 25198 24320 1.19 Block copoiymerisation Table, molar ratios of components used in reinitiation experiments Experiment Macroinitiator 1 [In] Monomer 2 pentyl [CuBr] [BzMA] ligand [Lig] 5 PMMA (A) 0.182 63.22 2 1 6 PMMA (S) 0.182 63.22 2 1 7 PMMA (P) 0.182 63.22 2 1 8 PMMA (L) 0.182 63.22 2 1 a PMMA I A) svntnesised following conations (MMA) [CuBr) (lig) (E2BI) = 100 1 2 1 PMMA (S) svnthesised following conditions [MMA] (CuBr) [Si-lig S ) [E2Bη - 100 1:1.1 PMMA (P) svnthesised following conditions (MMA) (CuBr) (PS-lig PS6] [E2BI) - 100 1.1.1 PMMA ( ) synthesised following conditions [MMA] (CuBr) (Si-lig S ] (E2BH = 100 1 2 1 Table. Data for macroinitiation experiments using different monomers Experiment Macroinit. Time Conv % Mnth Mnexp PDI (min) 2 nd pol 0 (g/mol) (gmol) 5 PMMA 0 0 7616 1.19 (A) 38 18.4 18890 17536 1.59 64 23.0 21670 19861 1.28 131 34.6 28790 26391 1.34 61%~3h 261 73.0 52308 51028 1.83 309 79.6 56348 45112 1.99 358 80.2 56680 42580 2.00 6 PMMA (S) 0 0 21828 1.47 s.2 33 19.9 33985 29395 1.75 59 22.6 35647 30172 1.62 126 35.4 43482 35658 1.58 3h 62% 256 59.6 58283 45600 1.83 304 71.1 65325 54698 1.80 353 75.8 68207 55380 1.79 7 PMMA (P) 0 0 14676 1.23 35 19.6 26689 24023 1.42 3h 66 29.1 32497 28194 1.51 52% 127 42.7 40790 35295 1.73 257 63.3 53397 44560 1.71 305 77.7 62208 53841 1.63 354 83.8 65984 48105 1.81 8 PMMA (L) 0 0 6896 1.46 36 16.7 17097 61 22.5 20673 128 37.0 29552 258 49.1 36922 69% 2h 306 52.2 38844 355 60.7 44070 28240 1.83 Recyclabiiity Table. Recycling experiments carried out with support PS7 for the polymerisation of MMA by polystyrene supported atom transfer polymerisation; [MMA] :[Cu]: [PS-lig P PQS771]-:r[PE2TBDTI]. = - I 1Λ0Λ0.: 11:.21:. 11 Experiment Time Conversion Mnth Mn(SEC) PDI (min) (%) (g/mol) (gmol) First polym. 31 28.5 2850 7580 1.39 60 35.7 3570 8110 1.43 123 50.8 5080 9970 1.39 186 59.8 5980 11130 1.36 251 63.4 6340 11070 1.4 300 70.0 7010 11890 1.39 Recycling 1 29 4.06 400 69 7.04 700 134 15.4 1540 12000 1.68 172 22.5 2250 13810 1.61 255 38.1 3810 14760 1.65 329 52.1 5210 16560 1.61 365 58.5 5850 16880 1.59 Recycling 2 76 1.90 190 125 4.45 445 176 8.00 801 265 17.1 1714 336 25.7 2575

Claims: CLAIMS 1. A supported ligand for use in catalysts for polymerisation of olefinically unsaturated monomers, especially vinylic monomers, said supported ligand having a general formula 1 ; Formula 1 S(D)„ where: S is the support. D is a compound attached to the support, said compound being capable of complexing with a transition metal ion. n is an integer of one or more. 2. A catalyst for use in the polymerisation of olefinically unsaturated monomers, comprising a compound of general formula: Formula 52 [(SD) c M] d+ A where: M = a transition metal in a low valency state or a transition metal co-ordinated to at least one co-ordinating non-charged ligand. S = a support. D = a compound attached to the support, the compound being capable of complexing with a transition metal, d = an integer of 1 or 2, c = an integer of 1 or 2, A = a monovalent or divalent counter ion. 3. A catalyst according to claim 2, wherein M is selected from Cu(I), Fe(II), Co(EI), Ru(II) and Ni(II). 4. A supported ligand or a catalyst according to any preceding claim, wherein D is an organic compound comprising a group capable of complexing with a transition metal ion. 5. A supported ligand or a catalyst according to claim 4, wherein the group capable of complexing with a transition metal ion is selected from a Schiff base, amine, hydroxyi, phosphine or diimine. 6. A supported ligand or a catalyst according to claim 4 or claim 5, wherein the group capable of complexing with a transition metal ion is separated from the support by a substituted or non-substituted aikyl group. 7. A supported ligand or a catalyst according to claim 6, wherein the aikyl group is a straight chain, branched chain, or aromatic aikyl group. 8. A supported ligand or a catalyst according to any preceding claim wherein compound D is a diimine. 9. A supported ligand or a catalyst according to claim 8, wherein one of the nitrogens of the diimine is not part of an aromatic ring. 10. A supported ligand or a catalyst according to claims 8 or 9, wherein the diimine is selected from: a 1.4-diaza- 1.3-butadiene Formula 2 R4 a 2-pyridinecarbaldehyde imine Formula 3 R10 an Oxazolidone Formula 4 or a Quinoline Carbaldehyde Formula 5 where Ri, R 2 , Rio, Rπ, R12 and Ri . may be varied independently and Rι, R 2 , Rio, Rπ, R12 and Ri , may be H, straight chain, branched chain or cyclic saturated aikyl, hydroxyalkyl, carboxyalkyl, aryl (such as phenyl or substituted phenyl where substitution is as described for R . to Rq), CF Ar (where Ar = aryl or substituted aryl) or a halogen; and R, to R 9 may independently be selected from the group described for Ri, R 2 , Rio, R11, R12 and Rι 3 or additionally OCnH 2n+ 1 (where n is an integer from 1 to 20), NO 2 , CN or O = CR (where R = aikyl. benzyl PhCH 2 or a substituted benzyl). 1 1. A supported ligand or a catalyst according to any one of claims 5-10, wherein D exhibits a chiral centre a to one of the nitrogen groups. 12. A supported ligand or a catalyst according to claim 10 or claim 1 1, wherein D is a compound of general Formula 3 which comprises one or more fused rings on the pyridine group. 13. A supported ligand or a catalyst according to claim 10 or claim 1 1, wherein one or more adjacent R, and R,, R , and R 4 , * and R 2 , Rι 0 and R 9 , R 8 and R 9 , R 8 and R 7 , R 7 and Re, Rό and R 5 groups are selected from C , to C 8 cycloalkyl, cycloalkenyl, polycydoaikyl, polycydoalkenyi or cyclicaryl, such as cyclohexyl, cyclohexenyl or norborneyl. 14. A supported ligand or a catalyst according to any one of claims 8 to 13, wherein the diimine compound is covalentiy attached to the support via positions RI, R2, R9, R10, Rl l, R12 or R13. 15. A supported ligand or a catalyst according to any preceding claim, wherein D is attached to support S via a linkage group such as a Schiff base. 16. A supported ligand or a catalyst according to any preceding claim, wherein the support is selected from an inorganic compound such as silica, an organic polymer, and magnetised beads. 17. In combination, a supported ligand according to claim 1 complexed with a transition metal ion. 18. A combination according to claim 17, wherein the transition metal ion is in a low valency state. 19. A combination according to claim 18, wherein the transition metal is selected from Cu(I), Fe(II), Co(II), Ru(II) and Ni(II). 20. A catalyst for the addition polymerisation of olefinically unsaturated monomers comprising a supported ligand according to any one of claims 1 or 4-16 in combination with: a) a compound of: Formula 30 MY where: M is a transition metal in a low valency state or a transition metal in a low valency state co-ordinated to at least one co-ordinating non-charged ligand. Y is a mono- or polyvalent counter ion: and b) an initiator compound comprising a homolytically cleavable bond with a halogen atom. 21. A catalyst according to claim 20. wherein the transition metal is selected from Cu(I), Fe(II), Co(II), Rufll) and Ni(II). 22. A catalyst according to any one of claims 2 to 16 additionally comprising an initiator compound comprising a homolytically cleavable bond with a halogen atom. 23. A catalyst according to any one of claims 2 to 16 or 20 to 22, wherein the co-ordinating ligand is (CFLCN) ... 24. A catalyst according to any one of claims 20-23, wherein the initiator compound is selected from: Formula 31 RX Formula 32 Formula 33 Formula 34 Formula 35 Formula 36 Formula 37 Formula 38 Formula 39 Formula 40 Formula 41 where: R is independently selectable and is selected from straight, branched or cyclic aikyl. hydrogen, substituted aikyl, hydroxyalkyl, carboxyalkyl or substituted benzyl. X is a halide, especially I, Br. F or CI. 25. A process for the production of a supported ligand, a catalyst or a combination according to any one of claims 8 to 24 comprising the steps of: a) providing a functionaiised support; b) providing a ligand precursor, wherein one of the functionaiised support or the ligand precursor comprises a primary amine. and the other of the functionaiised support or the ligand precursor comprises an aldehyde or ketone group; and c) reacting the primary amine with the aldehyde or ketone to form a diimine compound covalentiy attached to the support. 26. Process according to claim 25, wherein the diimine compound produced is then mixed with a transition metal halide to produce a diimine co-ordinated to a transition metal. 27. Process according to claim 26, wherein the transition metal halide is selected from CuCl and CuBr. 28. A process for the addition polymerisation of one or more olefinically unsaturated monomers comprising the use of a catalyst according to any one of claims 2 to 16 or 20 to 24. 29. A process according to claim 28, wherein the olefinically unsaturated monomer is selected from a methacrylic. an acrylate. a styrene. a methacrylonitrile or a diene. 30. A process according to claim 27 or claim 28, wherein the catalyst is used at a temperature between -20°C and 200°C. 31. A process according to any one of claims 28 to 30, additionally comprising the use of a free-radical inhibitor. 32. A process according to any one of claims 28 to 30, wherein the amount of D : MY is between 0.01 to 1000 and ratio of MY : initiator is 0.0001 to 1000.

Inventors: DUNCALF DAVID, HADDLETON DAVID MARK, KUKULJ DAX, RADIGUE ARNAUD, DUNCALF, DAVID, HADDLETON, DAVID, MARK, KUKULJ, DAX, RADIGUE, ARNAUD
Applicants: DUNCALF DAVID, HADDLETON DAVID MARK, KUKULJ DAX, RADIGUE ARNAUD, UNIV WARWICK, DUNCALF, DAVID, HADDLETON, DAVID, MARK, KUKULJ, DAX, RADIGUE, ARNAUD, UNIVERSITY OF WARWICK
Application year: 1998
Main classification: C08F4
IPC codes: C08F4