DE102011053470A1 - Preparing carbon monoxide-olefin copolymers useful as plasticizer for polymers, and for preparing polyols and polyamines, comprises radically copolymerizing carbon monoxide with olefin in solvent comprising cyclic ether compounds - Google Patents

Abstract

Preparing carbon monoxide-olefin copolymers, comprises radically copolymerizing carbon monoxide with at least one olefin in a solvent comprising cyclic ether compounds (I), which exhibit a boiling point of less than 230[deg] C, and excludes 1,2-dioxane, 1,3-dioxane, 1,4-dioxane and propylene oxide. Preparing carbon monoxide-olefin copolymers, comprises radically copolymerizing carbon monoxide with at least one olefin in a solvent comprising cyclic ether compounds of formula (I), which exhibit a boiling point of less than 230[deg] C, and excludes 1,2-dioxane, 1,3-dioxane, 1,4-dioxane and propylene oxide. m, n : >= 1; o : >= 0; and R1-R6 : 1-22C alkyl (optionally branched and optionally contains ether or ester groups), H, 6-18C aryl, 7-22C aralkyl, 7-22C alkylaryl, 5-12C cycloalkyl or 1-8C alkoxycarbonyl, where at least 2 groups of R1-R6 are optionally linked with each other. Provided that: m may have a different value for different values of repeating unit o; and at least one of the substituents R1-R6, which is bonded to a carbon atom and an oxygen atom, represents hydrogen. Independent claims are also included for: (1) the carbon monoxide-olefin copolymers obtainable by the above method; (2) preparing polyols, comprising reducing the above carbon monoxide-olefin copolymers; (3) polyols obtainable by the above method; (4) preparing polyamines, comprising carrying out reductive amination of the above carbon monoxide-olefin copolymers; and (5) polyamines obtainable by the above method. [Image].

Description

The present invention relates to a specific process for the preparation of CO / olefin copolymers comprising the step of radical copolymerization of CO with one or more olefins. By reduction or reductive amination can be obtained from polyols and polyamines. The invention further relates to the resulting polyketones, polyols and polyamines and their use as plasticizers or as crosslinkers in polymers.

Multiketone-functional oligomers (also referred to interchangeably in the context of the present invention as "multicarbonyl-functional oligomers" or as "polyketones") are very versatile, for example as plasticizers for PVC or as crosslinkers. Here, the carbonyl reacts with CH-acidic compounds in aldol reactions or with amines or hydrazine derivatives to azomethines. C-Hacid groups adjacent to the carbonyl group may also react with other carbonyl moieties.

The radical copolymerization of CO with olefins under mild conditions, usually with pressures below 300 bar and temperatures below 150 ° C, leads to such multiketone functional oligomers. However, so far, the yield of oligomer based on the initiator used is rather low. Furthermore, the space-time yield is not satisfactory.

For example, describes US 2008/0242895 A1 the radical copolymerization of CO and olefins in solvents. Here, toluene, benzene, dioxane, pentane, heptane, hexane, propylene oxide, cyclohexane, methyl ethyl ketone (MEK), acetone and their mixtures were mentioned, with hexane and / or MEK being preferred. Dioxane is a heterocycle with two oxygen atoms and has a relatively high boiling point. Therefore, the complete separation of the solvent is not always easily possible. Although propylene oxide is volatile, it is toxicologically hazardous for use as a solvent.

The multiketone-functional oligomers also serve as starting materials for polymer-analogous reactions in which the carbonyl group is converted to another functional group, resulting in oligomers with other functional groups. These include the reduction or hydrogenation of the carbonyl groups to hydroxy groups or the reductive amination to amino groups.

For use as a crosslinker, these compounds should meet certain requirements. An aliphatic backbone can ensure greater chemical resistance as well as thermal and UV stability. The linkage via functional groups such as ethers should be avoided as much as possible.

In view of a simpler processing, a low molecular weight is favorable, which may for example be in the range of 500 g / mol to 20,000 g / mol, and a lowest possible polydispersity index. The presence of aliphatic side chains to reduce viscosity is hereby expressly desired.

The functionality should be greater than 2 and preferably in the range of 3 to 20, where the functional groups should be at a certain minimum distance from each other to ensure accessibility in the course of the crosslinking reaction. Also, for use as a plasticizer, too high molecular weight or functionality is undesirable.

The polyketones, which serve as starting materials for the synthesis of corresponding functional oligomers, should meet various requirements. The products should preferably be present as a low-viscosity liquid. According to the multihydroxy- or multiamine-functional oligomers which are to be obtained by hydrogenation or reductive amination of these polyketones, the polyketones used should have a molecular weight in the range of 500 g / mol to 20,000 g / mol, the lowest possible polydispersity index, and aliphatic side chains.

The keto groups in the polymer should have a certain minimum distance from one another in order to ensure, on the one hand, a corresponding minimum distance of the hydroxyl or amino groups in the product, and on the other hand in the course of the hydrogenation or reductive amination the intramolecular formation of cyclic THF units and thus a reduction of the hydroxy Functionality, or to avoid the formation of Pyrrolidineinheiten with undesirable reactivity as far as possible.

In the reaction of the polyketones to corresponding functional oligomers, in particular the reaction to give hydroxy-functional oligomers (polyhydroxy-functional oligomers or polymers are also interchangeably referred to as "polyols" in the context of the present invention) with reduction or hydrogenation of the carbonyl groups to OH groups. The hydroxy-functional oligomers can in turn serve as plasticizers or as a reaction partner for isocyanates or formaldehyde resins to form crosslinked thermosets.

Such multihydroxy-functional oligomers can in principle be obtained by hydrogenation of corresponding polyketones. Here, the use of heterogeneous catalysts due to the easier separation and reuse the use of homogeneous catalysts is clearly preferable. Because of the lower energy consumption, hydrogenation at the lowest possible pressures would still be desirable.

For example, treat EP 0 791 615 A1 the hydrogenation of alternating carbon monoxide-ethylene copolymers on homogeneous ruthenium catalysts with trialkylphosphine ligands.

In J. Polymer Science (1998), 889 and Recent Research Developments in Polymer Science (1999), 355 describes the hydrogenation of free-radically obtained CO / ethylene copolymers in 1,3-dioxolane or cyclohexanol on heterogeneous ruthenium catalysts at pressures of 50 to 100 bar.

In JP 01-149828 describes the hydrogenation of CO / ethylene copolymers on hydrogenation catalysts such as Raney nickel in aliphatic alcohols at a pressure of 200 bar.

Also to be mentioned is the reaction of polyketones to amine-functional oligomers (multi-amine oligomers or polymers are also referred to interchangeably in the context of the present invention as "polyamines") by aminating hydrogenation or two-stage reactions, such as the preceding reaction to azomethines with hydroxylamine and subsequent hydrogenation , is possible.

Multiamine-functional oligomers are interesting reaction partners, for example for isocyanates or epoxides. Molecules containing more than two amine groups are interesting crosslinkers that can be used to connect linear or branched macromolecules to form three-dimensional networks. Furthermore, the amine groups can be reacted with phosgene to form isocyanates. These multiisocyanate-functional oligomers are also interesting polymer building blocks.

So far, only the so-called Jeffamine ^® are commercially available. Jeffamine ^® are polyoxyalkyleneamines: polyether containing primary amine groups at the end of Polyetherrückrats. The ether groups complicate a reaction with phosgene to form isocyanates, since the liberated HCl degrades the ether groups. Furthermore, the ether groups are susceptible to photodegradation.

A systematic investigation JACS (1956) 78, 860-861 describes that the hydrogenation of oximes is less selective with respect to the ratio of primary to secondary amines. For multifunctional oligomeric oximes, the formation of secondary amines should be avoided as far as possible, since oligomer chains are linked when they occur, which can lead to an undesirable increase in the molecular weight up to complete crosslinking (gel formation). Furthermore, secondary amines react with phosgene not to isocyanates, but to carbamic acid chlorides, the chlorine then remains in the oligomer. The primary amine selectivities observed in the hydrogenation of low molecular weight oximes are not sufficient for multiamine functional oligomers.

It would therefore be desirable to synthesize multi-amine oligomers whose amine groups are on a purely aliphatic hydrocarbon backbone. Furthermore, the molecular weight (M _n ) should be so low that the multi-amine-functional oligomers have the lowest possible viscosity.

From the foregoing it is clear that there is still a need for CO / olefin copolymers, which can be used on their own, but which also serve as intermediates for the preparation of novel and useful polyols and polyamines.

The object of the present invention is therefore to provide a process for preparing multiketone-functional oligomers using lower amounts of initiators with improved space-time yields. Moreover, lowering the polydispersity index of these multiketone-functional oligomers would be advantageous for performance reasons.

wobei gilt: m ≥ 1, n ≥ 1 und o ≥ 0;
wobei m in unterschiedlichen Wiederholungseinheiten o einen unterschiedlichen Wert haben kann;
wobei der Siedepunkt des zyklischen Ethers unterhalb von 230 °C liegt;
wobei R1, R2, R3, R4, R5 und R6 unabhängig voneinander bedeuten: Wasserstoff, lineare oder verzweigte C1- bis C22-Alkylreste, welche auch Ether- oder Estergruppen enthalten können, C6- bis C18-Arylreste, C7- bis C22-Aralkyl- oder Alkylarylreste, C5- bis C12-Cycloalkylreste oder C1- bis C8-Alkoxycarbonylreste; und wobei zwei oder mehrere Reste R1 bis R6 miteinander verknüpft sein können;
unter der Maßgabe, dass mindestens einer der Substituenten R1 bis R6, welche an ein Kohlenstoffatom gebunden sind, welches wiederum an ein Sauerstoffatom gebunden ist, Wasserstoff ist;
wobei weiterhin 1,2-Dioxan, 1,3-Dioxan und 1,4-Dioxan sowie Propylenoxid ausgenommen sind. This object is achieved in the context of the present invention by a process for the preparation of CO / olefin copolymers, comprising the step of the radical copolymerization of CO with one or more olefins, wherein the copolymerization is carried out in a solvent which is a cyclic ether of the general Formula (I) includes:

where: m ≥ 1, n ≥ 1 and o ≥ 0;
where m may have a different value in different repeating units o;
wherein the boiling point of the cyclic ether is below 230 ° C;
where R 1, R 2, R 3, R 4, R 5 and R 6 independently of one another are hydrogen, linear or branched C 1 - to C 22 -alkyl radicals which may also contain ether or ester groups, C 6 - to C 18 -aryl radicals, C 7 - to C 22 -aralkyl or alkylaryl radicals, C5 to C12 cycloalkyl radicals or C1 to C8 alkoxycarbonyl radicals; and wherein two or more radicals R1 to R6 may be linked together;
with the proviso that at least one of the substituents R 1 to R 6, which are bonded to a carbon atom, which in turn is bonded to an oxygen atom, is hydrogen;
further excluding 1,2-dioxane, 1,3-dioxane and 1,4-dioxane and propylene oxide are excluded.

Here, compounds with m = 1, n = 1 to 4 and o = 0 and 1 are preferred. Particular preference is given to compounds with THF skeleton (n = 3, o = 0), tetrahydropyran skeleton (n = 4, o = 0) and 1,3-dioxolane skeleton (m = 1, n = 1, o = 1 ).

Compared to radical copolymerization reactions of CO and olefins, which are carried out in solvents which do not correspond to a compound of formula (I), the use of compounds of formula (I) as solvent leads to increased yields of CO / olefin copolymers based on the Initiator use and to products with lower polydispersity index.

CO / olefin copolymers in the context of the invention are polyketones which are prepared by copolymerization of CO and one or more olefins. In particular, the olefin may be selected from the group comprising: ethylene, propylene, 1-butene, 2-butene and mixtures of 1-butene and 2-butene, pentene, hexene, heptene, octene, isooctene or higher α-olefins, and possible Isomers of the aforementioned compounds, styrene, α-methylstyrene and / or 3- and 4-methylstyrene.

The partial pressure of CO in the production of the polyketone may be, for example, 1 bar to 150 bar. The partial pressure of ethylene and / or other olefins gaseous at the polymerization temperature may be, for example, from 5 bar to 300 bar. The ratio of the partial pressures can then be adjusted so that a CO: olefin partial pressure ratio of 1:60 to 1: 2 is achieved, with a CO: olefin partial pressure ratio of 1:12 to 1: 2 being particularly preferred.

Suitable radical initiators include azo compounds or peroxides, with AIBN being preferred. For example, from 0.1 to 30% by weight of the radical initiator, based on the monomers, can be used.

The copolymerization is carried out at such temperatures that the half-life of the initiators used is in the range of 1 minute to 1 hour. The reaction is preferably carried out at a temperature of 30 ° C to 150 ° C (more preferably 50 ° C to 130 ° C). The reaction temperature depends on the Decomposition temperature of the starter used from and is at least above. In the most preferably used azobisisobutyronitrile, the temperatures are preferably 70 to 130 ° C.

The solvents used are compounds of the formula (I), for example in amounts of 10% by weight to 1000% by weight, based on the monomers. 0.01 part by weight to 2 parts by weight, preferably 0.01 to 0.5 parts by weight of other solvents, such as alkanes, cycloalkanes, aromatics, alkylaromatics, etc. may optionally be based on one part by weight of the solvent of the formula (I) open-chain or cyclic ethers, open-chain or cyclic carbonate esters or ketones may be added as co-solvents. But especially preferred is the renunciation of co-solvents.

During the copolymerization, monomers, free radical initiators and solvents can be metered in continuously or in portions independently of one another.

The molecular weight can be adjusted by the amount of radical initiator used and by adding a suitable regulator such as hydrogen or mercaptans.

The present invention will be described in conjunction with further aspects and embodiments. The embodiments can be combined as desired, unless clearly the opposite results from the context.

In one embodiment of the process for preparing CO / olefin copolymers, the cyclic ether is selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofurfurylmethylether, tetrahydrofurfurylethylether, 2,5-dimethoxymethyltetrahydrofuran, 2, 5-diethoxymethyltetrahydrofuran, furfuryl acetate, tetrahydrofuran-2-carboxylic acid methyl ester, 1,3-dioxolane and / or tetrahydropyran.

In another embodiment of the process for producing CO / olefin copolymers, CO is copolymerized with an olefin mixture comprising ethylene and an α-olefin. Preferably, in this case, the α-olefin is 1-hexene.

It is further preferable that the molar ratio of ethylene to the α-olefin in the reaction solution is from ≥ 0.1: 1 to ≦ 10: 1. Ratios of ≥ 0.5: 1 to ≦ 7: 1 are preferred.

The present invention further relates to CO / olefin copolymers which are obtainable by a process according to the invention or, preferably, were obtained. The polyketones obtained may have a molecular weight M _n (determined by GPC against polystyrene standards) of 500 g / mol to 20,000 g / mol. They usually contain at least 2 and an average of 3 to 20 carbonyl groups per molecule, with 3 to 10 carbonyl groups per molecule being preferred.

Preferably, the CO / olefin copolymer has a number average molecular weight M _n of ≥ 800 g / mol to ≦ 8000 g / mol, and more preferably ≥ 850 g / mol to ≦ 2000 g / mol.

Another aspect of the present invention is a process for preparing polyols comprising the step of reducing CO / olefin copolymers using a CO / olefin copolymer of the invention. The reduction may be carried out by reducing agents such as hydrides including complex hydrides such as alanates or boranates, alkali metals or else preferably by hydrogenation. The (catalytic) hydrogenation can be carried out in the presence or absence of solvents. Particularly suitable solvents are C ₁ -C ₈ -alcohols and mixtures of these with one another or with other solvents such as THF or 1,4-dioxane.

In the hydrogenation or reduction of multiketone-functional oligomers prepared with azobisisobutyronitrile (AIBN) or other nitrile-containing radical initiators, the nitrile groups contained in the oligomer can be reduced to the corresponding amines. Thus, the preferred AIBN used can transfer the following end groups to the polymer: -C (CH ₃ ) ₂ -CN or -CH ₂ -C (CH ₃ ) CN-C (CH ₃ ) ₂ -CN. The resulting amino-containing products are also included according to the invention.

In one embodiment of the process for preparing polyols, the reduction of the CO / olefin copolymer is a hydrogenation of CO / olefin copolymers in the presence of a heterogeneous hydrogenation catalyst, wherein the CO / olefin copolymer has a CO content of ≤25% by weight. and the heterogeneous Hydrogenation catalyst comprises a metal selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel and / or copper.

It has been found that under these conditions, heterogeneously catalyzed hydrogenations of the polyketones to polyols can also be achieved at pressures of less than 100 bar. In this way can be dispensed with the use of equipment for high pressure hydrogenation and the total energy consumption of the process decreases.

In own preliminary experiments it was determined that the hydrogenation of keto groups in polyketones with a CO content ≤ 25 wt .-%, which were obtained by radical polymerization of CO, ethylene and α-olefins, on common heterogeneous catalysts such as Pd / C and Pt / C at pressures below 100 bar takes place only insufficiently.

It is further contemplated that the CO content in the CO / olefin copolymer is ≦ 25% by weight. This is to be understood as meaning the content of CO monomers incorporated in the copolymer as carbonyl groups. The CO content can be controlled by choosing the CO partial pressure in the polymerization reaction and by evaluating the ¹ H NMR signals of the polyketone, as described in detail below, determine.

Without being limited to a theory, it is assumed that CO non-alternating CO / olefin copolymers are present at the stated CO contents.

The partial pressure of CO in the production of the polyketone may be, for example, 1 bar to 150 bar. The partial pressure of ethylene and / or other olefins gaseous at the polymerization temperature may be, for example, from 5 bar to 300 bar. The ratio of the partial pressures can then be adjusted so that a CO: olefin partial pressure ratio of 1:60 to 1: 2 is achieved, with a CO: olefin partial pressure ratio of 1:12 to 1: 2 being particularly preferred.

The polyketones used as starting materials in the hydrogenation may have a molecular weight M _n (determined by GPC against polystyrene standards) of 500 g / mol to 20,000 g / mol. They usually contain at least 2 and an average of 3 to 20 carbonyl groups, with 3 to 10 carbonyl groups per molecule being preferred. Such a carbonyl group content can be achieved by not exceeding the CO content required according to the invention in the CO / olefin copolymer.

It is particularly advantageous if the CO / olefin copolymer has a CO content of ≥ 1% by weight to ≦ 20% by weight. Preference is given to a CO content of ≥ 5% by weight to ≦ 17% by weight.

The reduction of the multiketone-functional oligomers to the corresponding multihydroxy-functional oligomers is carried out with molecular hydrogen using a heterogeneous hydrogenation catalyst. The hydrogenation is carried out, for example, at temperatures between 20 ° C and 200 ° C, preferably 140 ° C to 200 ° C, and at pressures between 10 bar and 200 bar, preferably 10 bar to 100 bar. The content of heterogeneous hydrogenation catalyst may be, for example, 0.01% by weight to 100% by weight (metal content based on the polymer), preferably 0.1% by weight to 40% by weight.

The catalysts can be used as Raney catalysts or on suitable supports. Particular preference is given to using Raney nickel, Raney cobalt or supported nickel, cobalt, ruthenium and rhodium catalysts. The catalysts can also be present as mixtures of the preferred elements cobalt, nickel, ruthenium, rhodium, iridium with one another or with ≦ 50% by weight, based on the metal content, of other elements such as, for example, rhenium, palladium or platinum.

Preferably, however, the heterogeneous hydrogenation catalyst is free of palladium and platinum, with "free of" also including the presence of technically unavoidable impurities.

Particularly suitable as support materials are carbon and oxides, such as silicon dioxide, aluminum dioxide, mixed oxides of silicon dioxide and aluminum dioxide and titanium dioxide.

The hydrogenation is preferably carried out at a hydrogen pressure of ≦ 120 bar. This is to be understood as the hydrogen pressure which prevails at the beginning of the hydrogenation reaction when the intended reaction temperature has already been reached. This hydrogen pressure is particularly preferably 40 bar to ≦ 100 bar.

It is further preferred that the hydrogenation takes place in the presence of a solvent or solvent mixture comprising hydroxyl groups. Included in the term of the hydroxyl group-containing solvent is water. An example of a particularly suitable solvent is 2-propanol (isopropanol). Another example is a mixture of 2-propanol with water in the volume ratio of ≥ 5: 1 to ≤ 10: 1. The hydroxyl group-containing component of the solvent mixture may also be provided by water alone. An example of this is a mixture of 1,4-dioxane with water in the volume ratio of ≥ 5: 1 to ≤ 10: 1.

The present invention furthermore relates to polyols obtainable by a process according to the invention or, preferably, obtained. The polyols obtained after the reduction and in particular after the hydrogenation preferably have a polydispersity index (PDI) M _w / M _n , determined by GPC against polystyrene standards, of ≦ 2.2.

Another aspect of the present invention is a process for producing polyamines comprising the step of reductive amination of CO / olefin copolymers using a CO / olefin copolymer of the present invention. The reductive amination can be carried out, for example, by reaction of the CO / olefin copolymers with hydroxylamine and / or ammonia and the subsequent reduction of the product thus obtained. The reaction with hydroxylamine and / or ammonia and the subsequent reduction can be carried out as two separate reaction steps. However, the reaction with hydroxylamine and / or ammonia and the subsequent reduction can also be carried out as a sequential reaction in a reactor without isolation of the intermediates.

For the formation of multioxime-functional oligomers hydroxylamine is usually used in one to ten-fold molar amounts, based on the carbonyl groups. Preferably, hydroxylamine is used as an aqueous solution or in bulk. However, it can also be released in situ from salts of hydroxylamine, such as hydrochloride or sulfate, in aqueous or alcoholic solution with bases.

The reaction of the multicarbonyl-functional oligomers with hydroxylamine can be carried out in a two-phase mixture. Preferably, a biphasic mixture formed from the multicarbonyl-functional oligomer or a solution of the multicarbonyl-functional oligomer in an inert solvent such as benzene, toluene, chlorobenzene or chloroform and the aqueous hydroxylamine solution is used.

In an alternative variant, the reaction with hydroxylamine takes place in a homogeneous phase. It is possible to add solubilizers, such as C ₁ -C ₃ -alcohols, for homogenizing the reaction mixture. It is preferably stirred for 10 minutes to 30 hours, preferably between 1 hour and 30 hours at temperatures of 0 ° C to 100 ° C, preferably 20 ° C to 80 ° C. Subsequently, the multifunctional oxime can be isolated by phase separation and / or distilling off the volatiles of the reaction mixture.

The reduction of the oxime groups can in principle be carried out by reducing agents such as hydrides including complex hydrides such as alanates or boranates, alkali metals or else preferably by means of hydrogenation.

In the reduction of multioxime-functional oligomers whose polyketone precursors were prepared with azobisisobutyronitrile (AIBN) or other nitrile-containing radical initiators, the nitrile groups contained in the oligomer can also be reduced to the corresponding amines. Thus, the preferred AIBN used may transfer the following end groups to the polyketone: -C (CH ₃ ) ₂ -CN or -CH ₂ -C (CH ₃ ) CN-C (CH ₃ ) ₂ -CN. The resulting amino groups are expressly desired.

In one embodiment of the process for preparing polyamines, the reduction of multioxime-functional oligomers is a heterogeneously catalyzed hydrogenation. The hydrogenation is usually carried out at temperatures of 20 ° C to 200 ° C and at pressures of 10 bar to 100 bar, more preferably from 10 to 50 bar in the presence of 0.1 wt% to 40 wt% of hydrogenation catalysts, such as cobalt, nickel, ruthenium, rhodium, palladium, iridium or platinum.

The catalysts can be used as Raney catalysts or on suitable supports. Particular preference is given to using Raney cobalt, Raney nickel, supported cobalt, nickel, ruthenium or rhodium catalysts. Particularly suitable as support materials are carbon and oxides, such as silicon dioxide, aluminum dioxide, mixed oxides of silicon dioxide and aluminum dioxide and titanium dioxide.

The hydrogenation is preferably carried out in the presence of ammonia, particularly preferably in equimolar amounts, based on the oxime groups. The hydrogenation can be carried out in the presence or absence of solvents. Suitable solvents are, for example, THF, dioxane or C ₁ - to C ₄ -alcohols.

In another embodiment of the process for producing polyamines, the reductive amination comprises the reaction of the CO / olefin copolymers with hydrogen in the presence of ammonia in the presence of a heterogeneous hydrogenation catalyst. Suitable catalysts are the aforementioned hydrogenation catalysts. The reductive amination is preferably carried out in a fixed bed reactor, in particular in a slurry or trickle bed reactor. The CO content in the CO / olefin copolymer used is preferably ≦ 25% by weight.

The present invention furthermore relates to polyamines obtainable by a process according to the invention or, preferably, obtained.

Another object of the present invention is the use of CO / olefin copolymers according to the invention as plasticizers for polymers.

The invention also relates to the use of polyols according to the invention or of polyamines according to the invention for the preparation of polyurethane polymers or formaldehyde resins or as plasticizers for polymers.

The present invention will be further illustrated by, but not limited to, the following examples.

methods:

The estimation of the CO content of the polyketones was based on the integration of the signals obtained in the corresponding ¹ H NMR spectrum. The ¹ H NMR spectra were measured at 400 MHz in CDCl ₃ with a Bruker AV400. The chemical shifts were calibrated relative to the solvent signal (CDCl ₃ , δ = 7.26 ppm).

The ¹ H NMR signals of the polyketones were assigned as follows (relevant H atoms are underlined): δ [ppm] ≈ 2.6-2.7 (CO-C H ^α ₂ -C H ^α ₂ -CO, integral A), 2.1- 2.5 (CO-C H ^{α _'2} - (CH _{2) ≥2,} integral B), 1.4-1.7 (CO-CH ₂ -C H ₂ -CH ₂ ^β, C (C H ₃ ^AIBN) ₂ CN, C C H ^Hex (C ₄ H ₉ ) -C, Integral C), 1.0-1.4 ((CH ₂ ) ₂ - (C H ^al ₂ ) - (CH ₂ ) ₂ , CH-CH ^al ₂ -CH ^al ₂ -CH ₃ , integral D), 0.7-1.0 ( H ^{Hex '} ₃ C (CH ₂ ) ₂ , integral E).

The determination of the CO content of the polyketones prepared by copolymerization of ethylene, CO and 1-hexene using AIBN as a radical initiator, with appropriate correction for the content of AIBN fragments C (CHAIBN ₃ ) ₂ CN and n-butyl side chains (from 1-hexene) from the integrals A to e carried out the following calculations for the relative molar content of n _rel: n _rel (CO) = [n (CH ^α ₂ ) + n (CH ^{α '} ₂ )] / 2 = (A / 2 + B / 2) / 2 = (A + B) / 4 n _rel (CH ^α ₂ ) = A / 2 n _rel (CH ^{α '} ₂ ) = B / 2 n _rel (CH ^β ₂ ) = n _rel (CH ^{α '} ₂ ) = B / 2 n _rel (CH ^Hex ) = n _rel (CH ^{Hex '} ₃ ) = E / 3 n _rel (C (CH ₃ ^AIBN) ₃ CN) = (C - 2 · B / 2 - E / 3) / 6 n _rel (CH ^al ₂ ) = D / 2

After multiplication of the relative molar content n _{rel of} the individual groups with their respective molecular weight M (with M (CO) = 28 g / mol, M (CH ₃ ) = 15 g / mol, M (CH ₂ ) = 14 g / mol, M (CH) = 13 g / mol, M (C (CH ₃ ) ₂ CN) = 68 g / mol) results for the CO content in% by weight: % By weight (CO) = 100% by weight * [28 * (A + B) / 4] / {[28 * (A + B) / 4] + 14 * A / 2 + 14 * B / 2 + 14 B / 2 + [68 * (C - 2 * B / 2 - E / 3) / 6] + 14 * D / 2 + 13 * E / 3 + 15 * E / 3

M _n and M _w were determined by gel permeation chromatography (GPC) on a SECurity GPC system from PSS Polymer Service against polystyrene standards with THF as eluent for polyketones and a solution of 0.1 vol% diethylaminoethylamine in THF for polyalcohols and polyamines , Columns: 2 × PSS SDV linear S, 8 × 300 mm, 5 μm; RID detector; BHT as internal standard.

The OH content in polyalcohols was determined by the following method:
A defined amount of _{polymer of} the polyalcohol (100-200 mg) was dissolved in 0.5 ml of CDCl ₃ and admixed with about 2 equivalents based on the CO content of the polyketone precursor to trifluoroacetic anhydride (TFAA), the exact mass m _{TFAA of} the TFAA used was held. The resulting mixture was heated in a closed reaction vessel with stirring at 50 ° C for 30 min. Then, 4 equivalents based on the CO content of the polyketone precursor were added to diethylamine and the mixture was heated once more for 30 minutes while stirring at 50 ° C. This was followed by ¹⁹ F NMR spectroscopic determination.

The ¹⁹ F NMR signals were assigned as follows:
δ [ppm] = -76.55 (TFA), -76.29 (Polymer-NH-C (O) CF ₃ ), -76.00 (b, Polymer-OC (O) CF ₃ ), -70.13 (Et ₂ NC (O) CF ₃ ).

The OH content of the polymer is given by A (i) = integral of group i and M _i = molar mass of compound / group i: % By weight OH = {A (polymer-OC (O) CF ₃ ) / [A (polymer-NH-C (O) CF ₃ ) + A (polymer-OC (O) CF ₃ ) + A (Et ₂ NC (O) CF ₃ )]} · {[m _TFAA · _MOH ] / [M _TFAA · m _Polymer ]}

Example 1: Preparation of a multiketone-functional oligomer in THF at 10 bar CO partial pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of tetrahydrofuran and 200 ml of 1-hexene were placed in a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene, the gas supply was closed and the mixture was stirred at 80 ° C. for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

There were obtained 24.6 g of a terpolymer of CO, ethylene and 1-hexene. The CO content was 11.2% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 987 g / mol and a polydispersity index PDI = 1.93.

Example 2: Preparation of a multiketone-functional oligomer in THF at 10 bar CO partial pressure and time-constant ethylene pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of tetrahydrofuran and 200 ml of 1-hexene were placed in a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

There were obtained 27.5 g of a terpolymer of CO, ethylene and 1-hexene. The CO content was 11.7% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 1069 g / mol and a polydispersity index PDI = 2.03. The elemental analysis showed the following composition: C 77.53%, H 12.105%, N 2.118%. The keto functionality, calculated from the CO content determined by ¹ H NMR and the molecular weight, results in 4.47 keto groups per molecule. The Nitrile functionality, calculated from the nitrogen content determined by elemental analysis and the molecular weight, results in 1.62 nitrile groups per molecule.

Example 3 Preparation of a Multiketonfunktionellen oligomer in THF at 5 bar CO partial pressure and constant time ethylene pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of tetrahydrofuran and 200 ml of 1-hexene were placed in a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 5 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 30 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

There were obtained 25.4 g of a terpolymer (polyketone 3.1) from CO, ethylene and 1-hexene. The CO content was 7.8% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 883 g / mol and a polydispersity index PDI = 2.03.

In repetitive experiments, the following polyketones were obtained:
Polyketone 3.2: CO content = 7.3% by weight; M _n = 938 g / mol, PDI = 1.85.
Polyketone 3.3: CO content = 8.6% by weight; M _n = 920 g / mol, PDI = 1.92.

Example 4: Preparation of a multiketone-functional oligomer in 2-methyl-THF at 10 bar CO partial pressure and time-constant ethylene pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of 2-methyltetrahydrofuran and 200 ml of 1-hexene were initially introduced into a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

26.7 g of a terpolymer of CO, ethylene and 1-hexene were obtained. The CO content was 10.3% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 897 g / mol and a polydispersity index PDI = 1.88.

Example 5: Preparation of a multiketone-functional oligomer in tetrahydropyran at 10 bar CO partial pressure and time-constant ethylene pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of tetrahydropyran and 200 ml of 1-hexene were placed in a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

26.7 g of a terpolymer of CO, ethylene and 1-hexene were obtained. The CO content was 15.5% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 1112 g / mol and a polydispersity index PDI = 2.07.

Example 6: Preparation of a multiketone-functional oligomer in 1,3-dioxolane at 10 bar CO partial pressure and time-constant ethylene pressure

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of 1,3-dioxolane and 200 ml of 1-hexene were placed in a 970 ml stainless steel glass reactor and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

There were obtained 30.4 g of a terpolymer of CO, ethylene and 1-hexene. The CO content was 15.3% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 1033 g / mol and a polydispersity index PDI = 1.93.

Comparative Example 1: Preparation of multiketone-functional oligomers in other solvents

In a 970 ml pressure reactor made of stainless steel with glass insert, 4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of the solvent and 200 ml of 1-hexene were introduced and the reactor was flooded with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 25 bar of ethylene to a total pressure of 35 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was carefully filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum. For the high-boiling 1,3,5-trioxane, the product was isolated by dissolving in THF and precipitating with water. The residue was then dried for 8 hours while stirring under high vacuum.

Depending on the solvent, the following yields and molecular weights were obtained: solvent yield CO content Mn [g / mol] PDI 1,4-dioxane 21.2 g 11.9% 1113 2.20 methylcyclohexane 17.9 g 10.5% 1137 2.29 diisopropylether 18.1 g 11.5% 1026 2.31 methyl ethyl ketone 18.2 g 11.7% 815 1.93 1,3,5-trioxane 15.9 g 11.6% 1064 1.91

The comparative examples clearly show that in solvents which do not correspond to the cyclic ethers of the general formula (I), the yields obtained are significantly lower. In addition, most products obtained using solvents without such a backbone have a higher polydispersity index. This applies to aliphatic solvents (methylcyclohexane), open-chain ethereal solvents (diisopropyl ether) and 1,4-dioxane.

This in US 2008/0242895 A1 preferred methyl ethyl ketone as a solvent also resulted in lower yields compared to solvents of the formula (I) as well as the dioxane mentioned there.

Example 7: Preparation of multioxime-functional oligomers from multiketone-functional oligomers

A solution of 20.1 g of an oligoketone according to Example 1 in 250 ml of THF was placed in a 500 ml one-necked flask and 17.35 g of a 50% strength aqueous hydroxylamine solution were added dropwise with stirring. After completion of the addition, the mixture was stirred at 80 ° C under reflux for 4 h. After cooling to room temperature, the organic solvent was removed on a rotary evaporator. The residue was extracted three times with 50 ml dichloromethane each time. After drying the combined organic phases over sodium sulfate and filtration, the volatiles were removed on a rotary evaporator and the residue was dried for 12 h under high vacuum. 19.7 g of a yellow oil were obtained. According to NMR and IR spectroscopic analysis, no keto groups were present in the product, but corresponding signals for oxime groups were found. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 991 g / mol and a polydispersity index PDI = 1.87.

Example 8: Preparation of multi-amine-functional oligomers by reduction of multioxime-functional oligomers

A solution of 5.00 g of an oligooxime of Example 5 in 100 ml of a 0.5M ammonia solution in 1,4-dioxane was added together with 1.1 g of Raney nickel in a 200 ml pressure reactor. After closing the reactor, 40 bar of hydrogen were pressed in and the mixture was heated to 160 ° C. with stirring for 4 h. After cooling, the mixture was filtered and the volatiles removed on a rotary evaporator. After drying under high vacuum, 4.82 g of a viscous yellow oil were obtained. According to NMR and IR spectroscopic analysis, the product contained neither oxime nor keto or nitrile groups. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 925 g / mol and a polydispersity index PDI = 2.26.

Example 9: Preparation of multihydroxy-functional oligomers by reduction of multiketone-functional oligomers

A solution of 1.00 g of an oligoketone according to Example 3 in 10 ml of solvent was added together with the amount of catalyst given in the table below in a 20 ml pressure reactor. After closing the reactor, 80 bar of hydrogen were pressed on and the mixture was heated with stirring for 16 h at 200 ° C, the total pressure increased to 100 bar. After cooling, the mixture was filtered and the volatiles removed on a rotary evaporator. After drying under high vacuum, the product was obtained as a viscous pale yellow oil. The content of OH groups was determined by derivatization with trifluoroacetic anhydride by ¹⁹ F NMR spectroscopy. The molecular weight was determined by GPC against polystyrene standards. The results are also listed in the table below.

Depending on the catalyst and solvent, the following products were obtained (PDI: polydispersity index, F: average OH functionality): No. Catalyst (wt%) polyketone solvent Sales CO [%] ^a M _n [g / mol] PDI F ^b 9-1 5% Ru / C (10) 3.2 2-propanol 99 997 1.89 2.40 9-2 5% Ru / C (10) 3.2 2-propanol / H ₂ O 9: 1 v: v 96 1307 1.82 3.05 9-3 5% Ru / C (10) 3.2 1,4-dioxane 51 1187 2.58 1.48 9-4 5% Ru / C (10) 3.2 1,4-dioxane / H ₂ O 9: 1 v: v 93 1169 1.95 2.63 9-5 0.1% Ru-Re / C (100) 3.2 2-propanol > 99 824 1.72 2.26 9-6 5% Rh / C (12) 3.3 2-propanol 50 1258 2.13 1.63 ^a conversion CO = mol% OH _product / mol% CO _educt . ^b Functionality F = average number of hydroxyl groups per molecule = [weight% (OH) / M _n ] .M _n .

Example 10: Preparation of multi-amine-functional oligomers by reductive amination

4 g of 2,2'-dimethyl-2,2'-azodipropionitrile (AIBN), 200 ml of tetrahydrofuran and 200 ml of 1-hexene were placed in a 970 ml stainless steel pressure reactor with glass insert and the reactor was rendered inert with argon. Subsequently, 10 bar of CO were pressed at room temperature, followed by 28 bar of ethylene to a total pressure of 38 bar. The mixture was then heated to 80 ° C with stirring with a gas introduction stirrer at 500 rpm. After reaching the reaction temperature, the total pressure was adjusted to 60 bar with ethylene and the mixture stirred at 80 ° C with open ethylene line for 7 hours. After completion of the reaction time, the reactor was cooled down to 25 ° C and the pressure was carefully released. The resulting reaction mixture was filtered and the solvent removed by rotary evaporation. The residue was then dried for 8 hours while stirring under high vacuum.

There were obtained 27.5 g of a terpolymer of CO, ethylene and 1-hexene. The CO content was 11.7% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a molecular weight M _n = 1069 g / mol and a polydispersity index PDI = 2.03. The elemental analysis showed the following composition: C 77.53%, H 12.105%, N 2.118%. The functionality calculated from the elemental composition and the molecular weight results in 1.62 nitrile groups and 5.51 keto groups per molecule.

A trickle bed reactor was charged with 10 g of Raney nickel, which was previously washed with 3 x 70 mL of 1,4-dioxane. The voids above and below the catalyst were filled with quartz beads. Subsequently, the catalyst bed was rinsed with 1,4-dioxane. The reactor was then connected to two HPLC pumps as well as a mass flow regulator for hydrogen at the inlet and a back pressure regulator at the outlet. Subsequently, 40 bar of hydrogen were injected, a flow of 10 ml of hydrogen / minute was established and the reactor bed was heated to 180.degree. A solution of ammonia in 1,4-dioxane (0.5 M) was passed through the reactor for 15 minutes at a flow rate of 0.7 mL / minute and then the flow rate was adjusted to 0.2 mL / minute. Further, a solution of 1.1402 g of the previously obtained oligoketone (CO / olefin copolymer) in 200 mL of 1,4-dioxane was passed through the reactor at a flow rate of 0.5 mL / min. The reactor temperature was maintained at 180 ° C for 1 hour. Subsequently, the temperature was raised to 200 ° C and the solution emerging from the reactor was collected for 1 hour.

There were obtained 0.1524 g of the multifunctional oligomer. The residual content of CO groups was 3.76% by weight according to ¹ H-NMR. GPC analysis of the product against polystyrene standards revealed a number average molecular weight M _n of 886 g / mol and a polydispersity index PDI of 1.61. This corresponds to a functionality of 1.2 keto groups per molecule. The elemental analysis showed the following composition: C 77.74%, H 12.631%, N 5.02%. The functionality calculated from the elemental composition and the molecular weight, including the keto functionality determined according to ¹ H-NMR, gives rise to 3.2 amino groups and 1.4 alcohol groups per molecule.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2008/0242895 A1 [0004, 0094]
• EP 0791615 A1 [0013]
• JP 01-149828 [0015]

Cited non-patent literature

• J. Polymer Science (1998), 889 and Recent Research Developments in Polymer Science (1999), 355 [0014]
• JACS (1956) 78, 860-861 [0019]

Claims (14)

Process for the preparation of CO / olefin copolymers, comprising the step of free-radical copolymerization of CO with one or more olefins, characterized in that the copolymerization is carried out in a solvent comprising a cyclic ether of the general formula (I):

where: m ≥ 1, n ≥ 1 and o ≥ 0; where m may have a different value in different repeating units o; wherein the boiling point of the cyclic ether is below 230 ° C; where R 1, R 2, R 3, R 4, R 5 and R 6 independently of one another are hydrogen, linear or branched C 1 - to C 22 -alkyl radicals which may also contain ether or ester groups, C 6 - to C 18 -aryl radicals, C 7 - to C 22 -aralkyl or alkylaryl radicals, C5 to C12 cycloalkyl radicals or C1 to C8 alkoxycarbonyl radicals; and wherein two or more radicals R1 to R6 may be linked together; with the proviso that at least one of the substituents R 1 to R 6, which are bonded to a carbon atom, which in turn is bonded to an oxygen atom, is hydrogen; further excluding 1,2-dioxane, 1,3-dioxane and 1,4-dioxane and propylene oxide are excluded. The process of claim 1, wherein the cyclic ether is selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofurfurylmethylether, tetrahydrofurfurylethylether, 2,5-dimethoxymethyltetrahydrofuran, 2,5-diethoxymethyltetrahydrofuran, furfurylacetate, tetrahydrofuran 2-carboxylic acid methyl ester, 1,3-dioxolane and / or tetrahydropyran. The process according to claim 1, wherein CO is copolymerized with an olefin mixture comprising ethylene and an α-olefin. The process according to claim 3, wherein the molar ratio of ethylene to the α-olefin in the reaction solution is from ≥ 0.1: 1 to ≤ 10: 1. CO / olefin copolymers obtainable by a process according to one or more of claims 1 to 4. A process for producing polyols, comprising the step of reducing CO / olefin copolymers, characterized in that a CO / olefin copolymer according to claim 5 is used. The process according to claim 6, wherein the reduction of the CO / olefin copolymer is a hydrogenation of CO / olefin copolymers in the presence of a heterogeneous hydrogenation catalyst, the CO / olefin copolymer has a CO content of ≤25% by weight, and the heterogeneous one Hydrogenation catalyst comprises a metal selected from the group consisting of manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel and / or copper. Process according to claim 7, wherein the hydrogenation is carried out at a hydrogen pressure of ≤ 120 bar. A process according to claim 7, wherein the hydrogenation is carried out in the presence of a solvent or solvent mixture comprising hydroxyl groups. Polyols obtainable by a process according to one or more of claims 6 to 9. A process for the preparation of polyamines, comprising the step of reductive amination of CO / olefin copolymers, characterized in that a CO / olefin copolymer according to claim 5 is used. The process of claim 11, wherein the reductive amination comprises reacting the CO / olefin copolymers with hydrogen in the presence of ammonia in the presence of a heterogeneous hydrogenation catalyst. Polyamines obtainable by a process according to claim 11 or 12. Use of CO / olefin copolymers according to claim 5 as a plasticizer for polymers. Use of polyols according to Claim 10 or of polyamines according to Claim 13 for the preparation of polyurethane polymers or formaldehyde resins or as plasticizers for polymers.