Temperature-responsive catalysts

The present invention relates to catalysts comprising a polymer and a catalytically-active metal compound wherein said catalysts have a critical solution temperatur. Furthermore, the present invention relates to polymers having a critical solution temperature. Another aspect of the present invention is a process for producing said catalysts and said polymers, as well as the use thereof in homogeneous and/or heterogeneous catalysis.

The work leading to this invention has received funding from the European Community Seventh Framework Programme (FP 7) under grant agreement number 214095.

Background of the invention

Homogeneous transition metal catalyzed reactions have been refined into important processes for the synthesis of high- valued organic compounds. Especially, functionalization of aryl halides or vinyl halides in C-C and C-X coupling

reactions, e.g. to aromatic olefins (Heck-coupling, Stille- coupling) , biaryls (Suzuki-coupling) , alkines ( Sonogashira- reaction) , derivatives of acid (Heck-carbonylation) , amines (Buchwald-Hartwig-coupling) , is a major field of application. From these, Palladium-catalyzed cross-coupling reactions have emerged as one of the most important reactions both in

industry and academia. In recent years there have been

numerous contributions in this area.

Palladium catalysts bearing an N-heterocyclic carbene and sterically demanding phosphine ligands display the most robust and active catalytic systems to date (G. Organ et al . , Angew. Chem. 2007, 46, 2768-2813) .

Conventional homogeneous catalysts exhibit a high catalytic activity and selectivity and are thus applied in minimal quantities to catalytic reactions. The recovery of ligands and especially of the metal, which is mainly a precious metal, e.g. Rh, Pd or Pt, of the homogeneous catalysts is

disadvantageous due to their low concentrations or the

decomposition of the active complexes in the recycling

process. Therefore, there is a demand to provide a catalyst with a good recovery rate.

In addition, the application of homogeneous transition metal catalysts can result in soluble metal contamination.

Furthermore, the loss of precious metal is the major cost factor in homogeneous catalysis. These soluble metal

contaminations can be detrimental to product quality and product yield. In the case of active pharmaceutical ingredient development, the metal catalysts have to be removed to a regulated level. This can be achieved by e.g. chemical metal scavenging substances or techniques where the metal residues are removed by physical methods such as extraction,

distillation or precipitation. From the industrial point of view on attractive physical method constitutes membrane filtration technology in which the organic materials are removed by filtration and the metal remains within the

membrane sphere.

It is thus an objective of the present invention to provide a catalyst with high catalytic activity and selectivity that allows simple and cost efficient separation of metal complexes and reaction solution.

This objective is achieved with catalysts comprising

(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.

In the following, the phrase (meth) acrylate stands for

acrylates as well as methacrylates .

Monomeric unit A is defined as non-functionalized

(meth) acrylates and monomers co-polymerizable with

(meth) acrylates , wherein one or more are selected from the group consisting of compounds of the general formulas I-VIII

(IV) (V) (VI) (VII) (VIII) wherein

R ^la , R ^lb , R ^lc , R ^ld , R ^le , R ^lf , R ^lg are each independently selected from H and methyl

R ² and R ² ' are each independently selected from the group consisting of Bilinear or branched Ci-C ₄ o ^_ alkyl, wherein linear or branched Ci- C20 are preferred, linear or branched C ₁ -C ₁ 0 are more preferred and linear or branched C ₁ -C5 are even more preferred;

C ₃ -Ci ₀ -cycloalkyl;

C6-Ci ₄ -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-C ₁₀ - cycloalkyl, C3-Cio-heterocycloalkyl , C6-Ci ₄ -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 R ^2a is selected from the group consisting of Bilinear or branched Ci-C ₄ o ^_ alkyl, wherein linear or branched Ci- Cio-alkyl is preferred, and linear or branched Ci-Cs-alkyl is even more preferred;

C3-C ₁ 0-cycloalkyl ;

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 R ³ is selected from the group consisting of H;

Ci-Cio-alkyl;

C3-C ₁ 0-cycloalkyl ;

C3-Cio-heterocycloalkyl ;

C ₆ -Ci ₄ -aryl; C ₅ -Ci ₄ -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

wherein n = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and wherein n = 1 or 2 is preferred

R ^x , R ^x' , R ^x" , R ^x"' and R ^x"" are each independently selected from the group consisting of linear or branched Ci -Cio-alkylene groups, wherein Ci -Cs-alkylenes are preferred;

C3-Cio-cycloalkylene groups, wherein Cs -Cs-cycloalkyl is

preferred;

and C6-Ci ₄ -arylene groups

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;

C3-Cio-cycloalkyl groups, wherein Cs -Cs-cycloalkyl is preferred; and C6-Ci ₄ -aryl groups.

In the sense of the present invention Ci -C _n ^_ alkyl is defined as linear or branched Ci -C _n alkyl group with 1 to 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-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-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.

In the sense of the present invention 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,

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-C _n -heterocycloalkyl is defined as cyclic alkyl group with 3 to n C-atoms, which comprises mono-, bi- and tricyclic alkyl groups wherein 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from N, 0 or S . Examples are pyrrolidinyl , piperidinyl, imidazolidinyl , pyrazolidinyl , oxazolidinyl , morpholidinyl , thiazolidinyl , isothiazolidinyl , isoxazolidinyl , piperazinyl, tetrahydrothiophenyl , tetrahydrofuranyl , tetrahydropyranyl , dioxanyl.

In the sense of the present invention C6-C _n -aryl is defined as cyclic aromatic group with 5-n C-atoms, which comprises unsubstituted and substituted aryl groups. Typical examples are phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl,

anthracenyl, phenanthrenyl , napthacenyl .

In the sense of the present invention 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 . In the sense of the present invention 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.

In the sense of the present invention C ₃ -C _n -cycloalkylene is defined as divalent C ₃ -C _n -cycloalkyl group with 3 to n C-atoms. In the sense of the present invention C6-C _n -arylene is defined as divalent C6-C _n -aryl group with 6 to n C-atoms.

Preferably, 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.

Preferably, R ³ is selected from the group consisting of butyl, pentyl, cyclohexyl, acetate, propionate, benzoate, versatate, chloride, fluoride, phenyl, methylphenyl , ethylphenyl,

pyridines, pyrimidines, piperidines, carbazoles, imidazoles, pyrrolidones , pyrrolidines, caprolactam, oxolanes, furan, thiophene, thiolane, thiazoles, wherein acetate and propionate are particulary preferred.

Preferably 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.

Preferably R ^y , R ^y' , R ^y" , R ^{y" '} and R ^{y" "} are each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, 1-ethylpropyl, 1, 2-dimethylpropyl, 1,1- dimethylpropyl , 2, 2-dimethylpropyl, n-butyl, iso-butyl, sec- butyl, tert-butyl, 2-methylbutyl, 3-methylbutyl, n-pentyl, 2- pentyl, 3-pentyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, mesityl, napthyl, fluorenyl, anthracenyl, phenanthrenyl, napthacenyl.

Examples of the aforementioned (meth) acrylates of formula (I) are alkyl (meth) acrylates of straight-chained or branched

aliphatic alcohols having 1 to 40 C atoms, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl (meth) acrylate, 1 , 2-dimethylpropyl (meth) acrylate, 1,1- dimethylpropyl (meth) acrylate, 2 , 2-dimethylpropyl

(meth) acrylate, l-ethyl-2-methylpropyl (meth) acrylate, 1,1,2- trimethylpropyl (meth) acrylate, 1,2,2, trimethylpropyl

(meth) acrylate, n-butyl (meth) acrylate, iso-butyl

(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl

(meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, 1-ethylbutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, 1-propylbutyl (meth) acrylate, 1,1- dimethylbutyl (meth) acrylate, 1 , 2-dimethylbutyl

(meth) acrylate, 1 , 3-dimethylbutyl (meth) acrylate, 2,2- dimethylbutyl (meth) acrylate, 2 , 3-dimethylbutyl

(meth) acrylate, 3 , 3-dimethylbutyl (meth) acrylate, n-pentyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl

(meth) acrylate, 2-methylpentyl (meth) acrylate, 3-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate, 2-ethylpentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl

(meth) acrylate, 3-ethylhexyl (meth) acrylate, 2-hexyl

(meth) acrylate, n-heptyl (meth) acrylate, 2-heptyl

(meth) acrylate, 3-heptyl (meth) acrylate, 3-isopropylheptyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl

(meth) acrylate, n-decyl (meth) acrylate, n-undecyl

(meth) acrylate, 5-methylundecyl (meth) acrylate, n-dodecyl (meth) acrylate, 2-methyldodecyl (meth) acrylate, n-tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-pentadecyl (meth) acrylate, n-hexadecyl

(meth) acrylate, 2-methylhexadecyl (meth) acrylate, n-heptadecyl (meth) acrylate, 5-isopropylheptadecyl (meth) acrylate, 4-tert- butyloctadecyl (meth) acrylate, 5-ethyloctadecyl

(meth) acrylate, 3-isopropyloctadecyl (meth) acrylate, n- octadecyl (meth) acrylate, n-nonadecyl (meth) acrylate, eicosyl (meth) acrylate; wherein methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 1-ethylpropyl

(meth) acrylate, 1 , 2-dimethylpropyl (meth) acrylate, 1,1- dimethylpropyl (meth) acrylate, 2 , 2-dimethylpropyl

(meth) acrylate, n-butyl (meth) acrylate, iso-butyl

(meth) acrylate, sec-butyl (meth) acrylate, tert-butyl

(meth) acrylate, 2-methylbutyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-pentyl (meth) acrylate, 2-pentyl

(meth) acrylate, 3-pentyl (meth) acrylate are particulary preferred;

substituted or unsubstituted (meth) acrylates of cycloaliphatic alcohols having 3 to 10 C atoms, such as, cyclopropyl

(meth) acrylate, cyclobutyl (meth) acrylate, cyclopentyl

(meth) acrylate, cyclohexyl (meth) acrylate, tert- butylcyclohexyl (meth) acrylate, trimethylcyclohexyl

(meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl

(meth) acrylate, norbornyl (meth) acrylate, methylnorbornyl (meth) acrylate, dimethylnorbornyl (meth) acrylate, bornyl

(meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl

(meth) acrylate, 2-adamantyl (meth) acrylate, menthyl

(meth) acrylate, 2,4, 5-tri-tert-butyl-3-vinylcyclohexyl

(meth) acrylate, 2,3,4, 5-tetra-tert-butylcyclohexyl

(meth) acrylate, wherein cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl

(meth) acrylate are preferred; aryl (meth) acrylates such as, for example, phenyl

(meth) acrylate, tolyl (meth) acrylate, xylyl (meth) acrylate, mesityl (meth) acrylate, which may in each case have

unsubstituted or mono- to tetra-substituted aryl radicals like napthyl (meth) acrylate, fluorenyl (meth) acrylate, anthracenyl (meth) acrylate, phenanthrenyl (meth) acrylate, wherein phenyl (meth) acrylate, tolyl (meth) acrylate, xylyl (meth) acrylate, mesityl (meth) acrylate, napthyl (meth) acrylate, fluorenyl (meth) acrylate, anthracenyl (meth) acrylate, phenanthrenyl (meth) acrylate, and napthacenyl (meth) acrylate are preferred; arylalkyl (meth) acrylates such as, for example, benzyl

(meth) acrylate ; mono (meth) acrylates of ethers, polyethylene glycoles, polypropylene glycoles or mixtures thereof, such as, for example, tetrahydrofurfuryl methacrylate, methoxymethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, 1- butoxypropyl methacrylate, cyclohexyloxymethyl methacrylate, benzyloxymethyl methacrylate, furfuryl methacrylate,

2-butoxyethyl methacrylate, 2-ethoxyethyl methacrylate, allyloxymethyl methacrylate, 1-ethoxybutyl methacrylate, 1- ethoxyethyl methacrylate, ethoxymethyl methacrylate,

poly (ethylene glycol) methylether (meth) acrylate and

poly (propylene glycol) methylether (meth) acrylate ; amino-functionalized (meth) acrylates like aminoalkyl

(meth) acrylates , dialkylaminoalkyl (meth) acrylates , or alkylaminoalkyl (meth) acrylates . Preferred more particularly are dimethylaminoalkyl (meth) acrylates and diethylaminoalkyl (meth) arylates , such as, 2-dimethylaminoethyl methacrylate (DMAEMA) , 2-diethylaminoethyl methacrylate (DEAEMA) , 2-tert- butylaminoethyl methacrylate (t-BAEMA) , 2-dimethylaminoethyl acrylate (DMAEA) , 2-diethylaminoethyl acrylate (DEAEA) ;

aminoalkyl (meth) acrylates , such as, 1-aminoethyl

(meth) acrylate, 2-aminoethyl (meth) acrylate, aminomethyl (meth) acrylate .

Preferred (meth) acrylates of formula (I) are linear Ci-Cio- alkyl (meth) acrylates , more preferred are linear Ci-Cs-alkyl (meth) acrylates , wherein methyl (meth) acrylate, ethyl

(meth) acrylate, n-propyl (meth) acrylate and n-butyl

(meth) acrylate are particularly preferred. (Meth) acrylates in the sense of the present invention further include (meth) acrylamides according to formula (II) like monoalkyl (meth) acrylamides , dialkyl (meth) acrylamides and mono- and dialkylaminoalkyl (meth) acrylamides . Preferred more particularly are methacrylamide and acrylamide, N-2-aminoethyl (meth) acrylamide, N, -dimethylaminoethyl (meth) acrylamide, N, -diethylaminoethyl (meth) acrylamide, N-3-aminopropyl

(meth) acrylamide, 3-dimethylaminopropyl methacrylamide

(DMAPMA) , 3-dimethylaminopropyl acrylamide (DMAPA) , 3- diethylaminopropyl (meth) acrylamide, N-methyl

(meth) acrylamide, N-ethyl (meth) acrylamide, N-n-propyl

(meth acrylamide N-isopropyl (meth) acrylamide, N-n-butyl (meth acrylamide N-iso-butyl (meth) acrylamide, N-sec-butyl ((mmeetthh) aaccrryyllaammiiddee , N-tert-butyl (meth) acrylamide, N- (n-pentyl) (meth acrylamide N- (n-hexyl) (meth) acrylamide, N- (n-heptyl (meth acrylamide N- (octyl) (meth) acrylamide, N- (tert-octyl) (meth acrylamide N- (1, 1, 3, 3-tetramethylbutyl )

(meth acrylamide N-3-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth acrylamide N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth acrylamide N-dodecyl (meth) acrylamide, N-tridecyl

(meth acrylamide N-tetradecyl (meth) acrylamide, N-pentadecyl (meth acrylamide N-hexadecyl (meth) acrylamide, N-heptadecyl (meth acrylamide N-octadecyl (meth) acrylamide, N-nonadecyl ((mmeetthh) aaccrryyllaammiiddee, N-eicosyl (meth) acrylamide, N-cyclohexyl (meth acrylamide Ν,Ν-dimethyl (meth) acrylamide, N,N-diethyl (meth acrylamide N, -di-n-propyl (meth) acrylamide, N,N- diisopropyl (meth) acrylamide, N, -di-n-butyl (meth) acrylamide, N, -di-iso-butyl (meth) acrylamide, N, -di-sec-butyl

(meth) acrylamide, N, -di-tert-butyl (meth) acrylamide, N,N-di- cyclohexyl (meth) acrylamide .

Furthermore, these copolymers may have hydroxyl

functionalities in one or more substituent, such as N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2- hydroxypropyl (meth) acrylamide, 2-hydroxybutyl

(meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 3- hydroxybutyl (meth) acrylamide, 4-hydroxybutyl

(meth) acrylamide, 6-hydroxyhexyl (meth) acrylamide, 3-hydroxy- 2-ethylhexyl (meth) acrylamide .

Besides the (meth) acrylates set out above it is possible for the compositions to be polymerized also to contain further unsaturated monomers of formula (III) which are

copolymerizable with aforementioned (meth) acrylates and by means of ATRP (= Atom Transfer Radical Polymerization) . These include, among others,

1-alkenes, such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,

dichlorostyrenes , tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,

4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3- vinylpyrrolidine, N-vinylcaprolactam, vinyloxolanes , vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles , and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles;

vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.

Particular preference is given to vinyl esters and vinyl ethers. Even more preferred are vinyl acetate and vinyl propionate .

The preferred (meth) acrylic monomers of formula (IV),

respectively, include, among others

acetylamide-ethyl (meth) acrylate,

acetylamide-propyl (meth) acrylate,

propylamide-ethyl (meth) acrylate,

propylamide-propyl (meth) acrylate,

butylamide-ethyl (meth) acrylate,

butylamide-propyl (meth) acrylate . The preferred (meth) acrylic monomers of formula (V) ,

respectively, include, among others,

acetic acid ester-ethyl (meth) acrylamide,

acetic acid ester-propyl (meth) acrylamide,

butanoic acid ester-ethyl (meth) acrylamide,

butanoic acid ester-propyl (meth) acrylamide,

propanoic acid ester-ethyl (meth) acrylamide,

propanoic acid ester-propyl (meth) acrylamide .

The preferred (meth) acrylic monomers of formula (VI),

respectively, include, among others,

acetylamide-ethyl (meth) acrylamide,

acetylamide-propyl (meth) acrylamide,

propylamide-ethyl (meth) acrylamide, butylamide-propyl (meth) acrylamide,

butylamide-ethyl (meth) acrylamide,

propylamide-propyl (meth) acrylamide . The preferred (meth) acrylic monomers of formula (VII), respectively, include, among others,

(meth) acryloyloxy-methyl-methyl ester,

(meth) acryloyloxy-methyl-ethyl ester,

(meth) acryloyloxy-methyl-propyl ester,

(meth) acryloyloxy-methyl-butyl ester,

(meth) acryloyloxy-ethyl-methyl ester,

(meth) acryloyloxy-ethyl-ethyl ester,

(meth) acryloyloxy-ethyl-propyl ester,

(meth) acryloyloxy-ethyl-butyl ester,

(meth) acryloyloxy-propyl-methyl ester,

(meth) acryloyloxy-propyl-ethyl ester,

(meth) acryloyloxy-propyl-propyl ester,

(meth) acryloyloxy-propyl-butyl ester,

(meth) acryloyloxy-butyl-methyl ester,

(meth) acryloyloxy-butyl-ethyl ester,

(meth) acryloyloxy-butyl-propyl ester,

(meth) acryloyloxy-butyl-butyl ester.

The preferred (meth) acrylic monomers of formula (VIII), respectively, include, among others,

(meth) acry1oyloxy-methy1-N-monomethy1amide,

(meth) acry1oyloxy-methy1-N-monoethy1amide,

(meth) acryloyloxy-methy1-N-monopropylamide,

(meth) acryloyloxy-methyl-N-monobutylamide,

(meth) acryloyloxy-ethyl-N-monomethylamide,

(meth) acry1oyloxy-ethy1-N-monoethy1amide,

(meth) acryloyloxy-ethy1-N-monopropylamide,

(meth) acryloyloxy-ethyl-N-monobutylamide,

(meth) acry1oyloxy-propy1-N-monomethy1amide, (meth) acryloyloxy-propyl-N-monoethy1amide,

(meth) acryloyloxy-propyl-N-monopropylamide,

(meth) acryloyloxy-propyl-N-monobutylamide,

(meth) acryloyloxy-butyl-N-monomethylamide,

(meth) acryloyloxy-butyl-N-monoethylamide,

(meth) acryloyloxy-butyl-N-monopropylamide,

(meth) acryloyloxy-butyl-N-monobutylamide .

Particularly preferred monomeric units A are selected from ethyl methacrylate (EMA) , N-isopropyl acrylamide (NIPAM) , vinylacetate (VA) and ethyl acrylate (EA) .

Monomeric unit B is selected from hydroxyl-functionalized (meth) acrylates and monomers co-polymerizable with

(meth) acrylates represented by the group consisting of

compounds of the general formulas IX-XI, wherein the hydroxyl- group is esterified as described later:

(IX) (X) (XI)

wherein

R 1' and R 1' ' are each independently selected from H and methyl R ^3' is selected from the group consisting of H;

Ci-Cio-alkyl;

C ₆ -Ci ₄ -aryl; C ₅ -Ci ₄ -heteroaryl ;

halide ;

COOR ^z , wherein R ^z is selected from the group consisting of methyl and ethyl;

and

wherein n = 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and wherein n = 1 or 2 is preferred and X, X' and X' ' are each a hydroxyl-functionalized linear or branched Ci-Cio-alkyl group. Preferably, X, X' and X' ' are each independently selected from -(CH ₂ ) _n ^_ OH and -C{ (CH ₂ ) _n ^_ OH} ₃ , wherein n = 1,2,3,4, or 5.

Preferred hydroxyl-functionalized (meth) acrylates and monomers copolymerizable with (meth) acrylates of formula (IX) are, for example,

mono (meth) acrylates of alkanediols, such as,

2-hydroxyethyl neopentyl glycol mono (meth) acrylate, 2- hydroxypropyl neopentyl glycol mono (meth) acrylate, 3- hydroxypropyl neopentyl glycol mono (meth) acrylate, 3- hydroxybutyl neopentyl glycol mono (meth) acrylate, 4- hydroxybutyl neopentyl glycol mono (meth) acrylate, 6- hydroxyhexyl neopentyl glycol mono (meth) acrylate, 3-hydroxy-2- ethylhexyl neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 1 , 5-pentanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate;

(meth) acrylates having a hydroxyl group in the alkyl radical, more particularly 2-hydroxyethyl (meth) acrylate, preferably 2- hydroxyethyl methacrylate (HEMA) , hydroxypropyl

(meth) acrylates , such as 2-hydroxypropyl (meth) acrylate and 3- hydroxypropyl (meth) acrylate, preferably 2-hydroxypropyl methacrylate (HPMA) , hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA) , 3, 4-dihydroxybutyl

(meth) acrylate, 2 , 5-dimethyl-l , 6-hexandiol (meth) acrylate, 1, 10-decandiol (meth) acrylate, glycerol mono (meth) acrylate, and polyalkoxylated derivatives of (meth) acrylic acid,

especially polypropylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6, propylene oxide units, preferably polypropylene glycol monomethacrylate having about 5 propylene oxide units (PPM5) , polyethylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6, ethylene oxide units, preferably polyethylene glycol monomethacrylate having about 5 ethylene oxide units (PEM5) , polybutylene glycol

mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate .

Examples of monomer of formula (X) are the same as those mentioned before according to formula (II) with the proviso that in addition functional group X is present. These include, among others, N-methyl (meth) acrylamide, N-ethyl

(meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-iso-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl (meth) acrylamide, N- (octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide, N- (1,1, 3,3- tetramethylbutyl ) (meth) acrylamide, N-3-ethylhexyl

(meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide .

Preferred are such as N-methylol (meth) acrylamide, 2- hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 2-hydroxybutyl (meth) acrylamide, 3- hydroxypropyl (meth) acrylamide, 3-hydroxybutyl

(meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6- hydroxyhexyl (meth) acrylamide, 3-hydroxy-2-ethylhexyl

(meth) acrylamide .

Examples of monomers of formula (XI) are the same as those mentioned before according to formula (III) with the proviso that in addition functional group X is present. These include, among others,

1-alkenes, such as 1-hexene, 1-heptene, branched alkenes such as, for example, vinylcyclohexane, 3, 3-dimethyl-l-propene, 3- methyl-l-diisobutylene, 4 -methyl -1-pentene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl versatate; vinyl halides such as, for example, vinyl chloride, vinyl fluoride ; styrene and substituted styrenes with an alkyl substituent on the vinyl group, such as a-methylstyrene and a-ethylstyrene, substituted styrenes with one or more alkyl substituents on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as, for example, monochlorostyrenes ,

dichlorostyrenes , tribromostyrenes and tetrabromostyrenes ; heterocyclic vinyl compounds such as 2-vinylpyridine, 3- vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine , 2 , 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole,

4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3- vinylpyrrolidine, N-vinylcaprolactam, vinyloxolanes ,

vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles , and hydrogenated vinylthiazoles , vinyloxazoles and hydrogenated vinyloxazoles;

vinyl ethers such as methylvinyl ether, ethylvinyl ether; isoprenyl ethers.

The hydroxyl-group of monomeric unit B is esterified after copolymerisation with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups. The uncharged electron donor is a functional group with coordinative properties to which the catalytically-active metal compound can be bound. Preferably, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from phosphines or nitrogen-containing carbenes (NHC) . More preferably, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor is selected from the group consisting of compounds of the general formulas (XII) -(XV),

(XIV) (XV)

wherein further n = 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h are each independently selected from the group consisting of Bilinear or branched Ci-C2o-alkyl, preferably linear or branched C ₃ -Cio-alkyl;

C3-Cio-cycloalkyl ;

C6-C2o ^_ arylalkyl

R ⁵ is selected from the group consisting of H;

Ci-C2o-alkyl;

and C ₅ -Ci8-heteroaryl

R ⁶ and R ⁶ ' are each independently selected from H and Me.

Preferably, R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g , R ^4h are each

independently selected from the group consisting of H,

isobutyl, cyclohexyl, phenyl and 1-adamantyl.

Preferably, R ⁵ is selected from the group consisting of H and mesityl .

In the context of the present invention an uncharged electron donor is a ligand without net-charge that contributes free electrons or orbitals filled with electrons for a coordinative bond with an acceptor. An acceptor is an atom that accepts the free electrons or electrons from a filled orbital of the donor. Donors are typically main group elements from groups 13-17 of the Periodic Table of Elements, e.g. C, N, P.

Importantly, carbon, too, can act as uncharged electron donor. Mostly found as carbene, wherein the carbon atom bears a pair of electrons in an orbital. These electrons are provided for an uncharged sigma bond with the acceptor atom. Acceptors are typically metal atoms, e.g. Pd(0), Pd(II), Ru (I), Ru(II) . Particularly preferred, the precursor of a phosphorous and/or nitrogen containing uncharged electron donor as coordinative group is selected from the group consisting of compounds of formula XII, wherein R ^4a and R ^4b are the same and are selected from the group consisting of phenyl, isobutyl, cyclohexyl and

1-adamantyl and n is 1, 2, 3, 4 or 5;

formula XIV, wherein R is H, R ⁵ is mesityl and n is 1, 2, 3, 4 or 5;

and formula XV, wherein R ^4g and R ^4h are the same and are selected from the group consisting of 1-adamantyl and phenyl and n is 1, 2, 3, 4 or 5. Preferred monomeric units B are selected from

2-hydroxyethyl (meth) acrylate,

2-hydroxypropyl (meth) acrylate, and

2-hydroxybutyl (meth) acrylate,

which may be esterified with one of

3- (diphenylphosphino) -propionic acid

3- (di-l-adamantyl-phosphino) -propionic acid

3- (dicyclohexyl-phosphino) -propionic acid and

3- (di-isobutyl-phosphino) -propionic acid;

and

Tris (hydroxymethyl ) methylacrylamide, which is esterified with

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=CH ₂ ), 1-propenyl (-CH=CH-CH ₃ ) , 2-propenyl (-CH ₂ -CH=CH ₂ ) , 1- butenyl (-CH=CH-CH ₂ -CH ₃ ) .

Suitable compounds are, for example, (meth) acrylic esters, vinyl esters or allyl esters of at least dihydric alcohols. These compounds include more particularly (meth) acrylates deriving from unsaturated alcohols, such as allyl

(meth) acrylate, vinyl (meth) acrylate and methylallyl

(meth) acrylate, for example;

(meth) acrylates deriving from substituted or unsubstituted diols, such as, 1 , 2-ethanediol di (meth) acrylate, 1,2- propanediol di (meth) acrylate, 1 , 3-propanediol

di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,2- butanediol di (meth) acrylate, 1 , 3-butanediol di (meth) acrylate, 2 , 3-butanediol di (meth) acrylate, 1 , 4-butanediol

di (meth) acrylate, 1 , 2-pentanediol di (meth) acrylate, 1,5- pentanediol di (meth) acrylate, 1 , 2-hexanediol di (meth) acrylte, 1 , 6-hexanediol di (meth) acrylate, 1, 10-decanediol

di (meth) acrylate, 1 , 2-dodecanediol di (meth) acrylate, 1,12- dodecandediol di (meth) acrylate, or higher polyfunctional alcohols, such as, for example, glycol di (meth) acrylates , such as ethylene glycol di (meth) acrylate, diethylene glycol

di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate, glycerol

di (meth) acrylate, diurethane dimethacrylate and methylene bisacrylamide ;

(meth) acrylates having three or more double bonds, such as glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate;

di- or polyvinyl compounds like triallylcyanurate,

divinylbenzenes , N, N' -divinylethylene urea;

divinylether of polyhydroxy compounds like butanediol-bis- vinylether, hexanediol-bis-vinylether , trimethylol- propanetrivinylether , pentaerythrit-tetra-vinylether .

Preferred cross-linking monomers are selected from the following group:

allyl (meth) acrylate, vinyl (meth) acrylate and methylallyl (meth) acrylate, divinylbenzenes, glycol di (meth) acrylates , Ν,Ν' -methylene-bisacrylamide, bis (2-methacryloyl) oxyethyl disulfide .

More preferably, cross-linking monomers are selected from the following group:

ethylene glycol dimethacrylate (XVI),

N, N' - ( 1 , 2-dihydroxyethylene) bis-acrylamide (XVI I )

p-divinylbenzene (XVIII),

N, N' -methylene-bisacrylamide (XIX), and

bis (2-methacryloyl) oxyethyl disulfide (XX) .

(XIX) (XX)

Catalytically-active metal compounds are metals, metal complexes or metal salts of elements of groups 6-11 of the Periodic Table of the Elements. Preferably, the catalytically- active metal compound contains a metal selected from the group consisting of Pd, Rh, Ru, Pt, Ir, Cu, Ni and Fe, wherein Pd, Rh and Ru are particularly preferred.

Preferred metal complexes are

[Pd (allyl) CI] 2 and

[Rh(cod) ₂ ]BF ₄ ,

In the present invention, the above-mentioned monomeric units A and B and cross-linking monomeric units C can arbitrarily and effectively be combined or co-polymerized to obtain an optionally cross-linked polymer, having a critical solution temperature and required stability and mechanical properties.

Particularly suitable are specific amounts of monomeric units A, B and cross-linking monomeric units C.

Monomeric unit A is present in the polymer in a range from 50 wt-% - 99.9 wt-%, preferably 80 wt-% - 99.9 wt-%, more

preferably 80 wt-% - 99.5 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit A is present in a range from 50 wt-% - 99.8 wt-%, preferably 80 wt-% - 99.5 wt-%, more preferably 90 wt-% - 97 wt-%.

Monomeric unit B is present in the polymer in a range from 0.1 wt-% - 50 wt-%, preferably 0.1 wt-% - 20 wt-%, more preferably 0.5 wt-% - 20 wt-%, most preferably 1 wt-% - 10 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit B is present in a range from 0.1 wt-% - 30 wt-%, preferably 0.1 wt-% - 10 wt-%, and most preferably 1 wt-% - 5 wt-%.

Monomeric unit C is present in the polymer in a range from 0 wt-% - 30 wt-%, more preferably 0.1 wt-% - 20 wt-%. In the case that the polymer is an intramolecularly cross-linked microgel, monomeric unit C is present in a range from 0.1 wt-%

- 20 wt-%, preferably 1 wt-% - 5 wt-%, more preferably 1 wt-%

- 3 wt-%. The following specific combinations are particularly

preferred .

Table 1: Specific compositions of monomeric units.

According to the present invention, for specific compositions of polymers in table 1, preferably, the monomeric units are selected as presented in table 2. Table 2: Specific combinations of monomeric units.

Precursor of Mononitrogen / meric monomeric unit A monomeric unit B

phosphorous unit compound C

EMA [a] [e] -

EMA [b] [e] -

EMA [c] [e] -

EMA [a] [f] -

EMA [b] [f] -

EMA [c] [f] -

EMA [a] [g] -

EMA [b] [g] -

EMA [c] [g] -

EMA [a] [h] -

EMA [b] [h] -

EMA [c] [h] -

EMA [d] -

NIPAM [a] [e] -

NIPAM [b] [e] -

NIPAM [c] [e] -

NIPAM [a] [f] -

NIPAM [b] [f] -

NIPAM [c] [f] -

NIPAM [a] [g] -

NIPAM [b] [g] -

NIPAM [c] [g] -

NIPAM [a] [h] -

NIPAM [b] [h] -

NIPAM [c] [h] -

NIPAM [d] -

VA [a] [e] -

VA [b] [e] -

VA [c] [e] -

VA [a] [f] -

VA [b] [f] -

VA [c] [f] -

VA [a] [g] -

VA [b] [g] -

VA [c] [g] -

VA [a] [h] -

VA [b] [h] - VA [ C ] [h] -

VA [d] -

EA [a] [e] -

EA [b] [e] -

EA [c] [e] -

EA [a] [f] -

EA [b] [f] -

EA [c] [f] -

EA [a] [g] -

EA [b] [g] -

EA [c] [g] -

EA [a] [h] -

EA [b] [h] -

EA [c] [h] -

EA [d] -

EMA [a] [e] XVI

EMA [b] [e] XVI

EMA [c] [e] XVI

EMA [a] [f] XVI

EMA [b] [f] XVI

EMA [c] [f] XVI

EMA [a] [g] XVI

EMA [b] [g] XVI

EMA [c] [g] XVI

EMA [a] [h] XVI

EMA [b] [h] XVI

EMA [c] [h] XVI

EMA [d] XVI

NIPAM [a] [e] XVI

NIPAM [b] [e] XVI

NIPAM [c] [e] XVI

NIPAM [a] [f] XVI

NIPAM [b] [f] XVI

NIPAM [c] [f] XVI

NIPAM [a] [g] XVI

NIPAM [b] [g] XVI

NIPAM [c] [g] XVI

NIPAM [a] [h] XVI

NIPAM [b] [h] XVI NIPAM [ C ] [h] XVI

NIPAM [d] XVI

VA [a] [e] XVI

VA [b] [e] XVI

VA [c] [e] XVI

VA [a] [f] XVI

VA [b] [f] XVI

VA [c] [f] XVI

VA [a] [g] XVI

VA [b] [g] XVI

VA [c] [g] XVI

VA [a] [h] XVI

VA [b] [h] XVI

VA [c] [h] XVI

VA [d] XVI

EA [a] [e] XVI

EA [b] [e] XVI

EA [c] [e] XVI

EA [a] [f] XVI

EA [b] [f] XVI

EA [c] [f] XVI

EA [a] [g] XVI

EA [b] [g] XVI

EA [c] [g] XVI

EA [a] [h] XVI

EA [b] [h] XVI

EA [c] [h] XVI

EA [d] XVI

EMA [a] [e] XVII

EMA [b] [e] XVII

EMA [c] [e] XVII

EMA [a] [f] XVII

EMA [b] [f] XVII

EMA [c] [f] XVII

EMA [a] [g] XVII

EMA [b] [g] XVII

EMA [c] [g] XVII

EMA [a] [h] XVII

EMA [b] [h] XVII EMA [ C ] [h] XVII

EMA [d] XVII

NIPAM [a] [e] XVII

NIPAM [b] [e] XVII

NIPAM [c] [e] XVII

NIPAM [a] [f] XVII

NIPAM [b] [f] XVII

NIPAM [c] [f] XVII

NIPAM [a] [g] XVII

NIPAM [b] [g] XVII

NIPAM [c] [g] XVII

NIPAM [a] [h] XVII

NIPAM [b] [h] XVII

NIPAM [c] [h] XVII

NIPAM [d] XVII

VA [a] [e] XVII

VA [b] [e] XVII

VA [c] [e] XVII

VA [a] [f] XVII

VA [b] [f] XVII

VA [c] [f] XVII

VA [a] [g] XVII

VA [b] [g] XVII

VA [c] [g] XVII

VA [a] [h] XVII

VA [b] [h] XVII

VA [c] [h] XVII

VA [d] XVII

EA [a] [e] XVII

EA [b] [e] XVII

EA [c] [e] XVII

EA [a] [f] XVII

EA [b] [f] XVII

EA [c] [f] XVII

EA [a] [g] XVII

EA [b] [g] XVII

EA [c] [g] XVII

EA [a] [h] XVII

EA [b] [h] XVII EA [C] [h] XVII

EA [d] XVII

EMA [a] [e] XVIII

EMA [b] [e] XVIII

EMA [c] [e] XVIII

EMA [a] [f] XVIII

EMA [b] [f] XVIII

EMA [c] [f] XVIII

EMA [a] [g] XVIII

EMA [b] [g] XVIII

EMA [c] [g] XVIII

EMA [a] [h] XVIII

EMA [b] [h] XVIII

EMA [c] [h] XVIII

EMA [d] XVIII

NIPAM [a] [e] XVIII

NIPAM [b] [e] XVIII

NIPAM [c] [e] XVIII

NIPAM [a] [f] XVIII

NIPAM [b] [f] XVIII

NIPAM [c] [f] XVIII

NIPAM [a] [g] XVIII

NIPAM [b] [g] XVIII

NIPAM [c] [g] XVIII

NIPAM [a] [h] XVIII

NIPAM [b] [h] XVIII

NIPAM [c] [h] XVIII

NIPAM [d] XVIII

VA [a] [e] XVIII

VA [b] [e] XVIII

VA [c] [e] XVIII

VA [a] [f] XVIII

VA [b] [f] XVIII

VA [c] [f] XVIII

VA [a] [g] XVIII

VA [b] [g] XVIII

VA [c] [g] XVIII

VA [a] [h] XVIII

VA [b] [h] XVIII VA [ C ] [h] XVIII

VA [d] XVIII

EA [a] [e] XVIII

EA [b] [e] XVIII

EA [c] [e] XVIII

EA [a] [f] XVIII

EA [b] [f] XVIII

EA [c] [f] XVIII

EA [a] [g] XVIII

EA [b] [g] XVIII

EA [c] [g] XVIII

EA [a] [h] XVIII

EA [b] [h] XVIII

EA [c] [h] XVIII

EA [d] XVIII

EMA [a] [e] XIX

EMA [b] [e] XIX

EMA [c] [e] XIX

EMA [a] [f] XIX

EMA [b] [f] XIX

EMA [c] [f] XIX

EMA [a] [g] XIX

EMA [b] [g] XIX

EMA [c] [g] XIX

EMA [a] [h] XIX

EMA [b] [h] XIX

EMA [c] [h] XIX

EMA [d] XIX

NIPAM [a] [e] XIX

NIPAM [b] [e] XIX

NIPAM [c] [e] XIX

NIPAM [a] [f] XIX

NIPAM [b] [f] XIX

NIPAM [c] [f] XIX

NIPAM [a] [g] XIX

NIPAM [b] [g] XIX

NIPAM [c] [g] XIX

NIPAM [a] [h] XIX

NIPAM [b] [h] XIX IPAM [C] [h] XIX

NIPAM [d] XIX

VA [a] [e] XIX

VA [b] [e] XIX

VA [c] [e] XIX

VA [a] [f] XIX

VA [b] [f] XIX

VA [c] [f] XIX

VA [a] [g] XIX

VA [b] [g] XIX

VA [c] [g] XIX

VA [a] [h] XIX

VA [b] [h] XIX

VA [c] [h] XIX

VA [d] XIX

EA [a] [e] XIX

EA [b] [e] XIX

EA [c] [e] XIX

EA [a] [f] XIX

EA [b] [f] XIX

EA [c] [f] XIX

EA [a] [g] XIX

EA [b] [g] XIX

EA [c] [g] XIX

EA [a] [h] XIX

EA [b] [h] XIX

EA [c] [h] XIX

EA [d] XIX

EA = ethylacrylate, EMA = ethylmethacrylate, VA =

vinylacetate , NIPAM = N-isopropylacrylamide, [a] = 2-hydroxyethyl (meth) acrylate, [b] = 2-hydroxypropyl (meth) acrylate, [c] = 2- hydroxybutyl (meth) acrylate, [d] = Tris (hydroxymethyl)

methacrylamide , [e] = 3- (diphenyl-phosphino ) -propionic acid, [f] = 3- (di-l-adamantyl-phosphino) -propionic acid, [g] = 3- (dicyclohexyl- phosphino) -propionic acid, [h] = 3- (di-isobutyl-phosphino ) -propionic acid Furthermore, the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B, and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.

In a special embodiment of the present invention the catalyst comprises

(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B, and 0 wt-% - 30 wt-% of one unit derived from a cross-linking monomeric unit C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.

Furthermore, the invention provides a catalyst comprising (a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A and 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.

In a special embodiment of the present invention the catalyst comprises

(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer consists of 50 wt-% - 99.9 wt-% of one unit derived from a non-functionalized monomeric unit A, and 0.1 wt-% - 50 wt-% of one unit derived from a monomeric unit B; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups;

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer.

Furthermore, the invention provides a catalyst comprising

(a) a polymer, which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;

wherein the critical solution temperature T _c of the polymer in solvent x is in a range of from -10°C to +150°C, wherein solvent x is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol , n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene .

The critical solution temperature T _c 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 T _sta rt-

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 T _star t- A

straight line (Li) which passes this starting point and exhibits the respective slope (tangent at T _sta rt) 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 T _c of the polymer. The critical solution temperature can be measured in different organic solvents. Suitable solvents are methanol, ethanol, n- propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene.

Preferably methanol, isopropanol, n-butanol and toluene are used. The critical solution temperature in at least one of these solvents is in a range from -10°C to +150°C, preferably the critical solution temperature in at least one of these solvents is in a range of from -10°C to +100°C, more

preferably the critical solution temperature in at least one of these solvents is in a range of from -10°C to +70°C, suitably preferred is a critical solution temperature in at least one of these solvents in a range of from +5°C to +50°C.

Polymers with a critical solution temperature are called temperature-responsive polymers. Temperature-responsive polymers, which are precipitable by increase or decrease of temperature, are well known (I. Dimitrov, B. Trzebicka, A. H. E. Muller, A. Dworak, C. B. Tsvetanov, Prog. Polym. Sci. 2007, 32,1275-1343; R. Pelton, Adv Coll Interface Sci 2000, 85,1; J. K. Oh, R. Drumright, D. J. Siegwart, K. Matyj aszewski, Prog. Polym. Sci. 2008, 33, 448-477; T. J. Freemont, B. R. Saunders, Soft Matter, 2008, 4, 919-924; S. Nayak, L.A. Lyon Angew. Chem. Int. Ed. 2005, 44, 7686-7708) .

They can be divided into polymers with upper critical solution temperature (UCST) and polymers with lower critical solution temperature (LCST) . A polymer with an UCST forms a colloidal solution with a solvent above this critical temperature but precipitates below the critical temperature. A polymer with a LCST forms a homogeneous solution with a solvent below the critical temperature but precipitates above this critical temperature . The afore-mentioned temperature-responsive polymers could furthermore be part of so-called microgels due to cross- linking of the monomers. According to Funke et al . microgels are intramolecularly cross-linked macromolecules of colloidal dimensions which are dispersed in normal or colloidal

solutions, in which, depending on the degree of cross-linking and on the nature of the solvent, they are more or less swollen (Funke et al . , Microgels - Intramolecularly

Crosslinked Macromolecules with Globular Structure, Adv.

Polym. Sci. 1998, 139) . The cross-linking is achieved by applying ternary copolymerization of non-functionalized monomers, functionalized monomers and cross-linking monomers in very diluted solutions with the monomer concentration below a critical value. Under these conditions, microgels do not react intermolecularly to build an insoluble polymer network, but intramolecularly to yield a stable solution. The critical monomer concentration is dependent on the type of monomer, the degree of cross-linking, the solvent and the polymerization conditions. The resulting microgel also exhibits temperature- responsive properties. Techniques for the preparation of microgels, surface modification and applications of microgels are well known to the person skilled in the art from the afore-mentioned review article of Funke et al ..

The advantage of microgels over linear polymers is their low viscosity even in solutions with high solid concentration and at low temperatures, which provides the opportunity to apply the microgel-based catalyst in high concentrations.

Furthermore, due to the structure of microgels, the

catalytically-active metal compound is localized at the surface of the microgel particles. This provides a better accessibility of the catalytically-active metal compounds and can lead to as high catalytic activity as conventional

homogeneous catalysts.

In addition, the intramolecular cross-linking provides a high structural stability of the colloids, which is a requirement for their application as recyclable catalyst or catalyst support .

Furthermore, the invention provides a catalyst comprising

(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from the group

consisting of ethyl methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) ;

wherein monomeric units B are selected from the group

consisting of 2-hydroxyethyl (meth) acrylate esterified with 3- (diphenyl-phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid, 2-hydroxypropyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid, and

Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane ; and

wherein cross-linking monomeric units C are selected from the roup consisting of compounds of formulas XVI-XX

(xix) (xx)

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer. Furthermore, the invention provides a catalyst comprising

(a) a polymer, which has a weight-average molecular weight in the range of from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C; wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and (b) a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;

wherein further the catalytically-active metal compound comprises a metal selected from the group consisting of Pd, Ru, Pt, Ir, Cu, Ni and Fe .

Furthermore, the invention provides a catalyst comprising

(a) a polymer, which has a weight-average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.9 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 50 wt-% of units derived from one or more monomeric units B, 0 wt-% - 30 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B,

and a catalytically-active metal compound that is bound to one or more phosphorous and/or nitrogen containing uncharged electron donors of said polymer;

wherein further the precursor of phosphorous and/or nitrogen containing uncharged electron donor is selected from

phosphines and N-heterocyclic carbenes.

Furthermore, the invention provides a process for producing a catalyst, comprising the steps

(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,

(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,

(c) reacting the resulting polymer with a catalytically-active metal compound, and

(d) separating the resulting catalyst from the reaction mixture .

Furthermore, the invention provides a process for producing a catalyst, comprising the steps

(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,

(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,

(c) reacting the resulting polymer with a catalytically-active metal compound, and (d) separating the resulting catalyst from the reaction mixture ;

wherein the catalytically-active metal compound comprises a metal selected from Pd, Rh, Ru, Pt, Co, Cu, Ni and Fe .

Furthermore, the invention provides a catalyst obtainable by a process comprising the steps

(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and where applicable cross-linking monomeric units C,

(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor,

(c) reacting the resulting polymer with a catalytically-active metal compound, and

(d) separating the resulting catalyst from the reaction mixture .

The polymers according to the invention may be obtained in particular by solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, it being possible to achieve surprising advantages by means of a radical solution polymerization. These methods are set out in Ullmann' s Encyclopedia of Industrial Chemistry, Sixth Edition.

As well as methods of conventional radical polymerization it is also possible to employ related methods of controlled radical polymerization, such as, for example, ATRP (= Atom Transfer Radical Polymerization) , NMP (Nitroxide-mediated Polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer) .

References describing typical free radical polymerization include Ullmanns's Encyclopedia of Industrial Chemistry, Sixth Edition. For such polymerization, generally speaking, a polymerization initiator and also, optionally, a molecular- weight-regulating chain-transfer agent are employed. The initiators which can be used include, among others, the azo initiators that are widely known in the art, such as

Azobisisobutyronitrile (AIBN) and 1,1-

Azobiscyclohexanecarbonitrile, and also peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert- butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, tert- butylperoxy-2-ethylhexanoate, tert-butylperoxy-3 , 5 , 5- trimethylhexanoate, dicumyl peroxide, 1,1 bis (tert

butylperoxy) cyclohexane, 1,1 bis (tert butylperoxy) -3 , 3 , 5- trimethylcyclohexane, cumyl hydroperoxide, tert-butyl

hydroperoxide, bis (4 tert butylcyclohexyl ) peroxydicarbonate, mixtures of two or more of the aforementioned compounds with one another, and mixtures of the aforementioned compounds with nonspecified compounds that may likewise form free radicals.

The stated initiators may be used either individually or in a mixture. They are used in an amount of 0.01 mol-% to 10.0 mol- %, preferably 0.1 mol-% to 5 mol-%, more preferably 0.5 mol-% to 2 mol-% based on the total weight of the monomers. It is also possible with preference to carry out the polymerization using a mixture of different polymerization initiators having different half-lives.

The polymerization can be carried out under atmospheric, subatmospheric or superatmospheric pressure. The

polymerization temperature as well is not critical. Generally speaking, however, it is in the range of -20°C - +200°C, preferably +50°C - +150°C and more preferably +70°C - +130°C.

The polymerization can be carried out with or without solvent. The term "solvent" should be understood widely in this

context. The preferred solvents include, in particular, aromatic hydrocarbons, such as toluene, xylene; esters, especially acetates, preferably butyl acetate, ethyl acetate, propyl acetate; ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone ; alcohols, especially methanol, isopropanol, n-butanol, isobutanol;

ethers, especially glycol monomethyl ethers, glycol monoethyl ethers, glycol monobutyl ethers; aliphatics, preferably pentane, hexane, cycloalkanes and substituted cycloalkanes , such as cyclohexane; mixtures of aliphatics and/or aromatics, preferably naphtha; benzine, biodiesel; tetrahydrofuran, dichloromethane ; but also plasticizers such as low molecular weight polypropylene glycols or phthalates. The stated

solvents may be used individually or as a mixture.

Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B. Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one non-functionalized monomeric unit A, 0.1 wt-% - 30 wt-% of units derived from one monomeric unit B, and 0.1 wt-% - 20 wt-% of units derived from one cross-linking

monomeric unit C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B.

Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from (meth) acrylates and monomers co-polymerizable with (meth) acrylates ;

wherein monomeric units B are selected from hydroxyl- functionalized (meth) acrylates and monomers co-polymerizable with (meth) acrylates , which are esterified with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donors as coordinative groups; and

wherein cross-linking monomeric units C are selected from compounds which comprise at least two olefinically unsaturated double bonds co-polymerizable with A and/or B; wherein the critical solution temperature of the polymer at room

temperature in at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, dichloromethane, diethylether , tetrahydrofuran, ethylacetate, acetone, dimethylformamide and toluene is in a range of from -10°C to +150°C.

Furthermore, the invention provides a polymer with a weight- average molecular weight in the range from 1000 g/mol - 100000 g/mol and which polymer comprises 50 wt-% - 99.8 wt-% of units derived from one or more non-functionalized monomeric units A, 0.1 wt-% - 30 wt-% of units derived from one or more monomeric units B and 0.1 wt-% - 20 wt-% of units derived from one or more cross-linking monomeric units C;

wherein monomeric units A are selected from the group

consisting of ethyl methacrylate (EMA) , N-isopropylacrylamide (NIPAM) , vinylacetate (VA) and ethylacrylate (EA) ;

wherein monomeric units B are selected from the group

consisting of

2-hydroxyethyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (diphenyl- phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid, 2-hydroxypropyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (di-1- adamantyl-phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (dicyclohexyl-phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (dicyclohexyl- phosphino) -propionic acid,

2-hydroxyethyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,

2-hydroxypropyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid,

2-hydroxybutyl (meth) acrylate esterified with 3- (di-isobutyl- phosphino) -propionic acid, and

Tris (hydroxymethyl ) methylacrylamid esterified with (3- iodopropyl) trimethoxysilane ;

and wherein cross-linking monomeric units C are selected from the roup consisting of compounds according to formulas XVI-XX

(XIX) (XX)

Furthermore, the invention relates to a process for producing the polymer, comprising the steps (a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,

(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor, and

(c) separating the resulting polymer from the reaction mixture . Furthermore, the invention relates to a polymer obtainable by a process comprising the steps

(a) co-polymerizing non-functionalized monomeric units A, hydroxyl-functionalized monomeric units B and cross-linking monomeric units C,

(b) esterifying hydroxyl-groups of monomeric units B with one or more suitable precursors of phosphorous and/or nitrogen containing uncharged electron donor, and

(c) separating the resulting polymer from the reaction mixture .

Furthermore, the invention relates to the use of the catalyst in homogeneous and/or heterogeneous catalysis. Preferred catalytic reactions are ring closing metathesis (RCM) ;

hydroformylation; C-X or C-C coupling reactions, e.g.

Mizoroki-Heck-coupling, Suzuki-Miyaura-coupling; and

hydrogenation reactions, e.g. hydrogenation of C-C double bonds, nitro groups, carbonyl groups, nitril groups, ketones, imines, arenes, heterocycles .

Molecular weight of polymer

The (meth) acrylate polymer of the invention has a weight- average molecular weight in the range of from 1000 g/mol to 100000 g/mol, preferably of from 10000 g/mol to 60000 g/mol, more preferably in the range of from 15000 to 40000 g/mol. The number-average molecular weight of preferred (meth) acrylate polymers is in the range of from 1000 g/mol to 60 000 g/mol, more preferably in the range of from 3000 g/mol to 25 000 g/mol. Also of particular interest are (meth) acrylate polymers which have a polydispersity index, Mw/Mn, in the range of from 1 to 10, more preferably in the range of from 1.5 to 7 and very preferably of from 1.7 to 3. The molecular weight can be determined by means of gel permeation chromatography (GPC) against a PMMA standard.

Determination of molecular weight

The molecular weight was determined via GPC. GPC columns from the manufacturer Varian/Polymer Laboratories were used, arranged in series with the pore sizes 105, 106, 104 and 103 A. The individual columns were 300 mm long and had a diameter of 7.5 mm. A polymer solution was prepared with an initial concentration of 2.5 g of polymer per litre of solvent. THF was used as eluent, and a flow rate of 1 ml/min was operated. The injection volume was 100 μΐ . The column oven is

conditioned to 35°C. Detection took place using the RI 150 detector from Thermo Electron. The data were evaluated using the WinGPC program from Polymerstandard-Service (PSS) . Mw denotes the weight-average molecular weight, D the

polydispersity index (D = Mw/Mn, Mn = number-average molecular weight) . Examples

1. Preparation of Copolymers a) EA/HEMA (95:5)

PROCEDURE :

20.024 g (200.00 mmol) ethylacrylate and 1.370 g (10.53 mmol) 2-hydroxyethyl methacrylate are dissolved in 200 mL abs . THF. Afterwares 173 mg (1.05 mmol) azobis ( isobutyronitril ) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min 2 bubbling) . An oil bath is heated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.

The cooled reaction mixture is diluted with 200 mL THF and added dropwise to 2000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo. b) EA/THMA (95:5)

PROCEDURE :

10.012 g (100.00 mmol) ethylacrylate and 922 mg (5.26 mmol) tris (hydroxymethyl) methylacrylamide are dissolved in 100 mL abs . THF. Afterwards 86 mg (0.53 mmol) azobis ( isobutyronitril ) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min N2 bubbling) . An oil bath is heated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.

The cooled reaction mixture is diluted with 100 mL THF and added dropwise to 1000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo. c) VAc/HEMA (95:5)

PROCEDURE :

17218 mg (200.00 mmol) vinyl acetate and 1370 mg (10.52 mmol) 2-hydroxyethyl methacrylate are dissolved in 150 mL THF.

Afterwards 172 mg (1.06 mmol) azobis (isobutyronitrile) (AIBN) are added and the reaction mixture is degassed thoroughly (ca. 15 min N2 bubbling) . An oil bath is preheated to 70 °C and the reaction mixture is stirred at this temperature for 16 h.

The cooled reaction mixture is diluted with 100 mL THF and added dropwise to 1000 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.

2. Esterification of Copolymers a) EA-HEMA-COO-Et-PPh ₂ (95:5)

PROCEDURE :

10697 mg (5.26 mmol hydroxy-funcionalities ) ethylacrylate/ 2- hydroxyethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 100 mL abs . DCM. Afterwards 1086 mg (5.26 mmol) dicyclohexylcarbodiimide (DCC), 129 mg (1.05 mmol) 4- (N, -Dimethylamino) pyridine (DMAP) and portionwise 1359 mg (5.26 mmol) 3- (diphenylphosphino) propionic acid are added and the reaction mixture is stirred for 16 h at room temperature.

The reaction mixture is cooled to 0 °C and the white precipitate is removed by filtration. The filtrate is evaporated in vacuo and purified by flash column chromatography using silica as stationary phase and DCM as eluent .

b) EA-THMA-Si-Pr-PAd ₂ (95:5)

M n

starting materials eq m [g]

[g/mol] [mmo1 ]

Ad ₂ PH 302.43 30.00 1.0 9.07

(MeO) ₃ Si-Pr-I 290.17 39.00 1.3 11.32

PROCEDURE :

Under argon atmosphere 9.07 g (30.00 mmol) di-(l- adamantyl ) phosphine are dissolved in xylene , 11.32 g (39.00 mmol) ( 3-iodopropyl ) trimethoxysilane are added dropwise and the reaction mixture is refluxed for 20 h. The white precipitate is removed by filtration. The filter cake is washed with diethylether and dried in high vacuo.

YIELD :

17.0479 (98%), white solid

c) VAc-HEMA-COO-Et-PPh ₂ (95:5)

M m starting materials n [mmo1 ] eq

[g/mol] [mg] copolymer VAc HEMA 95:5 (88.29) OH: 1.0 1.0 1766

3- (diphenylphosphino) propionic

258.25 1.0 1.0 258 acid

DCC 206.33 1.0 1.0 206

DMAP 122.17 0.1 0.1 12

PROCEDURE :

1766 mg (1.00 mmol hydroxy-funcionalities ) vinyl acetate / 2- hydroxyethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 20 mL abs . DCM. Afterwards 206 mg (1.00 mmol) dicyclohexylcarbodiimide (DCC), 12 mg (0.10 mmol) 4- (N, W-Dimethylamino) pyridine (DMAP) and portionwise 258 mg (1.00 mmol) 3- (diphenylphosphino) propionic acid are added and the reaction mixture is stirred for 16 h at room temperature.

The reaction mixture is cooled to 0 °C and the white

precipitate is removed by filtration. The filtrate is

evaporated in vacuo and purified by flash column

chromatography using silica as stationary phase and DCM as eluent.

3. Metal complexes a) Pd-complex of EA-HEMA-COQ-Et-PPh ₂ (95:5)

starting

M [g/mol] n [mmo1 ] eq m [mg] materials

EA-HEMA-COO-Et-

(113.63) P : 1.0 1.0 2273 PPh ₂ (95:5)

[Pd(allyl)Cl] ₂ 365.89 0.5 0.5 183

PROCEDURE :

Under argon atmosphere 2273 mg (1.0 mmol phosphine- functionalities ) ethylacrylate/ 2- ( (3- (diphenylphosphino) - propanoyl ) oxy) ethyl methacrylate copolymer (95:5) are

dissolved in 50 mL abs . dichloromethane (DCM) . Afterwards a solution of 183 mg (0.5 mmol) allylpalladium ( I I ) chloride-dimer in 10 mL abs. DCM is slowly added dropwise to the polymer solution. The reaction mixture is stirred for 2 h at room temperature .

The reaction mixture is concentrated in vacuo to ca. 5 mL . 50 mL hexane are added and the mixture is stirred for 2 h, wherein the polymer precipitates as yellow oily substance. Hexane is decanted and excessive hexane is removed in high vacuo . b) Rh-complex of EA / HEMA-COQ-Et-PPh ₂ (95:5)

PROCEDURE :

In a glovebox under argon atmosphere 1136 mg (0.5 mmol phosphine-functionalities ) ethylacrylate / 2- ( (3- (diphenylphosphino) -propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved in a mixture of 20 mL abs . DCM.

Afterwards a solution of 102 mg (0.25 mmol) bis (1,5- cyclooctadien) rhodium ( I ) tetrafluoroborate in 5 mL abs. DCM is slowly added dropwise to the polymer solution. The reaction mixture is stirred for 1 h at room temperature.

The reaction mixture is concentrated in vacuo to ca. 5 mL . 30 mL diethylether are added and the mixture is stirred for 2 h, wherein the polymer precipitates as orange oily substance. Diethylether is decanted and excessive diethylether is removed in high vacuo.

c) Pd-complex of VAc-HEMA-COO-Et-PPh ₂ (95:5)

PROCEDURE :

100 mg (0.05 mmol phosphine-funcionalities ) vinyl acetate / 2- ( (3- (diphenylphosphino) propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved under argon atmosphere in 10 mL abs. DCM. Afterwards 9 mg (0.025 mmol)

allylpalladium ( I I ) chloride-dimer are added and the reaction mixture is stirred for 2 h at room temperature.

The reaction mixture is added dropwise to 100 mL hexane, which leads to precipitation of the polymer. After ca. 2 h when the polymer has settled hexane is decanted and excessive hexane is removed in vacuo.

d) Rh-complex of VAc-HEMA-COO-Et-PPh ₂

m starting materials M [g/mol] n [mmo1 ] eq

[mg]

VAc-HEMA-COO-Et-PPh ₂

(100.30) P: 0.05 1.0 100 (95:5)

Rh (cod) ₂ BF ₄ 406.07 0.025 0.5 10

PROCEDURE :

In a glovebox under argon atmosphere 100 mg (0.05 mmol

phosphine-functionalities ) vinyl acetate / 2- ( (3- (diphenylphosphino) propanoyl) oxy) ethyl methacrylate copolymer (95:5) are dissolved in 10 mL abs . DCM. Afterwards a solution of 10 mg (0.025 mmol) bis ( 1 , 5-cyclooctadien) rhodium ( I )

tetrafluoroborate in 2 mL abs. DCM is slowly added to the polymer solution. The reaction mixture is stirred for 1 h at room temperature.

The reaction mixture is concentrated to ca. 2 mL and 10 mL abs. diethylether are added. The mixture is stirred for 2 h, which leads to the formation of an orange precipitate of the polymer. Excessive diethylether is decanted and the polymer dried in vacuo.

Catalytic activity Example 1

Catalytic activity of Pd-complexes linked with temperature- responsive polymers and microgel particles, respectively, has been proven for Mizoroki-Heck cross coupling. To exclude

Palladium leaching out of the polymer complexes, which might catalyze the reaction as well, a "blind" test has been

performed adding only [Pd (allyl) CI] 2 into the reaction mixture without any phosphine ligand (table 3, entry 1) . This

experiment shows that [Pd (allyl) CI] 2 alone has negligible activity .

In presence of the phosphine-functionalized polymer there is significant catalytic activity, which shows in-situ

interaction between the Pd complex and the phosphine-polymer entities (entry 2) . If the pre-formed Pd-phosphine-polymer catalyst is applied (entry 3) , the catalytic activity becomes even higher indicating that a tight interaction between Pd and phosphine is a prerequisite for catalytic conversion. For the more reactive iodide analogue (entry 4-5) even higher

catalytic activity for the Pd-phosphine-polymer catalyst has been observed compared to the experiments with phenyl bromide.

Mizoroki-Heck coupling

solvent Table 3: Catalytic results for Mizoroki-Heck coupling using EA-HEMA-COO-Et-PPh ₂ (95:5) - Pd(allyl)Cl ₂ adduct

Example 2

An additional catalytic reaction (hydrogenation of cinnamic acid) has been performed applying Rhodium immobilized polymer catalyst (Ethyl acrylate / 2- ( (3- (diphenyl-phosphino)

propanoyl) oxy) ethyl methacrylate copolymer (5 mol-%) - Rhodium (cyclooctadiene) tetrafluoroborate adduct) in different alcoholic solvents which are related to different UCST values (see table 4) . Results are summarized in table 4. Hydrogenation of cinnamic acid

solvent

Table 4: Catalytic results for hydrogenation of cinnamic acid using EA-HEMA-COQ-Et-PPh ₂ (95:5) - Rh(cod) ₂ BF ₄ adduct

The catalytic reaction tests have been performed at two different temperature levels a) a low temperature-level with T = 5°C < UCST and b) the high-temperature level T = 35°C > UCST (compare table 4) .

From table 4, it is evident that for the low-temperature level where the catalyst is in its precipitated state, only low TOF values are achieved whereas the switch to the dissolved catalyst state (reaction temperature 35°C) raises the catalyst activity significantly. For the hydrogenation of cinnamic acid, the order of magnitude of activity is even higher than that of conventional precious metal powder catalysts which are usually applied for this type of application (TOF = 30 h ^-1 to 400 h ^-1 ) . High activity may also be the reason for the partial ring-hydrogenation with

formation of 3-cyclohexyl propionic acid which has been observed as side product (table 4) .