WO2001007496A2 - Polymers, their precursors and processes for preparation thereof - Google Patents

Polymers, their precursors and processes for preparation thereof Download PDF

Info

Publication number
WO2001007496A2
WO2001007496A2 PCT/GB2000/002120 GB0002120W WO0107496A2 WO 2001007496 A2 WO2001007496 A2 WO 2001007496A2 GB 0002120 W GB0002120 W GB 0002120W WO 0107496 A2 WO0107496 A2 WO 0107496A2
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer precursor
polymer
substituted
integer
Prior art date
Application number
PCT/GB2000/002120
Other languages
French (fr)
Other versions
WO2001007496A3 (en
Inventor
David Mark Haddleton
Adam Peter Jarvis
Original Assignee
Bp Chemicals Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bp Chemicals Limited filed Critical Bp Chemicals Limited
Priority to AU50928/00A priority Critical patent/AU5092800A/en
Publication of WO2001007496A2 publication Critical patent/WO2001007496A2/en
Publication of WO2001007496A3 publication Critical patent/WO2001007496A3/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

  • the present invention relates to a process for preparing polymers, novel polymers, a process for preparing polymer precursors and novel polymer precursors.
  • Transition metal mediated, atom transfer polymerisation processes involve the polymerisation of a monomer in the presence of (i) a transition metal in a low valency state, usually present as the halide, preferably chloride or bromide, (ii) an organodiimine and (iii) an initiator compound comprising a homolytically cleavable bond with a halogen atom.
  • block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate
  • ethylenicaUy unsaturated monomers such as styrene, acrylates and methyacrylates
  • a process for the preparation of a block polymer which process comprises a transition metal mediated, atom transfer polymerisation of an ethylenicaUy unsaturated monomer with an ct, ⁇ di- functional polymer precursor having repeating units derived from an ethylenicaUy unsaturated carboxylate.
  • a preferred ethylenicaUy unsaturated carboxylate is vinyl acetate.
  • Such block polymers are believed to be of the ABA type.
  • the transition metal mediated, atom transfer polymerisation may be preformed in the presence of (i) a first component represented by 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, (ii) an organodiimine, (iii) the ⁇ , ⁇ di-functional polymer precursor and (iv) an ethylenicaUy unsaturated monomer.
  • 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 coordinating non-charged ligand and Y is a monovalent or polyvalent counterion.
  • Suitable transition metals, M may be Cu(I), Fe(II), Co(II), Ru(II) and Ni(II), preferably, Cu(I).
  • the non-charged ligand may be CH 3 CN.
  • Y may be chosen from CI, Br, F, I, NO 3 , PF 6 , BF 4 , SO 4 , CN, SPh, SCN, SePh or triflate (CF 3 SO 3 ).
  • the transition metal component and the organodiimine are present as a complex represented by the formula [ML m ] n+ A n" wherein M is a transition metal in a low valency state; L is an organodiimine; A n" is an anion; n is an integer of 1 to 3; and m is an integer of 1 to 2.
  • Suitable transition metals M may be Cu(I), Fe(II), Co(II), Ru(II) and Ni(II), preferably, Cu(I).
  • A represents CI, Br, F, I, NO 3 , PF 6 , BF 4 , SO 4 , CN, SPh, SCN, SePh or triflate (CF 3 SO 3 ).
  • [ML ⁇ T A n" there is used CuBr.
  • the organodiimine may be : a l,4-diaza-l,3-butadiene such as represented by Formula (1) :
  • Ri, R 2 , Rio, Rn, R ⁇ 2 , and R ⁇ may be a Ci to C 0 alkyl, hydroxyalkyl or carboxyalkyl in particular Ci to C alkyl, especially methyl or ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, cyclohexyl, 2-ethylhexyl, octyl, decyl or lauryl.
  • Ri, R 2 , R ⁇ 0 , Rn, R ⁇ 2 , and R i3 may especially be methyl.
  • the organodiimine may exhibit a chiral centre to one of the nitrogen groups.
  • Compounds of Formula (2) may comprise one or more fused rings on the pyridine group.
  • One or more adjacent Ri and R 3 , R 3 and R ⁇ , R4 and R 2 , R ⁇ 0 and R 9 , Rg and R 9 , R 3 and R 7 , R 7 and R ⁇ , R ⁇ and R 5 groups may be C 5 to C 8 cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclicaryl, such as cyclohexyl, cyclohexenyl or norborenyl.
  • the transition metal, mediated atom transfer polymerisation process may be preformed using conditions know in the art, for example such as described in International patent publication WO 97/47661, the contents of which are hereby incorporated by reference.
  • the atom transfer polymerisation process may be performed either using a solvent or in bulk, preferably in bulk due to the formation of gels.
  • Non protic solvents may be used. Suitable solvents include hydrocarbons, anisole, ethyl acetate, diphenyl ether, higher alcohols, water and ketones such as acetone.
  • Preferred solvents are xylene and toluene.
  • the atom transfer polymerisation process generally requires elevated temperature and this depends upon the catalyst system and monomers used.
  • the polymerisation may be performed at a temperature in the range of -40°C to +180°C, preferably 0°C to 150 °C, more preferably in the range 10° to 130°C.
  • 90 °C may be used, although 110°C may be used for styrene co-polymerisation.
  • the polymerisation process is suitably performed at atmospheric pressure, although a higher pressure might be used.
  • the molar ratio of ethylenicaUy unsaturated monomer : ⁇ , ⁇ di-functional polymer precursor initiator is suitably (3 to 100000) : 1, preferably (10 to 1000) : 1 more preferably (10 to 500) : 1.
  • the molar ratio of organodiimine ligand : transition metal is suitably (100 to 0.1) : 1, preferably (3 to 1) : 1.
  • the molar ratio of ⁇ , ⁇ di-functional polymer precursor initiator : transition metal is suitably (1000 to 0.01) : 1, preferably (10 to 0.5) : 1.
  • the concentration of monomer is suitably in the range 1 to 100 %, preferably in the range 20 to 50 % .
  • the ⁇ , ⁇ di-functional polymer precursor acts as an initiator for the transition metal, atom transfer polymerisation process.
  • the ⁇ , ⁇ di-functional polymer precursor may be a polymer precursor having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula : X-[-CH 2 -CY(OR)-] x -[-CY , (OR)-CH 2 -] y -X' wherein x and y are integers independently greater than 1 ; Y and Y' are independently H or -CH 3 ; R represents a hydrocarbyl group; and X and X 1 independently represent substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
  • R is CH 3 C(O)- .
  • X and X' groups preferably have homolytically cleavable CI and/or Br bonds.
  • X and X' are independently selected from the group consisting of : BrCH 2 C(O)O- ; BrC(Me) 2 C(O)O- ;
  • Such novel polymer precursors may be prepared by the steps (a) and (b) of the process hereinafterdescribed and may be used in a transition metal mediated, atom transfer polymerisation for the preparation of block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate, with ethylenicaUy unsaturated monomers such as styrene, ( ⁇ neth)acrylates, (meth)acrylonitriles and (meth)acrylamides.
  • ethylenicaUy unsaturated carboxylates such as vinyl acetate
  • ethylenicaUy unsaturated monomers such as styrene, ( ⁇ neth)acrylates, (meth)acrylonitriles and (meth)acrylamides.
  • step (b) substituting the functional groups on the product of step (a) with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
  • the ethylenicaUy unsaturated carboxylate is vinyl acetate optionaUy with other co-monomers known in the art.
  • the radical initiator has a functional group selected from hydroxyl, carboxylic acid and amides, preferably hydroxyl.
  • the radical initiator having a hydroxyl function group is selected from hydrogen peroxide, azobis compounds having hydroxyl or amide functional groups and benzoyl peroxide. Suitable azobis compounds are:
  • 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis ( 2-methyl-N-[ 1 , 1 -bis(hydroxymethyl)-2-hydroxyethyl]-propionamide ⁇ , 2,2'-azobis ⁇ 2-methyl-N-[l,l-bis(hydroxymethyl)-ethyl]-propionamide ⁇ , and 2,2 - azobis(isobutyramide) dihydrate.
  • step (b) The reaction between the ethylenicaUy unsaturated carboxylate with a radical initiator having a substitutable functional group in step (a) may be performed using conventional free radical polymerisation conditions, known in the art.
  • step (b) the functional groups on the product of step (a) are substituted with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
  • substituents have chlorine or bromine substituents ⁇ to an electron withdrawing activating group.
  • the electron withdrawing group of the substituent active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process is selected from nitrile, ester and phenyl.
  • step (b) the product from step (a) is reacted with BrC(CH 3 ) 2 C(O)Br.
  • step (b) the functional groups on the product of step (a) may be substituted with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process under conventional conditions known in the art.
  • a reaction temperature of 0°C or room temperature may be used, depending upon the exotherm. Atmospheric pressure may suitably be used.
  • Dry solvents are used, for example THF, pyridine and toluene.
  • the brominating agent is added in excess. Hydrogen bromide formed in the reaction may be removed, for example by precipitation as HBr.NEt 3 with triethylamine.
  • novel ⁇ , ⁇ di-functional polymer precursors prepared according to this aspect of the present invention may be used in a transition metal mediated, atom transfer polymerisation for the preparation of block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate, with ethylenicaUy unsaturated monomers such as styrene, (meth)acrylates, (meth)acrylonitriles and (meth)acrylamides.
  • a polymer precursor having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula :
  • Y" is an n-alkyl group having up to 18 carbon atoms
  • Ph is phenyl
  • z' is an integer up to 5000
  • z" is an integer up to 5000
  • the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO 2 , OMe, CN, NMe 2 , OH, CL, Br, and F.
  • R' is CH 3 C(O)- .
  • Such novel polymer precursors may be prepared by step (a) and used in step (b) of the process hereinbeforedescribed.
  • a block polymer comprising alternating repeating units of -[-A-]- and -[-B-]- in which : -A- represents a polymer block having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula : -[-CH 2 -CY(OR")-] x « -[-CY'(OR")-CH 2 -] y .
  • R" is CH 3 C(O)-.
  • Figures 1 (a) to (d) are NMR spectra data
  • Figure 2 is IR spectra data
  • Figure 3 is GPC data
  • Figure 4 is DSC data of polymer precursor II according to the present invention
  • Figures 5 (a) to (d) are NMR spectra data
  • Figure 6 is IR spectra data
  • Figure 7 is GPC data of polymer precursor III according to the present invention
  • Figures 8 (a) to (d) are NMR spectra data
  • Figure 9 is IR spectra data
  • Figure 10 is GPC data of polymer precursor IV according to the present invention
  • Figure 13 is GPC data
  • Figure 14 is DSC data
  • Figure 15 is NMR spectra data of polymer prepared in Example 6 (b) according to the present invention
  • Figure 16 is GPC data
  • Figure 17 is DSC data
  • Figure 18 is NMR spectra
  • Example 1 Preparation of Polymer Precursor I HO(CH 2 CH(OAc)) ⁇ (CH(OAc)CH 2 ) y OH This illustrates step (a) of the polymer precursor preparation process according to the present invention.
  • Vinyl acetate and 1-propanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use.
  • a mixture of vinyl acetate (100 mL), hydrogen peroxide (60 mL, 27.5 wt. % solution in water) and 1-propanol (100 mL) were refluxed at 100°C for 3 days under nitrogen.
  • 1 -Propanol was then removed in vacuo and the resulting viscous oil was dissolved in dichloromethane. The solution was washed with water (3 x 100 mL) and dried over anhydrous magnesium sulphate. Dichloromethane was then removed under high vacuum and any remaining water removed by an azeotropic distillation using toluene.
  • the molecular number Mn was determined by GPC using methyl methacrylate standards to be about 1055. The yield was about 30%.
  • the polymer precursor was characterised by 1H NMR, 13 C NMR and ! H- 13 C correlation NMR and as well as by COSY, IR and GPC.
  • Example 2 Preparation of Polymer Precursor I HO(CH 2 CH(OAc)) x (CH(OAc)CH 2 ) y OH
  • step (a) of the polymer precursor preparation process according to the present invention illustrates step (a) of the polymer precursor preparation process according to the present invention.
  • Vinyl acetate and ethanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use.
  • a mixture of vinyl acetate (100 mL), hydrogen peroxide (60 mL, 27.5 wt. % solution in water) and ethanol (100 mL) were refluxed at 84°C for 8 days under nitrogen.
  • Ethanol was then removed in vacuo and the resulting viscous oil was dissolved in dichloromethane.
  • the solution was washed with water (3 x 100 mL) and dried over anhydrous magnesium sulphate.
  • Dichloromethane was then removed under high vacuum and any remaining water removed by an azeotropic distillation using toluene.
  • the molecular number Mn was determined by GPC using methyl methacrylate standards to be about 1000.
  • the number of OH equivalents determined twice by titration was 2.08 and 2.20.
  • the yield was about 18%.
  • the polymer precursor was characterised by 1H NMR, I3 C NMR and 1H- 13 C correlation NMR and as well as by COSY, IR and GPC.
  • Example 3 Preparation of Polymer Precursor ⁇ Br(Me) 2 CC(O)O(CH 2 CH(OAc)) x (CH(OAc)CH 2 ) y OC(O) CMe 2 Br.
  • step (b) of the polymer precursor preparation process according to the present invention illustrates step (b) of the polymer precursor preparation process according to the present invention.
  • the polymer precursor I prepared in Example 2 (14.08 g, 15.3 mmol) was dissolved in anhydrous tetrahydrofuran (300 mL) with triethylamine (5.20 mL, 37.3 mmol) under nitrogen. 2-Bromoisobutyryl bromide (4.20 mL, 34.0 mmol) was added dropwise with vigorous stirring at 0°C and the reaction mixture stirred at room temperature overnight. The resulting precipitate was filtered off, the tetrahydrofuran removed in vacuo and the resulting viscous oil dissolved in dichloromethane. The solution was washed with saturated hydrogen carbonate (3 x 50 mL), dried over anhydrous magnesium sulphate and the dichloromethane removed under high vacuum to give a bright orange oil.
  • the polymer precursor was characterised by 1H NMR (Figure 1(a) ), 13 C pendants NMR ( Figure 1(b) ), COSY ( Figure 1(c) ) and 1H- 13 C correlation NMR ( Figure 1(d) ), IR ( Figure 2) and GPC ( Figure 3).
  • the compound prepared by the same method, but from a different batch was also characterised by DSC ( Figure 4) (sample weight 1.000 mg).
  • step (a) of the polymer precursor preparation process according to the present invention illustrates step (a) of the polymer precursor preparation process according to the present invention.
  • Vinyl acetate and 1-propanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use.
  • To a mixture of deoxygenated vinyl acetate (107.7 mL) and 1-propanol (200 mL) was added to the Azo initiator (Wako, VA-086) (2.8835g) having the formula : HOCH 2 CH 2 NH C(O)C(Me) 2 N NC(Me) 2 C(O)NH-CH 2 CH 2 OH.
  • the polymer precursor was characterised by 1H NMR (Figure 5(a) ), 13 C pendant NMR ( Figure 5(b) ), COSY ( Figure 5(c) ) and 1H- 13 C correlation NMR ( Figure 5(d) ) as well as by LR ( Figure 6) and GPC ( Figure 7).
  • step (b) of the polymer precursor preparation process This illustrates step (b) of the polymer precursor preparation process according to the present invention.
  • the polymer precursor III prepared in Example 4 (38.93 g, 4.36 mmol) was dissolved in anhydrous tetrahydrofuran (300 mL) with triethylamine (1.46 mL, 10.46 mmol) under nitrogen.
  • 2-Bromoisobutyryl bromide (1.29 mL, 10.5 mmol) was added dropwise with vigorous stirring at 0°C and the reaction mixture stirred at room temperature overnight.
  • the resulting precipitate was filtered off, the tetrahydrofuran removed in vacuo and the resulting viscous oil dissolved in dichloromethane.
  • Example 6 Polymerisation of methyl methacrylate with polymer precursor ⁇ .
  • Polymer precursor, initiator, prepared in Example 3 (1.48 g, 1.0 mmol) and a magnetic follower were placed in a Schlenk tube.
  • Toluene (10.70 mL), N-octyl-pyridinal methanimine (0.96 g, 4.2 mmol) prepared as hereinbeforedescribed and monomer (methyl methacrylate) (5.34 mL) were added.
  • the solution was deoxygenated via three freeze-pump-thaw cycles and added to Cu(I)Br (0.286g, 2.0 mmol). Reaction mixture subsequently heated to 90°C or 110°C depending on the monomer used. Samples were removed by syringe periodically (every 30 minutes) for analysis (GPC and gravimetrically). All molecular weight data was recorded on un-precipitated polymer.
  • the final polymer solution was passed down a basic alumina column and precipitated into n-pentane.
  • the polymer precursor was also characterised by DSC (Figure 12) (3.000 mg sample weight Total Mn - 33000 heat from -50.00°C to 140.00°C at 20.00°C/min).
  • This example (Example 6(a) ) was repeated using different monomers and different molar ratios of reagents as follows :
  • the polymer precursor was also characterised by DSC ( Figure 14) (sample weight 8.100 mg , Total Mn - 17000, heat from -60.00°C to 140.00°C at 20.00°C/min.) and by 1H NMR in CDC1 3 ( Figure 15).
  • the polymer precursor was also characterised by DSC ( Figure 17) (1.00 mg sample weight, total Mn - 17000, heat from -50.00°C to 140.00°C at 20.00°C/min) and by 1H NMR CDC1 3 ( Figure 18).
  • the polymer precursor was also characterised by 1H NMR in CDC1 3 ( Figure 20).
  • Example 6 (e) The monomer used was n-butyl methacrylate.
  • the polymer precursor was also characterised by DSC ( Figure 22) (sample weight 3.200 mg, heat from -50.00°C to 120.00°C at 20.00°C/min) and by 1H NMR in CDC1 3 ( Figure 23).
  • Example 7 Polymerisation of styrene with polymer precursor TV.
  • Polymer precursor IV prepared in Example 5 (1.1044 g, 0.4 mmol), Cu(I)Br (0.1139 g, 0.8 mmol) and a magnetic follower were placed in a Schlenk tube.
  • Deoxygenated toluene(4.40 mL) and N-propyl-2-pyridinal methanimine (0.26 g, 1.76 mmol) prepared as hereinbeforedescribed were added and the solution heated to 110°C.
  • the final polymer solution was passed down a basic alumina column and precipitated into n-pentane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Novel block polymers of ethylenically unsaturated monomers and ethylenically unsaturated carboxylates such as vinyl acetate may be made by transition metal mediated, atom transfer polymerisation of an ethylenically unsaturated monomer with an α, φ di-functional polymer precursor having repeating units derived from an ethylenically unsaturated carboxylate, such as vinyl acetate. Also, novel α, φ di-functional polymer precursors may be made by the steps of (a) reacting an ethylenically unsaturated carboxylate with a radical initiator having a substitutable functional group; and (b) substituting the functional groups on the product of step (a) with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.

Description

POLYMERS, THEIR PRECURSORS AND PROCESSES FORPREPARATION
THEREOF
The present invention relates to a process for preparing polymers, novel polymers, a process for preparing polymer precursors and novel polymer precursors.
The preparation of polymers by transition metal mediated, atom transfer polymerisation processes is known, see for example K. Matyjaszewski in 'Controlled Radical Polymerisation , American Chemical Society, 1998. Transition metal mediated, atom transfer polymerisation processes involve the polymerisation of a monomer in the presence of (i) a transition metal in a low valency state, usually present as the halide, preferably chloride or bromide, (ii) an organodiimine and (iii) an initiator compound comprising a homolytically cleavable bond with a halogen atom. Wang J-S et al in Macromolecules 1995, 28, 7901-7910 describe an atom transfer polymerisation process using an alkyl halide R-X (X= CI and Br) and a transition metal species complexed by suitable ligand(s) Mt7Lχ such as CuX/2,2'-bipyridine for the polymerisation of styrenes and (meth)acrylates.
International Patent Publication WO97/47661 describes a process for the atom transfer polymerisation of olefinically unsaturated monomers in the presence of (i) a transition metal such as copper, (ii) an organodiimine wherein at least one of the nitrogens of the diimine is not part of an aromatic ring such as a l,4-diaza-l,3-butadiene, a pyridinecarbaldehyde, an oxazolidone or a quinoline carbaldehyde and (iii) an initiator compound comprising a homolytically breakable bond with a halogen atom. It has now been found that block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate, with ethylenicaUy unsaturated monomers such as styrene, acrylates and methyacrylates can be prepared by transition metal mediated, atom transfer polymerisation.
According to a first aspect of the present invention there is provided a process for the preparation of a block polymer which process comprises a transition metal mediated, atom transfer polymerisation of an ethylenicaUy unsaturated monomer with an ct, ω di- functional polymer precursor having repeating units derived from an ethylenicaUy unsaturated carboxylate. A preferred ethylenicaUy unsaturated carboxylate is vinyl acetate. Such block polymers are believed to be of the ABA type.
According to this aspect of the present invention, the transition metal mediated, atom transfer polymerisation may be preformed in the presence of (i) a first component represented by 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, (ii) an organodiimine, (iii) the α, ω di-functional polymer precursor and (iv) an ethylenicaUy unsaturated monomer. The ethylenicaUy unsaturated monomer may be : styrene; acrylonitrile; methacrylonitrile; acrylamide; methacrylamide; acrylic acid; unsubstituted acrylate for example having a formula H2C=CH-CO2Z in which Z is methyl, allyl, or a functional group such as -CH2CH2OH or -CH2CH2N(CH3)2; or a methacrylate for example having a formula H2C=C(CH3)-CO2Z' in which Z' is H, methyl, allyl, benzyl, or a functional group such as -CH2CH2OH, -CH2CH2N(CH3)2 , -CH2-CH=CH2 , -CH2 H3 +C1" or
Figure imgf000003_0001
In the first component represented by MY, 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 coordinating non-charged ligand and Y is a monovalent or polyvalent counterion. Suitable transition metals, M may be Cu(I), Fe(II), Co(II), Ru(II) and Ni(II), preferably, Cu(I). The non-charged ligand may be CH3CN. Y may be chosen from CI, Br, F, I, NO3, PF6, BF4, SO4, CN, SPh, SCN, SePh or triflate (CF3SO3). Suitably, the transition metal component and the organodiimine are present as a complex represented by the formula [MLm]n+ An" wherein M is a transition metal in a low valency state; L is an organodiimine; An" is an anion; n is an integer of 1 to 3; and m is an integer of 1 to 2. Suitable transition metals M, may be Cu(I), Fe(II), Co(II), Ru(II) and Ni(II), preferably, Cu(I). Suitably, A represents CI, Br, F, I, NO3, PF6, BF4, SO4, CN, SPh, SCN, SePh or triflate (CF3SO3). Most preferably, as [ML^T An" there is used CuBr.
The organodiimine may be : a l,4-diaza-l,3-butadiene such as represented by Formula (1) :
Figure imgf000004_0001
Formula (1)
a 2-pyridinecarbaldehyde imine such as represented by the Formula (2)
Figure imgf000004_0002
Formula (2)
an oxazolidone such as represented by Formula (3)
Figure imgf000004_0003
Formula (3) or a quinoline carbaldehyde such as represented by Formula (4) :
Figure imgf000005_0001
Formula (4)
wherein Ri, R2, Rio, Rn, Rι , and R may be varied independently and Ri, R2, Rio, Rn, Rι2 and Rι3 may be H, straight chain, branched chain or cyclic saturated alkyl, hydroxyalkyl, carboxyalkyl, aryl (such as phenyl or substituted phenyl where substitution is as described for R to R9), CH2Ar (where Ar = aryl or substituted aryl) or a halogen. Preferably, Ri, R2, Rio, Rn, Rι2, and Rι may be a Ci to C 0 alkyl, hydroxyalkyl or carboxyalkyl in particular Ci to C alkyl, especially methyl or ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert. butyl, cyclohexyl, 2-ethylhexyl, octyl, decyl or lauryl. Ri, R2, Rι0, Rn, Rι2, and Ri3 may especially be methyl.
R3 to R9 may independently be selected from the group described for Ri, R2, Rio, Rn, Rι2, and Rϊ3 and OCH2n+ι (where n is an integer from 1 to 20), NO2, CN, and O=CR (where R = alkyl, benzyl PHCH2 or a substituted benzyl, preferably a Ci to C20 alkyl, especially a Ci to C4 alkyl). The organodiimine may exhibit a chiral centre to one of the nitrogen groups.
Compounds of Formula (2) may comprise one or more fused rings on the pyridine group.
One or more adjacent Ri and R3, R3 and R^, R4 and R2, Rι0 and R9, Rg and R9, R3 and R7, R7 and R^, R^ and R5 groups may be C5 to C8 cycloalkyl, cycloalkenyl, polycycloalkyl, polycycloalkenyl or cyclicaryl, such as cyclohexyl, cyclohexenyl or norborenyl.
Preferred organodiimines include compounds represented by Formula (2) in which R5 = R^ = R7 = Rg = R9 = H and R)0 is selected from the group consisting of : C2H5- , n-C3H7-, (CH3)2CH-, cycloC3H5-, n-C5H„-, n-C6Hι3-, n-C7H15-, n-C8Hπ-, n- C9H19-, n-Cι8H37-, CH3(C2H5)CH-CH2-, HO-CH2-CH2-, HO-CH2-CH2-CH2-, HC*(CH3)Ph (R form), HC*(CH3)Ph (S form), HC*(CH3)Ph (RS form), HO2CCH2- and HO2CC*H(Rι )- wherein * indicates a chiral centre, Ph is a phenyl group and Rι is hydrogen, Ci to Cio branched alkyl, carboxy- or hydroxy- Ci to Cio alkyl. Preferred organodiimines represented by Formula (2) include n-propyl-pyridinal methanimine and n-octyl-pyridinal methanimine.
Other suitable catalyst systems for the atom transfer polymerisation included :
(I) RuCl2(PPh3)3/CCl4/methylaluminium bis-(2,6-di-tert-butylphenoxide); NiBr2(PPh3)2, NiBr2(P«Bu3)2; and FeCl2(PPh3)2 being described in Macromolecules 1995, 28, 1721; Macromolecules 1997, 30, 2249; and Macromolecules 1997, 30, 4507, the contents of which are hereby incorporated by reference;
(II) Cu(I)Br/ligand/initiator/monomer/solvent in which the initiator is RX, methyl 2- bromopropionate, ethyl 2-bromopropionate, 1 -phenyl ethyl bromide or ethyl 2- bromoisobutyrate and the ligand is a derivative of 2,2'-bipyridine or simple aliphatic polyamines, being described in Macromolecules 1999, 32, 290 and 1 1; Macromolecules 1997, 30, 7967; Macromolecules 1995, 28, 7901; and J. Am. Chem. Soc. 1995, 117, 5614 the contents are hereby incorporated by reference.
(III) [Ni{o,o'-(CH2-NMe2)2C6H3}Br] with an initiator of CC14, 2- bromoisobutylrophenone or 2-bromoethylisobutrate, being described in
Macromolecules 1996, 29, 8576, the contents of which are hereby incorporated by reference.
(IV) RhCl(PPh3)3 with dichloroacetophenone and 7 equivalents of triphenylphosphine, being described va Macromolecules 1998, 31, 542, the contents of which are hereby incorporated by reference.
(V) [Pd(OAc)2] with carbon tetrachloride and triphenylphosphine, being described in Macromolecules 1997, 30, 7631, the contents of which are hereby incorporated by reference.
(VI) Cu(I)Cl/2,2'-bipyridine with arenesulfonyl chlorides being described in Macromolecules 1995, 28, 7970, the contents of which are hereby incorporated by reference. The transition metal, mediated atom transfer polymerisation process may be preformed using conditions know in the art, for example such as described in International patent publication WO 97/47661, the contents of which are hereby incorporated by reference. The atom transfer polymerisation process may be performed either using a solvent or in bulk, preferably in bulk due to the formation of gels. Non protic solvents may be used. Suitable solvents include hydrocarbons, anisole, ethyl acetate, diphenyl ether, higher alcohols, water and ketones such as acetone. Preferred solvents are xylene and toluene. The atom transfer polymerisation process generally requires elevated temperature and this depends upon the catalyst system and monomers used. In particular, the polymerisation may be performed at a temperature in the range of -40°C to +180°C, preferably 0°C to 150 °C, more preferably in the range 10° to 130°C. Suitably 90 °C may be used, although 110°C may be used for styrene co-polymerisation. The polymerisation process is suitably performed at atmospheric pressure, although a higher pressure might be used.
In the polymerisation process, the molar ratio of ethylenicaUy unsaturated monomer : α, ω di-functional polymer precursor initiator is suitably (3 to 100000) : 1, preferably (10 to 1000) : 1 more preferably (10 to 500) : 1. In the polymerisation process, the molar ratio of organodiimine ligand : transition metal is suitably (100 to 0.1) : 1, preferably (3 to 1) : 1.
In the polymerisation process, the molar ratio of α, ω di-functional polymer precursor initiator : transition metal is suitably (1000 to 0.01) : 1, preferably (10 to 0.5) : 1. In the polymerisation process the concentration of monomer is suitably in the range 1 to 100 %, preferably in the range 20 to 50 % .
The α, ω di-functional polymer precursor acts as an initiator for the transition metal, atom transfer polymerisation process.
The α, ω di-functional polymer precursor may be a polymer precursor having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula : X-[-CH2-CY(OR)-]x-[-CY,(OR)-CH2-]y-X' wherein x and y are integers independently greater than 1 ; Y and Y' are independently H or -CH3 ; R represents a hydrocarbyl group; and X and X1 independently represent substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
R may be selected from the group consisting of : CH3C(O)- , Y"-C(O)- , PhC(O)- , Ph-, PhCH2- , CH3-(CH2- CH2-CH2-CH2-)z€(O)- , CH3-(CH2- CH=CH-CH2-)z-C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO , OMe, CN, NMe2, OH, CL, Br, and F. Preferably, R is CH3C(O)- .
The X and X' groups preferably have homolytically cleavable CI and/or Br bonds. Preferably, X and X' are independently selected from the group consisting of : BrCH2C(O)O- ; BrC(Me)2C(O)O- ;
BrCH2C(O)OCH2CH2NHC(O)CMe2- ; and BrCMe2C(O)OCH2CH2NHC(O)CMe2- . wherein Me represents CH3-.
Such novel polymer precursors may be prepared by the steps (a) and (b) of the process hereinafterdescribed and may be used in a transition metal mediated, atom transfer polymerisation for the preparation of block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate, with ethylenicaUy unsaturated monomers such as styrene, (ιneth)acrylates, (meth)acrylonitriles and (meth)acrylamides.
Thus, according to another aspect of the present invention there is provided process for the production of an α, ω di-functional polymer precursor which process comprises the steps of :
(a) reacting an ethylenicaUy unsaturated carboxylate with a radical initiator having a substitutable functional group; and
(b) substituting the functional groups on the product of step (a) with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process. Preferably, the ethylenicaUy unsaturated carboxylate is vinyl acetate optionaUy with other co-monomers known in the art.
Preferably, the radical initiator has a functional group selected from hydroxyl, carboxylic acid and amides, preferably hydroxyl. Suitably, the radical initiator having a hydroxyl function group is selected from hydrogen peroxide, azobis compounds having hydroxyl or amide functional groups and benzoyl peroxide. Suitable azobis compounds are:
4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis ( 2-methyl-N-[ 1 , 1 -bis(hydroxymethyl)-2-hydroxyethyl]-propionamide } , 2,2'-azobis{2-methyl-N-[l,l-bis(hydroxymethyl)-ethyl]-propionamide} , and 2,2 - azobis(isobutyramide) dihydrate.
The reaction between the ethylenicaUy unsaturated carboxylate with a radical initiator having a substitutable functional group in step (a) may be performed using conventional free radical polymerisation conditions, known in the art. In step (b) the functional groups on the product of step (a) are substituted with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process. Preferably, such substituents have chlorine or bromine substituents α to an electron withdrawing activating group. Preferably, the electron withdrawing group of the substituent active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process is selected from nitrile, ester and phenyl.
Preferably, in step (b) the product from step (a) is reacted with BrC(CH3)2C(O)Br.
In step (b) the functional groups on the product of step (a) may be substituted with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process under conventional conditions known in the art. Thus a reaction temperature of 0°C or room temperature may be used, depending upon the exotherm. Atmospheric pressure may suitably be used. Dry solvents are used, for example THF, pyridine and toluene. The brominating agent is added in excess. Hydrogen bromide formed in the reaction may be removed, for example by precipitation as HBr.NEt3 with triethylamine. The novel α, ω di-functional polymer precursors prepared according to this aspect of the present invention may be used in a transition metal mediated, atom transfer polymerisation for the preparation of block co-polymers of ethylenicaUy unsaturated carboxylates such as vinyl acetate, with ethylenicaUy unsaturated monomers such as styrene, (meth)acrylates, (meth)acrylonitriles and (meth)acrylamides.
According to a further aspect of the present invention there is provided a polymer precursor having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula :
HO-[-CH2-CY(OR')-]x - [-CY"(OR')-CH2-]y- OH wherein x' and y' are integers independently greater than 1; Y and Y' are independently H or -CH3 ; and R' represents a hydrocarbyl group.
R' may be selected from the group consisting of : CH3C(O)- , Y"-C(O)- , PhC(O)- , Ph-, PhCH2- , CH3-(CH2- CH2-CH2-CH2-)Z. C(O)- , CH3-(CH2- CH=CH-CH2-)Z. C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO2, OMe, CN, NMe2, OH, CL, Br, and F. Preferably, R' is CH3C(O)- .
Such novel polymer precursors may be prepared by step (a) and used in step (b) of the process hereinbeforedescribed.
According to yet a further aspect of the present invention there is provided a block polymer comprising alternating repeating units of -[-A-]- and -[-B-]- in which : -A- represents a polymer block having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula : -[-CH2-CY(OR")-]x« -[-CY'(OR")-CH2-]y. - wherein x" and y" are integers independently greater than 1 ; Y and Y' are independently H or -CH3 and R" represents a hydrocarbyl group; and -B- represents at least one polymer repeating unit selected from the group consisting of acrylic; substituted acrylic for example, having a formula -HC-C-(CO2Z)- in which Z in which Z is methyl, allyl, or a functional group such as -CH2CH2OH or -CH2CH2N(CH3)2; methacrylic for example, having a formula -HC-C(CH3)-(CO2Z') in which Z' is H, methyl, allyl, benzyl, or a functional group such as -CH2CH2OH, -CH2CH2N(CH3)2 , - CH2-CH=CH2 , -CH2NH3 +Cr
Figure imgf000011_0001
; substituted methacrylic; acrylonitrile; methacrylonitrile; acylamide; methacrylamide and styrenic polymer repeating units and is preferably at least one methacrylic, styrenic and/or n- butyl methacrylic repeating unit. R" may be selected from the group consisting of : CH3C(O)- , Y"-C(O)- , PhC(O)- ,
Ph-, PhCH2- , CH3-(CH2- CH2-CH2-CH2-)z. C(O)- ,
CH3-(CH2- CH=CH-CH2-)z.C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO2, OMe, CN, NMe2, OH, CL, Br, and F. Preferably, R" is CH3C(O)-.
The invention will now be described by reference to the following examples and with reference to Figures 1 to 23 in which Figures 1 (a) to (d) are NMR spectra data, Figure 2 is IR spectra data, Figure 3 is GPC data and Figure 4 is DSC data of polymer precursor II according to the present invention; Figures 5 (a) to (d) are NMR spectra data, Figure 6 is IR spectra data and Figure 7 is GPC data of polymer precursor III according to the present invention; Figures 8 (a) to (d) are NMR spectra data, Figure 9 is IR spectra data, Figure 10 is GPC data of polymer precursor IV according to the present invention; Figure 11 is GPC data and Figure 12 is DSC data of polymer prepared in Example 6 (a) according to the present invention; Figure 13 is GPC data, Figure 14 is DSC data and Figure 15 is NMR spectra data of polymer prepared in Example 6 (b) according to the present invention; Figure 16 is GPC data, Figure 17 is DSC data and Figure 18 is NMR spectra data of polymer prepared in Example 6 (c) according to the present invention; Figure 19 is GPC data and Figure 20 is NMR spectra data of polymer prepared in Example 6 (d) according to the present invention; and Figure 21 is GPC data, Figure 22 is DSC data and Figure 23 is NMR spectra data of polymer prepared in
Example 6 (e) according to the present invention.
Preparation of Polymer Precursors
Example 1 : Preparation of Polymer Precursor I HO(CH2CH(OAc))ϊ(CH(OAc)CH2)yOH This illustrates step (a) of the polymer precursor preparation process according to the present invention.
Vinyl acetate and 1-propanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use. A mixture of vinyl acetate (100 mL), hydrogen peroxide (60 mL, 27.5 wt. % solution in water) and 1-propanol (100 mL) were refluxed at 100°C for 3 days under nitrogen. 1 -Propanol was then removed in vacuo and the resulting viscous oil was dissolved in dichloromethane. The solution was washed with water (3 x 100 mL) and dried over anhydrous magnesium sulphate. Dichloromethane was then removed under high vacuum and any remaining water removed by an azeotropic distillation using toluene.
The molecular number Mn was determined by GPC using methyl methacrylate standards to be about 1055. The yield was about 30%.
The polymer precursor was characterised by 1H NMR, 13C NMR and !H- 13C correlation NMR and as well as by COSY, IR and GPC. Example 2: Preparation of Polymer Precursor I HO(CH2CH(OAc))x(CH(OAc)CH2)yOH
This illustrates step (a) of the polymer precursor preparation process according to the present invention.
Vinyl acetate and ethanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use. A mixture of vinyl acetate (100 mL), hydrogen peroxide (60 mL, 27.5 wt. % solution in water) and ethanol (100 mL) were refluxed at 84°C for 8 days under nitrogen. Ethanol was then removed in vacuo and the resulting viscous oil was dissolved in dichloromethane. The solution was washed with water (3 x 100 mL) and dried over anhydrous magnesium sulphate. Dichloromethane was then removed under high vacuum and any remaining water removed by an azeotropic distillation using toluene.
The molecular number Mn was determined by GPC using methyl methacrylate standards to be about 1000. The number of OH equivalents determined twice by titration was 2.08 and 2.20. The yield was about 18%. The polymer precursor was characterised by 1H NMR, I3C NMR and 1H- 13C correlation NMR and as well as by COSY, IR and GPC. Example 3: Preparation of Polymer Precursor π Br(Me)2CC(O)O(CH2CH(OAc))x(CH(OAc)CH2)y OC(O) CMe2Br.
This illustrates step (b) of the polymer precursor preparation process according to the present invention.
The polymer precursor I prepared in Example 2 (14.08 g, 15.3 mmol) was dissolved in anhydrous tetrahydrofuran (300 mL) with triethylamine (5.20 mL, 37.3 mmol) under nitrogen. 2-Bromoisobutyryl bromide (4.20 mL, 34.0 mmol) was added dropwise with vigorous stirring at 0°C and the reaction mixture stirred at room temperature overnight. The resulting precipitate was filtered off, the tetrahydrofuran removed in vacuo and the resulting viscous oil dissolved in dichloromethane. The solution was washed with saturated hydrogen carbonate (3 x 50 mL), dried over anhydrous magnesium sulphate and the dichloromethane removed under high vacuum to give a bright orange oil.
The polymer precursor was characterised by 1H NMR (Figure 1(a) ), 13C pendants NMR (Figure 1(b) ), COSY (Figure 1(c) ) and 1H- 13C correlation NMR (Figure 1(d) ), IR (Figure 2) and GPC (Figure 3). The compound prepared by the same method, but from a different batch was also characterised by DSC (Figure 4) (sample weight 1.000 mg).
TABLE 1 - Data for Figure 1(a) Example 3 (APJ 36)
Figure imgf000014_0001
TABLE 2 - Data for Figure K ) Example 3 (APJ 36)
Figure imgf000015_0001
TABLE 3 -Data for Figure 1(c) Example 3 (APJ 36)
Figure imgf000016_0001
TABLE 4 - Data for Figure 1(d) Example 3 (APJ 36)
Figure imgf000017_0001
TABLE 5 - GPC ANALYSIS Figure 3 Example 3
Figure imgf000018_0001
Example 4 : Preparation of Polymer Precursor HI
HOCH2CH2NHC(0)-C(Me)2(CH2CH(OAc))I(CH(OAc)CHι)y C(Me)2 C(0)-NH-CH2-CHϊ-OH
This illustrates step (a) of the polymer precursor preparation process according to the present invention.
Vinyl acetate and 1-propanol were deoxygenated by a stream of nitrogen for at least 30 minutes immediately prior to use. To a mixture of deoxygenated vinyl acetate (107.7 mL) and 1-propanol (200 mL) was added to the Azo initiator (Wako, VA-086) (2.8835g) having the formula : HOCH2CH2NH C(O)C(Me)2N=NC(Me)2C(O)NH-CH2CH2OH.
The solution was refluxed under a nitrogen atmosphere overnight at 104°C. The initiator dissolved on warming. A biphasic solution was obtained on cooling the reaction mixture. The solvent was removed in vacuo and any remaining water removed by an azeotropic distillation using toluene. From GPC, Mn = 8930 (using methyl methacrylate standards). Yield was 85 %.
The polymer precursor was characterised by 1H NMR (Figure 5(a) ), 13C pendant NMR (Figure 5(b) ), COSY (Figure 5(c) ) and 1H- 13C correlation NMR (Figure 5(d) ) as well as by LR (Figure 6) and GPC (Figure 7).
TABLE 6 - Data for Figure 5(a) Example 4 ( APJ 14)
Figure imgf000020_0001
TABLE 7 - Data for Figure 5(b) Example 4 (APJ 14)
Figure imgf000021_0001
TABLE 8 - Data for Figure 5(c) Example 4 (APJ 14)
Figure imgf000022_0001
TABLE 9 - Data for Figure 5(d) Example 4 (APJ 14)
Figure imgf000023_0001
TABLE 10 - GPC ANALYSIS Figure 7 Example 4
Sample name : apj Raw date filename : 15072.002
Conditions :
Solvent : THF Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI
Data Processing :
Method : 2 Calibration using : Narrow standards
Calibration limits : 9.83 to 17.98 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=18.699185, B = 2.346432, C = 0.135302, D = 0.003040
Last calibrated : Fri Jun 25 08:41 :02 1999
Flow rate marker : found at 20.42 in standards at 20.37 Mins.
Broad peak start : 11.22 end : 17.15 Mins.
Standards Sample
K : 10.4000* 10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results Mp = 19056 Mn = 7501 Mw = 19315 Mz = 36240 Mz+1 = 53447 Mv = 17185 Polydispersity = 2.575 Peak area = 25182
Example 5 : Preparation of Polymer Precursor TV
Br(Me)2CC(O)OCH2CH2NHC(O)C(Me)2-(CH2CH(OAc))x-(CH(OAc)CH2)y-
-C(Me)2C(O)NHCH2CH2OC(O)C(Me)2Br.
This illustrates step (b) of the polymer precursor preparation process according to the present invention. The polymer precursor III prepared in Example 4 (38.93 g, 4.36 mmol) was dissolved in anhydrous tetrahydrofuran (300 mL) with triethylamine (1.46 mL, 10.46 mmol) under nitrogen. 2-Bromoisobutyryl bromide (1.29 mL, 10.5 mmol) was added dropwise with vigorous stirring at 0°C and the reaction mixture stirred at room temperature overnight. The resulting precipitate was filtered off, the tetrahydrofuran removed in vacuo and the resulting viscous oil dissolved in dichloromethane. The solution was washed with saturated hydrogen carbonate (3 x 50 mL), dried over anhydrous magnesium sulphate and the dichloromethane removed under high vacuum to give a bright orange oil. The polymer precursor was characterised by Η NMR (Figure 8(a) ), 13C pendant
NMR (Figure 8(b) ), COSY (Figure 8(c) ) and Η- 13C correlation NMR (Figure 8(d) ) as well as by IR (Figure 9) and GPC (Figure 10).
TABLE 11 - Data for Figure 8(a) Example 5 (APJ 58)
Figure imgf000026_0001
TABLE 12 - Data for Figure 8(b) Example 5 (APJ 58)
Figure imgf000027_0001
TABLE 13 - Data for Figure 8(c) Example 5 (APJ 58)
Figure imgf000028_0001
TABLE 14 - Data for Figure 8(d) Example 5 (APJ 58)
Figure imgf000029_0001
TABLE 15 - GPC ANALYSIS Figure 10 Example 5
Sample name : ajl 114 Raw date filename : 25062.002
Conditions :
Solvent : THF Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI
Data Processing :
Method : 2 Calibration using : Narrow standards
Calibration limits : 9.80 to 17.93 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=18.699185, B = 2.346432, C = 0.135302, D = 0.003040
Last calibrated : Fri Jun 25 08:41 :02 1999
Flow rate marker : found at 20.35 in standards at 20.37 Mins.
Broad peak start : 11.15 end : 16.97 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results
Mp = 19699 Mn = 9183 Mw = 20468
Mz = 35738 Mz+1 = 51313 Mv = 18502
Polydispersity = 2.229 Peak area = 25866
Atom transfer polymerisation of vinyl monomers using α, ω difunctional polymer precursors
Preparation of organodiimine ligands Preparation of N-propyl-pyridinal methanimine
To a solution of pyridine-2-carboxaldehyde (1.78 mL, 1.87 x 10"2 mol) and diethyl ether (30 mL) was added n-propylamine (1.55 mL, 1.88 x 10"2 mol). The reaction mixture was stirred for 10 minutes at room temperature prior to addition of anhydrous magnesium sulphate and stirring for a further 30 minutes. The magnesium sulphate was removed by filtration, and volatiles were removed under reduced pressure to give the product in quantitative yield as a pale yellow oil.
1H NMR (CDC13, 373 K, 400.13 MHz): d = 8.51 (d, J= 3.5 Hz, IH) 8.26 (s, IH), 7.87 (d, J= 7.8 Hz, IH), 7.59 (d, J= 7.8 Hz, IH), 7.16 (t, J= 4.6Hz, IH), 3.52 (t, J= 7.6 Hz, 2H), 1.63 (sext, J= 7.3 Hz, 2H), 0.84 (t, J= 7.5 Hz, 3H). 13C (CDC13, 373K,
100.61 MHz) : d = 161.51, 154.44, 149.18, 136.28, 124.37, 120.97, 63.08, 23.65, 11.65 ppm. IR (NaCl, film), 3053-2830, 1648, 1587, 1566, 772, 742 cm"1. Bp = 218°C. Preparation of N-octyl-pyridinal methanimine.
To a solution of pyridine-2-carboxaldehyde (19 mL, 0.20 mol) and diethyl ether (150 mL) in a 250 mL round-bottomed flask was added octylamine (33.9 mL, 0.20 mol). The reaction mixture was stirred for 1 hour prior to addition of anhydrous magnesium sulphate ( 25.2 g) and stirring for a further 2 hours. The magnesium sulphate was removed by filtration and was washed with diethyl ether. The ether was subsequently removed by rotary evaporation to give a dark yellow viscous liquid. The liquid was fractionally distilled at 96 °C at 0.04 torr to give a pale yellow liquid. Yield = 40.5 g (90.5%). 1H NMR (CDC13, 298 K, 250.13 MHz) d = 8.60 (d, J= 4.9 Hz, IH) 8.33 (s, IH), 7.95 (d, J= 7.8 Hz, IH), 7.69 (t, J= 7.6 Hz, IH), 7.26 (t, J= 6.2Hz, IH), 3.63 (t, J= 7.0 Hz, 2H), 1.68 (m, J= 7.0 Hz, 2H), 1.26 (m, J= 7.3 Hz, 10H), 0.82 (t, J = 7.0Hz, 3H). 13C (CDC13, 298K, 100.16 MHz) : 161.1, 154.5, 148.8, 135.7, 123.9, 120.5, 61.1, 31.5, 30.4, 29.1, 28.9, 27.0, 22.3, 13.7. Anal. Calc. for Cι4H22N2 : C= 77.01, H = 10.16, N = 12.82. Found C = 77.15, H = 10.25, N = 12.85. General procedure for atom transfer polymerisation.
Monomers were passed down a basic alumina column (Aldrich, Brockmann I grade) immediately prior to use, degassed by a stream of nitrogen for at least 30 minutes and freeze-pump-thawed (three times). Solvents were deoxygenated by a stream of nitrogen for at least 30 minutes prior to use. Cu(I)Br was purified according to a published procedure (Keller, R.N. and Wcycoff, M.D. Inorg. Synth. 1947, 2,1.). All atom transfer polymerisation experiments carried out at 90°C except for those involving styrene which were heated to 110°C. A slight excess of ligand (10%) is added to the reaction mixture.
The atom transfer polymerisation experiments have been carried out using slightly varying methods. Example 6 : Polymerisation of methyl methacrylate with polymer precursor π.
Polymer precursor, initiator, prepared in Example 3 (1.48 g, 1.0 mmol) and a magnetic follower were placed in a Schlenk tube. Toluene (10.70 mL), N-octyl-pyridinal methanimine (0.96 g, 4.2 mmol) prepared as hereinbeforedescribed and monomer (methyl methacrylate) (5.34 mL) were added. The solution was deoxygenated via three freeze-pump-thaw cycles and added to Cu(I)Br (0.286g, 2.0 mmol). Reaction mixture subsequently heated to 90°C or 110°C depending on the monomer used. Samples were removed by syringe periodically (every 30 minutes) for analysis (GPC and gravimetrically). All molecular weight data was recorded on un-precipitated polymer. The final polymer solution was passed down a basic alumina column and precipitated into n-pentane.
This illustrates preparation of a block polymer according to the present invention using a molar ratio of ratio of monomer : polymer precursor : metal : ligand of 100:1:2:4 in 66% toluene solution. The reaction was terminated at about 96% conversion. The molecular number Mn was determined by GPC using methyl methacrylate standards to be about 27340 (Figure 11).
TABLE 16 - GPC ANALYSIS Figure 11 Example 6(a)
Sample name : aj 1789 Raw date filename : 02112.017
Conditions :
Solvent : THF with toluene Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI/UV
Data Processing :
Method : 2 Calibration using : Narrow standards
Calibration limits : 10.00 to 20.65 Mins
Curve used : 3 rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=l 1.819727, B = 0.759678, C = 0.016374, D = 0.000144
Last calibrated : Wed Oct 21 10:54:26 1998
Flow rate marker : found at 20.67 in standards at 20.38 Mins.
Broad peak start : 11.08 end : 15.08 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results :
Mp = 35898 Mn = 27342 Mw = 41579
Mz = 58673 Mz+1 = 76178 Mv = 39238
Polydispersity = 1.521 Peak area = 5112
The polymer precursor was also characterised by DSC (Figure 12) (3.000 mg sample weight Total Mn - 33000 heat from -50.00°C to 140.00°C at 20.00°C/min). This example (Example 6(a) ) was repeated using different monomers and different molar ratios of reagents as follows :
Example 6 (b) : The monomer used was methyl methacrylate. Molar ratio of monomer : polymer precursor : metal : ligand = 50 : 1 : 2 : 4. Product Mn = 14490 using poly(methyl methacrylate) standard for GPC (Figure 13). TABLE 17 - GPC ANALYSIS Figure 13 Example 6(b)
Sample name : ajl569 Raw date filename : 02112.026
Conditions :
Solvent : THF with toluene Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI/UV
Data Processing
Method : 2 Calibration using : Narrow standards
Calibration limits : 9.97 to 20.60 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=l 1.819727, B = 0.759678, C = 0.016374, D = 0.000144
Last calibrated : Wed Oct 21 10:54:26 1998
Flow rate marker : found at 20.62 in standards at 20.38 Mins.
Broad peak start : 11.58 end : 15.78 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results :
Mp = 19651 Mn = 14489 Mw = 21615
Mz = 30835 Mz+1 = 41305 Mv = 20405
Polydispersity = 1.492 Peak area = 6773
The polymer precursor was also characterised by DSC (Figure 14) (sample weight 8.100 mg , Total Mn - 17000, heat from -60.00°C to 140.00°C at 20.00°C/min.) and by 1H NMR in CDC13 (Figure 15).
Example 6 (c) : The monomer used was styrene. Molar ratio of monomer : polymer precursor : metal : ligand = 100 : 1 : 2 : 4. Product Mn = 16440 using poly(styrene) standard for GPC (Figure 16). TABLE 18 - GPC ANALYSIS Figure 16 Example 6(c)
Sample name : apjl669 Raw date filename : 29102.009
Conditions
Solvent : THF with toluene Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI/UV
Data Processing :
Method : 21 Calibration using : Narrow standards
Calibration limits : 9.58 to 20.67 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=13.147278, B = 1.020344, C = 0.032583, D = 0.000469
Last calibrated : Wed Oct 21 11:04: 12 1998
Flow rate marker : found at 20.67 in standards at 20.40 Mins.
Broad peak start : 11.52 end : 15.85 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.700 0.700
Molecular weight results
Mp = 24042 Mn = 16442 Mw = 24927
Mz = 35106 Mz+1 = 45798 Mv = 23556
Polydispersity = 1.516 Peak area = 7693
The polymer precursor was also characterised by DSC (Figure 17) (1.00 mg sample weight, total Mn - 17000, heat from -50.00°C to 140.00°C at 20.00°C/min) and by 1H NMR CDC13 (Figure 18).
Example 6 (d) : The monomer used was n-butyl methacrylate. Molar ratio of monomer : polymer precursor : metal : ligand = 100 : 1 : 2 : 4. Product Mn = 13190 using poly(methyl methacrylate) standard for GPC (Figure 19). TABLE 19 - GPC ANALYSIS Figure 19 Example 6(d)
Sample name : apjl88 11 Raw date filename : 01122.038
Conditions :
Solvent : THF with toluene Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI/UV
Data Processing :
Method : 2 Calibration using : Narrow standards
Calibration limits : 9.88 to 20.42 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=l 1.821880, B = 0.759705, C = 0.016359, D = 0.000144
Last calibrated : Sun Nov 15 11:08:30 1998
Flow rate marker : found at 20.43 in standards at 20.38 Mins.
Broad peak start : 11.23 end : 16.10 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results
Mp = 17626 Mn = 13190 Mw = 21880
Mz = 33488 Mz+1 = 47717 Mv = 20421
Polydispersity = 1.659 Peak area = 2996
The polymer precursor was also characterised by 1H NMR in CDC13 (Figure 20). Example 6 (e) : The monomer used was n-butyl methacrylate.
Molar ratio of monomer : polymer precursor : metal : ligand = 50 : 1 : 2 : 4. Product Mn = 8490 using poly(methyl methacrylate) standard for GPC (Figure 21). TABLE 20 - GPC ANALYSIS Figure 21 Example 6(e)
Sample name : apj!88 30 Raw date filename : 01122.048
Conditions :
Solvent : THF with toluene Temperature : room temp.
Column set : one guard column and 2 mixed D Flow rate : 1.00 mL/min Detector : DRI/UV
Data Processing
Method : 2 Calibration using : Narrow standards
Calibration limits : 9.88 to 20.42 Mins
Curve used : 3rd order polynomial Coefficients : Log(M) = A + BT + CT2 + DT3
A=l 1.821880, B = 0.759705, C = 0.016359, D = 0.000144
Last calibrated : Sun Nov 15 11 :08:30 1998
Flow rate marker : found at 20.42 in standards at 20.38 Mins.
Broad peak start : 11.83 end : 16.55 Mins.
Standards Sample
K : 10.4000*10e-5 10.4000* 10e-5 alpha : 0.697 0.697
Molecular weight results
Mp = 12694 Mn = 8486 Mw = 13647
Mz = 20030 Mz+1 = 27335 Mv = 12805
Polydispersity = 1.608 Peak area = 6699
The polymer precursor was also characterised by DSC (Figure 22) (sample weight 3.200 mg, heat from -50.00°C to 120.00°C at 20.00°C/min) and by 1H NMR in CDC13 (Figure 23). Example 7: Polymerisation of styrene with polymer precursor TV.
Polymer precursor IV prepared in Example 5 (1.1044 g, 0.4 mmol), Cu(I)Br (0.1139 g, 0.8 mmol) and a magnetic follower were placed in a Schlenk tube. Deoxygenated toluene(4.40 mL) and N-propyl-2-pyridinal methanimine (0.26 g, 1.76 mmol) prepared as hereinbeforedescribed were added and the solution heated to 110°C. Deoxygenated inhibitor free styrene (4.40 mL) was then added (t = 0). Samples were removed periodically for analysis, via syringe. AU molecular weight data recorded on un-precipitated polymer. The final polymer solution was passed down a basic alumina column and precipitated into n-pentane.
This illustrates preparation of a block polymer according to the present invention using a molar ratio of monomer : polymer precursor : metal : ligand of 100 : 1 : 2 : 4 in 50% to toluene solution.

Claims

Claims :
1. A process for the preparation of a block polymer which process comprises a transition metal mediated, atom transfer polymerisation of an ethylenicaUy unsaturated monomer with an α, ω di-functional polymer precursor having repeating units derived from an ethylenicaUy unsaturated carboxylate.
2. A process as claimed in claim 1 wherein the ethylenicaUy unsaturated carboxylate is vinyl acetate.
3. A process as claimed in claim 1 wherein the ethylenicaUy unsaturated monomer is selected from the group consisting of styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylic acid, unsubstituted acrylate and methacrylate.
4. A process as claimed in claim 2 wherein the ethylenicaUy unsaturated monomer is selected from the group consisting of styrene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylic acid, unsubstituted acrylate and methacrylate.
5. An α, ω di-functional polymer precursor having a molecular weight in the range from 500 to 50000 and being represented by the formula : X-[-CH2-C Y(OR)-]x-[-C Y'(OR)-CH2-]y-X' wherein x and y are integers independently greater than 1; Y and Y are independently H or -CH3 ; R represents a hydrocarbyl group; and X and X' independently represent substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
6. A polymer precursor as claimed in claim 5 wherein R is selected from the group consisting of CH3C(O)- , Y"-C(O)- , PhC(O)- , Ph-, PhCH2- , CH3-(CH2- CH2-CH2-CH2-)z€(O)- , CH3-(CH2- CH=CH-CH2-)z.C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO , OMe, CN, NMe2, OH, CL, Br, and F.
7. A polymer precursor as claimed in claim 5 wherein R is CH3C(O)-.
8. A process for the production of an α, ω di-functional polymer precursor which process comprises the steps of :
(a) reacting an ethylenicaUy unsaturated carboxylate with a radical initiator having a substitutable functional group; and
(b) substituting the functional groups on the product of step (a) with substituents active for the formation of block polymers in a transition metal mediated, atom transfer polymerisation process.
9. A process as claimed in claim 8 wherein the ethylenicaUy unsaturated carboxylate is vinyl acetate.
10. A polymer precursor having a molecular weight in the range from 500 to 50000, preferably from 1000 to 20000 and being represented by the formula :
HO-[-CH2-CY(OR')-]x. [-CY'(OR')-CH2-] OH wherein x' and y' are integers independently greater than 1 ; Y and Y' are independently H or -CH3 ; and R represents a hydrocarbyl group.
11. A polymer precursor as claimed in claim 10 wherein R' is selected from the group consisting of CH3C(O)- , Y"-C(O)- , PhC(O)- , Ph-, PhCH2- ,
CH3-(CH2- CH2-CH2-CH2-)z. C(O)- , CH3-(CH2- CH=CH-CH2-)Z- C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO2, OMe, CN, NMe2, OH, CL, Br, and F.
12. A polymer precursor as claimed in claim 10 wherein R' is CH3C(O)-.
13. A block polymer comprising alternating repeating units of -[-A-]- and -[-B-]- in which -A- represents a polymer block having a molecular weight in the range from 500 to 50000 and being represented by the formula :
-[-CH2-CY(ORM)-]χ- [-CY(OR")-CH2-]y. - wherein x" and y" are integers independently greater than 1; Y and Y are independently H or -CH3 and R" represents a hydrocarbyl group and -B- represents at least one polymer repeating unit selected from the group consisting of acrylic, substituted acrylic, methacrylic, substituted methacrylic, acrylonitrile, methacrylonitrile, acylamide, methacrylamide and styrenic polymer units.
14. A block polymer as claimed in claim 13 wherein R" is selected from the group consisting of CH3C(O)- , Y"-C(O)- , PhC(O)- , Ph-, PhCH2- ,
CH3-(CH2- CH2-CH2-CH2-)z.C(O)- , CH3-(CH2- CH=CH-CH2-)Z. C(O)- and substituted phenyl; wherein Y" is an n-alkyl group having up to 18 carbon atoms, Ph is phenyl, z' is an integer up to 5000, z" is an integer up to 5000 and the substituted phenyl is substituted with at least one substituent selected from the group consisting of NO2, OMe, CN, NMe2, OH, CL, Br, and F.
15. A polymer precursor as claimed in claim 13 wherein R" is CH3C(O)-.
PCT/GB2000/002120 1999-07-22 2000-06-01 Polymers, their precursors and processes for preparation thereof WO2001007496A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50928/00A AU5092800A (en) 1999-07-22 2000-06-01 Polymers, their precursors and processes for preparation thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9917291.8A GB9917291D0 (en) 1999-07-22 1999-07-22 Process for preparing polymers
GB9917291.8 1999-07-22

Publications (2)

Publication Number Publication Date
WO2001007496A2 true WO2001007496A2 (en) 2001-02-01
WO2001007496A3 WO2001007496A3 (en) 2002-09-26

Family

ID=10857792

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2000/002120 WO2001007496A2 (en) 1999-07-22 2000-06-01 Polymers, their precursors and processes for preparation thereof

Country Status (3)

Country Link
AU (1) AU5092800A (en)
GB (1) GB9917291D0 (en)
WO (1) WO2001007496A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087081A1 (en) * 2003-04-01 2004-10-14 Unilever Plc Aba block copolymers for hair styling composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2239250A (en) * 1989-12-22 1991-06-26 Basf Corp Copolymers from polyalkylene oxides containing a maleate reactive double bond and vinyl acetate
US5789487A (en) * 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
WO2000011055A1 (en) * 1998-08-21 2000-03-02 Elf Atochem S.A. Method for making copolymers with controlled architecture and resulting copolymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2239250A (en) * 1989-12-22 1991-06-26 Basf Corp Copolymers from polyalkylene oxides containing a maleate reactive double bond and vinyl acetate
US5789487A (en) * 1996-07-10 1998-08-04 Carnegie-Mellon University Preparation of novel homo- and copolymers using atom transfer radical polymerization
WO2000011055A1 (en) * 1998-08-21 2000-03-02 Elf Atochem S.A. Method for making copolymers with controlled architecture and resulting copolymers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087081A1 (en) * 2003-04-01 2004-10-14 Unilever Plc Aba block copolymers for hair styling composition

Also Published As

Publication number Publication date
WO2001007496A3 (en) 2002-09-26
AU5092800A (en) 2001-02-13
GB9917291D0 (en) 1999-09-22

Similar Documents

Publication Publication Date Title
EP0906342B2 (en) Polymerisation catalyst and process
Wang et al. Controlled/" living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes
EP1386935B1 (en) Dual stimuli-responsive hydrogels and their synthetic methods
JP2003500378A (en) Polyalkoxyamines obtained from .BETA.-substituted nitroxides
JP4975904B2 (en) Alkoxyamines obtained from β-phosphite nitroxide
US20070219330A1 (en) Amide initiators
US6664350B1 (en) Supported polymerisation catalyst
Acar et al. Synthesis of hexylated triethylenetetramine: New ligand for homogeneous atom transfer radical polymerization
WO2001007496A2 (en) Polymers, their precursors and processes for preparation thereof
CN110799553A (en) Process for producing polymers
JPH1060028A (en) Production of polymer
EP1165628A1 (en) Use of an initiator for controlled polymerisation reactions
US6534605B2 (en) Living polymerization process
JP2008222821A (en) Initiator having radical polymerization starting point and cationic polymerization starting point, and block copolymer synthesized using the initiator
EP2089399B1 (en) Polymerisation of ethylene and alpha olefins with single site catalysts having an anionic scorpion-like ligand
KR100435105B1 (en) Homogeneous Atom Transfer Radical Polymerization(ATRP) of Methyl Methacrylate(MMA) Using the Novel Catalysts Based on Carboximidate Ligand
JP2752376B2 (en) New porphyrin compounds
WO2002059171A2 (en) Living radical graft copolymerization of vinyl monomers initiated from the structural defects of polyvinylchloride
JP2001226313A (en) Fluorinated vinyl ether compound, method for producing the same and fluorine-containing polymer
WO2000053643A1 (en) Catalyst composition and method for making a polymer or copolymer
US6649711B2 (en) Process for preparing vinylic polymers with catalyst system containing metal complex and Lewis acid
JP2002327007A (en) Polymerization method of anionic polymerizable monomer
JP2000178293A (en) Semi-sandwich complex of non-cross-linked mononucle, bisalkyl metal having polymerization activity based on rare earth metal
CA2335476A1 (en) Aluminium compounds for producing vinylic polymers
JPH02248403A (en) Production of vinyl polymer having acid anhydride group

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

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

AL Designated countries for regional patents

Kind code of ref document: A2

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

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

Ref country code: DE

Ref legal event code: 8642

AK Designated states

Kind code of ref document: A3

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

AL Designated countries for regional patents

Kind code of ref document: A3

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

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

Ref country code: JP