PATENT DOCUMENT

Abstract:
The invention relates to supported ligands and catalysts for use in the polymerization 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 carbaldeyde. Preferably the catalysts are used in conjunction with an initiator comprising a homolytically cleavable 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.

Full Description:
BACKGROUND OF THE INVENTION 
     1. Field of Invention 
     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. 
     2. Description of Related Art 
     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 alkyl lithiums 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 alkyl halide have been utilised. For example, Matyjasewski (Macromolecules (1995), vol. 28, pages 7901-7910 and WO96/30421) has described the use of CuX (where X=Cl, Br) in conjunction with bipyridine and an alkyl 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&#39;s work by utilising arenesulphonyl chlorides to replace alkyl 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 aluminum alkyl 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 &gt;0 due to normal radical-radical combination and disproportionation reactions. 
     The inventors have found that the use of diimines such as 1,4-diaza-1,3-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(II), 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 O 2  and functional monomers, and may even be conducted in aqueous media. This system is the subject of copending patent application number PCT/GB97/01587. 
     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 are 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. 
     SUMMARY OF THE INVENTION 
     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) n   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, and 
     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-divinylbenzone). 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, hydroxyl, phosphine or diimine capable of complexing with a transition metal ion. Each Schiff base, amine, hydroxyl, phosphine or diimine is preferably separated from the support by a branched or straight alkyl chain, especially a chain containing 1 to 20 carbon atoms. The chain may comprise one or more aromatic groups as part of the alkyl chain. 
     One preferred ligand is the use of a support attached to two or more alkyl-amines, such as aminopropyl-, aminobutyl-, aminopentyl-, aminohexyl-, 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 1,4-diaza-1,3-butadiene                           
     where R 1 , R 2 , R 10 , R 11 , R 12  and R 13  may be varied independently and R 1 , R 2 , R 10 , R 11 , R 12  and R 13  may be H, straight chain, branched chain or cyclic saturated alkyl, 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 1 , R 2 , R 10 , R 11 , R 12  and R 13  may be a C 1  to C 20  alkyl, hydroxyalkyl or carboxyalkyl, in particular C 1  to C 4  alkyl, especially methyl or ethyl, n-propylisopropyl, n-butyl, sec-butyl, tent-butyl, cyclohexyl, 2-ethylhexyl, octyl, decyl or lauryl. R 1 , R 2 , R 10 , R 11 , R 12  and R 13  may especially be methyl. 
     R 3  to R 9  may independently be selected from the group described for R 1 , R 2 , R 10 , R 11 , R 12  and R 13  or additionally OC n H 2n+1 , (where n is an integer from 1 to 20), NO 2 , CN or O═CR (where R=alkyl, benzyl PhCH 2  or a substituted benzyl, preferably a C 1  to C 20  alkyl, especially a C 1  to C 4  alkyl). 
     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 R 1  and R 3 , R 3  and R 4 , R 4  and R 2 , R 10  and R 9 , R 8  and R 9 , R 8  and R 7 , R 7  and R 6 , R 6  and R 5  groups may be C 5  to C 8  cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclicaryl, such as cyclohexyl, cyclohexenyl or norborneyl. 
     The diimine compounds are preferably covalently attached to the support via positions R1, R2, R9, R10, R11, R12 or R13. They maybe attached via a linkage group, such as a Schiff base to the support. 
     Preferred diimines include:                         
                         
                         
                           
     where: * indicates a chiral centre. 
     R14=Hydrogen, C 1  to C 10  branched chain alkyl, carboxy- or hydroxy-C 1  to C 10  alkyl. 
     The ligands, according to the first aspect of the invention, may be used to from 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 inhibitor 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(III), Cu(I) and Cu(II), a low valency state is the lower of the commonly occurring valencies, i.e. Fe(II) or Cu(I). Hence M in Formula 30 is preferably Cu(I), Fe(II), Co(II), Ru(II), Rh(I) or Ni(II), most preferably Cu(I). Preferably the coordinating ligand is (CH 3 CN) 4 . Y may be chosen from Cl, Br, F, I, NO 3 , PF 6 , BF 4 , SO 4 , CN, SPh, SCN, SePh or triflate (CF 3 SO 3 ). Copper (I) triflate may be, which may be in the form of a commercially available benzene complex (CF 3 SO 3 Cu) 2 C 6 H 6 . The especially preferred compound used is CuBr. 
     Preferably the second component (b) is selected from: 
     
       
                 
         
             
             
         
      
     
     where R is independently selectable and is selected from straight, branched or cyclic alkyl, hydrogen, substituted alkyl, hydroxyalkyl, carboxyalkyl or substituted benzyl. Preferably the or each alkyl, hydroxyalkyl or carboxyalkyl contains 1 to 20, especially 1 to 5 carbon atoms. 
     X is a halide, especially I, Br, F or Cl. 
     The second component (b) may especially be selected from Formulae 43 to 52:                           
     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 , SO 3 , COX— where X is Br, I or C) or:                           
     R 111 =—COOH, —COX (where X is Br, I, F or Cl), —OH, —NH 2  or —SO 3 H, especially 2-hydroxyethyl-2′-methyl-2′-bromopropionate.                           
     Especially preferred examples of Formula 45 are:                           
     Br may be used instead at Cl in Formulae 46A and 46B.                           
     The careful selection of functional alkyl halides allows the production of terminally functionalised polymers. For example, the selection of a hydroxy containing alkyl bromide allows the production of α-hydroxy terminal polymers. This can be achieved without the need of protecting group chemistry. 
     The transition metal may be precoordinated to the ligand covalently attached to its support. 
     Accordingly a second aspect 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: 
     
       
         [(SD) c M] d+ A  Formula 52 
       
     
     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, such as Cl, Br, F, I, NO 3 , PF 6 , BF 4 , SO 4 , CN, SPh. 
     Preferably M is a defined for Formula 30 above. S may be as defined for Formula 1. 
     D may be adsorbed or covalently attached to the support. 
     D may be a compound as described earlier for the first aspect 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 aspect 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 covalently 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 functionalised support; 
     (b) providing a ligand precusor comprising an aldehyde group or ketone group; and 
     (c) reacting the primary amine functionalised support with the ligand precursor to form a diimine compound covalently attached to the support. 
     The primary amine of the functionalised 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 product, the reaction with the primary amine producing the second imine group. This is shown in the reaction scheme below which shows the reaction of a support functionalised with a primary amine with 2-pyridine carbaldehyde 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.                           
     Alternatively an aldehyde or a ketone group may be provided separately on a diimine ligand precursor. Such a suitable precursor is shown in Formula 53                           
     This allows the diimine to be decoupled from the support to allow controlled polymerisation. 
     Alternatively the following reaction scheme may be followed:                           
     The primary amine group may alternatively be provided on the ligand precursor and reacted with a ketone or aldehyde functionalised support. 
     The support material may be functionalised inorganic material, such as silica, especially silica gel. Alternatively functionalised organic support, especially a functionalised cross-linked polymeric support, such as poly(styrene-w-divinylbenzene) may be used. Such supports are preferably usually used for absorbing compounds or in chromatography. 
     Preferably the reaction to form the Schiff base occurs at room temperature. 
     Preferably the functionalised support is an aminopropyl 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 continuous 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 130° C., more preferably 90° C. 
     The olefinically unsaturated monomer may be a methacrylic, an acrylate, a styrene, methacrylonitrile or a diene such as butadiene. 
     Examples of olefinically unsaturated monomers that may be polymerised include methyl methacrylate, vinylacetate, vinyl chloride acylonitonile, methacylamide, acrylamide, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), and other alkyl methacrylates; corresponding acrylates; also functionalised methacrylates and acrylates including glycidyl methacrylate, trimethoxsysilyl propyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylaminoalkyl methacrylates; fluoroalkyl (meth)acrylates; methacrylic acid, acrylic acid; fumaric acid (and esters), itaconic acid (and esters), maleic anhydride; styrene, α-methyl styrene; vinyl halides such as vinyl chloride and vinyl fluoride; acrylonitrile, methacrylonitrile; vinylidene halides of formula CH 2 ═C(Hal) 2  where each halogen is independently Cl or F; optionally substituted butadienes of the formula CH 2 ═C(R 15 )C(R 15 )═CH 2  where R 15  is independently H, C 1  to C 10  alkyl, Cl, or F; sulphonic acids or derivatives thereof of formula CH 2 ═CHSO 2 OM wherein M is Na, K, Li, N(R 16 ) 4  where each R 16  is independently H or C 1  to C 10  alkyl, D is COZ, ON, N(R 16  ) 2  or SO 2 OZ and Z is H, Li, Na, K or N(R 16 ) 4 ; acrylamide or derivatives thereof of formula CH 2 ═CHCON(R 16 ) 2 ; and methacryiamide or derivative thereof of formula CH 2 ═C(CH 3 )CON(R 16 ) 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 methoxyplenol. 
     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 molar 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, diphenylether, 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 copolymers may be produced using the catalysts according to the invention. Such copolymers may use 2 or more monomers in a range of ca.0-100% by weight of each of the monomers used. 
     Block copolymers may also be prepared by sequential addition of monomers to the reaction catalyst. 
     Telechelic polymers, may be produced using catalysts 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 —CO 2 H via use of a suitable reactant such as sodium azide. 
     Comb and graft copolymers may be produced using the catalysts of the invention to allow, for example, polymers having functional side chains to be produced, by use of suitable reagents. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     Embodiments of the invention will now be described by way of example and with reference to the following figure: 
     FIG. 1 show the polymerisation of methylmethacrylate for four monomer additions to supported catalyst which has been collected at the end of each previous polymerisation reaction. 
     FIG. 2 shows infrared spectra for the stepwise synthesis of pyridyl ligand onto cross-linked polystyrene beads. 
     FIG. 3 shows kinetic reproducibility of silica supported atom transfer polymerisation from experiments carried out with different silica supported ligands synthesised at different times. 
     FIG. 4 shows recycling experiments carried out with support S4 using the same conditions: 
     [MMA]:[Cu]:[Si-lig]:[E2 BI]=100:1:3:1 
     FIG. 5 shows reinitiation of PMMA. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     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 &amp; Wycoff. Toluene (Fisons, 99.8%) was dried over sodium. Ethyl-bromoisobutyrate (Aldrich, 9%), 2-pyridene carboxaldehyde, 3-aminipropyl-functionalised silica gel (Aldrich, 98% functionalised), silica gel (Merck), and diethyl ether (BDH, 98%) were used as received. 
     Ref: Keller, R. N.; Wycoff, H. D.  Inorg. Synth . 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 −1  as an eluent. Poly(MMA) standards in the range (10 6 -200 g.mol −1 ) were used to calibrate the SEC. 
     SiO 2  Supported Catalyst-covalently Bound Schiff Bases 
     EXAMPLE 1 
     2-pyridine carboxaldehyde (0.714 g, 6.67×10 −3  mol) was added to 3-aminopropylfunctionalised silica gel (3.00 g, 3.15×10 −3  mol of active NH 2 ) dispersed in diethyl ether (50 mL) and stirred for 1 hr. The diethyl ether was removed and the ligand functionalised silica gel washed with two aliquots of diethyl ether (50 mL), and dried under vacuum. The ligand functionalised silica gel was added to a Schlenk flask and purged with nitrogen. To this, a solution of toluene (30 g), MMA (10 g) and ethyl 2-bromoisobutyrate (0.138 g) that was degassed by three freeze-pump-thaw cycles, was added. This was followed by the addition of copper(I) bromide (0.144 g). 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 90° C. to commence reaction. Samples were taken periodically for conversion and molecular weight analysts. 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 cannula, and the SiO 2  supported catalyst washed with two aliquots of toluene (50 mL). 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 90° C. This procedure was repeated for two more monomer additions, demonstrating that the SiO 2  supported catalyst could be used at least four times for consecutive reactions. The results are shown in table 1 and FIG.  1 . 
     Poly(stryene-w-divinylbenzene) Supplied Catalyst-covaltently Bound Schiff Base 
     EXAMPLE 2 
     2-pyridine carboxaldehyde (0.5 g, 6.67×10 −3 ) was added to aminofunctionalised cross-linked polystryene beads (1.30 g) dispersed in tetrahydrofuran (50 mL) and stirred for 1 hr. The tetrahydrofuran was removed and the ligand functionalised polystryene beads washed with two aliquots of tetrahydrofuran (50 mL) and dried under vacuum. The ligand functionalised polystryene was added to a Schlenk flask and purges with nitrogen. To this, a solution of toluene (12 g), MMA (4.0 g) and ethyl 2-bromoisbutyrate (0.075 g), that was degassed by three freeze-pump-thaw cycles, was added. This was followed by the addition of copper(I) bromide (0.057 g). 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 90° C. 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 cannula. The results are shown in table 1 and FIG.  2 . 
     SiO 2  Adsorbed Catalyst 
     EXAMPLE 3 
     A solution of toluene (21 g), MMA (7.1 g), ethyl 2-bromoisobutyrate (0.139 g) and N- n octyl pyridylmethanimine (0.465 g) that was degassed by three freeze-pump-thaw cycles, was added to Schlenk flask containing silica gel (3.0 g). 
     To this, copper(I) bromide (0.095 g) was added. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90° C. 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 2  Adsorbed Catalyst (II)—Non Covalently Bound on Amino Functionalised Silica 
     EXAMPLE 4 
     A solution of toluene (21 g), MMA (7.1 g), ethyl 2-bromoisobutyrate (0.139 g) and N- n octyl pyridyimethamine (0.465 g) that was degassed by three freeze-pump-thaw cycles was added to Schlenk flask containing 3-aminopropyl-functionalised silica gel (3.0 g). To this, copper(I) bromide (0.095 g) was added. Agitation was effected by a magnetic stirrer. The mixture was then placed in an oil bath at 90° C. 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 
               
               
                   
                   
               
             
             
               
                   
                   
                   
                 Conver- 
                   
                   
                   
               
               
                   
                 Example 
                 Time/Hr 
                 sion 
                 Mn 
                 Mw 
                 PDI 
               
               
                   
                   
               
               
                   
                 1A 
                 1.33 
                 0.458 
                 21400 
                 45800 
                 2.14 
               
               
                   
                 1B 
                 20 
                 0.98 
                 21000 
                 45600 
                 2.18 
               
               
                   
                 1C 
                 26 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 1D 
                 28 
                 0.38 
                 13600 
                 40400 
                 2.97 
               
               
                   
                 1E 
                 30.5 
                 0.726 
                 18600 
                 44600 
                 2.39 
               
               
                   
                 1F 
                 45 
                 0.976 
                 18700 
                 46300 
                 2.48 
               
               
                   
                 1G 
                 49.25 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 1H 
                 51.75 
                 0.149 
                 25000 
                 46100 
                 1.85 
               
               
                   
                 1I 
                 70 
                 0.942 
                 24800 
                 49600 
                 2.00 
               
               
                   
                 1J 
                 77.25 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 1K 
                 77.83 
                 0.031 
                 21200 
                 38500 
                 1.81 
               
               
                   
                 1L 
                 78.75 
                 0.085 
                 18300 
                 37300 
                 2.03 
               
               
                   
                 1M 
                 92.5 
                 0.760 
                 11200 
                 32200 
                 2.87 
               
               
                   
                 2A 
                 1 
                 0.388 
                  9030 
                 17600 
                 1.95 
               
               
                   
                 2B 
                 2.33 
                 0.681 
                 11500 
                 18900 
                 1.64 
               
               
                   
                 2C 
                 3.58 
                 0.876 
                 12800 
                 21300 
                 1.67 
               
               
                   
                 2D 
                 17.92 
                 0.986 
                 13300 
                 22600 
                 1.70 
               
               
                   
                 3A 
                 1 
                 0.446 
                  8950 
                 15000 
                 1.67 
               
               
                   
                 3B 
                 2.33 
                 0.666 
                 10600 
                 17000 
                 1.61 
               
               
                   
                 3C 
                 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 
                 11800 
                 21100 
                 1.79 
               
               
                   
                 4D 
                 17.92 
                 0.922 
                 11300 
                 20800 
                 1.84 
               
               
                   
                   
               
               
                   
                   
                 Time 
                 Conver- 
                   
                   
                   
               
               
                   
                   
                 (min) 
                 sion (%) 
                 M n   
                 M w   
                 PDi 
               
               
                   
                   
               
               
                   
                 5A 
                 120 
                 59 
                  8600 
                 15400 
                 1.78 
               
               
                   
                 5B 
                 300 
                 83 
                  9700 
                 15600 
                 1.61 
               
               
                   
                 5C 
                 1380 
                 96 
                 11300 
                 19200 
                 1.70 
               
               
                   
                   
               
             
          
         
       
     
     EXAMPLE 5 
     Ru(PPh 3 ) 3 Cl 2  on 3-Aminopropyl-functionalised Silica Gel 
     0.14 g Ru(PPh 3 ) 3  (1.461×10 −4  mol) together with 0.558 g (5.84×10 −4  mol) 3-aminopropyl-functionalised silica gel (˜9% functionalised; ˜1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum-argon cycles. To this mixture was added 1.5 ml degassed MMA (1.395×10 −2  mol) and 5 ml degassed xylene and the mixture heated to 96° C. and stirred. The polymerisation reaction was initiated by the addition of ethyhl-2-bromoisobutyrate, 0.021 ml (1.430×10 −4  mol), and the timer was started. 
     Samples were removed at regular intervals and the percentage conversion and molecular weight of the product polymer determined (conversions were by  1 H NMR). 
     EXAMPLE 6 
     RuCl 3  on 3-Aminopropyl-functionalised Silica Gel 
     0.095 g RuCl 3  4.65×10 −6  mol) together with 1.86 g (1.395×10 −3  mol) 3-aminopropyl-functionalised silica gel (˜9% functionalised; ˜1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum/argon cycles. To this mixture was added 5 ml degassed MMA (4.65×10 −2  mol) and 15 ml degassed xylene and the mixture heated to 90° C. and stirred. The polymerisation reaction was initiated by the addition of ethyl 2-bromoisobutyrate, 0.069 ml (4.65×10 −4  mol), and the timer was started. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Time (min) 
                 Conversion % 
                 Mn 
                 Mw 
                 PDi 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 6A 
                  120 
                 6.9 
                 209000 
                 336000 
                 1.61 
               
               
                   
                 6B 
                  300 
                 15.1 
                 192000 
                 341000 
                 1.775 
               
               
                   
                 6C 
                 1380 
                 74.2 
                  84700 
                 225000 
                 2.65 
               
               
                   
                   
               
             
          
         
       
     
     EXAMPLE 7 
     RhCl 3  (H 2 O) 3  on 3-Aminopropyl-functionalised Silica Gel 
     0.122 g RhCl 3 (H 2 O) 3  (4.65×10 −4  mol) together with 1.86 g (1.395×10 −3  mol) 3-aminpropyl-functionalised silica gel (˜9% functionalised; ˜1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum argon cycles. To this mixture was added 5 ml degassed MMA (4.65×10 −2  mol) and 15 ml degassed xylene and the mixture heated to 90° C. and stirred. The polymerisation reaction was initiated by the addition of ethyl-2-bromoisobutyrate, 0.069 ml (4.65×10 −4  mol), 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 
     Ag(CF 3 CO 3 ) on 3-Aminopropyl-functionalised Silica Gel 
     0.10 g Ag(CF 3 CO 2 ) (4.65×10 −4  mol) together with 1.86 g (1.395×10 −3  mol) 3-aminoproply-functionalised silica gel (˜9% functionalised; ˜1.05 mmol NH 2 /gram) was added to a schlenk and subjected to three vacuum/argon cycles. To this mixture was added 5 ml degassed MMA (4.65×10 −2  mol) and 15 ml degassed xylene and the mixture heated to 90° C. and stirred. The polymerisation reaction was initiated by the addition of ethyl 2-bromoisobutyrate, 0.069 ml (4.65×10 −4  mol) and the timer was started. 
     
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Time (min) 
                 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 to Formula 53 may be produced by reacting 2-pyridine carbaldehyde with an α-aminocarboxylic acid, such as 8-amino caprylic acid, followed by mild reduction or by coupling 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                           
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Comparison of synthesis techniques and characterisation of polystyrene 
               
               
                 supports synthesized via the pyridyl route. 
               
             
          
           
               
                   
                   
                   
                   
                   
                 n ligand/g 
                 n Cu/g by 
                 % retention 
               
               
                   
                   
                 Step 1 
                 Step 1 
                   
                 by NMR 
                 ICP 
                 between ICP 
               
               
                 n o   
                 type 
                 part 1* 
                 part 2** 
                 Step 2*** 
                 (% vs th) 
                 (% vs theory) 
                 and NMR 
               
               
                   
               
             
          
           
               
                 PS1 
                 PS 
                 1 
                 1 
                 1 
                 1.75 × 10 −3   
                 1.38 × 10 −3   
                 98.5 
               
               
                   
                   
                   
                   
                   
                 (55.7) 
                 (63.5) 
               
               
                 PS2 
                 PS 
                 1 
                 2 
                 2 
                 2.32 × 10 −3   
                 5.82 × 10 −4   
                 33.4 
               
               
                   
                   
                   
                   
                   
                 (71) 
                 (26.8) 
               
               
                 PS3 
                 PS 
                 2 
                 2 
                 2 
                 3.09 × 10 −3   
                 ? 
                 ? 
               
               
                   
                   
                   
                   
                   
                 (98.5) 
               
               
                 PS4 
                 PSm 
                 2 
                 3 
                 2 
                 1.27 × 10 −3   
                 ? 
                 ? 
               
               
                   
                   
                   
                   
                   
                 (40.4) 
               
               
                 PS5 
                 PSp 
                 2 
                 2 
                 2 
                 2.84 × 10 −3   
                 ? 
                 ? 
               
               
                   
                   
                   
                   
                   
                 (90.7) 
               
               
                 PS6 
                 PSp 
                 2 
                 2 
                 2 
                 2.77 × 10e −3   
                 1.39 × 10 −3   
                 87.8 
               
               
                   
                   
                   
                   
                   
                 (88.6) 
                 (80.6) 
               
               
                 PS7 
                 PSp 
                 2 
                 2 
                 2 
                 2.94 × 10 −3   
                 1.44 × 10 −3   
                 69.9 
               
               
                   
                   
                   
                   
                   
                 (94) 
                 (66.9) 
               
               
                   
               
               
                 *Step 1-part 1: 1 = DMF, 50° C.; 2 = DMF, 110° C.  
               
               
                 **Step 1-part 2: 1 = DMF, RT; 2 = EtOH, 80° C.; 3 = DMF, 90° C.  
               
               
                 ***Step 2: 1 = 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 
               
             
          
           
               
                   
                   
                 functional 
                 IR peak assignment 
               
               
                 Support 
                 type 
                 groups 
                 (cm −1 ) 
               
               
                   
               
               
                 A 
                 chloromethylated 
                 CH2—Cl 
                 1250 
               
               
                 B 
                 Phthalimido 
                 C═O 
                 1710, 1770 
               
               
                   
                 functions 
               
               
                 C 
                 amino functions 
                 NH2 
                 1630, 3200 
               
               
                 D 
                 ligand functions 
                 C═N 
                 1490, 1600, 1660 
               
               
                   
               
             
          
         
       
     
     FIG. 2 shows infrared spectra for the stepwise synthesis of the pyridyl ligand onto cross-linked polystyrene beads. 
     Typical Procedure for the Synthesis of Support PSS, PS6 and PS7 
     Step 1-Part1: Plthalimidomethylated 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 (11.19 g, 60.4 mmol) and the reaction mixture was heated at 110° C. for 7 h. After cooling, toluene (100 ml) was added and the reaction mixture was filtrated then washed with water (100 ml), methanol (100 ml) and diethyl 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). 
     Step 1-Part 2: Aminomethylated Cross-linked Polystyrene Beads (C) 
     To a stirred suspension of phthalimide derivative (4.07 g, 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 3 h 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 the solid washed with water (100 ml), methanol (50 ml) and diethyl ether (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). 
     Step 2: Pyridiniminemthylated Cross-linked Polystyrene Beads (D) 
     To a suspension of amino derivated support C (1.94 g, 7.74 mmol NH 2 ) 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 3A molecular sieves. The support was removed by filtration and washed successively with THF (50 ml), methanol (50 ml) and diethyl 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, 1490cm−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                                                     
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Summary of cross-linked polystyrene supports 
               
               
                 synthesised following the (di)amine route. 
               
             
          
           
               
                   
                   
                   
                 Amine 
                   
               
               
                   
                   
                   
                 func- 
               
               
                   
                   
                   
                 tion- 
                 n ligand/g by 
               
               
                   
                 Support 
                 Amine 
                 alisation 
                 NMR 
               
               
                 Support 
                 code 
                 used 
                 reaction 
                 ( % vs th) 
               
               
                   
               
             
          
           
               
                 E 
                 PS-EDA-lig 
                 ethylene diamine 
                 DA1 
                 2.75 e −3   
               
               
                   
                   
                   
                 (99.7) 
               
               
                 F 
                 PS-DETA-lig 
                 diethylene triamine 
                 DA1 
                 4.02 e −3   
               
               
                   
                   
                   
                   
                 (99.5) 
               
               
                 G 
                 PS-TAEA-lig 
                 tris(2-aminoethyl)- 
                 DA3 
                 2.63 e −3   
               
               
                   
                   
                 amine 
                   
                 (70.8) 
               
               
                 H 
                 PS-HEMDA-lig 
                 hexamethylene- 
                 DA2 
                 ? 
               
               
                   
                   
                 diamine 
               
               
                   
               
             
          
         
       
     
     Procedure for Synthesis of PS Supports Following the (di)Amine Route 
     Synthesis DA1: (Supports E &amp; F) 
     A suspension of chloromethylated cross-linked polystyrene beads (3 g, 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% trietylamine in dimethylformamide, once with DMF, four times with 10% Et3N 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 DA1 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 (3 g, 4 mmol of Cl/g resin, 12 mmol) in DMF (100 ml) was shaken in round bottom flask with tris(2-aminoetyl)amine (5 ml, 33.4 mmol) for 6 h 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 three times with methanol. The solid was then dried under vacuum at RT then 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 hexenoxy supported ligand                           
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Functionalisation of supports synthesised 
               
               
                 following the amino-hexanol route 
               
             
          
           
               
                   
                 n ligand/g by NMR 
                 n Cu/g by ICP 
                 % retention between 
               
               
                 Support 
                 (% vs th) 
                 (% vs theory) 
                 ICP and NMR 
               
               
                   
               
             
          
           
               
                 K1 
                 2.13 × 10 −3   
                 1.43 × 10 −3   
                 87.6 
               
               
                   
                 (90) 
                 (80.5) 
               
               
                 K2 
                 2.16 × 10 −3   
                 1.12 × 10 −3   
                 68 
               
               
                   
                 (91) 
                 (63.1) 
               
               
                 L 
                 ? 
                 9.25 × 10 −4   
                 ? 
               
               
                   
                   
                 (52.1) 
               
               
                   
               
             
          
         
       
     
     Procedure for Synthesis of Polystyrene Supports Via the Amino-hexanol Route. 
     N- n Hexanehydroxy-2-pyridine Methanimine (2): 
     6-Phthalimido-1-hexanol (5): 
     A solution of 6-amino-1-hexanol (7.54 g, 62.4 mmol) in 15 ml THF was added to a stirred slurry of N-(ethoxycarbonyl)phthalimide (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 crystallisation started with scratching the product with spatula to give a light brown solid (13.9 g, 90% yield). 
       1 H 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-plithalimido-1-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. Cl) in tetrahydrofuran (50 ml) was added. The reaction mixture was stirred and heated under reflex 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 diethyl ether. The polymer was dried under reduce 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: Pyridinimenehexanoxy 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.                           
     Supports S1 to S4 were found to be bright orange solids, although S5 was light yellow and S6 beige. Supports S1 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. 
               
             
          
           
               
                   
                   
                   
                   
                 % retention 
               
               
                 Silica 
                 Step 
                 n ligand/g by NMR 
                 n Cu/g by ICP 
                 between 
               
               
                 support 
                 2 a   
                 (% vs th) 
                 (% vs theory) 
                 ICP and NMR 
               
               
                   
               
             
          
           
               
                 S1 
                  2 b   
                 1.04 e −3   
                 7.08 e −3   
                 84 
               
               
                   
                   
                 (&gt;100) 
                 (84)   
               
               
                 S2 
                 2 
                 1.15 e −3   
                 7.92 e −4   
                 93.8 
               
               
                   
                   
                 (&gt;100) 
                 (93.8) 
               
               
                 S3 
                 2 
                 1.16 e −3   
                 ? 
                 ? 
               
               
                   
                   
                 (&gt;100) 
               
               
                 S4 
                 2 
                 1.16 e −3   
                 7.22 × 10 −4   
                 85.6 
               
               
                   
                   
                 (&gt;100) 
                 (85.6) 
               
               
                 S5 
                 3 
                 9.88 e −3   
                 ? 
                 ? 
               
               
                   
                   
                 (&gt;100) 
               
               
                 S6 
                 1 
                 ? 
                 ? 
                 ? 
               
               
                   
               
               
                   a Step 2: 1 = Et2O, RT; 2 = Toluene, 130° C., soxhlet, 3 = Toluene, RT  
               
               
                   b Step 2 method 2: Typically mixture of 3-aminopropyl silica gel (15 g, 15.75 mmol) in toluene (150 ml) with pyridine carbaldehyde (3.6 g, 33 mmol).  
               
             
          
         
       
     
     Silica Supported Atom Transfer Polymerisation 
     In a typical SSATP reaction, CuBr (0.134 g, 9.34×10 −4  mol) and the support (x grams, depending on the experimentally calculated loading of ligand onto the support; [Si-lig]:[Cu]=n:1, 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, 9.36×10 −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, 9.34×10 −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 aluminum oxide in order to remove the copper catalyst which has gone into solution. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Silica Supported Atom Transfer Polymerisations of MMA in toluene 
               
             
          
           
               
                   
                   
                 [lig]/ 
                 Time 
                 Conv. 
                 Mn th   d   
                 Mn (SEC)   
                   
               
               
                 Type a   
                 Support b   
                 [Cu] 
                 (min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 ATP1 
                 / 
                 2 
                 60 
                 15 
                 1 500 
                 3 430 
                 1.14 
               
               
                   
                   
                   
                 360 
                 80 
                 8 010 
                 9 050 
                 1.11 
               
               
                 SS1 
                 SiNH 2   c   
                 1 
                 60 
                 13 
                 1 300 
                 18 2800 
                 2.1 
               
               
                   
                   
                   
                 300 
                 34 
                 3 400 
               
               
                 SS2 
                 SiNH 2   
                 2 
                 60 
                 19 
                 1 900 
               
               
                   
                   
                   
                 300 
                 52 
                 5 200 
                 146 300 
                 1.94 
               
               
                 SSATP 
                 S1 
                 1 
                 60 
                 27 
                 2 700 
                 19 700 
                 1.63 
               
               
                 1 
                   
                   
                 360 
                 67 
                 6 700 
                 18 500 
                 1.8 
               
               
                 SSATP 
                 S2 
                 1 
                 60 
                 33 
                 3 300 
                 12 250 
                 1.59 
               
               
                 2 
                   
                   
                 360 
                 75 
                 7 510 
                 15 950 
                 1.56 
               
               
                 SSATP 
                 S2 
                 2 
                 60 
                 48 
                 4 800 
                 12 200 
                 1.6 
               
               
                 3 
                   
                   
                 360 
                 98 
                 9 810 
                 14 900 
                 1.68 
               
               
                 SSATP 
                 S2bis 
                 1 
                 30 
                 29 
                 2 900 
                 12 300 
                 1.65 
               
               
                 4 
                   
                   
                 300 
                 76 
                 7 610 
                 18 200 
                 1.64 
               
               
                 SSATP 
                 S3 
                 2 
                 30 
                 35 
                 3 500 
                 12 800 
                 1.68 
               
               
                 5 
                   
                   
                 250 
                 86 
                 8 610 
                 15 500 
                 1.71 
               
               
                 SSATP 
                 S4 
                 2 
                 30 
                 36 
                 3 600 
                 12 800 
                 1.68 
               
               
                 6 
                   
                   
                 260 
                 91 
                 9 110 
                 16 350 
                 1.78 
               
               
                 SSATP 
                 S5 
                 2 
                 30 
                 30 
                 3 000 
                 18 900 
                 2.1 
               
               
                 7 
                   
                   
                 300 
                 91 
                 9 110 
                 16 500 
                 2.1 
               
               
                 SSATP 
                 S6 
                 ? 
                 60 
                 40 
                 4 000 
                 50 850 
                 2.5 
               
               
                 8 
                   
                   
                 240 
                 74 
                 7 410 
                 50 800 
                 2.4 
               
               
                   
               
               
                   a further data are available  
               
               
                   b See table V-7.  
               
               
                   c 3-aminopropyl silica gel; here [lig] is equal to the concentration of amine functions on the silica support.  
               
               
                   d Mn (th)  = ([M MMA ] 0 /[I] 0  × MW MMA ) × conversion, where MW MMA  is the molecular weight of methyl methacrylate and [M MMA ] 0 /[I] 0  is the initial concentration ratio of MMA to initiator.  
               
             
          
         
       
     
     FIG. 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. 
     FIG. 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 reduced 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 recyclings. 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 polymerisation; 
               
               
                 [MMA]:[Cu]:[Si-lig]:[E2BI] 100:1:3:1 
               
             
          
           
               
                   
                 Time 
                 Conversion 
                 Mnth 
                 Mn(SEC) 
                   
               
               
                 Experiment a   
                 (min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 First polym. 
                  30 
                 41 
                 4100 
                 11600 
                 1.76 
               
               
                   
                 180 
                 90 
                 9010 
                 13800 
                 1.8 
               
               
                 Recycling 1 
                 130 
                 43 
                 4300 
                 1900 
                 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 MMA 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Influence of initiator and solvent on silica supported atom transfer 
               
               
                 polymerisation of MMA 
               
             
          
           
               
                   
                 [lig]/ 
                   
                   
                 Conv. 
                 Mn th   c   
                 Mn (SEC)   
                   
               
               
                 Support 
                 [Cu] 
                 Initiator b   
                 Solvent 
                 % (6 h) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
               
                 S1 
                 1 
                 E2BI 
                 Toluene 
                 67 
                 6 500 
                 18 500 
                 1.79 
               
               
                 S1 
                 1 
                 DPB 
                 Toluene 
                 25 
                 2 500 
                 8 300 
                 1.74 
               
               
                 S1 
                 1 
                 TS 
                 Toluene 
                 38 
                 3 800 
                 9 200 
                 1.74 
               
               
                 S1 
                 1 
                 E2BI 
                 Anisole 
                 60 
                 6 000 
                 14 250 
                 1.68 
               
               
                 S1 
                 1 
                 E2BI 
                 Phe 2 O 
                 84 
                 8 410 
                 17 580 
                 1.71 
               
               
                   
               
               
                   b E2BI: ethyl-2-bromoisobutyrate; DPB: 1,1,1-diphenyl methyl bromide; TS: tosyl bromide  
               
               
                   c Mn (th)  = ([M MMA ] 0 /[I] 0  × conversion, where MW MMA  is the molecular weight of methyl methacrylate and [M MMA ] 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 RuCl2(PPh3)3 (˜0.45 g, 4.69×10 −4  mol) and the support (˜0.90 g, 9.49×10 −4 ) 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, 4.67×10 −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 (0.069 mL, 4.69×10 −4  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 aluminum oxide in order to remote the ruthenium catalyst which has gone into solution. 
     
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Molar ratios of components used in Silica 
               
               
                 supported-Ruthenium mediated-ATP 
               
             
          
           
               
                 Experiment 
                 [MMA] 
                 [E2BI] 
                 [RUCl 2 (PPh 3 ) 3 ] 
                 [support] a   
               
               
                   
               
             
          
           
               
                 1 
                 100 
                 2 
                 1 
                 4 
               
               
                 2 
                 100 
                 1 
                 1 
                 4 
               
               
                 3 
                 100 
                 0.5 
                 1 
                 4 
               
               
                 4 
                 100 
                 1 
                 2 
                 8 
               
               
                 5 
                 100 
                 1 
                 0.5 
                 2 
               
               
                 6 
                 100 
                 1 
                 1 
                 8 
               
               
                 7 
                 100 
                 1 
                 1 
                 2 
               
               
                 8 
                 100 
                 1 
                 0.5 
                 silica b   
               
               
                 9 
                 100 
                 1 
                 0.5 
                 Al 2 O 3   c   
               
               
                 10 d   
                 100 
                 2 
                 1 
                 4 
               
               
                   
               
               
                   a concentration of NH 2  on 3-aminopropyl functionalised silica gel  
               
               
                   b silica gel  
               
               
                   c basic alumina  
               
               
                   d reused the catalyst from experiment 1  
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Results for silica supported-ruthenium 
               
               
                 medicated-ATP (SS-Ru-ATP) 
               
             
          
           
               
                   
                 Experi- 
                   
                 Conversion 
                 Mnth 
                 Mn 
                   
               
               
                   
                 ment 
                 t(min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
                   
               
             
          
           
               
                   
                 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 
               
               
                   
                 3 
                 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 PMMA1 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 
               
             
          
           
               
                 Experi- 
                 Macroinitiator a   
                 Monomer 2 
                   
                   
               
               
                 ment 
                 ([m]) 
                 ([M]) 
                 [RUCl(PPh3)3] 
                 [support] b   
               
               
                   
               
               
                 11 
                 PMMA1 
                 MMA 
                 2 
                 8 
               
               
                   
                 (0.317) 
                 (100) 
               
               
                 12 
                 PMMA1 
                 BzMA 
                 2 
                 8 
               
               
                   
                 (0.317) 
                  (63) 
               
               
                 13 
                 PMMA2 
                 MMA 
                 1 
                 2 
               
               
                   
                 (0.338) 
                 (100) 
               
               
                 14 
                 PMMA2 
                 BzMA 
                 1 
                 2 
               
               
                   
                 (0.338) 
                  (63) 
               
               
                   
               
               
                   a PMMA1 synthesised following conditions [E2BI]:[Ru]:[NH2]= 1:2:8, experiment 4  
               
               
                 PMMA2 synthesised following conditions [E2BI]:[Ru]:[NH2]= 1:1:2, experiment 7  
               
               
                   b concentration of NH2 on 3-aminopropyl functionalised silica gel  
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Data for SS-Ru-ATP macroinitiation 
               
               
                 experiments using different monomers 
               
             
          
           
               
                 Experi- 
                 Macr 
                 Time 
                 Conv % 
                 Mnth 
                 Mnexp 
                   
               
               
                 ment 
                 targeted 
                 (min) 
                 2 nd  pol° 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 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, 9.34×10 −4  mol) and the support (x grams, depending on the experimentally calculated loading of ligand onto the support; [PS-lig]:[Cu]=n:1, 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. Decoxygenated toluene (20 ml, 66% v/v) and deoxygenated methyl methacrylate (10 mL, 9.36×10 −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, 9.34×10 −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 aluminum oxide in order to remove the copper catalyst which has gone into solution. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Polystyrene Supported Atom Transfer Polymerisation of MMA in 
               
               
                 toluene 
               
             
          
           
               
                   
                   
                 [lig]/ 
                 Time 
                 Conv. 
                 Mnth c   
                 Mn(SEC) 
                   
               
               
                 Type 
                 Support 
                 [Cu] b   
                 (min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 ATP 
                 / 
                 2 
                 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 
                 14 020 
                 1.55 
               
               
                 P 
                   
                   
                 83 
                 47.2 
                 4 720 
                 14 760 
                 1.62 
               
               
                   
                   
                   
                 120 
                 55.6 
                 5 560 
                 16 510 
                 1.51 
               
               
                   
                   
                   
                 185 
                 66.3 
                 6 630 
                 16 520 
                 1.56 
               
               
                   
                   
                   
                 245 
                 72.2 
                 7 230 
                 15 500 
                 1.66 
               
               
                   
                   
                   
                 300 
                 77.5 
                 7 760 
                 15 590 
                 1.66 
               
               
                   
                   
                   
                 363 
                 83.6 
                 8 370 
                 16 230 
                 1.62 
               
               
                 PS-SAT 
                 PS4 
                 2 
                 35 
                 25.6 
                 2 600 
                 8 125 
                 1.47 
               
               
                 P 
                   
                   
                 310 
                 84 
                 8 400 
                 11 150 
                 1.63 
               
               
                 PS-SAT 
                 PS6 
                 1.25 
                 30 
                 25.1 
                 2 510 
                 7 530 
                 1.45 
               
               
                 P 
                   
                   
                 61 
                 36.7 
                 3 670 
                 8 670 
                 1.54 
               
               
                   
                   
                   
                 120 
                 49.4 
                 4 940 
                 10 215 
                 1.51 
               
               
                   
                   
                   
                 180 
                 60.1 
                 6 010 
                 11 140 
                 1.53 
               
               
                   
                   
                   
                 240 
                 68.6 
                 6 860 
                 11 740 
                 1.51 
               
               
                   
                   
                   
                 300 
                 75.2 
                 7 530 
                 11 670 
                 1.56 
               
               
                 PS-SAT 
                 PS6 bis 
                 1.25 
                 32 
                 25.1 
                 2 510 
                 6 950 
                 1.41 
               
               
                 P 
                   
                   
                 60 
                 35.5 
                 3 550 
                 8 170 
                 1.41 
               
               
                   
                   
                   
                 147 
                 55.1 
                 5 510 
                 9 880 
                 1.41 
               
               
                   
                   
                   
                 196 
                 62.6 
                 6 260 
                 10 590 
                 1.41 
               
               
                   
                   
                   
                 240 
                 67.5 
                 6 750 
                 10 710 
                 1.43 
               
               
                   
                   
                   
                 300 
                 73.5 
                 7 360 
                 11 370 
                 1.42 
               
               
                 PS-SAT 
                 PS7 
                 1 
                 31 
                 20.9 
                 2 100 
                 8 320 
                 1.42 
               
               
                 P 
                   
                   
                 300 
                 53.3 
                 5 300 
                 12 050 
                 1.45 
               
               
                 PS-SAT 
                 PS7 
                 2 
                 31 
                 28.5 
                 2 800 
                 7 580 
                 1.39 
               
               
                 P 
                   
                   
                 300 
                 70 
                 7 010 
                 11 890 
                 1.39 
               
               
                   
               
               
                   b Here [lig] is equal to the concentration of ligand functions on the polystyrene support.  
               
               
                   c Mn(th) = ([MMMA]0/[I]0 × MWMMA) × 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 
               
             
          
           
               
                 Sup- 
                 [lig]/ 
                 Time 
                 Conv. 
                 Mnth c   
                 Mn[SEC] 
                   
               
               
                 port 
                 [Cu] b   
                 (min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 PS7 
                 1 
                  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 
                 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 
                 11390 
                 1.39 
               
               
                 PS7 
                 3 
                  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 
                 4 
                  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 
               
               
                   
               
               
                   b Here [lig] is equal to the concentration of ligand functions on the polystyrene support.  
               
               
                   c Mn(th) = ([MMMA]0/[I]0 × MWMMA) × 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 
               
             
          
           
               
                   
                   
                   
                 time 
                 Conv. 
                 Mn 
                 Mn 
                 PDI 
               
               
                 Support 
                 name 
                 [Lig]0/[Cu]0 
                 (min) 
                 (%) 
                 (th) b   
                 (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-lig 
                 2.9 
                 36 
                 36.6 
                 3 660 
                 12 375 
                 2.06 
               
               
                   
                   
                   
                 312 
                 95.2 
                 9 530 
                 15 890 
                 1.95 
               
               
                 H 
                 PS-HEMDA-lig 
                 2 
                 30 
                 25.8 
                 2 580 
                 16 050 
                 1.78 
               
               
                   
                   
                   
                 180 
                 74.7 
                 7 480 
                 16 250 
                 1.77 
               
               
                   
                   
                   
                 292 
                 93.5 
                 9 360 
                 16 150 
                 1.8 
               
               
                 F1 
                 PS-DETA-lig 
                 ˜5 
                 36 
                 44.1 
                 4 410 
                 10 440 
                 2.61 
               
               
                   
                   
                   
                 67 
                 62.3 
                 6 230 
                 11 570 
                 2.31 
               
               
                   
                   
                   
                 131 
                 83.1 
                 8 320 
                 12 950 
                 2.15 
               
               
                   
                   
                   
                 188 
                 92.7 
                 9 280 
                 14 120 
                 2.08 
               
               
                   
                   
                   
                 250 
                 99.1 
                 9 920 
                 17 110 
                 1.79 
               
               
                 F2 
                 PS-DETA-lig 
                 ˜5 
                 29 
                 38.6 
                 3 860 
                 9 200 
                 2.02 
               
               
                   
                   
                   
                 62 
                 62.0 
                 6 200 
                 11 080 
                 1.92 
               
               
                   
                   
                   
                 126 
                 82.2 
                 8 230 
                 13 250 
                 1.86 
               
               
                   
                   
                   
                 181 
                 90.9 
                 9 100 
                 14 340 
                 1.86 
               
               
                   
                   
                   
                 241 
                 96.6 
                 9 670 
                 14 640 
                 1.89 
               
               
                   
               
               
                   b Mn(th) = ([MMMA]0/[I]0 × MWMMA) × 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 synthesized following the amino-hexanol route 
               
             
          
           
               
                   
                   
                   
                 time 
                 Conv. 
                   
                 Mn 
                 PDI 
               
               
                 Support 
                 name 
                 [Lig]0/[Cu]0 
                 (min) 
                 (%) 
                 Mn(th) b   
                 (SEC) 
                 (SEC) 
               
               
                   
               
             
          
           
               
                 PS7 
                 PS-lig 
                 2 
                 31 
                 28.5 
                 2 850 
                 7 580 
                 1.39 
               
               
                   
                   
                   
                 60 
                 35.7 
                 3 570 
                 8 110 
                 1.43 
               
               
                   
                   
                   
                 123 
                 50.8 
                 5 080 
                 9 970 
                 1.39 
               
               
                   
                   
                   
                 186 
                 59.8 
                 5 980 
                 11 130 
                 1.36 
               
               
                   
                   
                   
                 251 
                 63.4 
                 6 340 
                 11 070 
                 1.4 
               
               
                   
                   
                   
                 300 
                 70.0 
                 7 010 
                 11 890 
                 1.39 
               
               
                 K1 
                 PS-AHO-lig 
                 2 
                 30 
                 27.1 
                 2 710 
                 13 880 
                 1.81 
               
               
                   
                   
                   
                 64 
                 42.4 
                 4 240 
                 14 540 
                 1.78 
               
               
                   
                   
                   
                 119 
                 58.9 
                 5 890 
                 15 670 
                 1.75 
               
               
                   
                   
                   
                 180 
                 70.6 
                 7 070 
                 15 870 
                 1.76 
               
               
                   
                   
                   
                 244 
                 79.8 
                 7 990 
                 18 040 
                 1.6 
               
               
                   
                   
                   
                 292 
                 85.6 
                 8 570 
                 18 250 
                 1.63 
               
               
                 K2 
                 PS-AHO-lig 
                 2 
                 30 
                 26.8 
                 2 680 
                 10 370 
                 1.6 
               
               
                   
                   
                   
                 64 
                 44.0 
                 4 400 
                 12 660 
                 1.53 
               
               
                   
                   
                   
                 119 
                 61.0 
                 6 100 
                 14 730 
                 1.53 
               
               
                   
                   
                   
                 180 
                 72.9 
                 7 300 
                 16 230 
                 1.48 
               
               
                   
                   
                   
                 244 
                 82.5 
                 8 260 
                 16 660 
                 1.51 
               
               
                   
                   
                   
                 292 
                 87.4 
                 8 750 
                 18 080 
                 1.46 
               
               
                 L 
                 PS-AHO-lig 
                 2 
                 30 
                 12.9 
                 1 290 
                 26 130 
                 1.8 
               
               
                   
                   
                   
                 64 
                 19.1 
                 1 910 
                 26 950 
                 1.81 
               
               
                   
                   
                   
                 119 
                 27.3 
                 2 730 
                 29 210 
                 1.79 
               
               
                   
                   
                   
                 180 
                 33.9 
                 3 390 
                 29 390 
                 1.83 
               
               
                   
                   
                   
                 244 
                 38.1 
                 3 810 
                 30 750 
                 1.78 
               
               
                   
                   
                   
                 292 
                 42.9 
                 4 290 
                 29 920 
                 1.84 
               
               
                   
               
               
                   b Mn(th) = ([MMMA]0/[I]0 × MWMMA) × 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, 9.34×10 −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 with nitrogen three times. Deoxygenated toluene (30 ml, 75% v/v) and deoxygenated methyl methacrylate (10 mL, 9.36×10 −2  mol, [MMA]0:[Cu]0=900:1) or deoxygenated benzyl methacrylate (10 ml, 5.92×10 −2  mol, [BzMA]0:[Cu]0=63.22:1) 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, 1.87×10 −3  mol [Lig]0:[Cu]0=2:1) 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 aluminum oxide in order to remove the copper catalyst which has gone into solution. 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 molar ratios of components used in reinitiation experiments*** 
               
             
          
           
               
                 Ex- 
                   
                   
                 Monomer 
                 pentyl 
                   
               
               
                 peri- 
                 Macro- 
                   
                 2 
                 ligand 
                   
               
               
                 ment 
                 initiator a   
                 [In] 
                 [MMA] 
                 [Lig] 
                 [CuBr] 
               
               
                   
               
             
          
           
               
                 1 
                 PMMA(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) synthesised 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 FIG.  5 . 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Data for macrointiation experiments using different monomers 
               
             
          
           
               
                 Experi- 
                 Macro- 
                 Time 
                 Conv % 
                 Mnth 
                 Mnexp 
                   
               
               
                 ment 
                 init. 
                 (min) 
                 2 nd  pol ° 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 1 
                 PMMA (A) 
                 0 
                 0 
                   
                  7616 
                 1.19 
               
               
                   
                   
                  34 
                 10.5 
                 13374 
                 12546 
                 1.17 
               
               
                   
                   
                  63 
                 15.1 
                 15898 
                 14760 
                 1.21 
               
               
                   
                   
                 130 
                 22.1 
                 19749 
                 19230 
                 1.25 
               
               
                   
                 61%-3 h 
                 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 
               
               
                   
                 2 h 
                 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 
                 1.5 
               
               
                   
                   
                 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 
                 23.2 
                 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 Copolymerisation 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Molar ratios of components used in reinitiation experiments 
               
             
          
           
               
                 Ex- 
                   
                   
                   
                 pentyl 
                   
               
               
                 peri- 
                 Macro- 
                   
                 Monomer 2 
                 ligand 
                   
               
               
                 ment 
                 initiator a   
                 [In] 
                 [MMA] 
                 [Lig] 
                 [CuBr] 
               
               
                   
               
             
          
           
               
                 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 (A) synthesised following conditions [MMA]:[CuBr]:[lig]:[E2BI] = 100:1:2:1  
               
               
                 PMMA (S) synthesised 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  
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Data for macrointiation experiments using different monomers 
               
             
          
           
               
                 Experi- 
                 Macro- 
                 Time 
                 Conv % 
                 Mnth 
                 Mnexp 
                   
               
               
                 ment 
                 init. 
                 (min) 
                 2 nd  pol ° 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 1 
                 PMMA (A) 
                 0 
                 0 
                   
                  7616 
                 1.19 
               
               
                   
                   
                 38 
                 18.4 
                 18890 
                 17536 
                 1.59 
               
               
                   
                   
                 64 
                 23.0 
                 21670 
                 19861 
                 1.28 
               
               
                   
                   
                 131 
                 34.6 
                 28790 
                 26391 
                 1.34 
               
               
                   
                 61%-3 h 
                 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 
               
               
                   
                 2 
                 33 
                 19.9 
                 33985 
                 29395 
                 1.75 
               
               
                   
                   
                 59 
                 22.6 
                 35647 
                 30172 
                 1.62 
               
               
                   
                   
                 126 
                 35.4 
                 43482 
                 35658 
                 1.58 
               
               
                   
                 3 h 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 
               
               
                   
                 3 h 
                 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 
                 43105 
                 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% 2 h 
                 306 
                 52.2 
                 38444 
               
               
                   
                   
                 355 
                 60.7 
                 44070 
                 28240 
                 1.83 
               
               
                   
               
             
          
         
       
     
     Recyclability 
     
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 
               
             
             
               
                   
               
               
                 Recycling experiments carried out with support 
               
               
                 PS7 for the polymerisation of MMA by polystyrene 
               
               
                 supported atom transfer polymerisation; 
               
               
                 [MMA]:[Cu]:[PS-lig PS7]:[E2BI] = 100:1:2:1 
               
             
          
           
               
                 Ex- 
                   
                 Conver- 
                   
                   
                   
               
               
                 peri- 
                 Time 
                 sion 
                 Mnth 
                 Mn(SEC) 
               
               
                 ment 
                 (min) 
                 (%) 
                 (g/mol) 
                 (g/mol) 
                 PDI 
               
               
                   
               
             
          
           
               
                 First 
                  31 
                 28.5 
                 2850 
                 7580 
                 1.39 
               
               
                 polym. 
                  60 
                 35.7 
                 3570 
                 8110 
                 1.43 
               
               
                   
                 123 
                 50.8 
                 5080 
                 −9970 
                 1.39 
               
               
                   
                 136 
                 59.8 
                 5980 
                 11130 
                 1.36 
               
               
                   
                 231 
                 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