DE102016120134B4 - Isomerizing copolymerization of internally unsaturated fatty acid derivatives with alpha-olefins - Google Patents

Abstract

Process for producing a copolymer, comprising the following step: setting reaction conditions in a reaction mixture comprising at least one α-olefin selected from ethylene, propylene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene and styrene, - at least one unsaturated compound of the formula (I) RG (I) where in each case, independently of one another, R denotes an aliphatic, internally monounsaturated radical and G denotes a group selected from carboxy group, carboxyl ester group, Glycerol ester group, hydroxyl group, alkoxy group and aryloxy group, the compound of the formula (I) being selected from (i) alkyl esters of monounsaturated fatty acids having 14 to 24 carbon atoms and (ii) vegetable oils, - at least one isomerization catalyst for producing an isomer of the unsaturated compound, which has a terminal double bond selected from [MeCN] 2PdCl2 and [(t-Bu3P) Pd (µ-Br)] 2 or an in situ thereof g e formed product, and at least one polymerization catalyst for the copolymerization of the α-olefin with the isomer with a terminal double bond, wherein the polymerization catalyst is a compound of the formula (II) where R1 is selected from H, alkyl, halogenated alkyl and acrylate, R2 and R3 each independently aryl or alkyl M is metal, L is selected from SbF6-, OTf-, BF4, CF3SO3- and BAr4undAr = aryl and where the polymerization catalyst of the formula (II) is generated in situ by replacing a halide or cyanide ligand with a ligand L andM = Pd, so that a copolymer of the α-olefin with the isomer with a terminal double bond is formed, the isomerization and the copolymerization taking place in a one-pot reaction.

Description

The present invention relates to a method for producing a copolymer as defined in claim 1.

In addition, the present invention also relates to the use of a combination of an isomerization catalyst and a polymerization catalyst for the production of a copolymer as defined in claim 2.

In terms of volume, the production of polymers is at around 300 million tons per year (2013), the second largest area in the chemical industry after fuel production (Association of the Chemical Industry, Chemical Industry in Figures 2015, Frankfurt, 2015). For the most part, fossil raw materials are currently used. Due to climate issues and the limited availability of fossil raw materials, there is a growing interest in polymers made from renewable raw materials (Agency for Renewable Raw Materials, Series Renewable Raw Materials 34: Market Analysis Renewable Raw Materials, Gülzow, 2014). Unsaturated fatty acid derivatives from vegetable oils are interesting starting materials because they contain a double bond that can in principle be polymerized. In addition to the long, non-polar alkyl chain, they have a polar carboxyl function as a second structural element, which can be converted into an amide or alcohol function through simple, industrially feasible transformations, for example, but can also be cross-linked through reaction with multiply functionalized linkers. Unsaturated fatty acids are therefore not only suitable for the production of thermoplastics, it should also be possible to obtain thermoset materials.

The manufacture of unfunctionalized polyolefins has achieved immense industrial importance at the latest through the discoveries of Ziegler and Natta for the catalytic polymerization of ethylene and propylene ( LL Böhm, Angew. Chem. 2003, 115, 5162-5183; K. Ziegler, Angew. Chem. 1955, 67, 541-547 and K. Ziegler, H. Breil, E. Holzkamp, H. Martin, DPB No. 973626, 1960 ). They used heterogeneous catalysts based on titanium or zirconium to activate the C = C bond. Kaminsky et al. were able to extend this concept to soluble, homogeneous catalysts and thus not only gain mechanistic knowledge about the polymerization reaction, but also develop industrially applicable catalysts which, in addition to outstanding activities, also enable a controllable control of the tacticity of the polymers obtained ( H. Sinn, W. Kaminsky, H.-J. Vollmer, R. Woldt, Angew. Chem. 1980, 92, 396-399 and W. Kaminsky, K. Külper, HH Brintzinger, FRWP Wild, Angew. Chem. 1985, 97, 507-508 .). A decisive disadvantage of these systems, however, is the low tolerance of the strongly Lewis acidic metal centers towards functional groups.

Monomers based on vegetable oils can already be polymerized today. By self-metathesis (PB van Dam, MC Mittelmeijer, C. Boelhouven, JCS Chem. Commun. 1972, 1221-1222), isomerizing alkoxycarbonylation ( C. Jimenez-Rodriguez, GR Eastham, DJ Cole-Hamilton, Inorg. Chem. Commun. 2005, 8, 878-881 ) or ozonolysis ( M. Naudet, J. Pasero, Fette, Seifen, Anstrichmittel 1960, 62, 1110-1112 ) Unsaturated fatty acid derivatives, unsaturated and saturated α, ω-diesters can be obtained, which can be reacted with diols to form polyesters (D. Quinzler, S. Mecking, Angew. Chem. Int. Ed. 2010, 49, 4306-4308). By pyrolysis of ricinoleic acid ( Naughton FC, J. Am. Oil Chem. Soc. 1974, 51, 65-71) or ethenolysis of unsaturated fatty acid derivatives (RHA Bosma, F. van den Aardweg, JC Mol, J. Chem. Soc., Chem. Commun. 1981, 1132-1133 ) ω-unsaturated fatty acid derivatives are accessible, which can be copolymerized with ethene ( S. Warwel, F. Brüse, C. Demes, M. Kunz, M. Rüsch gen. Klaas, Chemosphere 2001, 39-48 and P. Aaltonen, B. Löfgren, Eur. Polym. J. 1997, 33, 1187-1190 ).

Polar modified polyolefins are obtained by reacting (poly) olefins with polar monomers such as acrylates, vinyl esters or maleate. (S. Koltzenburg, M. Maskos, O. Nuyken: Polymers. Chap. 14.1.3.2., Springer Berlin 2014). Such polar modified polyolefins expand the range of applications of pure polyolefins considerably. They are used, among other things, as adhesive and sealing components, for protective wax layers, as absorbers and as ion exchangers. All of these applications are based on increased adhesive forces due to the polar modification. In principle, it should also be possible to achieve such a polar modification using natural fatty acids and their structural derivatives. This would have the additional advantage that, in contrast to the polar monomers mentioned above, these fatty acids are of biogenic origin and non-toxic. So far, however, it has not been possible to copolymerize the internal C = C bond of natural fatty acids without upstream, difficult reaction steps (such as metathesis) with olefins.

A decisive disadvantage of the previous methods for polymerizing fat-based monomers is therefore that the starting materials have to be converted into (co) polymerizable monomers in a first reaction step. Here, in some cases, highly pure starting materials have to be used or by-products arise that have to find meaningful applications in other processes in order to achieve sustainable use of raw materials. A direct polymerization of internal (internal) double bonds, as they only occur in natural fats, which is also compatible with carboxyl groups, the essential structural feature of fats, has not been possible until now. It has also not been possible so far to bring the double bond in unsaturated fatty acid derivatives quantitatively into the terminal position by double bond isomerization and in this way to prepare terminally unsaturated fatty acid derivatives without stoichiometrically occurring by-products. What is already possible, however, is an ω-functionalization of unsaturated fatty acid derivatives, such as the isomerizing alkoxycarbonylation ( C. Jimenez-Rodriguez, GR Eastham, DJ Cole-Hamilton, Inorg. Chem. Commun. 2005, 8, 878-881 ) or isomerizing hydroformulations ( A. Behr, D. Obst, A. Westfechtel, Eur. J. Lidip Sci. Technol. 2005, 107, 213-219 ) and hydroborations ( KY Ghebreyessus, RJ Angelici, Organometallics 2006, 25, 3040-3044 ). A catalyst is added to the double bond, migrates along the saturated carbon chain and can then selectively bring about the desired subsequent reaction as soon as it has reached the terminal position. It is different with the isomerizing metathesis of unsaturated fatty acid esters described by Goossen (DM Ohlmann, N. Tschauder, J.-P. Stockis, K. Goossen, M. Dierker, LJ Goossen, J. Am. Chem. Soc. 2012, 134, 13716-13729). Here an isomerization catalyst is combined with a metathesis catalyst, whereby unsaturated products with different chain lengths are obtained. This indicates that the isomerization catalyst shifts the double bond and is also split off from it in the process. In a further reaction that takes place at the same time, the metathesis catalyst then forms cross-coupling and homo-coupling products of different chain lengths.

It was an object of the present invention to make renewable raw materials such as natural fatty acids and their derivatives, in particular vegetable oils and compounds derived therefrom, accessible to efficient copolymerization and thus to provide materials, copolymers, which can be sustainably produced and used in a variety of ways.

In particular, it was an object of the present invention to provide a process for copolymerization using internally unsaturated compounds (in particular natural fatty acids, their esters, in particular triglycerides such as vegetable oils) and α-olefins.

Furthermore, it was an object of the present invention to provide a process for copolymerization using internally unsaturated compounds (as described above) in which the copolymerization takes place in a one-pot reaction with the most quantitative conversion possible of the starting materials.

Furthermore, in the process (as described above) products (copolymers) with defined properties should be obtained which allow targeted use and further functionalization.

The objects defined above are achieved by a method for producing a copolymer as defined in claim 1.

By combining an isomerization catalyst with a polymerization catalyst, it is possible to isomerize the double bond of internally unsaturated compounds and to achieve copolymerization in the presence of α-olefins. The isomerization catalyst ensures that a mixture of the different double bond isomers is formed. This mixture contains a proportion of terminal double bond isomers. The terminal double bond of such isomers is then copolymerized with an α-olefin by the polymerization catalyst. The reaction of the terminal double bond isomer consumes it and thus removes it from the equilibrium established by the isomerization catalyst. According to the principle of Le Chatelier, such an external compulsion, which is exerted on an equilibrium, leads to the equilibrium being re-established or attempted with the same ratio of the different isomers. The required terminal double bond isomer is thus continuously reproduced as soon as it has been consumed in the polymerization reaction. It is therefore possible, for example, to use native, unsaturated fatty acid esters directly and to arrive at copolymers with α-olefins. The copolymers obtained are random copolymers which have a high degree of branching. Different polymers can be obtained depending on the choice of reaction conditions.

Surprisingly, a direct conversion of the internally unsaturated starting compound into a copolymer is possible in this way. In addition, the copolymerization takes place with complete integration of the compound of the formula (I) including its polar group G, as a result of which polar modified polymerization products are obtained which can be further modified or widely used, for example as adhesive and sealing components, for protective wax layers, as absorbers and are accessible as ion exchangers. In particular, it was not to be expected that such a reaction would be so successful, since the proportion of the terminal double bond isomer is very low in equilibrium and it therefore had to be possible to polymerize this small proportion out of equilibrium so that it is reproduced. A further complicating factor is that the polar group G of the unsaturated compound of the formula (I) reduces the activity of the polymerization catalyst.

1 shows schematically the copolymerization of oleic acid methyl ester with ethene as an example of the process according to the invention. The isomerization catalyst (Cat. A) causes the formation of a mixture of double bond isomers comprising terminal double bond isomers. The terminal double bond isomers are copolymerized with the ethene in the presence of the polymerization catalyst (cat. B) and thus irreversibly removed from the isomer mixture. As a result, terminal double bond isomers are reproduced. The copolymer formed can have branched and unbranched alkyl radicals and CH ₂ chains of different lengths, which is indicated in the illustration by the integer multiples m, n and the alk- radical.

According to the invention, the isomerization and the copolymerization take place in a one-pot reaction.

Since the isomerization catalyst tries to establish an equilibrium of all the double bond isomers of the unsaturated compound, it is particularly advantageous if the terminal double bond isomers are continuously withdrawn from the isomer mixture by polymerization and then appropriately reproduced. As a result, the unsaturated compound used can be largely converted.

In the process according to the invention, the isomerization catalyst is a homogeneous or heterogeneous catalyst. In the process according to the invention, the polymerization catalyst is a homogeneous or heterogeneous catalyst.

According to the invention, at least the polymerization catalyst is formed in situ.

A particularly active form of the isomerization catalyst and the polymerization catalyst can be formed in situ if the necessary starting materials are initially introduced into the reaction mixture. Examples of this are described below.

In the process according to the invention, the isomerization catalyst is a catalyst for preparing various double bond isomers of the aliphatic, internally monounsaturated radical R of the compound of the formula (I).

The isomerization catalyst is preferably set up to isomerize an internal double bond in the aliphatic radical in such a way that a mixture is formed in which terminal double bond isomers of the unsaturated radical are present in a certain proportion and can be converted in a (co) polymerization reaction.

In the process according to the invention, the isomerization catalyst comprises Pd.

According to the invention, the isomerization catalyst is a coordination compound of Pd.

Transition metal complexes are particularly suitable as catalysts for the isomerization of double bonds in the unsaturated aliphatic radical R of the compound of the formula (I). Particularly suitable examples of isomerization catalysts are described below.

According to the invention, the isomerization _{catalyst is [MeCN] 2 PdCl 2} , [(t-Bu ₃ P) Pd (μ-Br)] ₂ , PdBr ₂ or a product formed therefrom in situ; the isomerization catalyst can be used in combination with one or more further isomerization catalysts.

[MeCN] ₂ PdCl ₂ is particularly stable and is therefore used with preference.

A product formed in situ as indicated above arises in particular from a halide complex by exchanging the halide with a weakly coordinating counterion, such as SbF _6, to form an activated catalyst complex and a halide salt, eg AgCl. For the activation of the dimer [(t-Bu ₃ P) Pd (μ-Br)] ₂ in situ, Goossen et al., Org. Lett. 2012, 14, 3716-3719 proposed a mechanism.

According to the invention, the polymerization catalyst is a coordination compound of Pd.

Suitable compounds for polymerization catalysts are described below.

According to the invention, the polymerization catalyst in its active form has a free coordination site which consists of a cationic compound with a preferably weakly coordinating counterion as the first ligand, preferably selected from the group consisting of SbF ₆ ^- , OTf ^- , BF ₄ ^- , CF ₃ SO ₃ ^- and BAr ₄ ^- , arises.

In connection with the present invention, a weakly coordinating counterion is to be understood as meaning an anion which has little interaction with the metal center of the polymerization catalyst. Dissociation therefore takes place particularly easily, as a result of which a free coordination site is created at the metal center, which then serves as a coordination site for the monomers during the polymerization. A weakly coordinating counterion can also be a solvent molecule.

According to the invention, the polymerization catalyst is therefore produced in situ by reacting a metal halide complex, in particular a chloride, iodide, bromide or cyanide of the metal complex with a metal salt of the counterion, preferably by reacting the chlorometal complex with AgSbF ₆ .

Alternatively, the active polymerization catalyst can also be synthesized beforehand. Examples of this can be found in Brookhart et al, J. Am. Chem. Soc. 1995, 117, 6414-6415 (BAF complexes) and Brookhart et al., J. Am. Chem. Soc. 1996, 118, 267-268 (Acrylate complexes).

According to the invention, a process is as described above, wherein the polymerization catalyst - in addition to the halide or the weakly coordinating counterion - carries a second ligand which allows insertion into the metal-ligand bond, namely a ligand selected from the group consisting of H, Alkyl, preferably methyl, halogenated alkyl and acrylate.

Acrylate is a bidentate chelate ligand and can also act as a first ligand at the same time.

In addition, carbanions are suitable as a second ligand.

It is currently believed that the polymerization preferably occurs according to a coordination / insertion mechanism (Cossee-Arlman mechanism), in which an intermediate coordination complex is formed with the monomer and the growing polymer chain as ligands, and it then leads to an insertion of the monomer between polymer chain and metal comes within the coordination sphere of the metal center.

In the process according to the invention, the polymerization catalyst is stabilized by a further ligand. Most transition metals form complexes with more than two ligands. In the case of Pd, these are in particular the stable, square-planar complexes with d ⁸ configuration. Suitable ligands for these complexes, which are preferred polymerization catalysts for the process according to the invention, are described below.

According to the invention is a polymerization catalyst, the further ligand coordinating via a heteroatom, namely N, to the metal center.

According to the invention, the further ligand is a bidentate ligand, namely a diimino ligand.

The use of sterically demanding ligands advantageously prevents the exchange of the growing polymer chain for new monomer, which leads to an increase in the degree of polymerization.

Examples of the other ligand or ligands and their synthesis can be found in Qing et al, Macromolecules 2009, 42, 7789-7796.

wobei

R1

ausgewählt ist aus H, Alkyl, halogeniertem Alkyl und Acrylat,

R2 und R3

jeweils unabhängig Aryl oder Alkyl bedeuten,

M

Metall bedeutet,

L

ausgewählt ist aus SbF₆ ^-, OTf^-, BF₄ ^-, CF₃SO₃ ^- und BAr₄

und

Ar

Aryl bedeutet.

In the process according to the invention, the polymerization catalyst is a compound of the formula (II)

in which

R1

is selected from H, alkyl, halogenated alkyl and acrylate,

R2 and R3

each independently represent aryl or alkyl,

M.

Metal means

L.

is selected from SbF ₆ ^- , OTf ^- , BF ₄ ^- , CF ₃ SO ₃ ^- and BAr ₄

and

Ar

Means aryl.

The polymerization catalyst of the formula (II) is generated in situ by replacing a halide or cyanide ligand with a ligand L. Where M = Pd.

A process as described above is particularly preferred, the polymerization catalyst being an α-diimino-palladium complex, preferably [(2,6- (i-Pr) ₂ C ₆ H ₃ -N = C (Me) C (Me) = N-2,6- (i-Pr) ₂ C ₆ H ₃ ) Pd (CH ₃ )] SbF ₆ .

Since the isomerization catalyst and the polymerization catalyst each have the same metal as the central atom of the transition metal complex used, it is advantageously possible for the most part to avoid undesired interactions between the two catalysts which could restrict or prevent the activity.

In the process according to the invention, two, three or more different unsaturated compounds of the formula (I) and / or two, three or more different α-olefins can be present in the reaction mixture; this is preferred in some cases.

In this case, the polymerization gives rise to random copolymers of the starting materials present in the reaction mixture. The properties of the polymerization product can be controlled via the composition of the starting mixture and the reaction conditions.

In the process according to the invention, the two, three, more or all of the unsaturated compound (s) of the formula (I) is or are selected from the group consisting of alkyl esters of monounsaturated fatty acids having 14 to 24 carbon atoms.

Preferred monounsaturated fatty acids with 14 to 24 carbon atoms are natural fatty acids from vegetable oils. They and their derivatives and precursors, e.g. triglycerides, can be made available on an economical scale from renewable raw materials. By using such starting materials in a direct copolymerization with α-olefins, a sustainable and efficient production of versatile copolymers is made possible for the first time. In particular, such copolymers can be used as adhesive and sealing components, for protective wax layers, as absorbers and as ion exchangers.

Oleic acid occurs to a large extent in common vegetable oils such as sunflower oil, soybean oil and rapeseed oil and can therefore easily be obtained on a large scale and, if necessary, derivatized.

A method according to the invention is very particularly preferred, where the, two, three, more or all of the unsaturated compound (s) of the formula (I) are triglycerides, in particular vegetable oils, preferably selected from sunflower oil, soybean oil, rapeseed oil and palm oil.

Surprisingly, it has been shown that triglycerides can be used directly as starting materials in the process according to the invention. This means that vegetable oils, in particular sunflower oil, soybean oil, rapeseed oil and palm oil (palm olein), are directly accessible to the copolymerization without prior, separate conversion steps. Two or even all three of the unsaturated fatty acid residues of a triglyceride can be involved in a copolymerization reaction, which leads to branching or crosslinking of the polymerization product.

According to the invention, the α-olefin (s) is or are selected from the group consisting of ethylene, propylene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -Octadecene and styrene.

In particular, any mixtures of two, three, four, five or more α-olefins can also be used and the properties of the polymerization product can be controlled accordingly.

R

einen aliphatischen, innenständig einfach ungesättigten Rest bezeichnet

und

G

eine Gruppe (polare Gruppe, siehe oben) bezeichnet, die ausgewählt ist aus Carboxygruppe, Carboxylestergruppe, Glycerinestergruppe, Hydroxygruppe, Alkoxygruppe und Aryloxygruppe,

zur Herstellung eines Copolymers mit einem α-Olefin, wobei die Verbindung der Formel (I) unter vollständiger Beibehaltung sämtlicher Kohlenstoffatome ihres aliphatischen Restes R sowie unter Beibehaltung ihrer Gruppe G in das Copolymer integriert wird.Disclosed herein is the use of an unsaturated compound of the formula (I) RG (I) each being independent of one another

R.

denotes an aliphatic, internally monounsaturated radical

and

G

denotes a group (polar group, see above) which is selected from carboxy group, carboxyl ester group, glycerol ester group, hydroxyl group, alkoxy group and aryloxy group,

for the preparation of a copolymer with an α-olefin, the compound of the formula (I) being integrated into the copolymer with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G.

With regard to the process for producing the copolymer, reference is made to the statements on the corresponding process according to the invention, which apply here accordingly.

The copolymer is particularly preferably prepared in a one-pot reaction, i.e. without upstream, separate reaction steps for the compound of the formula (I). The compound of the formula (I) is integrated into the copolymer with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G. Advantageously, there is therefore hardly any formation of by-products.

Internally monounsaturated compounds of the formula (I) have hitherto not been amenable to direct use in a copolymerization with α-olefins. The present invention has made it possible to make such compounds, in particular natural fatty acids and even triglycerides such as vegetable oils, available for direct use in a copolymerization. This means that, for the first time, renewable raw materials can be used economically for the production of versatile polymers.

With regard to the identity of the unsaturated compound of the formula (I) in connection with the use according to the invention, what has been said above in connection with the process according to the invention applies accordingly.

R

einen aliphatischen, innenständig einfach ungesättigten Rest bezeichnet

und

G

eine Gruppe (polare Gruppe, siehe oben) bezeichnet, die ausgewählt ist aus Carboxygruppe, Carboxylestergruppe, Hydroxygruppe, Glycerinestergruppe, Alkoxygruppe und Aryloxygruppe,

mit einem α-Olefin, wobei die Verbindung der Formel (I) unter vollständiger Beibehaltung sämtlicher Kohlenstoffatome ihres aliphatischen Restes R sowie unter Beibehaltung ihrer Gruppe G in das Copolymer integriert wird.Also disclosed herein is the use of an isomerization catalyst, preferably an isomerization catalyst as defined above, for the preparation of a copolymer of a compound of the formula (I) RG (I) each being independent of one another

R.

denotes an aliphatic, internally monounsaturated radical

and

G

denotes a group (polar group, see above) which is selected from carboxy group, carboxyl ester group, hydroxyl group, glycerol ester group, alkoxy group and aryloxy group,

with an α-olefin, the compound of the formula (I) being integrated into the copolymer with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G.

The use of an isomerization catalyst makes it possible to obtain a mixture of double bond isomers of the internally unsaturated compound of the formula (I) from which the terminal double bond isomers are continuously withdrawn by the polymerization and correspondingly reproduced. As a result of the use according to the invention, internally monounsaturated compounds of the formula (I), in particular natural fatty acids and even triglycerides such as vegetable oils, can be copolymerized directly with α-olefins for the first time.

R

einen aliphatischen, innenständig einfach ungesättigten Rest bezeichnet

und

G

eine Gruppe bezeichnet, die ausgewählt ist aus Carboxygruppe, Carboxylestergruppe, Hydroxygruppe, Glycerinestergruppe, Alkoxygruppe und Aryloxygruppe,

mit einem α-Olefin, wobei die Verbindung der Formel (I) unter vollständiger Beibehaltung sämtlicher Kohlenstoffatome ihres aliphatischen Restes R sowie unter Beibehaltung ihrer Gruppe G in das Copolymer integriert wird.The use of a polymerization catalyst, preferably a polymerization catalyst as defined above, for the preparation of a copolymer of a compound of the formula (I) is also disclosed RG (I) each being independent of one another

R.

denotes an aliphatic, internally monounsaturated radical

and

G

denotes a group selected from carboxy group, carboxyl ester group, hydroxyl group, glycerol ester group, alkoxy group and aryloxy group,

with an α-olefin, the compound of the formula (I) being integrated into the copolymer with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G.

By using a polymerization catalyst in the preparation of a copolymer, the terminal double bond isomers of the monounsaturated compounds of the formula (I) are copolymerized and thus continuously removed from the mixture of all double bond isomers. The monounsaturated compounds of the formula (I) are advantageously integrated into the copolymer with complete retention of all carbon atoms of their aliphatic radical R and with retention of their group G, so that hardly any by-products are formed.

Finally, the present invention also relates to the use of a combination of an isomerization catalyst and a polymerization catalyst as defined in claim 2.

The production of the copolymer takes place in a one-pot reaction, i.e. without upstream, separate conversion steps of the compound of the formula (I). The combination of an isomerization catalyst and a polymerization catalyst allows the complete incorporation of the compound of the formula (I) into the copolymer, ie with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G. Advantageously, there is therefore hardly any formation of by-products and the efficient production of versatile polymers from renewable raw materials such as fatty acids and their derivatives and triglycerides such as vegetable oils as a starting material becomes possible. The resulting polymers modified by the incorporation of the radical G polar are particularly suitable for further functionalization or use as adhesive and sealing components, for protective wax layers, as absorbers and as ion exchangers.

Different polymers can be obtained depending on the choice of reaction conditions. The most efficient catalyst system is the combination of the isomerization catalyst [(tBu ₃ P) Pd [µ-Br)] ₂ with the polymerization catalyst (Ar-N = C (Me) C (Me) = N-Ar) Pd (CH ₃ ) SbF ₆ (Ar = 2,6-diisopropylphenyl), which is formed in situ by reaction of the corresponding chloro complex with AgSbF ₆ . Here, the activity of (Ar-N = C (Me) C (Me) = N-Ar) Pd (CH ₃ ) SbF _{6 is} the highest compared to other combinations and the largest amount of polymer is obtained. However, [(tBu ₃ P) Pd [µ-Br)] ₂ is very sensitive to oxidation, especially in solution. For this reason, it will in some cases advantageously be replaced by the much more stable [MeCN] ₂ PdCl ₂ . Reactions at or below room temperature give the greatest polymer yield with the highest degrees of polymerization. However, increasing the temperature, like reducing the amount of solvent or doing without it, leads to polymers with a higher rate of incorporation of the polar olefin.

The present invention is explained in more detail below with the aid of some examples, which, however, are not to be understood as limiting.

Figure list

• 1 shows schematically the copolymerization of oleic acid methyl ester with ethene as an example of the process according to the invention using an isomerization catalyst (Cat. A) and a polymerization catalyst (Cat. B).

Example 1: Isomerizing copolymerization using a Pd (I) complex as isomerization catalyst

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (4.5 mg, 0.008 mmol), AgSbF ₆ (14.1 mg, 0.041 mmol), [(tBu ₃ P) Pd [µ -Br)] ₂ (12.8 mg, 0.016 mmol) and oleic acid methyl ester (489 mg, 1.65 mmol) are dissolved in 5 mL dichloromethane in a high pressure autoclave, the silver halides precipitating as a white solid. Ethene is injected and relaxed several times in order to displace the nitrogen in the gas space. The reaction is stirred for 19 hours at room temperature under a constant ethene pressure of 2 bar. To end the reaction, the highly viscous solution is diluted with dichloromethane, poured into methanol / aqueous hydrochloric acid (30 mL; 90:10 v / v) and stirred for 2 hours, the polymer precipitating immediately. It is decanted and the polymer is washed several times with methanol to remove residual monomer. The polymer is dissolved in petroleum ether and filtered. After the solvents have been removed on a rotary evaporator, the product is dried under reduced pressure for 2 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with methanol. This is repeated until there is no more monomer in the sample. 2.16 g are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1754 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 0.07 mol% (= 0.7% by weight) was determined.

Example 2: Isomerizing copolymerization in the absence of solvent

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (5.0 mg, 0.009 mmol), AgSbF ₆ (15.0 mg, 0.04 mmol), [(tBu ₃ P) Pd [μ-Br)] ₂ (7.2 mg, 0.009 mmol) and oleic acid methyl ester (1.19 g, 4.10 mmol) are placed in a high-pressure autoclave, the silver halides precipitating as a white solid. Ethene is injected and relaxed several times in order to displace the nitrogen in the gas space. The reaction is stirred for 18 hours at 70 ° C. under a constant ethene pressure of 1 bar. To end the reaction, the highly viscous solution is diluted with dichloromethane, poured into methanol / aqueous hydrochloric acid (50 mL; 90:10 v / v) and stirred for 2 hours, the polymer precipitating immediately. It is decanted and the polymer is washed several times with methanol to remove residual monomer. The polymer is dissolved in petroleum ether and filtered. After the solvents have been removed on a rotary evaporator, the product is dried under reduced pressure for 2 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with methanol. This is repeated until there is no more monomer in the sample. 204 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1754 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 0.4 mol% (= 4% by weight) was determined.

Example 3: Isomerizing copolymerization using an air-stable Pd (II) complex as isomerization catalyst

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (16.9 mg, 0.03 mmol), AgSbF ₆ (61.8 mg, 0.18 mmol), [MeCN] ₂ PdCl ₂ (15.6 mg, 0.06 mmol) and oleic acid methyl ester (3.56 g, 12.0 mmol) are placed in a high pressure autoclave, AgCl precipitating out as a white solid. Ethene is injected and relaxed several times in order to displace the nitrogen in the gas space. The reaction is stirred for 18 hours at 30 ° C. under a constant ethene pressure of 1 bar. To end the reaction, the highly viscous solution is diluted with dichloromethane, poured into methanol / aqueous hydrochloric acid (50 mL; 90:10 v / v) and stirred for 2 hours, the polymer precipitating immediately. It is decanted and the polymer is washed several times with methanol to remove residual monomer. The polymer is dissolved in petroleum ether and filtered. After removing the solvents on a rotary evaporator, the product is dried under reduced pressure for 16 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with methanol. This is repeated until there is no more monomer in the sample. 138 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1746 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 0.4 mol% (= 4% by weight) was determined.

Example 4: Isomerizing copolymerization of triglycerides in the absence of solvents

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (8.0 mg, 0.014 mmol), AgSbF ₆ (19.6 mg, 0.057 mmol), [(tBu ₃ P) Pd [µ -Br)] ₂ (11.1 mg, 0.0143 mmol) and oleic acid-rich sunflower oil (1.691 g, 1.90 mmol) are placed in a high-pressure autoclave, the silver halides precipitating as a white solid. Ethene is injected and relaxed several times in order to displace the nitrogen in the gas space. The reaction is stirred for 19 hours at 70 ° C. under a constant ethene pressure of 1 bar. To end the reaction, the highly viscous solution is diluted with dichloromethane, acetone (50 mL) is added and the mixture is stirred for 2 hours. The polymer is collected by filtration through Celite®, washed several times with acetone to remove residual monomer and dissolved from the filter with petroleum ether. After the solvents have been removed on a rotary evaporator, the product is dried under reduced pressure for 2 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with acetone. This is repeated until there is no more monomer in the sample. 90 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1748 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 0.3 mol% (10% by weight) was determined.

Example 5: Isomerizing copolymerization of triglycerides using an air-stable Pd (II) complex as isomerization catalyst

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (5.6 mg, 0.01 mmol), AgSbF ₆ (20.6 mg, 0.06 mmol), [MeCN] ₂ PdCl ₂ (5.2 mg, 0.02 mmol) and oleic acid-rich sunflower oil (3.56 g, 4.00 mmol) are dissolved in 1 mL dichloromethane in a high-pressure autoclave, AgCl precipitating as a white solid. Ethene is injected and relaxed several times in order to displace the nitrogen in the gas space. The reaction is stirred for 17 hours at 40 ° C. under a constant ethene pressure of 1 bar. To end the reaction, the highly viscous solution is diluted with dichloromethane, acetone (50 mL) is added and the mixture is stirred for 2 hours, the polymer immediately precipitating out. It is decanted and the polymer is washed several times with acetone to remove residual monomer. The polymer is dissolved in dichloromethane and filtered. After removing the solvents on a rotary evaporator, the product is dried under reduced pressure for 16 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with acetone. This is repeated until there is no more monomer in the sample. 323 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1748 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 0.2 mol% (= 5% by weight) was determined.

Example 6: Isomerizing copolymerization of oleic acid methyl ester with 1-hexene

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (5.6 mg, 0.01 mmol), AgOTf (15.4 mg, 0.06 mmol), [MeCN] ₂ PdCl ₂ (5.2 mg, 0.02 mmol), 1-hexene (339 mg, 4.03 mmol) and oleic acid methyl ester (437 mg, 1.47 mmol) are placed in a Schlenk flask at 0 ° C. with 20 ml of DCM , whereby AgCl precipitates as a white solid. The reaction is stirred for 18 hours while thawing to room temperature. To end the reaction, the solution is added to methanol / aqueous hydrochloric acid (30 mL; 90:10 v / v) and stirred for 2 hours, the polymer immediately precipitating out. It is decanted and the polymer is washed several times with methanol to remove residual monomer. The polymer is dissolved in petroleum ether and filtered. After the solvents have been removed on a rotary evaporator, the product is dried under reduced pressure for 2 hours. To remove any residual monomer that may remain, the residue is taken up in dichloromethane and precipitated with methanol. This is repeated until there is no more monomer in the sample. 53 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is detected by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1747 cm ⁻¹ and an incorporation of the comonomer of 0.6 mol% (= 2% by weight) is estimated from this.

Example 7: Isomerizing copolymerization of oleic acid methyl ester with 1-decene

The work is carried out under a protective gas atmosphere (N ₂ ). (Ar-N = C (Me) C (Me) = N-Ar) PdMeCl (5.6 mg, 0.01 mmol), AgSbF ₆ (20.6 mg, 0.06 mmol), [MeCN] ₂ PdCl ₂ (5.2 mg, 0.02 mmol), 1-decene (370 mg, 2.64 mmol) and oleic acid methyl ester (437 mg, 1.47 mmol) are placed in a Schlenk flask with 10 mL DCM, whereby AgCl precipitates as a white solid. The reaction is stirred for 20 hours at room temperature. To end the reaction, methanol / aqueous hydrochloric acid (10 mL; 90:10 v / v) is added to the reaction mixture and stirred for 2 hours, the polymer immediately precipitating out. It is decanted and the polymer is washed several times with methanol to remove residual monomer. The polymer is dissolved in dichloromethane and filtered. After the solvents have been removed on a rotary evaporator, the product is dried under reduced pressure for 2 hours. To remove any residual monomer that may remain, the residue is taken up in tetrahydrofuran and precipitated with methanol. This is repeated until there is no more monomer in the sample. 46 mg are obtained. Analytical GPC shows that there is no residual monomer in the sample. The incorporation of the comonomer is demonstrated by FT-IR spectroscopy on the basis of the characteristic band of the ester group at 1746 cm ⁻¹ . By integrating the signals in the ¹ H-NMR spectrum, an incorporation of the comonomer of 1.1 mol% (= ̂ 2% by weight) was determined.

Claims (2)

Process for producing a copolymer, having the following step: setting reaction conditions in a reaction mixture comprising - at least one α-olefin selected from ethylene, propylene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene and styrene, - at least one unsaturated compound of the formula (I) RG (I) where each independently R denotes an aliphatic, internally monounsaturated radical and G denotes a group which is selected from carboxy group, carboxyl ester group, glycerol ester group, hydroxyl group, alkoxy group and aryloxy group, the compound of formula (I) being selected from (i) alkyl esters of monounsaturated fatty acids with 14 to 24 carbon atoms and (ii) vegetable oils, - at least one isomerization catalyst for generating an isomer of the unsaturated compound which has a terminal double bond selected from [MeCN] ₂ PdCl ₂ and [(t-Bu ₃ P) Pd (µ- Br)] ₂ or a product formed therefrom in situ, and at least one polymerization catalyst for the copolymerization of the α-olefin with the isomer having a terminal double bond, the polymerization catalyst being a compound of the formula (II)

where R ^{1 is} selected from H, alkyl, halogenated alkyl and acrylate, R ² and R ^{3 are} each independently aryl or alkyl, M is metal, L is selected from SbF ₆ ^- , OTf ^- , BF ₄ , CF ₃ SO ₃ ^- and BAr ₄ and Ar = aryl and where the polymerization catalyst of the formula (II) is generated in situ by replacing a halide or cyanide ligand with a ligand L and M = Pd, so that a copolymer of the α-olefin with the isomer with Terminal double bond is formed, the isomerization and the copolymerization taking place in a one-pot reaction. Use of a combination of an isomerization catalyst and a polymerization catalyst for the preparation of a copolymer of a compound of the formula (I) RG (I) where in each case, independently of one another, R denotes an aliphatic, internally monounsaturated radical and G denotes a group selected from carboxy group, carboxyl ester group, hydroxyl group, glycerol ester group, alkoxy group and aryloxy group, the compound of the formula (I) being selected from (i) alkyl esters Monounsaturated fatty acids with 14 to 24 carbon atoms and (ii) vegetable oils, with an α-olefin selected from ethylene, propylene, isobutene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene and styrene, the compound of the formula (I) being integrated into the copolymer with complete retention of all carbon atoms of its aliphatic radical R and with retention of its group G, the isomerization catalyst _{[MeCN] 2 PdCl 2} or [(t -Bu ₃ P) Pd (μ-Br)] ₂ or a product formed therefrom in situ, the polymerization catalyst being a compound of the formula (II)

where R ^{1 is} selected from H, alkyl, halogenated alkyl and acrylate, R ² and R ^{3 are} each independently aryl or alkyl, M is metal, L is selected from SbF ₆ ^- , OTf ^- , BF ₄ , CF ₃ SO ₃ ^- and BAr ₄ and Ar = aryl and where the polymerization catalyst of the formula (II) is generated in situ by replacing a halide or cyanide ligand with a ligand L and M = Pd, and where the isomerization and the copolymerization in a one-pot Reaction take place.

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