WO2014147192A1 - Temperature-responsive catalysts - Google Patents

Temperature-responsive catalysts Download PDF

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Publication number
WO2014147192A1
WO2014147192A1 PCT/EP2014/055632 EP2014055632W WO2014147192A1 WO 2014147192 A1 WO2014147192 A1 WO 2014147192A1 EP 2014055632 W EP2014055632 W EP 2014055632W WO 2014147192 A1 WO2014147192 A1 WO 2014147192A1
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meth
acrylate
monomeric units
polymer
acrylates
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PCT/EP2014/055632
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French (fr)
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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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    • 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
    • B01J31/165—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
    • 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
    • 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
    • B01J2231/40—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
    • 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
    • B01J2231/50—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
    • 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
    • B01J2531/10—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
    • 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
    • B01J2531/827—Iridium
    • 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
    • B01J2531/828—Platinum
    • 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
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • 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
    • B01J2531/84—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 catalyst has to be removed to 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
  • 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 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- Cio-alkyl are preferred, and linear or branched Ci-Cs-alkyl 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 , and 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 H
  • Ci-C 4 o _ alkyl linear or branched Ci-C 4 o _ alkyl, wherein Ci-Cio _ alkyl are preferred, and Ci-Cs-alkyl are even more preferred;
  • R is a linear Ci-Cio-alkylene group and R' ' are each independently selected from the group consisting of H, methyl and ethyl
  • 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-alkylene is 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-n C-atoms.
  • Typical examples of 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-dimethylbut
  • 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 .
  • C6-C n -aryl is defined as cyclic aromatic group with 6 to 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,
  • 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 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, 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 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 glycol ethers, polypropylene glycol ethers or mixtures thereof, such as, for example, tetrahydrofurfuryl (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
  • 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-diethylaminoethyl methacrylate
  • t-BAEMA 2-tert- butylaminoethyl methacrylate
  • DAEA 2-dimethylaminoethyl acrylate
  • DEAEA 2-diethylaminoethyl acrylate
  • aminoalkyl (meth) acrylates such as, 1-aminoethyl
  • Preferred (meth) acrylates of formula (I) are linear Ci-Cio- alkyl (meth) acrylates , more preferred are linear C2-Cs-alkyl
  • (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
  • DMAPMA 3-dimethylaminopropyl acrylamide
  • DMAPA 3-dimethylaminopropyl acrylamide
  • meth 3- diethylaminopropyl (meth) acrylamide
  • copolymers may have hydroxyl
  • 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
  • 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-l-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.
  • copolymers may also be prepared such that they have hydroxyl functionalities in one or more substituent.
  • vinyl esters and vinyl ethers Particular preference is given to vinyl esters and vinyl ethers. Even more preferred are vinyl acetate and vinyl propionate.
  • butylamide-propyl (meth) acrylate butylamide-propyl (meth) acrylate .
  • the preferred (meth) acrylic monomers of formula (VII), respectively, include, among others,
  • the preferred (meth) acrylic monomers of formula (VIII), respectively, include, among others,
  • Particulary 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 (meth) acrylates and monomers copolymerizable with (meth) acrylates represented by the group consisting of compounds of the general formulas IX-XI which contain one or more phosphorous and/or nitrogen containing uncharged electron donor as coordinative group X:
  • R 1' and R 1" are each independently selected from H and methyl R 3' is selected from the group consisting of H;
  • n 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, wherein
  • X, X' and X' ' are each a functional group with
  • X, X' and X' ' are each independently selected from the group consisting of phosphorous and/or nitrogen containing uncharged electron donor as coordinative group, like phosphines or nitrogen- containing carbenes (NHC) . More preferably, X, X' and X' ' are each independently selected from the group consisting of compounds of the general formulas (XI I ) - (XXI I ) ,
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4g , R 4h , R 4i , R 4] , R 4k , R 41 , R 4 ⁇ R 4n are each independently selected from the group consisting of Bilinear or branched Ci-C2o-alkyl, preferably linear or branched C 3 -Cio-alkyl;
  • R 5a , R 5b , R 5c , R 5d , R 5e , R 5f are each selected from the group consisting of H;
  • R 6a , R 6b , R 6c , R 6d , R 6e , R 6f , R 6g , R 6h , R Sl , R 6] , R 6k , R 61 are each independently selected from H and Me.
  • R 41 , R 4m , R 4n are each independently selected from the group consisting of H, isobutyl, cyclohexyl, phenyl and 1-adamantyl.
  • R 5a , R 5b , R 5c , R 5d , R 5e , R 5f are each 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.
  • Acceptors are typically metal atoms, e.g. Pd(0), Pd(II), Ru(I), Ru(II) .
  • X, X' and X' ' are each independently selected from the group consisting of compounds of formula XII, wherein R 4a and R 4b are the same and are phenyl and n is 1, 2, 3, 4 or 5, formula XIV, wherein R 6a and R 6b are the same and are H, R 5a is mesityl and n is 1, 2, 3, 4 or 5, and formulas
  • R 6c , R 6d , R 6e , R 6f , R 6g , R 6h , R 6 ⁇ R 6] , R 6k , R 61 are each H and R 5b , R 5c , R 5d , R 5e , R 5f are each mesityl.
  • 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
  • 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,
  • copolymers may also be prepared such that they have hydroxyl functionalities in one or more
  • Preferred monomeric units B are selected from the group consisting of
  • 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) 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
  • (meth) acrylates having three or more double bonds such as glycerol tri (meth) acrylate, trimethylolpropane
  • 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 group consisting of the following compounds
  • Catalytically-active metal compounds are metals, metal
  • 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.
  • RuC ⁇ 2 (PCy 3 ) 2 CHR , wherein R is selected from the group consisting of Ci-Cio-alkyl, C6-Ci 4 -aryl and C 5 -Ci 4 -heteroaryl , wherein R 7 is preferably selected from the group consisting of methyl, ethyl, tert-butyl, phenyl and thiophenyl.
  • 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-%
  • 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-%
  • the monomeric units are selected as presented in table 2.
  • Table 2 Specific combinations of monomeric units.
  • EA ethyl acrylate
  • EMA ethyl methacrylate
  • NIPAM INT- isopropylaery1amide
  • VA vinylacetate
  • [a] 3- (diphenyl- phosphino) -propyl methacrylate
  • [b] 3- (di-l-adamantyl- phosphino) -propyl methacrylate
  • [c] 3- (dicyclohexyl- phosphino) -propyl methacrylate
  • [d] 3- (di-isobutyl- phosphino) -propyl methacrylate
  • [e] l-mesityl-3- (3- (methacryloyloxy) propyl ) -1H- imidazole- 3 -iumbromide
  • 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 w-% - 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;
  • 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 functionalized monomeric units B;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • (meth) acrylates which contain one or more 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 comprises 50 wt-% - 99.9 wt-% of units derived from one non- functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one functionalized monomeric units B;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • (meth) acrylates which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups ;
  • the catalyst comprises
  • 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 units derived from one non- functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one functionalized monomeric units B;
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • (meth) acrylates which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups ;
  • 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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;
  • 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,
  • 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 (L 2 ) which passes this turning point and exhibits the
  • 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.
  • 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.
  • Chem. Int. Ed. 2005, 44, 7686-7708) 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
  • 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.
  • microgels 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.
  • 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) 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 functionalized 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 consisting of 3- (diphenyl-phosphino) -propyl (meth) acrylate, 3- (di-l-adamantyl- phosphino) -propyl (meth) acrylate, 3- (dicyclohexyl-phosphino) - propyl (meth) acrylate, 3- (di-isobutyl-phosphino) -propyl
  • 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 monomers A, 0.1 wt-% - 50 wt-% of units derived from one or more functionalized monomers B, 0 wt-% - 30 wt-% of units derived from one or more cross- linking monomers C,
  • monomers A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomers B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomers 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,
  • 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) 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 monomers A, 0.1 wt-% - 50 wt-% of units derived from one or more functionalized monomers B, 0 wt-% - 30 wt-% of units derived from one or more cross- linking monomers C,
  • monomers A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomers B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
  • cross-linking monomers C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B;
  • phosphorous and/or nitrogen containing uncharged electron donor is selected from phosphines and N- heterocyclic carbenes.
  • the invention provides a process for producing a catalyst comprising the steps (a) co-polymerizing non-functionalized monomeric units A, functionalized monomeric units B and where applicable cross- linking monomeric units C,
  • the invention provides a process for producing a catalyst comprising the steps
  • the catalytically-active metal compound comprises a metal selected from the group consisting of 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.
  • a radical solution polymerization These methods are set out in Ullmann' s Encyclopedia of Industrial Chemistry, Sixth Edition.
  • ATRP Atom Transfer Radical Polymerization
  • NMP Nonroxide-mediated Polymerization
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • 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, dil
  • 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
  • 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 from -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.
  • the invention provides a polymer with 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 functionalized monomeric units B, 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 ;
  • monomeric units B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 of from 1000 g/mol -
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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. Furthermore, the invention relates to a polymer, with a weight-average molecular weight in the range of from
  • monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
  • monomeric units B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 relates to 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 functionalized monomeric units B, 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
  • EMA ethyl methacrylate
  • NIPAM vinylacetate
  • VA vinylacetate
  • EA ethyl acrylate
  • monomeric units B are selected from the group
  • cross-linking monomeric units C are selected from the group consisting of compounds of formulas XXI I I -XXVI I
  • the invention relates to a process for producing the polymer, comprising the steps
  • the invention relates to a polymer obtainable by a process comprising the steps (a) co-polymerizing non-functionalized monomeric units A, functionalized monomeric units B and cross-linking monomeric units C, and
  • 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 g/mol to 40000 g/mol.
  • (meth) acrylate polymers is in the range of from 1000 g/mol to 60000 g/mol, more preferably in the range of from 3000 g/mol to 25000 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
  • 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
  • LAH lithium aluminum hydride
  • PROCEDURE
  • reaction mixture is transferred to a separatory funnel, mixed with 10 mL 1 M HCl and the aqueous phase is extracted twice with DCM.
  • the merged organic phases are washed with saturated NaHC0 3 -solution .
  • the organic phase is dried with a 2 S0 4 and the solvent is removed in a rotary evaporator.
  • PROCEDURE
  • ammoniumacetate are dissolved in a mixture of 20 mL water and 60 mL glacial acetic acid. Under constant stirring the second solution is added dropwise over a period of 30 min to the glyoxal solution. This reaction mixture is stirred for 18 h at 70 °C. The cooled reaction mixture is added dropwise to 500 mL of a saturated NaHC0 3 -solution . The formed precipitate is filtered and recrystallized from heptane/ ethylacetate.
  • triethylamine hydrochloride are removed by filtration.
  • the filtrate is dried in high vacuo.
  • the product is cleaned by flash-chromatography in a short neutral alox column with DCM/ ethanol 4:1 as eluent.
  • the cooled reaction mixture is diluted with 20 mL methanol and added dropwise to 500 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. Copolymers with other stoichiometries are also available according to this 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
  • phosphine-functionalities ethylacrylate/ 3- (diphenylphosphino) propylmethacrylate copolymer (95:5) are dissolved in a mixture of 5 mL abs . THF and 3 mL abs . DCM.
  • 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 is dried in vacuo.
  • allylpalladium ( I I ) chloride dimer are added to the filtrate and this mixture is stirred for 16 h at 50 °C.
  • reaction mixture is filtered and the filtrate is dried in high vacuo.
  • AIBN azobis (isobutyronitrile)
  • the crude product is purified by ultrafiltration.
  • dodecyl (trimethyl) -ammoniumbromide DTAB
  • DTAB dodecyl (trimethyl) -ammoniumbromide
  • AIBN azobis (isobutyronitrile)
  • the crude product is purified by ultrafiltration.
  • Microgels with other stoichiometries are also available according to this procedure.

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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-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more functionalized 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 (meth)acrylates and monomers co-polymerizable with (meth)acrylates, which contain one or more 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 relates to corresponding polymers of 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 .
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 catalyst has 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 R , R , R , R , Rie, R , Rig are each independently selected from H and metyhl
R2 and R2' are each independently selected from the group consisting of Bilinear or branched Ci-C4o_alkyl, wherein linear or branched Ci- Cio-alkyl are preferred, and linear or branched Ci-Cs-alkyl are even more preferred;
C3-Cio-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 , and 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 H;
linear or branched Ci-C4o_alkyl, wherein Ci-Cio_alkyl are preferred, and Ci-Cs-alkyl are even more preferred;
C3-Cio-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 and ethyl
R3 is selected from the group consisting of H;
Ci-Cio-alkyl;
C3-Cio-cycloalkyl ;
C3-Cio-heterocycloalkyl ;
Figure imgf000005_0003
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
with n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 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-alkylene is 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-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 6 to 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 glycol ethers, polypropylene glycol ethers or mixtures thereof, such as, for example, tetrahydrofurfuryl (meth) acrylate,
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 ; 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 ; 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 C2-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 (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, 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 (meth) acrylamide, 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-l-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.
Furthermore, these copolymers may also be prepared such that they have hydroxyl functionalities in one or more substituent.
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-methyl-N-monopropylamide,
(meth) acryloyloxy-methyl-N-monobutylamide,
(meth) acry1oyloxy-ethy1-N-monomethy1amide,
(meth) acry1oyloxy-ethy1-N-monoethy1amide,
(meth) acryloyloxy-ethy1-N-monopropylamide, (meth) acryloyloxy-ethyl-N-monobutylamide,
(meth) acryloyloxy-propyl-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 .
Particulary 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 (meth) acrylates and monomers copolymerizable with (meth) acrylates represented by the group consisting of compounds of the general formulas IX-XI which contain one or more phosphorous and/or nitrogen containing uncharged electron donor as coordinative group X:
Figure imgf000018_0001
(IX) (X) (XI)
wherein
R1' and R1" are each independently selected from H and methyl R3' is selected from the group consisting of H;
Ci-Cio-alkyl;
Figure imgf000019_0001
C5-Ci4-heteroaryl ;
halide ;
COORz, wherein Rz is selected from the group consisting of methyl and ethyl;
and
Figure imgf000019_0002
wherein n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, wherein
is preferred, and X, X' and X' ' are each a functional group with
coordinative properties to which the catalytically-active metal compound can be bound. Preferably, X, X' and X' ' are each independently selected from the group consisting of phosphorous and/or nitrogen containing uncharged electron donor as coordinative group, like phosphines or nitrogen- containing carbenes (NHC) . More preferably, X, X' and X' ' are each independently selected from the group consisting of compounds of the general formulas (XI I ) - (XXI I ) ,
Figure imgf000020_0001
wherein further n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4h, R4i, R4], R4k, R41, R4\ R4n 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 imgf000020_0002
C6-C2o_arylalkyl
R5a, R5b, R5c, R5d, R5e, R5f are each selected from the group consisting of H;
Ci-C2o-alkyl;
Figure imgf000020_0003
and C5-Ci8-heteroaryl
R6a, R6b, R6c, R6d, R6e, R6f, R6g, R6h, RSl, R6] , R6k, R61 are each independently selected from H and Me. Preferably, R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4h, R4i, R4],
Figure imgf000021_0001
R41, R4m, R4n are each independently selected from the group consisting of H, isobutyl, cyclohexyl, phenyl and 1-adamantyl. Preferably, R5a, R5b, R5c, R5d, R5e, R5f are each 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, X, X' and X' ' are each independently selected from the group consisting of compounds of formula XII, wherein R4a and R4b are the same and are phenyl and n is 1, 2, 3, 4 or 5, formula XIV, wherein R6a and R6b are the same and are H, R5a is mesityl and n is 1, 2, 3, 4 or 5, and formulas
XXIII-XXII, wherein R6c, R6d, R6e, R6f, R6g, R6h, R6\ R6] , R6k, R61 are each H and R5b, R5c, R5d, R5e, R5f are each mesityl.
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; isoprenyl ethers.
Furthermore, these copolymers may also be prepared such that they have hydroxyl functionalities in one or more
substituents . Preferred monomeric units B are selected from the group consisting of
3- (diphenyl-phosphino) -propyl (meth) acrylate, - (di-l-adamantyl-phosphino) -propyl (meth) acrylate, - (dicyclohexyl-phosphino) -propyl (meth) acrylate, - (di-isobutyl-phosphino) -propyl (meth) acrylate and
Figure imgf000023_0001
Figure imgf000024_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 group consisting of the following compounds
ethylene glycol dimethacrylate (XXIII),
N, N' - ( 1 , 2-dihydroxyethylene) bis-acrylamide (XXIV)
p-divinylbenzene (XXV) ,
N, N' -methylene-bisacrylamide (XXVI), and
bis (2-methacryloyl) oxyethyl disulfide (XXVII) .
Figure imgf000026_0001
(XXVI) (XXVII)
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.
Examples of said catalytically-active metal compounds are
[Pd(allyl)Cl]2,
[Rh (cod) 2] BF4,
Figure imgf000027_0001
Figure imgf000027_0002
RuC±2 (PCy3) 2=CHR , wherein R is selected from the group consisting of Ci-Cio-alkyl, C6-Ci4-aryl and C5-Ci4-heteroaryl , wherein R7 is preferably selected from the group consisting of methyl, ethyl, tert-butyl, phenyl and thiophenyl.
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 compositions of table 1 are
particularly preferred.
Table 1: Specific compositions of polymers.
Figure imgf000028_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.
monomeric unit A monomeric unit B monomeric unit
C
EMA [a] -
EMA [b] -
EMA [c] -
EMA [d] -
EMA [e] - IPAM [a] - IPAM [b]
NIPAM [c] -
NIPAM [d] -
NIPAM [e] -
VA [a] -
VA [b] -
VA [c] -
VA [d] -
VA [e] -
EA [a] -
EA [b] -
EA [c] -
EA [d] -
EA [e] -
EMA [a] XXIII
EMA [b] XXIII
EMA [c] XXIII
EMA [d] XXIII
EMA [e] XXIII
NIPAM [a] XXIII
NIPAM [b] XXIII
NIPAM [c] XXIII
NIPAM [d] XXIII
NIPAM [e] XXIII
VA [a] XXIII
VA [b] XXIII
VA [c] XXIII
VA [d] XXIII
VA [e] XXIII
EA [a] XXIII
EA [b] XXIII
EA [c] XXIII
EA [d] XXIII
EA [e] XXIII
EMA [a] XXIV
EMA [b] XXIV
EMA [c] XXIV
EMA [d] XXIV
EMA [e] XXIV NIPAM [a] XXIV
NIPAM [b] XXIV
NIPAM [c] XXIV
NIPAM [d] XXIV
NIPAM [e] XXIV
VA [a] XXIV
VA [b] XXIV
VA [c] XXIV
VA [d] XXIV
VA [e] XXIV
EA [a] XXIV
EA [b] XXIV
EA [c] XXIV
EA [d] XXIV
EA [e] XXIV
EMA [a] XXV
EMA [b] XXV
EMA [c] XXV
EMA [d] XXV
EMA [e] XXV
NIPAM [a] XXV
NIPAM [b] XXV
NIPAM [c] XXV
NIPAM [d] XXV
NIPAM [e] XXV
VA [a] XXV
VA [b] XXV
VA [c] XXV
VA [d] XXV
VA [e] XXV
EA [a] XXV
EA [b] XXV
EA [c] XXV
EA [d] XXV
EA [e] XXV
EMA [a] XXVI
EMA [b] XXVI
EMA [c] XXVI
EMA [d] XXVI
EMA [e] XXVI
NIPAM [a] XXVI
NIPAM [b] XXVI
NIPAM [c] XXVI
NIPAM [d] XXVI
NIPAM [e] XXVI
VA [a] XXVI
VA [b] XXVI
VA [c] XXVI VA [d] XXVI
VA [e] XXVI
EA [a] XXVI
EA [b] XXVI
EA [c] XXVI
EA [d] XXVI
EA [e] XXVI
EA = ethyl acrylate, EMA = ethyl methacrylate, NIPAM = INT- isopropylaery1amide , VA = vinylacetate, [a] = 3- (diphenyl- phosphino) -propyl methacrylate, [b] = 3- (di-l-adamantyl- phosphino) -propyl methacrylate, [c] = 3- (dicyclohexyl- phosphino) -propyl methacrylate, [d] = 3- (di-isobutyl- phosphino) -propyl methacrylate, [e] = l-mesityl-3- (3- (methacryloyloxy) propyl ) -1H- imidazole- 3 -iumbromide
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 w-% - 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 functionalized monomeric units B;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
and wherein monomeric units B are selected from
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , which contain one or more 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 comprises 50 wt-% - 99.9 wt-% of units derived from one non- functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one functionalized monomeric units B;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
and wherein monomeric units B are selected from
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , which contain one or more 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 further 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 units derived from one non- functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one functionalized monomeric units B;
wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
and wherein monomeric units B are selected from
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , which contain one or more 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 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 functionalized 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 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 functionalized 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) ;
monomeric units B are selected from the group consisting of 3- (diphenyl-phosphino) -propyl (meth) acrylate, 3- (di-l-adamantyl- phosphino) -propyl (meth) acrylate, 3- (dicyclohexyl-phosphino) - propyl (meth) acrylate, 3- (di-isobutyl-phosphino) -propyl
(meth) acrylate and l-mesityl-3- (3- (methacryloyloxy) propyl) -1H- imidazole-3-iumbromide ; and where applicable cross-linking monomeric units C are selected from the group consisting of compounds of formulas XXI I I -XXVI I
Figure imgf000038_0001
(XXVI) (XXVII)
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 monomers A, 0.1 wt-% - 50 wt-% of units derived from one or more functionalized monomers B, 0 wt-% - 30 wt-% of units derived from one or more cross- linking monomers C,
wherein monomers A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomers B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomers 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 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 monomers A, 0.1 wt-% - 50 wt-% of units derived from one or more functionalized monomers B, 0 wt-% - 30 wt-% of units derived from one or more cross- linking monomers C,
wherein monomers A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;
wherein monomers B are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and
wherein cross-linking monomers 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 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, functionalized monomeric units B and where applicable cross- linking monomeric units C,
(b) reacting the resulting polymer with a catalytically-active metal compound, and
(c) 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, functionalized monomeric units B and where applicable cross- linking monomeric units C,
(b) reacting the resulting polymer with a catalytically-active metal compound, and
(c) separating the resulting catalyst from the reaction mixture ;
wherein the catalytically-active metal compound comprises a metal selected from the group consisting of 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, functionalized monomeric units B and where applicable cross- linking monomeric units C,
(b) reacting the resulting polymer with a catalytically-active metal compound, and
(c) 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 from -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 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 functionalized monomeric units B, 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 of from 1000 g/mol -
100000 g/mol and which polymer comprises 50 wt-% - 99.8wt-% of units derived from one non-functionalized (meth) acrylate A, 0.1 wt-% - 30 wt-% of units derived from one functionalized (meth) acrylate B, and 0.1 wt-% - 20 wt-% of units 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 relates to a polymer, with 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 functionalized monomeric units B, 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 (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which contain one or more 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 relates to 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 functionalized monomeric units B, 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 ethyl acrylate (EA) ;
wherein monomeric units B are selected from the group
consisting of 3- (diphenyl-phosphino) -propyl methacrylate, 3-
(di-l-adamantyl-phosphino) -propyl methacrylate, 3-
(dicyclohexyl-phosphino) -propyl methacrylate, 3- (di-isobutyl- phosphino) -propyl methacrylate and l-mesityl-3- (3-
(methacryloyloxy) propyl ) -lH-imidazole-3-iumbromide; and wherein cross-linking monomeric units C are selected from the group consisting of compounds of formulas XXI I I -XXVI I
Figure imgf000045_0001
(XXVI ) (XXVII )
Furthermore, the invention relates to a process for producing the polymer, comprising the steps
(a) co-polymerizing non-functionalized monomeric units A, functionalized monomeric units B and cross-linking monomeric units C, and
(b) 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, functionalized monomeric units B and cross-linking monomeric units C, and
(b) 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 imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
51
Figure imgf000052_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 g/mol to 40000 g/mol. The number-average molecular weight of preferred
(meth) acrylate polymers is in the range of from 1000 g/mol to 60000 g/mol, more preferably in the range of from 3000 g/mol to 25000 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 functionalized monomeric unit B a) Phosphine-functionalized monomer
Figure imgf000054_0001
Figure imgf000054_0002
PROCEDURE :
1.47 g (38.72 mmol) lithium aluminum hydride (LAH) are
dissolved under ice-cooling in 50 mL abs . THF. Afterwards 5.00 g (19.36 mmol) 3- (diphenylphosphino) propionic acid are added in portions, ice-cooling is removed and the reaction mixture is stirred for 2 h.
Under ice-cooling 1.5 mL ¾0, 1.5 mL 15%ige NaOH-solution and 4.5 mL ¾0 are added sequentially and slowly to the reaction mixture so that the temperature does not increase
significantly. The formed precipitate is removed by filtration and the filter cake is washed thoroughly with dichloromethane (DCM) . The filtrate is dried with Na2SC>4 and the solvent is removed in a rotary evaporator. The crude product can be applied in the following acrylation step without further flash-chromatographic cleaning. YIELD :
(colourless crystals)
Figure imgf000055_0001
Figure imgf000055_0002
PROCEDURE :
Under argon atmosphere 2.00 g (8.19 mmol) 3- (diphenylphosphino) propan-l-ol are dissolved in 20 mL abs . DCM. Afterwards 994 mg (9.83 mmol) abs. Triethylamine and 941 mg (9.01 mmol) methacryloyl chloride are added dropwise and the reaction mixture is stirred for 2 h at room temperature.
The reaction mixture is transferred to a separatory funnel, mixed with 10 mL 1 M HCl and the aqueous phase is extracted twice with DCM. The merged organic phases are washed with saturated NaHC03-solution . The organic phase is dried with a2S04 and the solvent is removed in a rotary evaporator.
Afterwards the product is cleaned by flash-chromatography in a short neutral alox column with hexane/DCM/ethylacetate 1:1:0.1 as eluent. YIELD :
.231 g (48%), colourless oil NHC-functionalized monomer
Figure imgf000056_0001
Figure imgf000056_0002
PROCEDURE :
35.4 g (244.1 mmol) of a 40 wt-% glyoxal-solution (in water) and 7.3 g (244.1 mmol) para-formaldehyde are dissolved in 60 mL glacial acetic acid and heated to 70 °C. Separately, 30.0 g (221.9 mmol) mesitylamine and 17.1 g (221.9 mmol)
ammoniumacetate are dissolved in a mixture of 20 mL water and 60 mL glacial acetic acid. Under constant stirring the second solution is added dropwise over a period of 30 min to the glyoxal solution. This reaction mixture is stirred for 18 h at 70 °C. The cooled reaction mixture is added dropwise to 500 mL of a saturated NaHC03-solution . The formed precipitate is filtered and recrystallized from heptane/ ethylacetate.
YIELD :
22.1356 g (54 %) , rosy crystals
Figure imgf000057_0001
M n
starting material eq m [g]
[g/mol] [mmo1 ]
mesitylimidazole 186.25 53.69 1.0 10.00
3-bromopropan-l-ol 138.99 64.53 1.2 8.96 PROCEDURE :
10.00 g (53.69 mmol) mesitylimidazole and 8.96 g (54.53 mmol) 3-bromopropan-l-ol are refluxed in 100 mL abs . toluene for 16 h. The reaction mixture is cooled to room temperature and the solvent is removed in a rotary evaporator. Afterwards 100 mL acetone are added and the reaction mixture is stirred for 30 min under ice-cooling. The formed white precipitate is filtered, washed with ice-cold acetone and dried in high vacuo.
YIELD :
13.4252 g (77%)
Figure imgf000057_0002
M n
starting material eq m [g]
[g/mol] [mmo1 ]
1- ( 3-hydroxypropyl ) -3- mesityl-lfi-imidazole-3- 325.24 15.37 1.0 5.00 iumbromide
methacryloyl chloride 104.53 15.53 1.01 1.62
NEt3 101.19 15.68 1.02 1.59 PROCEDURE :
Under argon atmosphere 5.00 g (15.37 mmol) 1- (3- hydroxypropyl ) -3-mesityl-lH-imidazole-3-iumbromide are
dissolved in 20 mL abs . DCM and cooled to 0 °C. Afterwards 1.59 g (15.68 mmol) abs. triethylamine and 1.62 g (15.53 mmol) methacryloyl chloride are added dropwise. The reaction mixture is stirred for 16 h while it is let to warm to room
temperature . The solvent is removed in a rotary evaporator. Afterwards 50 mL acetone are added and the reaction mixture is cooled over night in a refrigerator. The precipitated crystals of
triethylamine hydrochloride are removed by filtration. The filtrate is dried in high vacuo. Afterwards the product is cleaned by flash-chromatography in a short neutral alox column with DCM/ ethanol 4:1 as eluent.
YIELD :
5.8663 g (97%)
2. Preparation of Copolymers a) Phosphine-functionalized Copolymer EA-MA-QPr-PPh2 (95:5)
Figure imgf000058_0001
M n
starting material eq m [mg]
[g/mol] [mmo1 ]
ethylacrylate 100.12 20.00 95 2002
3- (eiphenylphosphino) -
312.34 1.05 5 329 propylmethacrylate
AIBN 164.21 0.21 1 35 PROCEDURE :
2002 mg (20.00 mmol) ethylacrylate and 329 mg (1.05 mmol) 3- (diphenylphosphino) -propylmethacrylate are dissolved in 20 mL THF. Afterwards 35 mg (0.21 mmol) azobis (isobutyronitrile) (AIBN) are added and the reaction mixture is degassed
thoroughly (ca. 15 min 2 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 20 mL THF and added dropwise to 500 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. Copolymers with other stoichiometries are also available according to this procedure. b) NHC-functionalized Copolymer EA-MA-Q-Pr- Im-Mes (95:5)
Figure imgf000059_0001
M n
starting material eq m [mg]
[g/mol] [mmo1 ]
ethyl acrylate 100.12 20.00 95 2002 l-mesityl-3-
(3- (methacryloyloxy) propyl ) - 393.32 1.05 5 414
1H-imidazole-3-iumbromide
AIBN 164.21 0.21 1 35 PROCEDURE :
2002 mg (20.00 mmol) ethyl acrylate and 414 mg (1.05 mmol) 1- mesityl-3- (3- (methacryloyloxy) propyl ) -lH-imidazole-3- iumbromide are dissolved in 20 mL abs . methanol. Afterwards 35 mg (0.21 mmol) azobis ( isobutyronitril ) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min 2 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 20 mL methanol and added dropwise to 500 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. Copolymers with other stoichiometries are also available according to this procedure.
3. Metal complexes a) EA-MA-OPr-PPh2 (95:5) [Pd (allyl) CI] 2
Figure imgf000060_0001
starting material M [g/mol] n [mmo1 ] eq m [mg]
EA-MA-OPr-PPh2 (95:5) (110.73) 0.1 1.0 221
[Pd(allyl)Cl]2 365.89 0.05 0.5 18 PROCEDURE :
221 mg (0.1 mmol phosphine-funcionalities ) ethylacrylate/ 3- (ciiphenylphosphino) -propylmethacrylate copolymer (95:5) are dissolved under argon atmosphere in 5 mL abs . DCM. Afterwards 18 mg (0.05 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.
EA-MA-OPr-PPh2 (95:5) / Rh(cod)2BF4
Figure imgf000061_0001
Figure imgf000061_0002
PROCEDURE :
In a glovebox under argon atmosphere 443 mg (0.2 mmol
phosphine-functionalities ) ethylacrylate/ 3- (diphenylphosphino) propylmethacrylate copolymer (95:5) are dissolved in a mixture of 5 mL abs . THF and 3 mL abs . DCM.
Afterwards a solution of 41 mg (0.1 mmol) bis (1,5- cyclooctadien) rhodium ( I ) tetrafluoroborate in 2 mL abs. DCM are 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 is dried in vacuo.
EA-MA-O-Pr-Im-Mes (95:5) / [Pd (allyl) CI]
Figure imgf000062_0001
M n
starting material eq m [mg]
[g/mol] [mmo1 ]
ethylacrylate / l-mesityl-3- (3- (methacryloyloxy) propyl ) - 1H- imidazole- 3 -iumbromide (114.78) 0.05 1.0 115 copolymer (95:5) EA-MA-O-Pr- Im-Mes
Ag20 231.74 0.10 2.0 23
[Pd(allyl)Cl]2 365.89 0.025 0.5 9 PROCEDURE :
Under argon atmosphere 115 mg (0.05 mmol imidazolium- functionalities ) ethylacrylate / l-mesityl-3- (3- (methacryloyloxy) propyl ) -lH-imidazole-3-iumbromide copolymer (95:5) are dissolved in a mixture of 10 mL abs . THF and 10 mL abs . DCM. Afterwards 23 mg (0.10 mmol) silver ( I ) oxide are added and the flask is shielded against sunlight with aluminum foil. The reaction mixture is stirred for 16 h at 50 °C.
The reaction mixture is filtered, 9 mg (0.025 mmol)
allylpalladium ( I I ) chloride dimer are added to the filtrate and this mixture is stirred for 16 h at 50 °C.
The reaction mixture is filtered and the filtrate is dried in high vacuo.
4. Microgels
a) Phosphine-functionalized
Figure imgf000063_0001
M n
starting material eq m [mg]
[g/mol] [mmo1 ]
ethylacrylate 100.12 20.00 93 2002
3- (diphenylphosphino) -
312.34 1.08 5 336 propylmethacrylate
crosslinker
N, N' - (1,2- 200.19 0.43 2 86 dihydroxyethylene) bisacrylamide
SDS 288.38 0.43 2 124
AIBN 164.21 0.22 1 35 PROCEDURE :
2002 mg (20.00 mmol) ethylacrylate, 336 mg (1.08 mmol) 3- (diphenylphosphino) -propylmethacrylate, 86 mg (0.43 mmol) N, N' - (1, 2-dihydroxyethylene) bisacrylamide and 124 mg (0.43 mmol) sodiumdodecylsulfate (SDS) are emulsified in 100 mL water (nanopure) . Afterwards 35 mg (0.22 mmol)
azobis (isobutyronitrile) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min 2 bubbling) . An oil bath is preheated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.
The crude product is purified by ultrafiltration.
Microgels with other stoichiometries are also available according to this procedure. b) HC-functionalized
Figure imgf000064_0001
n m starting material M [g/mol] eq
[mmo1 ] [mg] ethylacrylate 100.12 20.00 96 2002 l-mesityl-3- (3-
164 (methacryloyloxy) propyl ) -1H- 393.32 0.42 2
imidazole-3-iumbromide
N, N' - (1,2-
200.19 0.42 2 83 dihydroxyethylene) bisacrylamide
DTAB 308.34 0.42 2 128
AIBN 164.21 0.21 1 35 PROCEDURE :
2002 mg (20.00 mmol) ethylacrylate, 164 mg (0.42 mmol) 1- mesityl-3- (3- (methacryloyloxy) propyl ) -lfi-imidazole-3- iumbromide, 83 mg (0.42 mmol) N, N' - ( 1 , 2- dihydroxyethylene) bisacrylamide and 128 mg (0.42 mmol)
dodecyl (trimethyl) -ammoniumbromide (DTAB) are emulsified in 100 mL water (nanopure) . Afterwards 35 mg (0.21 mmol)
azobis (isobutyronitrile) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min 2 bubbling) . An oil bath is preheated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.
The crude product is purified by ultrafiltration.
Microgels with other stoichiometries are also available according to this procedure.
Table 4: Critical solution temperature
Figure imgf000066_0001
Figure imgf000067_0001

Claims

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 functionalized 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
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , which contain one or more 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 w-% - 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
functionalized 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 functionalized 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 3- (diphenyl-phosphino) -propyl (meth) acrylate, 3- (di- 1-adamantyl-phosphino) -propyl (meth) acrylate, 3- (dicyclohexyl-phosphino) -propyl (meth) acrylate, 3- (di- isobutyl-phosphino) -propyl (meth) acrylate and 1-mesityl- 3- (3- (methacryloyloxy) propyl ) -lH-imidazole-3-iumbromide, and where applicable cross-linking monomeric unit C is selected from the group consisting of compounds of formulas XXI I I -XXVI I
Figure imgf000070_0001
(XXVI) (XXVII)
6. Catalyst according to claims 1-4, 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 1-5, wherein the
phosphorous and/or nitrogen containing uncharged
electron donor is selected from phosphines and N- heterocyclic carbenes.
8. A process for producing the catalyst according to claims 1-7, comprising the steps
co-polymerizing non-functionalized monomeric units A, functionalized monomeric units B and where applicable cross-linking monomeric units C, reacting the resulting polymer with a
catalytically active metal compound, and separating the resulting catalyst from the
reaction mixture.
9. 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.
10. A catalyst obtainable by a process according to claim 8 or 9. 11. 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
functionalized monomeric units B, 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
(meth) acrylates and monomers co-polymerizable with
(meth) acrylates , which contain one or more 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 (meth) acrylate A, 0.1 wt-% - 30 wt-% of units derived from one functionalized (meth) acrylate 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.
Polymer according to claims 11-13, 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 3- (diphenyl-phosphino) -propyl methacrylate, 3- (di-1- adamantyl-phosphino) -propyl methacrylate, 3-
(dicyclohexyl-phosphino) -propyl methacrylate, 3- (di- isobutyl-phosphino) -propyl methacrylate and l-mesityl-3
(3- (methacryloyloxy) propyl ) -lH-imidazole-3-iumbromide, and cross-linking monomeric unit C is selected from the group consisting of compounds of formulas XXI I I -XXVI I
Figure imgf000072_0001
(XXVI) (XXVII)
A process for producing the polymer according to claims 11-14, comprising the steps co-polymerizing non-functionalized monomeric units A, functionalized monomeric units B and cross- linking monomeric units C, and
separating the resulting polymer from the reaction mixture .
16. A polymer obtainable by the process according to claim 15.
17. Use of the catalyst according to claims 1-7 in
homogeneous and/or heterogeneous catalysis.
18. 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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