WO2014147188A1 - Temperature-responsive catalysts - Google Patents

Temperature-responsive catalysts Download PDF

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Publication number
WO2014147188A1
WO2014147188A1 PCT/EP2014/055626 EP2014055626W WO2014147188A1 WO 2014147188 A1 WO2014147188 A1 WO 2014147188A1 EP 2014055626 W EP2014055626 W EP 2014055626W WO 2014147188 A1 WO2014147188 A1 WO 2014147188A1
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meth
acrylate
monomeric units
phosphino
propionic acid
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PCT/EP2014/055626
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French (fr)
Inventor
Dorit Wolf
Rüdiger BORRMANN
Cengiz Azap
Maria VAMVAKAKI
George PASPARAKIS
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Evonik Industries Ag
Foundation For Research And Technology - Hellas
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Publication of WO2014147188A1 publication Critical patent/WO2014147188A1/en

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/827—Iridium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • the present invention relates to catalysts comprising a polymer and a catalytically-active metal compound wherein said catalysts have a critical solution temperatur. Furthermore, the present invention relates to polymers having a critical solution temperature. Another aspect of the present invention is a process for producing said catalysts and said polymers, as well as the use thereof in homogeneous and/or heterogeneous catalysis.
  • Palladium catalysts bearing an N-heterocyclic carbene and sterically demanding phosphine ligands display the most robust and active catalytic systems to date (G. Organ et al . , Angew. Chem. 2007, 46, 2768-2813) .
  • homogeneous catalysts exhibit a high catalytic activity and selectivity and are thus applied in minimal quantities to catalytic reactions.
  • the recovery of ligands and especially of the metal, which is mainly a precious metal, e.g. Rh, Pd or Pt, of the homogeneous catalysts is mainly a precious metal, e.g. Rh, Pd or Pt.
  • the metal catalysts have to be removed to a regulated level. This can be achieved by e.g. chemical metal scavenging substances or techniques where the metal residues are removed by physical methods such as extraction,
  • a polymer which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • Monomeric unit A is defined as non-functionalized
  • R la , R lb , R lc , R ld , R le , R lf , R lg are each independently selected from H and methyl
  • R 2 and R 2 ' are each independently selected from the group consisting of Bilinear or branched Ci-C 4 o _ alkyl, wherein linear or branched Ci- C20 are preferred, linear or branched C 1 -C 1 0 are more preferred and linear or branched C 1 -C5 are even more preferred;
  • R is a linear Ci-Cio-alkylene group and R' is selected from the group consisting of H, Ci-Cio-alkyl, C3-C 10 - cycloalkyl, C3-Cio-heterocycloalkyl , C6-Ci 4 -aryl ;
  • R is a linear Ci-Cio-alkylene group and R' ' are each independently selected from the group consisting of H, methyl, ethyl and tert-butyl
  • R 2a is selected from the group consisting of Bilinear or branched Ci-C 4 o _ alkyl, wherein linear or branched Ci- Cio-alkyl is preferred, and linear or branched Ci-Cs-alkyl is even more preferred;
  • R is a linear Ci-Cio-alkylene group and R' ' are each independently selected from the group consisting of H, methyl, ethyl and tert-butyl R 3 is selected from the group consisting of H;
  • R' is selected from the group consisting of H, Ci - Cio-alkyl, C3-Cio-cycloalkyl , C3-Cio-heterocycloalkyl , and C6-C14- aryl;
  • R x , R x' , R x" , R x"' and R x"" are each independently selected from the group consisting of linear or branched Ci -Cio-alkylene groups, wherein Ci -Cs-alkylenes are preferred;
  • R y , R y' , R y" , R y" ' and R y" are each independently selected from the group consisting of Bilinear or branched Ci -Cio _ alkyl groups, wherein Ci -Cs-alkyl is preferred;
  • Ci -C n _ alkyl is defined as linear or branched Ci -C n alkyl group with 1 to n C-atoms.
  • Ci -C n _ alkyl groups are methyl, ethyl, n- propyl, isopropyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1,1- dimethylpropyl , 2, 2-dimethylpropyl, l-ethyl-2-methylpropyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, n-butyl, iso- butyl, sec-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl , 1- ethylbutyl, 2-ethylbutyl, 1-propylbutyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1 , 3-dimethylbutyl , 2, 2-dimethylbutyl, 2,3- dimethylbutyl , 3 , 3-dimethylbutyl , n-pentyl, 2-pentyl, 3- pentyl, 1-
  • Ci-C n -alkylene is defined as divalent linear or branched Ci-C n alkyl group with 1 to n C- atoms .
  • Typical examples of Ci-C n -alkylenes are methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, n-hexylene, n-heptylene, n- octylene, n-nonylene, n-decylene.
  • C3-C n -cycloalkyl is defined as cyclic alkyl group with 3 to n C-atoms, which comprises mono-, bi- and tricyclic alkyl groups.
  • Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tert- butylcyclohexyl , trimethylcyclohexyl , cycloheptyl, cyclooctyl, norbornyl, methylnorbornyl , dimethylnorbornyl , bornyl,
  • C3-C n -heterocycloalkyl is defined as cyclic alkyl group with 3 to n C-atoms, which comprises mono-, bi- and tricyclic alkyl groups wherein 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from N, 0 or S .
  • Examples are pyrrolidinyl , piperidinyl, imidazolidinyl , pyrazolidinyl , oxazolidinyl , morpholidinyl , thiazolidinyl , isothiazolidinyl , isoxazolidinyl , piperazinyl, tetrahydrothiophenyl , tetrahydrofuranyl , tetrahydropyranyl , dioxanyl.
  • C6-C n -aryl is defined as cyclic aromatic group with 5-n C-atoms, which comprises unsubstituted and substituted aryl groups.
  • Typical examples are phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl,
  • C6-C n -arylalkyl is a group which comprises both alkyl groups and aryl groups and contains 6 to n C-atoms in total.
  • This C6-C n -arylalkyl group can be linked to the molecule carrying this group via any of its carbon atoms.
  • a typical example of C6-C n -arylalkyl is benzyl .
  • Cs-C n -heteroaryl is defined as cyclic aromatic group with 5 to n C-atoms wherein 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from N, 0 or S .
  • Typical examples are thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
  • C 3 -C n -cycloalkylene is defined as divalent C 3 -C n -cycloalkyl group with 3 to n C-atoms.
  • C6-C n -arylene is defined as divalent C6-C n -aryl group with 6 to n C-atoms.
  • R 2 and R 2' are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, 1- ethylpropyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2- dimethylpropyl , n-butyl, iso-butyl, sec-butyl, tert-butyl, 2- methylbutyl, 3-methylbutyl , n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl, anthracenyl, phenanthrenyl , napthacenyl, and benzyl.
  • R 3 is selected from the group consisting of butyl, pentyl, cyclohexyl, acetate, propionate, benzoate, versatate, chloride, fluoride, phenyl, methylphenyl , ethylphenyl,
  • pyridines pyrimidines, piperidines, carbazoles, imidazoles, pyrrolidones , pyrrolidines, caprolactam, oxolanes, furan, thiophene, thiolane, thiazoles, wherein acetate and propionate are particulary preferred.
  • R x , R x' , R x" , R x"' and R x"" are each independently selected from the group consisting of methylene, ethylene, n- propylene, isopropylene, n-butylene, isobutylene, tert- butylene, cyclohexylene, wherein ethylene and n-propylene are particularly preferred.
  • R y , R y' , R y" , R y" ' and R y" are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1,1- dimethylpropyl , 2, 2-dimethylpropyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, n-pentyl, 2- pentyl, 3-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl, anthracenyl, phenanthrenyl, napthacenyl.
  • Examples of the aforementioned (meth) acrylates of formula (I) are alkyl (meth) acrylates of straight-chained or branched
  • aliphatic alcohols having 1 to 40 C atoms such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl (meth) acrylate, 1 , 2-dimethylpropyl (meth) acrylate, 1,1- dimethylpropyl (meth) acrylate, 2 , 2-dimethylpropyl
  • (meth) acrylate 5-methylundecyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, n-tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl
  • (meth) acrylate 3-isopropyloctadecyl (meth) acrylate, n- octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, eicosyl (meth) acrylate; wherein methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl
  • (meth) acrylate are preferred; aryl (meth) acrylates such as, for example, phenyl
  • arylalkyl (meth) acrylates such as, for example, benzyl
  • (meth) acrylate mono (meth) acrylates of ethers, polyethylene glycoles, polypropylene glycoles or mixtures thereof, such as, for example, tetrahydrofurfuryl methacrylate, methoxymethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1- butoxypropyl methacrylate, cyclohexyloxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate,
  • poly (propylene glycol) methylether (meth) acrylate poly (propylene glycol) methylether (meth) acrylate ; amino-functionalized (meth) acrylates like aminoalkyl
  • (meth) acrylates dialkylaminoalkyl (meth) acrylates , or alkylaminoalkyl (meth) acrylates .
  • Preferred more particularly are dimethylaminoalkyl (meth) acrylates and diethylaminoalkyl (meth) arylates , such as, 2-dimethylaminoethyl methacrylate (DMAEMA) , 2-diethylaminoethyl methacrylate (DEAEMA) , 2-tert- butylaminoethyl methacrylate (t-BAEMA) , 2-dimethylaminoethyl acrylate (DMAEA) , 2-diethylaminoethyl acrylate (DEAEA) ;
  • DMAEMA 2-dimethylaminoethyl methacrylate
  • DEAEMA 2-diethylaminoethyl methacrylate
  • t-BAEMA 2-dimethylaminoethy
  • aminoalkyl (meth) acrylates such as, 1-aminoethyl
  • Preferred (meth) acrylates of formula (I) are linear Ci-Cio- alkyl (meth) acrylates , more preferred are linear Ci-Cs-alkyl (meth) acrylates , wherein methyl (meth) acrylate, ethyl
  • (meth) acrylate are particularly preferred.
  • (Meth) acrylates in the sense of the present invention further include (meth) acrylamides according to formula (II) like monoalkyl (meth) acrylamides , dialkyl (meth) acrylamides and mono- and dialkylaminoalkyl (meth) acrylamides .
  • Preferred more particularly are methacrylamide and acrylamide, N-2-aminoethyl (meth) acrylamide, N, -dimethylaminoethyl (meth) acrylamide, N, -diethylaminoethyl (meth) acrylamide, N-3-aminopropyl
  • DMAPMA 3-dimethylaminopropyl acrylamide
  • DMAPA 3-dimethylaminopropyl acrylamide
  • meth 3- diethylaminopropyl (meth) acrylamide
  • copolymers may have hydroxyl
  • compositions Besides the (meth) acrylates set out above it is possible for the compositions to be polymerized also to contain further unsaturated monomers of formula (III) which are
  • 1-alkenes such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,
  • dichlorostyrenes tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
  • vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.
  • vinyl esters and vinyl ethers Particular preference is given to vinyl esters and vinyl ethers. Even more preferred are vinyl acetate and vinyl propionate .
  • the preferred (meth) acrylic monomers of formula (VII), respectively, include, among others,
  • the preferred (meth) acrylic monomers of formula (VIII), respectively, include, among others,
  • Particularly preferred monomeric units A are selected from ethyl methacrylate (EMA) , N-isopropyl acrylamide (NIPAM) , vinylacetate (VA) and ethyl acrylate (EA) .
  • EMA ethyl methacrylate
  • NIPAM N-isopropyl acrylamide
  • VA vinylacetate
  • EA ethyl acrylate
  • Monomeric unit B is selected from hydroxyl-functionalized (meth) acrylates and monomers co-polymerizable with
  • R 1' and R 1' ' are each independently selected from H and methyl R 3' is selected from the group consisting of H;
  • Preferred hydroxyl-functionalized (meth) acrylates and monomers copolymerizable with (meth) acrylates of formula (IX) are, for example,
  • (meth) acrylates having a hydroxyl group in the alkyl radical, more particularly 2-hydroxyethyl (meth) acrylate, preferably 2- hydroxyethyl methacrylate (HEMA) , hydroxypropyl
  • (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and 3- hydroxypropyl (meth) acrylate, preferably 2-hydroxypropyl methacrylate (HPMA) , hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA) , 3, 4-dihydroxybutyl
  • (meth) acrylate 2 , 5-dimethyl-l , 6-hexandiol (meth) acrylate, 1, 10-decandiol (meth) acrylate, glycerol mono (meth) acrylate, and polyalkoxylated derivatives of (meth) acrylic acid,
  • Examples of monomer of formula (X) are the same as those mentioned before according to formula (II) with the proviso that in addition functional group X is present. These include, among others, N-methyl (meth) acrylamide, N-ethyl
  • (meth) acrylamide N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-iso-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl (meth) acrylamide, N- (octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide, N- (1,1, 3,3- tetramethylbutyl ) (meth) acrylamide, N-3-ethylhexyl
  • N-methylol (meth) acrylamide 2- hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 2-hydroxybutyl (meth) acrylamide, 3- hydroxypropyl (meth) acrylamide, 3-hydroxybutyl
  • Examples of monomers of formula (XI) are the same as those mentioned before according to formula (III) with the proviso that in addition functional group X is present. These include, among others,
  • 1-alkenes such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride ; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,
  • dichlorostyrenes tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
  • vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.
  • the hydroxyl-group of monomeric unit B is esterified after copolymerisation with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups.
  • the uncharged electron donor is a functional group with coordinative properties to which the catalytically-active metal compound can be bound.
  • the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from phosphines or nitrogen-containing carbenes (NHC) . More preferably, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor is selected from the group consisting of compounds of the general formulas (XII) -(XV),
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4g , R 4h are each independently selected from the group consisting of Bilinear or branched Ci-C2o-alkyl, preferably linear or branched C 3 -Cio-alkyl;
  • R 5 is selected from the group consisting of H
  • R 6 and R 6 ' are each independently selected from H and Me.
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4g , R 4h are each
  • R 5 is selected from the group consisting of H and mesityl .
  • an uncharged electron donor is a ligand without net-charge that contributes free electrons or orbitals filled with electrons for a coordinative bond with an acceptor.
  • An acceptor is an atom that accepts the free electrons or electrons from a filled orbital of the donor.
  • Donors are typically main group elements from groups 13-17 of the Periodic Table of Elements, e.g. C, N, P.
  • carbon too, can act as uncharged electron donor.
  • uncharged electron donor Usually found as carbene, wherein the carbon atom bears a pair of electrons in an orbital. These electrons are provided for an uncharged sigma bond with the acceptor atom.
  • Acceptors are typically metal atoms, e.g. Pd(0), Pd(II), Ru (I), Ru(II) .
  • the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from the group consisting of compounds of formula XII, wherein R 4a and R 4b are the same and are selected from the group consisting of phenyl, isobutyl, cyclohexyl and
  • n 1, 2, 3, 4 or 5;
  • R 4g and R 4h are the same and are selected from the group consisting of 1-adamantyl and phenyl and n is 1, 2, 3, 4 or 5.
  • Preferred monomeric units B are selected from
  • a further class of monomers is presented by monomeric units C, which are cross-linking monomers. These monomers have at least two olefinically unsaturated double bonds possessing similar reactivity in the context of a free-radical polymerization.
  • Suitable compounds are, for example, (meth) acrylic esters, vinyl esters or allyl esters of at least dihydric alcohols. These compounds include more particularly (meth) acrylates deriving from unsaturated alcohols, such as allyl
  • (meth) acrylates deriving from substituted or unsubstituted diols, such as, 1 , 2-ethanediol di (meth) acrylate, 1,2- propanediol di (meth) acrylate, 1 , 3-propanediol
  • glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol
  • (meth) acrylates having three or more double bonds such as glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate;
  • divinylbenzenes N, N' -divinylethylene urea
  • divinylether of polyhydroxy compounds like butanediol-bis- vinylether, hexanediol-bis-vinylether , trimethylol- propanetrivinylether , pentaerythrit-tetra-vinylether .
  • Preferred cross-linking monomers are selected from the following group:
  • allyl (meth) acrylate vinyl (meth) acrylate and methylallyl (meth) acrylate, divinylbenzenes, glycol di (meth) acrylates , ⁇ , ⁇ ' -methylene-bisacrylamide, bis (2-methacryloyl) oxyethyl disulfide .
  • cross-linking monomers are selected from the following group:
  • Catalytically-active metal compounds are metals, metal complexes or metal salts of elements of groups 6-11 of the Periodic Table of the Elements.
  • the catalytically- active metal compound contains a metal selected from the group consisting of Pd, Rh, Ru, Pt, Ir, Cu, Ni and Fe, wherein Pd, Rh and Ru are particularly preferred.
  • the above-mentioned monomeric units A and B and cross-linking monomeric units C can arbitrarily and effectively be combined or co-polymerized to obtain an optionally cross-linked polymer, having a critical solution temperature and required stability and mechanical properties.
  • Monomeric unit A is present in the polymer in a range from 50 wt-% - 99.9 wt-%, preferably 80 wt-% - 99.9 wt-%, more
  • monomeric unit A is present in a range from 50 wt-% - 99.8 wt-%, preferably 80 wt-% - 99.5 wt-%, more preferably 90 wt-% - 97 wt-%.
  • Monomeric unit B is present in the polymer in a range from 0.1 wt-% - 50 wt-%, preferably 0.1 wt-% - 20 wt-%, more preferably 0.5 wt-% - 20 wt-%, most preferably 1 wt-% - 10 wt-%.
  • monomeric unit B is present in a range from 0.1 wt-% - 30 wt-%, preferably 0.1 wt-% - 10 wt-%, and most preferably 1 wt-% - 5 wt-%.
  • Monomeric unit C is present in the polymer in a range from 0 wt-% - 30 wt-%, more preferably 0.1 wt-% - 20 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit C is present in a range from 0.1 wt-%
  • Table 1 Specific compositions of monomeric units.
  • the monomeric units are selected as presented in table 2.
  • Table 2 Specific combinations of monomeric units.
  • EA ethylacrylate
  • EMA ethylmethacrylate
  • VA ethylmethacrylate
  • NIPAM N-isopropylacrylamide
  • [a] 2-hydroxyethyl (meth) acrylate
  • [b] 2-hydroxypropyl (meth) acrylate
  • [c] 2- hydroxybutyl (meth) acrylate
  • [d] Tris (hydroxymethyl)
  • the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B, and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking mono
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • a polymer which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B, and 0 wt-% - 30 wt-% of one unit derived from a cross-linking monomeric unit C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
  • a polymer which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, and 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
  • the invention provides a catalyst comprising
  • a polymer which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • the critical solution temperature T c of the polymer in solvent x is in a range of from -10°C to +150°C, wherein solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol , n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene .
  • solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol , n-pentano
  • the slope is determined at the turning point of the
  • the point of intersection of lines Li and L2 is defined as the critical solution temperature T c of the polymer.
  • the critical solution temperature can be measured in different organic solvents. Suitable solvents are methanol, ethanol, n- propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene.
  • methanol, isopropanol, n-butanol and toluene are used.
  • the critical solution temperature in at least one of these solvents is in a range from -10°C to +150°C, preferably the critical solution temperature in at least one of these solvents is in a range of from -10°C to +100°C, more
  • the critical solution temperature in at least one of these solvents is in a range of from -10°C to +70°C, suitably preferred is a critical solution temperature in at least one of these solvents in a range of from +5°C to +50°C.
  • Temperature-responsive polymers Polymers with a critical solution temperature are called temperature-responsive polymers. Temperature-responsive polymers, which are precipitable by increase or decrease of temperature, are well known (I. Dimitrov, B. Trzebicka, A. H. E. Muller, A. Dworak, C. B. Tsvetanov, Prog. Polym. Sci. 2007, 32,1275-1343; R. Pelton, Adv Coll Interface Sci 2000, 85,1; J. K. Oh, R. Drumright, D. J. Siegwart, K. Matyj aszewski, Prog. Polym. Sci. 2008, 33, 448-477; T. J. Freemont, B. R. Saunders, Soft Matter, 2008, 4, 919-924; S. Nayak, L.A. Lyon Angew. Chem. Int. Ed. 2005, 44, 7686-7708) .
  • microgels are intramolecularly cross-linked macromolecules of colloidal dimensions which are dispersed in normal or colloidal
  • the cross-linking is achieved by applying ternary copolymerization of non-functionalized monomers, functionalized monomers and cross-linking monomers in very diluted solutions with the monomer concentration below a critical value. Under these conditions, microgels do not react intermolecularly to build an insoluble polymer network, but intramolecularly to yield a stable solution.
  • the critical monomer concentration is dependent on the type of monomer, the degree of cross-linking, the solvent and the polymerization conditions.
  • the resulting microgel also exhibits temperature- responsive properties. Techniques for the preparation of microgels, surface modification and applications of microgels are well known to the person skilled in the art from the afore-mentioned review article of Funke et al ..
  • microgels over linear polymers are their low viscosity even in solutions with high solid concentration and at low temperatures, which provides the opportunity to apply the microgel-based catalyst in high concentrations.
  • catalytically-active metal compound is localized at the surface of the microgel particles. This provides a better accessibility of the catalytically-active metal compounds and can lead to as high catalytic activity as conventional
  • the intramolecular cross-linking provides a high structural stability of the colloids, which is a requirement for their application as recyclable catalyst or catalyst support .
  • the invention provides a catalyst comprising
  • a polymer which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
  • EMA ethyl methacrylate
  • NIPAM N-isopropylacrylamide
  • VA vinylacetate
  • EA ethylacrylate
  • monomeric units B are selected from the group
  • cross-linking monomeric units C are selected from the roup consisting of compounds of formulas XVI-XX
  • the invention provides a catalyst comprising
  • a polymer which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • catalytically-active metal compound comprises a metal selected from the group consisting of Pd, Ru, Pt, Ir, Cu, Ni and Fe .
  • the invention provides a catalyst comprising
  • a polymer which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
  • precursor of phosphorous and/or nitrogen containing uncharged electron donor is selected from
  • the invention provides a process for producing a catalyst, comprising the steps
  • the invention provides a process for producing a catalyst, comprising the steps
  • the catalytically-active metal compound comprises a metal selected from Pd, Rh, Ru, Pt, Co, Cu, Ni and Fe .
  • the invention provides a catalyst obtainable by a process comprising the steps
  • the polymers according to the invention may be obtained in particular by solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, it being possible to achieve surprising advantages by means of a radical solution polymerization. These methods are set out in Ullmann' s Encyclopedia of Industrial Chemistry, Sixth Edition.
  • references describing typical free radical polymerization include Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition.
  • a polymerization initiator and also, optionally, a molecular- weight-regulating chain-transfer agent are employed.
  • the initiators which can be used include, among others, the azo initiators that are widely known in the art, such as
  • Azobiscyclohexanecarbonitrile, and also peroxy compounds such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert- butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, tert- butylperoxy-2-ethylhexanoate, tert-butylperoxy-3 , 5 , 5- trimethylhexanoate, dicumyl peroxide, 1,1 bis (terttylacetone peroxide,
  • hydroperoxide bis (4 tert butylcyclohexyl ) peroxydicarbonate, mixtures of two or more of the aforementioned compounds with one another, and mixtures of the aforementioned compounds with nonspecified compounds that may likewise form free radicals.
  • the stated initiators may be used either individually or in a mixture. They are used in an amount of 0.01 mol-% to 10.0 mol- %, preferably 0.1 mol-% to 5 mol-%, more preferably 0.5 mol-% to 2 mol-% based on the total weight of the monomers. It is also possible with preference to carry out the polymerization using a mixture of different polymerization initiators having different half-lives.
  • the polymerization can be carried out under atmospheric, subatmospheric or superatmospheric pressure.
  • polymerization temperature as well is not critical. Generally speaking, however, it is in the range of -20°C - +200°C, preferably +50°C - +150°C and more preferably +70°C - +130°C.
  • the polymerization can be carried out with or without solvent.
  • solvent should be understood widely in this specification
  • the preferred solvents include, in particular, aromatic hydrocarbons, such as toluene, xylene; esters, especially acetates, preferably butyl acetate, ethyl acetate, propyl acetate; ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone ; alcohols, especially methanol, isopropanol, n-butanol, isobutanol;
  • aromatic hydrocarbons such as toluene, xylene
  • esters especially acetates, preferably butyl acetate, ethyl acetate, propyl acetate
  • ketones preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone
  • alcohols especially methanol, isopropanol, n-butanol, isobutanol;
  • ethers especially glycol monomethyl ethers, glycol monoethyl ethers, glycol monobutyl ethers; aliphatics, preferably pentane, hexane, cycloalkanes and substituted cycloalkanes , such as cyclohexane; mixtures of aliphatics and/or aromatics, preferably naphtha; benzine, biodiesel; tetrahydrofuran, dichloromethane ; but also plasticizers such as low molecular weight polypropylene glycols or phthalates.
  • solvents may be used individually or as a mixture.
  • the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B.
  • the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one non-functionalized monomeric unit A, 0.1 wt-% - 30 wt-% of units derived from one monomeric unit B, and 0.1 wt-% - 20 wt-% of units derived from one cross-linking
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B.
  • the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B; wherein the critical solution temperature of the polymer at room
  • the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
  • EMA ethyl methacrylate
  • NIPAM N-isopropylacrylamide
  • VA vinylacetate
  • EA ethylacrylate
  • monomeric units B are selected from the group
  • cross-linking monomeric units C are selected from the roup consisting of compounds according to formulas XVI-XX
  • the invention relates to a process for producing the polymer, comprising the steps (a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,
  • the invention relates to a polymer obtainable by a process comprising the steps
  • the invention relates to the use of the catalyst in homogeneous and/or heterogeneous catalysis.
  • Preferred catalytic reactions are ring closing metathesis (RCM) ;
  • hydrogenation reactions e.g. hydrogenation of C-C double bonds, nitro groups, carbonyl groups, nitril groups, ketones, imines, arenes, heterocycles .
  • the (meth) acrylate polymer of the invention has a weight- average molecular weight in the range of from 1000 g/mol to 100000 g/mol, preferably of from 10000 g/mol to 60000 g/mol, more preferably in the range of from 15000 to 40000 g/mol.
  • the number-average molecular weight of preferred (meth) acrylate polymers is in the range of from 1000 g/mol to 60 000 g/mol, more preferably in the range of from 3000 g/mol to 25 000 g/mol.
  • (meth) acrylate polymers which have a polydispersity index, Mw/Mn, in the range of from 1 to 10, more preferably in the range of from 1.5 to 7 and very preferably of from 1.7 to 3.
  • Mw/Mn polydispersity index
  • the molecular weight can be determined by means of gel permeation chromatography (GPC) against a PMMA standard.
  • the molecular weight was determined via GPC. GPC columns from the manufacturer Varian/Polymer Laboratories were used, arranged in series with the pore sizes 105, 106, 104 and 103 A. The individual columns were 300 mm long and had a diameter of 7.5 mm. A polymer solution was prepared with an initial concentration of 2.5 g of polymer per litre of solvent. THF was used as eluent, and a flow rate of 1 ml/min was operated. The injection volume was 100 ⁇ . The column oven is
  • Mw denotes the weight-average molecular weight
  • PROCEDURE
  • PROCEDURE
  • PROCEDURE
  • the cooled reaction mixture is diluted with 100 mL THF and added dropwise to 1000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.
  • PROCEDURE
  • reaction mixture is cooled to 0 °C and the white precipitate is removed by filtration.
  • the filtrate is evaporated in vacuo and purified by flash column chromatography using silica as stationary phase and DCM as eluent .
  • PROCEDURE
  • PROCEDURE
  • reaction mixture is cooled to 0 °C and the white
  • PROCEDURE
  • PROCEDURE
  • reaction mixture is concentrated in vacuo to ca. 5 mL .
  • 30 mL diethylether are added and the mixture is stirred for 2 h, wherein the polymer precipitates as orange oily substance.
  • Diethylether is decanted and excessive diethylether is removed in high vacuo.
  • PROCEDURE
  • reaction mixture is added dropwise to 100 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.
  • PROCEDURE
  • reaction mixture is concentrated to ca. 2 mL and 10 mL abs. diethylether are added.
  • the mixture is stirred for 2 h, which leads to the formation of an orange precipitate of the polymer.
  • Excessive diethylether is decanted and the polymer dried in vacuo.

Abstract

The present invention relates to a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol –100000 g/mol and which polymer comprises 50 wt-% -99.9 wt-% ofunits derived from one or more non-functionalized monomeric units A, 0.1 wt-% -50 wt-% of units derived from one or more monomeric units B, 0wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates; wherein monomeric units B are selected from hydroxyl-functionalized (meth) acrylates and monomers copolymerizable with (meth) acrylates,which are esterified with one or more suitable precursors of phosphorousand/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which compriseat least two olefinically unsaturated double bondsco-polymerizable with A and/or B, and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer. Furthermore, the invention relates to corresponding polymers to afore-mentioned catalyst, a process for producing the catalyst and the polymer as well as the use of the catalyst in homogeneous and/or heterogeneous catalysis.

Description

Temperature-responsive catalysts
The present invention relates to catalysts comprising a polymer and a catalytically-active metal compound wherein said catalysts have a critical solution temperatur. Furthermore, the present invention relates to polymers having a critical solution temperature. Another aspect of the present invention is a process for producing said catalysts and said polymers, as well as the use thereof in homogeneous and/or heterogeneous catalysis.
The work leading to this invention has received funding from the European Community Seventh Framework Programme (FP 7) under grant agreement number 214095.
Background of the invention
Homogeneous transition metal catalyzed reactions have been refined into important processes for the synthesis of high- valued organic compounds. Especially, functionalization of aryl halides or vinyl halides in C-C and C-X coupling
reactions, e.g. to aromatic olefins (Heck-coupling, Stille- coupling) , biaryls (Suzuki-coupling) , alkines ( Sonogashira- reaction) , derivatives of acid (Heck-carbonylation) , amines (Buchwald-Hartwig-coupling) , is a major field of application. From these, Palladium-catalyzed cross-coupling reactions have emerged as one of the most important reactions both in
industry and academia. In recent years there have been
numerous contributions in this area.
Palladium catalysts bearing an N-heterocyclic carbene and sterically demanding phosphine ligands display the most robust and active catalytic systems to date (G. Organ et al . , Angew. Chem. 2007, 46, 2768-2813) .
Conventional homogeneous catalysts exhibit a high catalytic activity and selectivity and are thus applied in minimal quantities to catalytic reactions. The recovery of ligands and especially of the metal, which is mainly a precious metal, e.g. Rh, Pd or Pt, of the homogeneous catalysts is
disadvantageous due to their low concentrations or the
decomposition of the active complexes in the recycling
process. Therefore, there is a demand to provide a catalyst with a good recovery rate.
In addition, the application of homogeneous transition metal catalysts can result in soluble metal contamination.
Furthermore, the loss of precious metal is the major cost factor in homogeneous catalysis. These soluble metal
contaminations can be detrimental to product quality and product yield. In the case of active pharmaceutical ingredient development, the metal catalysts have to be removed to a regulated level. This can be achieved by e.g. chemical metal scavenging substances or techniques where the metal residues are removed by physical methods such as extraction,
distillation or precipitation. From the industrial point of view on attractive physical method constitutes membrane filtration technology in which the organic materials are removed by filtration and the metal remains within the
membrane sphere.
It is thus an objective of the present invention to provide a catalyst with high catalytic activity and selectivity that allows simple and cost efficient separation of metal complexes and reaction solution.
This objective is achieved with catalysts comprising
(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
In the following, the phrase (meth) acrylate stands for
acrylates as well as methacrylates .
Monomeric unit A is defined as non-functionalized
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , wherein one or more are selected from the group consisting of compounds of the general formulas I-VIII
Figure imgf000004_0001
(IV) (V) (VI) (VII) (VIII) wherein
Rla, Rlb, Rlc, Rld, Rle, Rlf, Rlg are each independently selected from H and methyl
R2 and R2' are each independently selected from the group consisting of Bilinear or branched Ci-C4o_alkyl, wherein linear or branched Ci- C20 are preferred, linear or branched C1-C10 are more preferred and linear or branched C1-C5 are even more preferred;
C3-Ci0-cycloalkyl;
Figure imgf000005_0001
C6-Ci4-arylalkyl ;
ROR' , wherein R is a linear Ci-Cio-alkylene group and R' is selected from the group consisting of H, Ci-Cio-alkyl, C3-C10- cycloalkyl, C3-Cio-heterocycloalkyl , C6-Ci4-aryl ;
and RNR' '2, wherein R is a linear Ci-Cio-alkylene group and R' ' are each independently selected from the group consisting of H, methyl, ethyl and tert-butyl R2a is selected from the group consisting of Bilinear or branched Ci-C4o_alkyl, wherein linear or branched Ci- Cio-alkyl is preferred, and linear or branched Ci-Cs-alkyl is even more preferred;
C3-C10-cycloalkyl ;
Figure imgf000005_0002
and RNR' '2, wherein R is a linear Ci-Cio-alkylene group and R' ' are each independently selected from the group consisting of H, methyl, ethyl and tert-butyl R3 is selected from the group consisting of H;
Ci-Cio-alkyl;
C3-C10-cycloalkyl ;
C3-Cio-heterocycloalkyl ;
C6-Ci4-aryl; C5 -Ci4-heteroaryl ;
halide ;
OR' , wherein R' is selected from the group consisting of H, Ci - Cio-alkyl, C3-Cio-cycloalkyl , C3-Cio-heterocycloalkyl , and C6-C14- aryl;
and
Figure imgf000006_0001
wherein n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and wherein n = 1 or 2 is preferred
Rx, Rx' , Rx" , Rx"' and Rx"" are each independently selected from the group consisting of linear or branched Ci -Cio-alkylene groups, wherein Ci -Cs-alkylenes are preferred;
C3-Cio-cycloalkylene groups, wherein Cs -Cs-cycloalkyl is
preferred;
and C6-Ci4-arylene groups
Ry, Ry' , Ry" , Ry" ' and Ry" " are each independently selected from the group consisting of Bilinear or branched Ci -Cio_alkyl groups, wherein Ci -Cs-alkyl is preferred;
C3-Cio-cycloalkyl groups, wherein Cs -Cs-cycloalkyl is preferred; and C6-Ci4-aryl groups.
In the sense of the present invention Ci -Cn _alkyl is defined as linear or branched Ci -Cn alkyl group with 1 to n C-atoms.
Typical examples of Ci -Cn _alkyl groups are methyl, ethyl, n- propyl, isopropyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1,1- dimethylpropyl , 2, 2-dimethylpropyl, l-ethyl-2-methylpropyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, n-butyl, iso- butyl, sec-butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl , 1- ethylbutyl, 2-ethylbutyl, 1-propylbutyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1 , 3-dimethylbutyl , 2, 2-dimethylbutyl, 2,3- dimethylbutyl , 3 , 3-dimethylbutyl , n-pentyl, 2-pentyl, 3- pentyl, 2-methylpentyl, 3-methylpentyl , 4-methylpentyl, 2- ethylpentyl, n-hexyl, 2-ethylhexyl, 3-ethylhexyl , 2-hexyl, n- heptyl, 2-heptyl, 3-heptyl, 3-isopropylheptyl , n-octyl, n- nonyl, n-decyl, n-undecyl , 5-methylundecyl , n-dodecyl, 2- methyldodecyl , n-tridecyl, 5-methyltridecyl , n-tetradecyl , n- pentadecyl, n-hexadecyl, 2-methylhexadecyl, n-heptadecyl , 5- isopropylheptadecyl , 4-tert-butyloctadecyl, 5-ethyloctadecyl , 3-isopropyloctadecyl , n-octadecyl, n-nonadecyl, eicosyl. In the sense of the present invention Ci-Cn-alkylene is defined as divalent linear or branched Ci-Cn alkyl group with 1 to n C- atoms . Typical examples of Ci-Cn-alkylenes are methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, n-hexylene, n-heptylene, n- octylene, n-nonylene, n-decylene.
In the sense of the present invention C3-Cn-cycloalkyl is defined as cyclic alkyl group with 3 to n C-atoms, which comprises mono-, bi- and tricyclic alkyl groups. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tert- butylcyclohexyl , trimethylcyclohexyl , cycloheptyl, cyclooctyl, norbornyl, methylnorbornyl , dimethylnorbornyl , bornyl,
isobornyl, 1-adamantyl, 2-adamantyl, menthyl, 2 , 4 , 5-tri-tert- butyl-3-vinylcyclohexyl , 2,3,4, 5-tetra-tert-butylcyclohexyl .
In the sense of the present invention C3-Cn-heterocycloalkyl is defined as cyclic alkyl group with 3 to n C-atoms, which comprises mono-, bi- and tricyclic alkyl groups wherein 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from N, 0 or S . Examples are pyrrolidinyl , piperidinyl, imidazolidinyl , pyrazolidinyl , oxazolidinyl , morpholidinyl , thiazolidinyl , isothiazolidinyl , isoxazolidinyl , piperazinyl, tetrahydrothiophenyl , tetrahydrofuranyl , tetrahydropyranyl , dioxanyl.
In the sense of the present invention C6-Cn-aryl is defined as cyclic aromatic group with 5-n C-atoms, which comprises unsubstituted and substituted aryl groups. Typical examples are phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl,
anthracenyl, phenanthrenyl , napthacenyl .
In the sense of the present invention C6-Cn-arylalkyl is a group which comprises both alkyl groups and aryl groups and contains 6 to n C-atoms in total. This C6-Cn-arylalkyl group can be linked to the molecule carrying this group via any of its carbon atoms. A typical example of C6-Cn-arylalkyl is benzyl . In the sense of the present invention Cs-Cn-heteroaryl is defined as cyclic aromatic group with 5 to n C-atoms wherein 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from N, 0 or S . Typical examples are thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
In the sense of the present invention C3-Cn-cycloalkylene is defined as divalent C3-Cn-cycloalkyl group with 3 to n C-atoms. In the sense of the present invention C6-Cn-arylene is defined as divalent C6-Cn-aryl group with 6 to n C-atoms.
Preferably, R2 and R2' are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, 1- ethylpropyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2- dimethylpropyl , n-butyl, iso-butyl, sec-butyl, tert-butyl, 2- methylbutyl, 3-methylbutyl , n-pentyl, 2-pentyl, 3-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl, anthracenyl, phenanthrenyl , napthacenyl, and benzyl.
Preferably, R3 is selected from the group consisting of butyl, pentyl, cyclohexyl, acetate, propionate, benzoate, versatate, chloride, fluoride, phenyl, methylphenyl , ethylphenyl,
pyridines, pyrimidines, piperidines, carbazoles, imidazoles, pyrrolidones , pyrrolidines, caprolactam, oxolanes, furan, thiophene, thiolane, thiazoles, wherein acetate and propionate are particulary preferred.
Preferably Rx, Rx' , Rx" , Rx"' and Rx"" are each independently selected from the group consisting of methylene, ethylene, n- propylene, isopropylene, n-butylene, isobutylene, tert- butylene, cyclohexylene, wherein ethylene and n-propylene are particularly preferred.
Preferably Ry, Ry' , Ry" , Ry" ' and Ry" " are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1,1- dimethylpropyl , 2, 2-dimethylpropyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, n-pentyl, 2- pentyl, 3-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl, anthracenyl, phenanthrenyl, napthacenyl.
Examples of the aforementioned (meth) acrylates of formula (I) are alkyl (meth) acrylates of straight-chained or branched
aliphatic alcohols having 1 to 40 C atoms, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl (meth) acrylate, 1 , 2-dimethylpropyl (meth) acrylate, 1,1- dimethylpropyl (meth) acrylate, 2 , 2-dimethylpropyl
(meth) acrylate, l-ethyl-2-methylpropyl (meth) acrylate, 1,1,2- trimethylpropyl (meth) acrylate, 1,2,2, trimethylpropyl
(meth) acrylate, n-butyl (meth) acrylate, iso-butyl
(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl
(meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 1-ethylbutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 1-propylbutyl (meth) acrylate, 1,1- dimethylbutyl (meth) acrylate, 1 , 2-dimethylbutyl
(meth) acrylate, 1 , 3-dimethylbutyl (meth) acrylate, 2,2- dimethylbutyl (meth) acrylate, 2 , 3-dimethylbutyl
(meth) acrylate, 3 , 3-dimethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl
(meth) acrylate, 2-methylpentyl (meth) acrylate, 3-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate, 2-ethylpentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl
(meth) acrylate, 3-ethylhexyl (meth) acrylate, 2-hexyl
(meth) acrylate, n-heptyl (meth) acrylate, 2-heptyl
(meth) acrylate, 3-heptyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl
(meth) acrylate, n-decyl (meth) acrylate, n-undecyl
(meth) acrylate, 5-methylundecyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, n-tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl
(meth) acrylate, 2-methylhexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert- butyloctadecyl (meth) acrylate, 5-ethyloctadecyl
(meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, n- octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, eicosyl (meth) acrylate; wherein methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl
(meth) acrylate, 1 , 2-dimethylpropyl (meth) acrylate, 1,1- dimethylpropyl (meth) acrylate, 2 , 2-dimethylpropyl
(meth) acrylate, n-butyl (meth) acrylate, iso-butyl
(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl
(meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-pentyl (meth) acrylate, 2-pentyl
(meth) acrylate, 3-pentyl (meth) acrylate are particulary preferred;
substituted or unsubstituted (meth) acrylates of cycloaliphatic alcohols having 3 to 10 C atoms, such as, cyclopropyl
(meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl
(meth) acrylate, cyclohexyl (meth) acrylate, tert- butylcyclohexyl (meth) acrylate, trimethylcyclohexyl
(meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl
(meth) acrylate, norbornyl (meth) acrylate, methylnorbornyl (meth) acrylate, dimethylnorbornyl (meth) acrylate, bornyl
(meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl
(meth) acrylate, 2-adamantyl (meth) acrylate, menthyl
(meth) acrylate, 2,4, 5-tri-tert-butyl-3-vinylcyclohexyl
(meth) acrylate, 2,3,4, 5-tetra-tert-butylcyclohexyl
(meth) acrylate, wherein cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl
(meth) acrylate are preferred; aryl (meth) acrylates such as, for example, phenyl
(meth) acrylate, tolyl (meth) acrylate, xylyl (meth) acrylate, mesityl (meth) acrylate, which may in each case have
unsubstituted or mono- to tetra-substituted aryl radicals like napthyl (meth) acrylate, fluorenyl (meth) acrylate, anthracenyl (meth) acrylate, phenanthrenyl (meth) acrylate, wherein phenyl (meth) acrylate, tolyl (meth) acrylate, xylyl (meth) acrylate, mesityl (meth) acrylate, napthyl (meth) acrylate, fluorenyl (meth) acrylate, anthracenyl (meth) acrylate, phenanthrenyl (meth) acrylate, and napthacenyl (meth) acrylate are preferred; arylalkyl (meth) acrylates such as, for example, benzyl
(meth) acrylate ; mono (meth) acrylates of ethers, polyethylene glycoles, polypropylene glycoles or mixtures thereof, such as, for example, tetrahydrofurfuryl methacrylate, methoxymethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1- butoxypropyl methacrylate, cyclohexyloxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate,
2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1- ethoxyethyl methacrylate, ethoxymethyl methacrylate,
poly (ethylene glycol) methylether (meth) acrylate and
poly (propylene glycol) methylether (meth) acrylate ; amino-functionalized (meth) acrylates like aminoalkyl
(meth) acrylates , dialkylaminoalkyl (meth) acrylates , or alkylaminoalkyl (meth) acrylates . Preferred more particularly are dimethylaminoalkyl (meth) acrylates and diethylaminoalkyl (meth) arylates , such as, 2-dimethylaminoethyl methacrylate (DMAEMA) , 2-diethylaminoethyl methacrylate (DEAEMA) , 2-tert- butylaminoethyl methacrylate (t-BAEMA) , 2-dimethylaminoethyl acrylate (DMAEA) , 2-diethylaminoethyl acrylate (DEAEA) ;
aminoalkyl (meth) acrylates , such as, 1-aminoethyl
(meth) acrylate, 2-aminoethyl (meth) acrylate, aminomethyl (meth) acrylate .
Preferred (meth) acrylates of formula (I) are linear Ci-Cio- alkyl (meth) acrylates , more preferred are linear Ci-Cs-alkyl (meth) acrylates , wherein methyl (meth) acrylate, ethyl
(meth) acrylate, n-propyl (meth) acrylate and n-butyl
(meth) acrylate are particularly preferred. (Meth) acrylates in the sense of the present invention further include (meth) acrylamides according to formula (II) like monoalkyl (meth) acrylamides , dialkyl (meth) acrylamides and mono- and dialkylaminoalkyl (meth) acrylamides . Preferred more particularly are methacrylamide and acrylamide, N-2-aminoethyl (meth) acrylamide, N, -dimethylaminoethyl (meth) acrylamide, N, -diethylaminoethyl (meth) acrylamide, N-3-aminopropyl
(meth) acrylamide, 3-dimethylaminopropyl methacrylamide
(DMAPMA) , 3-dimethylaminopropyl acrylamide (DMAPA) , 3- diethylaminopropyl (meth) acrylamide, N-methyl
(meth) acrylamide, N-ethyl (meth) acrylamide, N-n-propyl
(meth acrylamide N-isopropyl (meth) acrylamide, N-n-butyl (meth acrylamide N-iso-butyl (meth) acrylamide, N-sec-butyl ((mmeetthh) aaccrryyllaammiiddee , N-tert-butyl (meth) acrylamide, N- (n-pentyl) (meth acrylamide N- (n-hexyl) (meth) acrylamide, N- (n-heptyl (meth acrylamide N- (octyl) (meth) acrylamide, N- (tert-octyl) (meth acrylamide N- (1, 1, 3, 3-tetramethylbutyl )
(meth acrylamide N-3-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth acrylamide N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth acrylamide N-dodecyl (meth) acrylamide, N-tridecyl
(meth acrylamide N-tetradecyl (meth) acrylamide, N-pentadecyl (meth acrylamide N-hexadecyl (meth) acrylamide, N-heptadecyl (meth acrylamide N-octadecyl (meth) acrylamide, N-nonadecyl ((mmeetthh) aaccrryyllaammiiddee, N-eicosyl (meth) acrylamide, N-cyclohexyl (meth acrylamide Ν,Ν-dimethyl (meth) acrylamide, N,N-diethyl (meth acrylamide N, -di-n-propyl (meth) acrylamide, N,N- diisopropyl (meth) acrylamide, N, -di-n-butyl (meth) acrylamide, N, -di-iso-butyl (meth) acrylamide, N, -di-sec-butyl
(meth) acrylamide, N, -di-tert-butyl (meth) acrylamide, N,N-di- cyclohexyl (meth) acrylamide .
Furthermore, these copolymers may have hydroxyl
functionalities in one or more substituent, such as N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2- hydroxypropyl (meth) acrylamide, 2-hydroxybutyl
(meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 3- hydroxybutyl (meth) acrylamide, 4-hydroxybutyl
(meth) acrylamide, 6-hydroxyhexyl (meth) acrylamide, 3-hydroxy- 2-ethylhexyl (meth) acrylamide .
Besides the (meth) acrylates set out above it is possible for the compositions to be polymerized also to contain further unsaturated monomers of formula (III) which are
copolymerizable with aforementioned (meth) acrylates and by means of ATRP (= Atom Transfer Radical Polymerization) . These include, among others,
1-alkenes, such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,
dichlorostyrenes , tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3- vinylpyrrolidine, N-vinylcaprolactam, vinyloxolanes , vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles , and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;
vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.
Particular preference is given to vinyl esters and vinyl ethers. Even more preferred are vinyl acetate and vinyl propionate .
The preferred (meth) acrylic monomers of formula (IV),
respectively, include, among others
acetylamide-ethyl (meth) acrylate,
acetylamide-propyl (meth) acrylate,
propylamide-ethyl (meth) acrylate,
propylamide-propyl (meth) acrylate,
butylamide-ethyl (meth) acrylate,
butylamide-propyl (meth) acrylate . The preferred (meth) acrylic monomers of formula (V) ,
respectively, include, among others,
acetic acid ester-ethyl (meth) acrylamide,
acetic acid ester-propyl (meth) acrylamide,
butanoic acid ester-ethyl (meth) acrylamide,
butanoic acid ester-propyl (meth) acrylamide,
propanoic acid ester-ethyl (meth) acrylamide,
propanoic acid ester-propyl (meth) acrylamide .
The preferred (meth) acrylic monomers of formula (VI),
respectively, include, among others,
acetylamide-ethyl (meth) acrylamide,
acetylamide-propyl (meth) acrylamide,
propylamide-ethyl (meth) acrylamide, butylamide-propyl (meth) acrylamide,
butylamide-ethyl (meth) acrylamide,
propylamide-propyl (meth) acrylamide . The preferred (meth) acrylic monomers of formula (VII), respectively, include, among others,
(meth) acryloyloxy-methyl-methyl ester,
(meth) acryloyloxy-methyl-ethyl ester,
(meth) acryloyloxy-methyl-propyl ester,
(meth) acryloyloxy-methyl-butyl ester,
(meth) acryloyloxy-ethyl-methyl ester,
(meth) acryloyloxy-ethyl-ethyl ester,
(meth) acryloyloxy-ethyl-propyl ester,
(meth) acryloyloxy-ethyl-butyl ester,
(meth) acryloyloxy-propyl-methyl ester,
(meth) acryloyloxy-propyl-ethyl ester,
(meth) acryloyloxy-propyl-propyl ester,
(meth) acryloyloxy-propyl-butyl ester,
(meth) acryloyloxy-butyl-methyl ester,
(meth) acryloyloxy-butyl-ethyl ester,
(meth) acryloyloxy-butyl-propyl ester,
(meth) acryloyloxy-butyl-butyl ester.
The preferred (meth) acrylic monomers of formula (VIII), respectively, include, among others,
(meth) acry1oyloxy-methy1-N-monomethy1amide,
(meth) acry1oyloxy-methy1-N-monoethy1amide,
(meth) acryloyloxy-methy1-N-monopropylamide,
(meth) acryloyloxy-methyl-N-monobutylamide,
(meth) acryloyloxy-ethyl-N-monomethylamide,
(meth) acry1oyloxy-ethy1-N-monoethy1amide,
(meth) acryloyloxy-ethy1-N-monopropylamide,
(meth) acryloyloxy-ethyl-N-monobutylamide,
(meth) acry1oyloxy-propy1-N-monomethy1amide, (meth) acryloyloxy-propyl-N-monoethy1amide,
(meth) acryloyloxy-propyl-N-monopropylamide,
(meth) acryloyloxy-propyl-N-monobutylamide,
(meth) acryloyloxy-butyl-N-monomethylamide,
(meth) acryloyloxy-butyl-N-monoethylamide,
(meth) acryloyloxy-butyl-N-monopropylamide,
(meth) acryloyloxy-butyl-N-monobutylamide .
Particularly preferred monomeric units A are selected from ethyl methacrylate (EMA) , N-isopropyl acrylamide (NIPAM) , vinylacetate (VA) and ethyl acrylate (EA) .
Monomeric unit B is selected from hydroxyl-functionalized (meth) acrylates and monomers co-polymerizable with
(meth) acrylates represented by the group consisting of
compounds of the general formulas IX-XI, wherein the hydroxyl- group is esterified as described later:
Figure imgf000017_0001
(IX) (X) (XI)
wherein
R 1' and R 1' ' are each independently selected from H and methyl R3' is selected from the group consisting of H;
Ci-Cio-alkyl;
C6-Ci4-aryl; C5-Ci4-heteroaryl ;
halide ;
COORz, wherein Rz is selected from the group consisting of methyl and ethyl;
and
Figure imgf000018_0001
wherein n = 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and wherein n = 1 or 2 is preferred and X, X' and X' ' are each a hydroxyl-functionalized linear or branched Ci-Cio-alkyl group. Preferably, X, X' and X' ' are each independently selected from -(CH2)n _OH and -C{ (CH2) n _OH}3, wherein n = 1,2,3,4, or 5.
Preferred hydroxyl-functionalized (meth) acrylates and monomers copolymerizable with (meth) acrylates of formula (IX) are, for example,
mono (meth) acrylates of alkanediols, such as,
2-hydroxyethyl neopentyl glycol mono (meth) acrylate, 2- hydroxypropyl neopentyl glycol mono (meth) acrylate, 3- hydroxypropyl neopentyl glycol mono (meth) acrylate, 3- hydroxybutyl neopentyl glycol mono (meth) acrylate, 4- hydroxybutyl neopentyl glycol mono (meth) acrylate, 6- hydroxyhexyl neopentyl glycol mono (meth) acrylate, 3-hydroxy-2- ethylhexyl neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1 , 5-pentanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate;
(meth) acrylates having a hydroxyl group in the alkyl radical, more particularly 2-hydroxyethyl (meth) acrylate, preferably 2- hydroxyethyl methacrylate (HEMA) , hydroxypropyl
(meth) acrylates , such as 2-hydroxypropyl (meth) acrylate and 3- hydroxypropyl (meth) acrylate, preferably 2-hydroxypropyl methacrylate (HPMA) , hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA) , 3, 4-dihydroxybutyl
(meth) acrylate, 2 , 5-dimethyl-l , 6-hexandiol (meth) acrylate, 1, 10-decandiol (meth) acrylate, glycerol mono (meth) acrylate, and polyalkoxylated derivatives of (meth) acrylic acid,
especially polypropylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6, propylene oxide units, preferably polypropylene glycol monomethacrylate having about 5 propylene oxide units (PPM5) , polyethylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6, ethylene oxide units, preferably polyethylene glycol monomethacrylate having about 5 ethylene oxide units (PEM5) , polybutylene glycol
mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate .
Examples of monomer of formula (X) are the same as those mentioned before according to formula (II) with the proviso that in addition functional group X is present. These include, among others, N-methyl (meth) acrylamide, N-ethyl
(meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-iso-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl (meth) acrylamide, N- (octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide, N- (1,1, 3,3- tetramethylbutyl ) (meth) acrylamide, N-3-ethylhexyl
(meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide .
Preferred are such as N-methylol (meth) acrylamide, 2- hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 2-hydroxybutyl (meth) acrylamide, 3- hydroxypropyl (meth) acrylamide, 3-hydroxybutyl
(meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6- hydroxyhexyl (meth) acrylamide, 3-hydroxy-2-ethylhexyl
(meth) acrylamide .
Examples of monomers of formula (XI) are the same as those mentioned before according to formula (III) with the proviso that in addition functional group X is present. These include, among others,
1-alkenes, such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride ; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,
dichlorostyrenes , tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,
4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3- vinylpyrrolidine, N-vinylcaprolactam, vinyloxolanes ,
vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles , and hydrogenated vinylthiazoles , vinyloxazoles and hydrogenated vinyloxazoles;
vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.
The hydroxyl-group of monomeric unit B is esterified after copolymerisation with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups. The uncharged electron donor is a functional group with coordinative properties to which the catalytically-active metal compound can be bound. Preferably, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from phosphines or nitrogen-containing carbenes (NHC) . More preferably, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor is selected from the group consisting of compounds of the general formulas (XII) -(XV),
Figure imgf000021_0001
(XIV) (XV)
wherein further n = 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4h are each independently selected from the group consisting of Bilinear or branched Ci-C2o-alkyl, preferably linear or branched C3-Cio-alkyl;
C3-Cio-cycloalkyl ;
Figure imgf000022_0001
C6-C2o_arylalkyl
R5 is selected from the group consisting of H;
Ci-C2o-alkyl;
Figure imgf000022_0002
and C5-Ci8-heteroaryl
R6 and R6' are each independently selected from H and Me.
Preferably, R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4h are each
independently selected from the group consisting of H,
isobutyl, cyclohexyl, phenyl and 1-adamantyl.
Preferably, R5 is selected from the group consisting of H and mesityl .
In the context of the present invention an uncharged electron donor is a ligand without net-charge that contributes free electrons or orbitals filled with electrons for a coordinative bond with an acceptor. An acceptor is an atom that accepts the free electrons or electrons from a filled orbital of the donor. Donors are typically main group elements from groups 13-17 of the Periodic Table of Elements, e.g. C, N, P.
Importantly, carbon, too, can act as uncharged electron donor. Mostly found as carbene, wherein the carbon atom bears a pair of electrons in an orbital. These electrons are provided for an uncharged sigma bond with the acceptor atom. Acceptors are typically metal atoms, e.g. Pd(0), Pd(II), Ru (I), Ru(II) . Particularly preferred, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from the group consisting of compounds of formula XII, wherein R4a and R4b are the same and are selected from the group consisting of phenyl, isobutyl, cyclohexyl and
1-adamantyl and n is 1, 2, 3, 4 or 5;
formula XIV, wherein R is H, R5 is mesityl and n is 1, 2, 3, 4 or 5;
and formula XV, wherein R4g and R4h are the same and are selected from the group consisting of 1-adamantyl and phenyl and n is 1, 2, 3, 4 or 5. Preferred monomeric units B are selected from
2-hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, and
2-hydroxybutyl (meth) acrylate,
which may be esterified with one of
3- (diphenylphosphino) -propionic acid
3- (di-l-adamantyl-phosphino) -propionic acid
3- (dicyclohexyl-phosphino) -propionic acid and
3- (di-isobutyl-phosphino) -propionic acid;
and
Tris (hydroxymethyl ) methylacrylamide, which is esterified with
Figure imgf000023_0001
A further class of monomers is presented by monomeric units C, which are cross-linking monomers. These monomers have at least two olefinically unsaturated double bonds possessing similar reactivity in the context of a free-radical polymerization. Free-radically polymerizable, olefinically unsaturated double bonds are, for example, alkenyl groups which arise formally by detaching an H atom from an alkene. These include vinyl (- CH=CH2), 1-propenyl (-CH=CH-CH3) , 2-propenyl (-CH2-CH=CH2) , 1- butenyl (-CH=CH-CH2-CH3) .
Suitable compounds are, for example, (meth) acrylic esters, vinyl esters or allyl esters of at least dihydric alcohols. These compounds include more particularly (meth) acrylates deriving from unsaturated alcohols, such as allyl
(meth) acrylate, vinyl (meth) acrylate and methylallyl
(meth) acrylate, for example;
(meth) acrylates deriving from substituted or unsubstituted diols, such as, 1 , 2-ethanediol di (meth) acrylate, 1,2- propanediol di (meth) acrylate, 1 , 3-propanediol
di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,2- butanediol di (meth) acrylate, 1 , 3-butanediol di (meth) acrylate, 2 , 3-butanediol di (meth) acrylate, 1 , 4-butanediol
di (meth) acrylate, 1 , 2-pentanediol di (meth) acrylate, 1,5- pentanediol di (meth) acrylate, 1 , 2-hexanediol di (meth) acrylte, 1 , 6-hexanediol di (meth) acrylate, 1, 10-decanediol
di (meth) acrylate, 1 , 2-dodecanediol di (meth) acrylate, 1,12- dodecandediol di (meth) acrylate, or higher polyfunctional alcohols, such as, for example, glycol di (meth) acrylates , such as ethylene glycol di (meth) acrylate, diethylene glycol
di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate, glycerol
di (meth) acrylate, diurethane dimethacrylate and methylene bisacrylamide ;
(meth) acrylates having three or more double bonds, such as glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate;
di- or polyvinyl compounds like triallylcyanurate,
divinylbenzenes , N, N' -divinylethylene urea;
divinylether of polyhydroxy compounds like butanediol-bis- vinylether, hexanediol-bis-vinylether , trimethylol- propanetrivinylether , pentaerythrit-tetra-vinylether .
Preferred cross-linking monomers are selected from the following group:
allyl (meth) acrylate, vinyl (meth) acrylate and methylallyl (meth) acrylate, divinylbenzenes, glycol di (meth) acrylates , Ν,Ν' -methylene-bisacrylamide, bis (2-methacryloyl) oxyethyl disulfide .
More preferably, cross-linking monomers are selected from the following group:
ethylene glycol dimethacrylate (XVI),
N, N' - ( 1 , 2-dihydroxyethylene) bis-acrylamide (XVI I )
p-divinylbenzene (XVIII),
N, N' -methylene-bisacrylamide (XIX), and
bis (2-methacryloyl) oxyethyl disulfide (XX) .
Figure imgf000025_0001
(XIX) (XX)
Catalytically-active metal compounds are metals, metal complexes or metal salts of elements of groups 6-11 of the Periodic Table of the Elements. Preferably, the catalytically- active metal compound contains a metal selected from the group consisting of Pd, Rh, Ru, Pt, Ir, Cu, Ni and Fe, wherein Pd, Rh and Ru are particularly preferred.
Preferred metal complexes are
[Pd (allyl) CI] 2 and
[Rh(cod)2]BF4,
In the present invention, the above-mentioned monomeric units A and B and cross-linking monomeric units C can arbitrarily and effectively be combined or co-polymerized to obtain an optionally cross-linked polymer, having a critical solution temperature and required stability and mechanical properties.
Particularly suitable are specific amounts of monomeric units A, B and cross-linking monomeric units C.
Monomeric unit A is present in the polymer in a range from 50 wt-% - 99.9 wt-%, preferably 80 wt-% - 99.9 wt-%, more
preferably 80 wt-% - 99.5 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit A is present in a range from 50 wt-% - 99.8 wt-%, preferably 80 wt-% - 99.5 wt-%, more preferably 90 wt-% - 97 wt-%.
Monomeric unit B is present in the polymer in a range from 0.1 wt-% - 50 wt-%, preferably 0.1 wt-% - 20 wt-%, more preferably 0.5 wt-% - 20 wt-%, most preferably 1 wt-% - 10 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit B is present in a range from 0.1 wt-% - 30 wt-%, preferably 0.1 wt-% - 10 wt-%, and most preferably 1 wt-% - 5 wt-%.
Monomeric unit C is present in the polymer in a range from 0 wt-% - 30 wt-%, more preferably 0.1 wt-% - 20 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit C is present in a range from 0.1 wt-%
- 20 wt-%, preferably 1 wt-% - 5 wt-%, more preferably 1 wt-%
- 3 wt-%. The following specific combinations are particularly
preferred .
Table 1: Specific compositions of monomeric units.
Figure imgf000027_0001
According to the present invention, for specific compositions of polymers in table 1, preferably, the monomeric units are selected as presented in table 2. Table 2: Specific combinations of monomeric units.
Precursor of Mononitrogen / meric monomeric unit A monomeric unit B
phosphorous unit compound C
EMA [a] [e] -
EMA [b] [e] -
EMA [c] [e] -
EMA [a] [f] -
EMA [b] [f] -
EMA [c] [f] -
EMA [a] [g] -
EMA [b] [g] -
EMA [c] [g] -
EMA [a] [h] -
EMA [b] [h] -
EMA [c] [h] -
EMA [d] -
NIPAM [a] [e] -
NIPAM [b] [e] -
NIPAM [c] [e] -
NIPAM [a] [f] -
NIPAM [b] [f] -
NIPAM [c] [f] -
NIPAM [a] [g] -
NIPAM [b] [g] -
NIPAM [c] [g] -
NIPAM [a] [h] -
NIPAM [b] [h] -
NIPAM [c] [h] -
NIPAM [d] -
VA [a] [e] -
VA [b] [e] -
VA [c] [e] -
VA [a] [f] -
VA [b] [f] -
VA [c] [f] -
VA [a] [g] -
VA [b] [g] -
VA [c] [g] -
VA [a] [h] -
VA [b] [h] - VA [ C ] [h] -
VA [d] -
EA [a] [e] -
EA [b] [e] -
EA [c] [e] -
EA [a] [f] -
EA [b] [f] -
EA [c] [f] -
EA [a] [g] -
EA [b] [g] -
EA [c] [g] -
EA [a] [h] -
EA [b] [h] -
EA [c] [h] -
EA [d] -
EMA [a] [e] XVI
EMA [b] [e] XVI
EMA [c] [e] XVI
EMA [a] [f] XVI
EMA [b] [f] XVI
EMA [c] [f] XVI
EMA [a] [g] XVI
EMA [b] [g] XVI
EMA [c] [g] XVI
EMA [a] [h] XVI
EMA [b] [h] XVI
EMA [c] [h] XVI
EMA [d] XVI
NIPAM [a] [e] XVI
NIPAM [b] [e] XVI
NIPAM [c] [e] XVI
NIPAM [a] [f] XVI
NIPAM [b] [f] XVI
NIPAM [c] [f] XVI
NIPAM [a] [g] XVI
NIPAM [b] [g] XVI
NIPAM [c] [g] XVI
NIPAM [a] [h] XVI
NIPAM [b] [h] XVI NIPAM [ C ] [h] XVI
NIPAM [d] XVI
VA [a] [e] XVI
VA [b] [e] XVI
VA [c] [e] XVI
VA [a] [f] XVI
VA [b] [f] XVI
VA [c] [f] XVI
VA [a] [g] XVI
VA [b] [g] XVI
VA [c] [g] XVI
VA [a] [h] XVI
VA [b] [h] XVI
VA [c] [h] XVI
VA [d] XVI
EA [a] [e] XVI
EA [b] [e] XVI
EA [c] [e] XVI
EA [a] [f] XVI
EA [b] [f] XVI
EA [c] [f] XVI
EA [a] [g] XVI
EA [b] [g] XVI
EA [c] [g] XVI
EA [a] [h] XVI
EA [b] [h] XVI
EA [c] [h] XVI
EA [d] XVI
EMA [a] [e] XVII
EMA [b] [e] XVII
EMA [c] [e] XVII
EMA [a] [f] XVII
EMA [b] [f] XVII
EMA [c] [f] XVII
EMA [a] [g] XVII
EMA [b] [g] XVII
EMA [c] [g] XVII
EMA [a] [h] XVII
EMA [b] [h] XVII EMA [ C ] [h] XVII
EMA [d] XVII
NIPAM [a] [e] XVII
NIPAM [b] [e] XVII
NIPAM [c] [e] XVII
NIPAM [a] [f] XVII
NIPAM [b] [f] XVII
NIPAM [c] [f] XVII
NIPAM [a] [g] XVII
NIPAM [b] [g] XVII
NIPAM [c] [g] XVII
NIPAM [a] [h] XVII
NIPAM [b] [h] XVII
NIPAM [c] [h] XVII
NIPAM [d] XVII
VA [a] [e] XVII
VA [b] [e] XVII
VA [c] [e] XVII
VA [a] [f] XVII
VA [b] [f] XVII
VA [c] [f] XVII
VA [a] [g] XVII
VA [b] [g] XVII
VA [c] [g] XVII
VA [a] [h] XVII
VA [b] [h] XVII
VA [c] [h] XVII
VA [d] XVII
EA [a] [e] XVII
EA [b] [e] XVII
EA [c] [e] XVII
EA [a] [f] XVII
EA [b] [f] XVII
EA [c] [f] XVII
EA [a] [g] XVII
EA [b] [g] XVII
EA [c] [g] XVII
EA [a] [h] XVII
EA [b] [h] XVII EA [C] [h] XVII
EA [d] XVII
EMA [a] [e] XVIII
EMA [b] [e] XVIII
EMA [c] [e] XVIII
EMA [a] [f] XVIII
EMA [b] [f] XVIII
EMA [c] [f] XVIII
EMA [a] [g] XVIII
EMA [b] [g] XVIII
EMA [c] [g] XVIII
EMA [a] [h] XVIII
EMA [b] [h] XVIII
EMA [c] [h] XVIII
EMA [d] XVIII
NIPAM [a] [e] XVIII
NIPAM [b] [e] XVIII
NIPAM [c] [e] XVIII
NIPAM [a] [f] XVIII
NIPAM [b] [f] XVIII
NIPAM [c] [f] XVIII
NIPAM [a] [g] XVIII
NIPAM [b] [g] XVIII
NIPAM [c] [g] XVIII
NIPAM [a] [h] XVIII
NIPAM [b] [h] XVIII
NIPAM [c] [h] XVIII
NIPAM [d] XVIII
VA [a] [e] XVIII
VA [b] [e] XVIII
VA [c] [e] XVIII
VA [a] [f] XVIII
VA [b] [f] XVIII
VA [c] [f] XVIII
VA [a] [g] XVIII
VA [b] [g] XVIII
VA [c] [g] XVIII
VA [a] [h] XVIII
VA [b] [h] XVIII VA [ C ] [h] XVIII
VA [d] XVIII
EA [a] [e] XVIII
EA [b] [e] XVIII
EA [c] [e] XVIII
EA [a] [f] XVIII
EA [b] [f] XVIII
EA [c] [f] XVIII
EA [a] [g] XVIII
EA [b] [g] XVIII
EA [c] [g] XVIII
EA [a] [h] XVIII
EA [b] [h] XVIII
EA [c] [h] XVIII
EA [d] XVIII
EMA [a] [e] XIX
EMA [b] [e] XIX
EMA [c] [e] XIX
EMA [a] [f] XIX
EMA [b] [f] XIX
EMA [c] [f] XIX
EMA [a] [g] XIX
EMA [b] [g] XIX
EMA [c] [g] XIX
EMA [a] [h] XIX
EMA [b] [h] XIX
EMA [c] [h] XIX
EMA [d] XIX
NIPAM [a] [e] XIX
NIPAM [b] [e] XIX
NIPAM [c] [e] XIX
NIPAM [a] [f] XIX
NIPAM [b] [f] XIX
NIPAM [c] [f] XIX
NIPAM [a] [g] XIX
NIPAM [b] [g] XIX
NIPAM [c] [g] XIX
NIPAM [a] [h] XIX
NIPAM [b] [h] XIX IPAM [C] [h] XIX
NIPAM [d] XIX
VA [a] [e] XIX
VA [b] [e] XIX
VA [c] [e] XIX
VA [a] [f] XIX
VA [b] [f] XIX
VA [c] [f] XIX
VA [a] [g] XIX
VA [b] [g] XIX
VA [c] [g] XIX
VA [a] [h] XIX
VA [b] [h] XIX
VA [c] [h] XIX
VA [d] XIX
EA [a] [e] XIX
EA [b] [e] XIX
EA [c] [e] XIX
EA [a] [f] XIX
EA [b] [f] XIX
EA [c] [f] XIX
EA [a] [g] XIX
EA [b] [g] XIX
EA [c] [g] XIX
EA [a] [h] XIX
EA [b] [h] XIX
EA [c] [h] XIX
EA [d] XIX
EA = ethylacrylate, EMA = ethylmethacrylate, VA =
vinylacetate , NIPAM = N-isopropylacrylamide, [a] = 2-hydroxyethyl (meth) acrylate, [b] = 2-hydroxypropyl (meth) acrylate, [c] = 2- hydroxybutyl (meth) acrylate, [d] = Tris (hydroxymethyl)
methacrylamide , [e] = 3- (diphenyl-phosphino ) -propionic acid, [f] = 3- (di-l-adamantyl-phosphino) -propionic acid, [g] = 3- (dicyclohexyl- phosphino) -propionic acid, [h] = 3- (di-isobutyl-phosphino ) -propionic acid Furthermore, the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B, and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
In a special embodiment of the present invention the catalyst comprises
(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B, and 0 wt-% - 30 wt-% of one unit derived from a cross-linking monomeric unit C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
Furthermore, the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
In a special embodiment of the present invention the catalyst comprises
(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, and 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
Furthermore, the invention provides a catalyst comprising
(a) a polymer, which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;
wherein the critical solution temperature Tc of the polymer in solvent x is in a range of from -10°C to +150°C, wherein solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol , n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene .
The critical solution temperature Tc of the polymers is measured at standard ambient temperature and pressure (SATP conditions: T = 298.15 K, p = 1013 hPa) via UV-VIS
spectroscopy in cuvettes which can be heated and cooled by a cryostatic temperature regulator. The polymer is suspended in a solvent at an amount of 1 wt-%, transferred to a cuvette, placed in the UV-Vis spectrometer and heated until a clear solution occurs. This temperature is defined as starting temperature Tstart-
Then the solution is cooled and the transmission of the solution is measured at a wavelength of 500nm against pure solvent in intervals of 30 sec. The critical solution
temperature can be determined graphically based on the plot of transmittance versus temperature. Hereby, the slope of the transmission-temperature-plot is determined at Tstart- A
straight line (Li) which passes this starting point and exhibits the respective slope (tangent at Tstart) is
extrapolated to the lower temperature range. In a second step, the slope is determined at the turning point of the
transmission-temperature-plot, which corresponds to the maximum absolute value of slope of this curve. A straight line (L2) which passes this turning point and exhibits the
respective slope (tangent at turning point) is extrapolated to the higher temperature range. The point of intersection of lines Li and L2 is defined as the critical solution temperature Tc of the polymer. The critical solution temperature can be measured in different organic solvents. Suitable solvents are methanol, ethanol, n- propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene.
Preferably methanol, isopropanol, n-butanol and toluene are used. The critical solution temperature in at least one of these solvents is in a range from -10°C to +150°C, preferably the critical solution temperature in at least one of these solvents is in a range of from -10°C to +100°C, more
preferably the critical solution temperature in at least one of these solvents is in a range of from -10°C to +70°C, suitably preferred is a critical solution temperature in at least one of these solvents in a range of from +5°C to +50°C.
Polymers with a critical solution temperature are called temperature-responsive polymers. Temperature-responsive polymers, which are precipitable by increase or decrease of temperature, are well known (I. Dimitrov, B. Trzebicka, A. H. E. Muller, A. Dworak, C. B. Tsvetanov, Prog. Polym. Sci. 2007, 32,1275-1343; R. Pelton, Adv Coll Interface Sci 2000, 85,1; J. K. Oh, R. Drumright, D. J. Siegwart, K. Matyj aszewski, Prog. Polym. Sci. 2008, 33, 448-477; T. J. Freemont, B. R. Saunders, Soft Matter, 2008, 4, 919-924; S. Nayak, L.A. Lyon Angew. Chem. Int. Ed. 2005, 44, 7686-7708) .
They can be divided into polymers with upper critical solution temperature (UCST) and polymers with lower critical solution temperature (LCST) . A polymer with an UCST forms a colloidal solution with a solvent above this critical temperature but precipitates below the critical temperature. A polymer with a LCST forms a homogeneous solution with a solvent below the critical temperature but precipitates above this critical temperature . The afore-mentioned temperature-responsive polymers could furthermore be part of so-called microgels due to cross- linking of the monomers. According to Funke et al . microgels are intramolecularly cross-linked macromolecules of colloidal dimensions which are dispersed in normal or colloidal
solutions, in which, depending on the degree of cross-linking and on the nature of the solvent, they are more or less swollen (Funke et al . , Microgels - Intramolecularly
Crosslinked Macromolecules with Globular Structure, Adv.
Polym. Sci. 1998, 139) . The cross-linking is achieved by applying ternary copolymerization of non-functionalized monomers, functionalized monomers and cross-linking monomers in very diluted solutions with the monomer concentration below a critical value. Under these conditions, microgels do not react intermolecularly to build an insoluble polymer network, but intramolecularly to yield a stable solution. The critical monomer concentration is dependent on the type of monomer, the degree of cross-linking, the solvent and the polymerization conditions. The resulting microgel also exhibits temperature- responsive properties. Techniques for the preparation of microgels, surface modification and applications of microgels are well known to the person skilled in the art from the afore-mentioned review article of Funke et al ..
The advantage of microgels over linear polymers is their low viscosity even in solutions with high solid concentration and at low temperatures, which provides the opportunity to apply the microgel-based catalyst in high concentrations.
Furthermore, due to the structure of microgels, the
catalytically-active metal compound is localized at the surface of the microgel particles. This provides a better accessibility of the catalytically-active metal compounds and can lead to as high catalytic activity as conventional
homogeneous catalysts.
In addition, the intramolecular cross-linking provides a high structural stability of the colloids, which is a requirement for their application as recyclable catalyst or catalyst support .
Furthermore, the invention provides a catalyst comprising
(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from the group
consisting of ethyl methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) ;
wherein monomeric units B are selected from the group
consisting of 2-hydroxyethyl (meth) acrylate esterified with 3- (diphenyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid, 2-hydroxypropyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid, and
Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane ; and
wherein cross-linking monomeric units C are selected from the roup consisting of compounds of formulas XVI-XX
Figure imgf000042_0001
(xix) (xx)
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer. Furthermore, the invention provides a catalyst comprising
(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;
wherein further the catalytically-active metal compound comprises a metal selected from the group consisting of Pd, Ru, Pt, Ir, Cu, Ni and Fe .
Furthermore, the invention provides a catalyst comprising
(a) a polymer, which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;
wherein further the precursor of phosphorous and/or nitrogen containing uncharged electron donor is selected from
phosphines and N-heterocyclic carbenes.
Furthermore, the invention provides a process for producing a catalyst, comprising the steps
(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,
(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,
(c) reacting the resulting polymer with a catalytically-active metal compound, and
(d) separating the resulting catalyst from the reaction mixture .
Furthermore, the invention provides a process for producing a catalyst, comprising the steps
(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,
(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,
(c) reacting the resulting polymer with a catalytically-active metal compound, and (d) separating the resulting catalyst from the reaction mixture ;
wherein the catalytically-active metal compound comprises a metal selected from Pd, Rh, Ru, Pt, Co, Cu, Ni and Fe .
Furthermore, the invention provides a catalyst obtainable by a process comprising the steps
(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,
(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,
(c) reacting the resulting polymer with a catalytically-active metal compound, and
(d) separating the resulting catalyst from the reaction mixture .
The polymers according to the invention may be obtained in particular by solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, it being possible to achieve surprising advantages by means of a radical solution polymerization. These methods are set out in Ullmann' s Encyclopedia of Industrial Chemistry, Sixth Edition.
As well as methods of conventional radical polymerization it is also possible to employ related methods of controlled radical polymerization, such as, for example, ATRP (= Atom Transfer Radical Polymerization) , NMP (Nitroxide-mediated Polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer) .
References describing typical free radical polymerization include Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition. For such polymerization, generally speaking, a polymerization initiator and also, optionally, a molecular- weight-regulating chain-transfer agent are employed. The initiators which can be used include, among others, the azo initiators that are widely known in the art, such as
Azobisisobutyronitrile (AIBN) and 1,1-
Azobiscyclohexanecarbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert- butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, tert- butylperoxy-2-ethylhexanoate, tert-butylperoxy-3 , 5 , 5- trimethylhexanoate, dicumyl peroxide, 1,1 bis (tert
butylperoxy) cyclohexane, 1,1 bis (tert butylperoxy) -3 , 3 , 5- trimethylcyclohexane, cumyl hydroperoxide, tert-butyl
hydroperoxide, bis (4 tert butylcyclohexyl ) peroxydicarbonate, mixtures of two or more of the aforementioned compounds with one another, and mixtures of the aforementioned compounds with nonspecified compounds that may likewise form free radicals.
The stated initiators may be used either individually or in a mixture. They are used in an amount of 0.01 mol-% to 10.0 mol- %, preferably 0.1 mol-% to 5 mol-%, more preferably 0.5 mol-% to 2 mol-% based on the total weight of the monomers. It is also possible with preference to carry out the polymerization using a mixture of different polymerization initiators having different half-lives.
The polymerization can be carried out under atmospheric, subatmospheric or superatmospheric pressure. The
polymerization temperature as well is not critical. Generally speaking, however, it is in the range of -20°C - +200°C, preferably +50°C - +150°C and more preferably +70°C - +130°C.
The polymerization can be carried out with or without solvent. The term "solvent" should be understood widely in this
context. The preferred solvents include, in particular, aromatic hydrocarbons, such as toluene, xylene; esters, especially acetates, preferably butyl acetate, ethyl acetate, propyl acetate; ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone ; alcohols, especially methanol, isopropanol, n-butanol, isobutanol;
ethers, especially glycol monomethyl ethers, glycol monoethyl ethers, glycol monobutyl ethers; aliphatics, preferably pentane, hexane, cycloalkanes and substituted cycloalkanes , such as cyclohexane; mixtures of aliphatics and/or aromatics, preferably naphtha; benzine, biodiesel; tetrahydrofuran, dichloromethane ; but also plasticizers such as low molecular weight polypropylene glycols or phthalates. The stated
solvents may be used individually or as a mixture.
Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B. Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one non-functionalized monomeric unit A, 0.1 wt-% - 30 wt-% of units derived from one monomeric unit B, and 0.1 wt-% - 20 wt-% of units derived from one cross-linking
monomeric unit C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B.
Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B; wherein the critical solution temperature of the polymer at room
temperature in at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene is in a range of from -10°C to +150°C.
Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from the group
consisting of ethyl methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) ;
wherein monomeric units B are selected from the group
consisting of
2-hydroxyethyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid, 2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid, and
Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane ;
and wherein cross-linking monomeric units C are selected from the roup consisting of compounds according to formulas XVI-XX
Figure imgf000050_0001
(XIX) (XX)
Furthermore, the invention relates to a process for producing the polymer, comprising the steps (a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,
(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor, and
(c) separating the resulting polymer from the reaction mixture . Furthermore, the invention relates to a polymer obtainable by a process comprising the steps
(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,
(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor, and
(c) separating the resulting polymer from the reaction mixture .
Furthermore, the invention relates to the use of the catalyst in homogeneous and/or heterogeneous catalysis. Preferred catalytic reactions are ring closing metathesis (RCM) ;
hydroformylation; C-X or C-C coupling reactions, e.g.
Mizoroki-Heck-coupling, Suzuki-Miyaura-coupling; and
hydrogenation reactions, e.g. hydrogenation of C-C double bonds, nitro groups, carbonyl groups, nitril groups, ketones, imines, arenes, heterocycles .
Figure imgf000052_0001
Figure imgf000053_0001
Molecular weight of polymer
The (meth) acrylate polymer of the invention has a weight- average molecular weight in the range of from 1000 g/mol to 100000 g/mol, preferably of from 10000 g/mol to 60000 g/mol, more preferably in the range of from 15000 to 40000 g/mol. The number-average molecular weight of preferred (meth) acrylate polymers is in the range of from 1000 g/mol to 60 000 g/mol, more preferably in the range of from 3000 g/mol to 25 000 g/mol. Also of particular interest are (meth) acrylate polymers which have a polydispersity index, Mw/Mn, in the range of from 1 to 10, more preferably in the range of from 1.5 to 7 and very preferably of from 1.7 to 3. The molecular weight can be determined by means of gel permeation chromatography (GPC) against a PMMA standard.
Determination of molecular weight
The molecular weight was determined via GPC. GPC columns from the manufacturer Varian/Polymer Laboratories were used, arranged in series with the pore sizes 105, 106, 104 and 103 A. The individual columns were 300 mm long and had a diameter of 7.5 mm. A polymer solution was prepared with an initial concentration of 2.5 g of polymer per litre of solvent. THF was used as eluent, and a flow rate of 1 ml/min was operated. The injection volume was 100 μΐ . The column oven is
conditioned to 35°C. Detection took place using the RI 150 detector from Thermo Electron. The data were evaluated using the WinGPC program from Polymerstandard-Service (PSS) . Mw denotes the weight-average molecular weight, D the
polydispersity index (D = Mw/Mn, Mn = number-average molecular weight) . Examples
1. Preparation of Copolymers a) EA/HEMA (95:5)
Figure imgf000055_0001
Figure imgf000055_0002
PROCEDURE :
20.024 g (200.00 mmol) ethylacrylate and 1.370 g (10.53 mmol) 2-hydroxyethyl methacrylate are dissolved in 200 mL abs . THF. Afterwares 173 mg (1.05 mmol) azobis ( isobutyronitril ) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min 2 bubbling) . An oil bath is heated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.
The cooled reaction mixture is diluted with 200 mL THF and added dropwise to 2000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo. b) EA/THMA (95:5)
Figure imgf000056_0001
Figure imgf000056_0002
PROCEDURE :
10.012 g (100.00 mmol) ethylacrylate and 922 mg (5.26 mmol) tris (hydroxymethyl) methylacrylamide are dissolved in 100 mL abs . THF. Afterwards 86 mg (0.53 mmol) azobis ( isobutyronitril ) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min N2 bubbling) . An oil bath is heated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.
The cooled reaction mixture is diluted with 100 mL THF and added dropwise to 1000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo. c) VAc/HEMA (95:5)
Figure imgf000057_0001
Figure imgf000057_0002
PROCEDURE :
17218 mg (200.00 mmol) vinyl acetate and 1370 mg (10.52 mmol) 2-hydroxyethyl methacrylate are dissolved in 150 mL THF.
Afterwards 172 mg (1.06 mmol) azobis (isobutyronitrile) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min N2 bubbling) . An oil bath is preheated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.
The cooled reaction mixture is diluted with 100 mL THF and added dropwise to 1000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.
2. Esterification of Copolymers a) EA-HEMA-COO-Et-PPh2 (95:5)
Figure imgf000058_0001
Figure imgf000058_0002
PROCEDURE :
10697 mg (5.26 mmol hydroxy-funcionalities ) ethylacrylate/ 2- hydroxyethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 100 mL abs . DCM. Afterwards 1086 mg (5.26 mmol) dicyclohexylcarbodiimide (DCC), 129 mg (1.05 mmol) 4- (N, -Dimethylamino) pyridine (DMAP) and portionwise 1359 mg (5.26 mmol) 3- (diphenylphosphino) propionic acid are added and the reaction mixture is stirred for 16 h at room temperature.
The reaction mixture is cooled to 0 °C and the white precipitate is removed by filtration. The filtrate is evaporated in vacuo and purified by flash column chromatography using silica as stationary phase and DCM as eluent .
b) EA-THMA-Si-Pr-PAd2 (95:5)
Figure imgf000059_0001
M n
starting materials eq m [g]
[g/mol] [mmo1 ]
Ad2PH 302.43 30.00 1.0 9.07
(MeO) 3Si-Pr-I 290.17 39.00 1.3 11.32
PROCEDURE :
Under argon atmosphere 9.07 g (30.00 mmol) di-(l- adamantyl ) phosphine are dissolved in xylene , 11.32 g (39.00 mmol) ( 3-iodopropyl ) trimethoxysilane are added dropwise and the reaction mixture is refluxed for 20 h. The white precipitate is removed by filtration. The filter cake is washed with diethylether and dried in high vacuo.
YIELD :
17.0479 (98%), white solid
c) VAc-HEMA-COO-Et-PPh2 (95:5)
Figure imgf000059_0002
M m starting materials n [mmo1 ] eq
[g/mol] [mg] copolymer VAc HEMA 95:5 (88.29) OH: 1.0 1.0 1766
3- (diphenylphosphino) propionic
258.25 1.0 1.0 258 acid
DCC 206.33 1.0 1.0 206
DMAP 122.17 0.1 0.1 12
PROCEDURE :
1766 mg (1.00 mmol hydroxy-funcionalities ) vinyl acetate / 2- hydroxyethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 20 mL abs . DCM. Afterwards 206 mg (1.00 mmol) dicyclohexylcarbodiimide (DCC), 12 mg (0.10 mmol) 4- (N, W-Dimethylamino) pyridine (DMAP) and portionwise 258 mg (1.00 mmol) 3- (diphenylphosphino) propionic acid are added and the reaction mixture is stirred for 16 h at room temperature.
The reaction mixture is cooled to 0 °C and the white
precipitate is removed by filtration. The filtrate is
evaporated in vacuo and purified by flash column
chromatography using silica as stationary phase and DCM as eluent.
3. Metal complexes a) Pd-complex of EA-HEMA-COQ-Et-PPh2 (95:5)
Figure imgf000061_0001
starting
M [g/mol] n [mmo1 ] eq m [mg] materials
EA-HEMA-COO-Et-
(113.63) P : 1.0 1.0 2273 PPh2 (95:5)
[Pd(allyl)Cl]2 365.89 0.5 0.5 183
PROCEDURE :
Under argon atmosphere 2273 mg (1.0 mmol phosphine- functionalities ) ethylacrylate/ 2- ( (3- (diphenylphosphino) - propanoyl ) oxy) ethyl methacrylate copolymer (95:5) are
dissolved in 50 mL abs . dichloromethane (DCM) . Afterwards a solution of 183 mg (0.5 mmol) allylpalladium ( I I ) chloride-dimer in 10 mL abs. DCM is slowly added dropwise to the polymer solution. The reaction mixture is stirred for 2 h at room temperature .
The reaction mixture is concentrated in vacuo to ca. 5 mL . 50 mL hexane are added and the mixture is stirred for 2 h, wherein the polymer precipitates as yellow oily substance. Hexane is decanted and excessive hexane is removed in high vacuo . b) Rh-complex of EA / HEMA-COQ-Et-PPh2 (95:5)
Figure imgf000062_0001
PROCEDURE :
In a glovebox under argon atmosphere 1136 mg (0.5 mmol phosphine-functionalities ) ethylacrylate / 2- ( (3- (diphenylphosphino) -propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved in a mixture of 20 mL abs . DCM.
Afterwards a solution of 102 mg (0.25 mmol) bis (1,5- cyclooctadien) rhodium ( I ) tetrafluoroborate in 5 mL abs. DCM is slowly added dropwise to the polymer solution. The reaction mixture is stirred for 1 h at room temperature.
The reaction mixture is concentrated in vacuo to ca. 5 mL . 30 mL diethylether are added and the mixture is stirred for 2 h, wherein the polymer precipitates as orange oily substance. Diethylether is decanted and excessive diethylether is removed in high vacuo.
c) Pd-complex of VAc-HEMA-COO-Et-PPh2 (95:5)
Figure imgf000063_0001
Figure imgf000063_0002
PROCEDURE :
100 mg (0.05 mmol phosphine-funcionalities ) vinyl acetate / 2- ( (3- (diphenylphosphino) propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 10 mL abs. DCM. Afterwards 9 mg (0.025 mmol)
allylpalladium ( I I ) chloride-dimer are added and the reaction mixture is stirred for 2 h at room temperature.
The reaction mixture is added dropwise to 100 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.
d) Rh-complex of VAc-HEMA-COO-Et-PPh2
Figure imgf000064_0001
m starting materials M [g/mol] n [mmo1 ] eq
[mg]
VAc-HEMA-COO-Et-PPh2
(100.30) P: 0.05 1.0 100 (95:5)
Rh (cod) 2BF4 406.07 0.025 0.5 10
PROCEDURE :
In a glovebox under argon atmosphere 100 mg (0.05 mmol
phosphine-functionalities ) vinyl acetate / 2- ( (3- (diphenylphosphino) propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved in 10 mL abs . DCM. Afterwards a solution of 10 mg (0.025 mmol) bis ( 1 , 5-cyclooctadien) rhodium ( I )
tetrafluoroborate in 2 mL abs. DCM is slowly added to the polymer solution. The reaction mixture is stirred for 1 h at room temperature.
The reaction mixture is concentrated to ca. 2 mL and 10 mL abs. diethylether are added. The mixture is stirred for 2 h, which leads to the formation of an orange precipitate of the polymer. Excessive diethylether is decanted and the polymer dried in vacuo.
Catalytic activity Example 1
Catalytic activity of Pd-complexes linked with temperature- responsive polymers and microgel particles, respectively, has been proven for Mizoroki-Heck cross coupling. To exclude
Palladium leaching out of the polymer complexes, which might catalyze the reaction as well, a "blind" test has been
performed adding only [Pd (allyl) CI] 2 into the reaction mixture without any phosphine ligand (table 3, entry 1) . This
experiment shows that [Pd (allyl) CI] 2 alone has negligible activity .
In presence of the phosphine-functionalized polymer there is significant catalytic activity, which shows in-situ
interaction between the Pd complex and the phosphine-polymer entities (entry 2) . If the pre-formed Pd-phosphine-polymer catalyst is applied (entry 3) , the catalytic activity becomes even higher indicating that a tight interaction between Pd and phosphine is a prerequisite for catalytic conversion. For the more reactive iodide analogue (entry 4-5) even higher
catalytic activity for the Pd-phosphine-polymer catalyst has been observed compared to the experiments with phenyl bromide.
Mizoroki-Heck coupling
Figure imgf000065_0001
solvent Table 3: Catalytic results for Mizoroki-Heck coupling using EA-HEMA-COO-Et-PPh2 (95:5) - Pd(allyl)Cl2 adduct
Figure imgf000066_0001
Example 2
An additional catalytic reaction (hydrogenation of cinnamic acid) has been performed applying Rhodium immobilized polymer catalyst (Ethyl acrylate / 2- ( (3- (diphenyl-phosphino)
propanoyl) oxy) ethyl methacrylate copolymer (5 mol-%) - Rhodium (cyclooctadiene) tetrafluoroborate adduct) in different alcoholic solvents which are related to different UCST values (see table 4) . Results are summarized in table 4. Hydrogenation of cinnamic acid
Figure imgf000067_0001
solvent
Table 4: Catalytic results for hydrogenation of cinnamic acid using EA-HEMA-COQ-Et-PPh2 (95:5) - Rh(cod)2BF4 adduct
Figure imgf000067_0002
The catalytic reaction tests have been performed at two different temperature levels a) a low temperature-level with T = 5°C < UCST and b) the high-temperature level T = 35°C > UCST (compare table 4) .
From table 4, it is evident that for the low-temperature level where the catalyst is in its precipitated state, only low TOF values are achieved whereas the switch to the dissolved catalyst state (reaction temperature 35°C) raises the catalyst activity significantly. For the hydrogenation of cinnamic acid, the order of magnitude of activity is even higher than that of conventional precious metal powder catalysts which are usually applied for this type of application (TOF = 30 h-1 to 400 h-1) . High activity may also be the reason for the partial ring-hydrogenation with
formation of 3-cyclohexyl propionic acid which has been observed as side product (table 4) .

Claims

Catalyst comprising
a polymer, which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;
wherein monomeric units A are selected from
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates;
wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co- polymerizable with (meth) acrylates , which are
esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,
and a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.
Catalyst according to claim 1, wherein the polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B, and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C. Catalyst according to claim 1, wherein the polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A and 0.1 wt- % - 50 wt-% of units derived from one or more monomeric units B.
Catalyst according to claims 1-3, wherein the critical solution temperature Tc of the polymer in solvent x is in a range of from -10°C to +150°C, wherein solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert- butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether, tetrahydrofuran, ethylacetate, acetone,
dimethylformamide and toluene.
Catalyst according to claims 1-4, wherein monomeric unit A is selected from the group consisting of ethyl
methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) ,
monomeric unit B is selected from the group consisting of 2-hydroxyethyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid, 2-hydroxyethyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3-
(dicyclohexyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid, and
Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane,
and where applicable cross-linking monomeric unit C is selected from the group consisting of compounds
Figure imgf000071_0001
(XIX) (XX) 6. Catalyst according to claims 1-5, wherein the
catalytically-active metal compound comprises a metal selected from the group consisting of Pd, Rh, Ru, Pt, Ir, Cu, Ni and Fe .
7. Catalyst according to claims 1-6, wherein the precursor of phosphorous and/or nitrogen containing uncharged electron donor is selected from phosphines and N- heterocyclic carbenes.
A process for producing the catalyst according to claims 1-8, comprising the steps
- co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,
- esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,
- reacting the resulting polymer with a catalytically- active metal compound, and
- separating the resulting catalyst from the reaction mixture .
Process according to claim 8, wherein the catalytically- active metal compound comprises a metal selected from the group consisting of Pd, Rh, Ru, Pt, Co, Cu, Ni and Fe.
Catalyst obtainable by a process according to claim 8 or 9.
Polymer with a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with
(meth) acrylates;
wherein monomeric units B are selected from hydroxyl- functionalize (meth) acrylates and monomers co- polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B. 12. Polymer according to claim 11, which comprises 50 wt-% -
99.8 wt-% of units derived from one non-functionalized monomeric unit A, 0.1 wt-% - 30 wt-% of units derived from one monomeric unit B, and 0.1 wt-% - 20 wt-% of units derived from one cross-linking monomeric unit C.
13. Polymer according to claim 11 or 12, wherein the
critical solution temperature Tc of the polymer in solvent x is in a range of from -10°C to +150°C, wherein solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol , n-pentanol, isopentanol, n- hexanol, isohexanol, n-heptanol, isoheptanol,
dichloromethane, diethylether , tetrahydrofuran,
ethylacetate, acetone, dimethylformamide and toluene.
14. Polymer according to claims 11-13, wherein monomeric
unit A is selected from the group consistsing of ethyl methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) , monomeric unit B is selected from the group consisting of 2-hydroxyethyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3-
(diphenyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3-
(dicyclohexyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3-
(dicyclohexyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3-
(dicyclohexyl-phosphino) -propionic acid,
2-hydroxyethyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid,
2-hydroxypropyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid,
2-hydroxybutyl (meth) acrylate esterified with 3- (di- isobutyl-phosphino) -propionic acid, and
Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane,
and cross-linking monomeric unit C is selected from the group consisting of compounds of formulas XVI-XX
Figure imgf000075_0001
(XVI) (XVII) (XVIII)
Figure imgf000075_0002
(XIX) (XX)
A process for producing the polymer according to claims 11-14, comprising the steps
- co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,
- esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor, and
- separating the resulting polymer from the reaction mixture .
16. Polymer obtainable by a process according to claim 15
Use of the catalyst according to claims 1- homogeneous and/or heterogeneous catalysis
Use according to claim 17 in ring closing metathesis (RCM) , in hydroformylation, in C-X or C-C coupling reactions and in hydrogenation reactions.
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