DE102010018785A1 - Preparing multi-amine functional oligomers, useful e.g. as reaction partner for isocyanates and epoxides as starting material for phosgenation, comprises e.g. radically co-polymerizing carbon monoxide and olefin - Google Patents

Abstract

Preparing multi-amine functional oligomers, comprises radically co-polymerizing carbon monoxide and at least one olefin, reacting carbonyl groups of the resulting co-polymers with hydroxylamine to obtain multi-oxime functional oligomers, and subsequently reducing the oligomers to obtain multi-amine functional oligomers. Independent claims are also included for: (1) the multi-amine functional oligomers obtained by the above mentioned method; (2) preparing the multi-oxime functional oligomers, comprising reacting copolymers, which are obtained by radical copolymerization of carbon monoxide with (c) ethylene and/or propylene and at least one terminal and/or internal olefin (d) different from (c), with hydroxylamine; and (3) the multi-oxime functional oligomers obtained by the above mentioned method.

Description

The present invention relates to multi-amine functional oligomers which are accessible by free-radical copolymerization of carbon monoxide with olefins, subsequent reaction of the keto groups with hydroxylamine to give oximes and subsequent reduction to amines.

Multiamine-functional oligomers are interesting reactants z. B. for isocyanates or epoxides. Molecules containing more than two amine groups are interesting crosslinkers that can be linked to three-dimensional networks along with amine-reactive compounds such as polyisocyanates or polyepoxides. To control the reactivity, the primary amino groups can also be reacted with maleic acid esters to aspartic acid esters or with ketones or aldehydes to ketamines or aldimines. 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 available. Jeffamines are polyoxyalkylene amines, polyethers containing primary amine groups at the end of the polyether backbone. 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.

It was therefore desirable to synthesize multi-amine oligomers whose amine groups are located on a purely aliphatic hydrocarbon backbone. Such products have not yet been described. Furthermore, the molecular weight (M _n ) and the glass transition temperature (T _g ) should be so low that the multi-amine-functional oligomers have the lowest possible viscosity. There are several reactions that introduce amine groups into molecules. One of them is the reduction, preferably hydrogenation, of oximes to amines, wherein the oximes are obtainable from the corresponding ketones by reaction with hydroxylamine. A systematic investigation JACS (1956) 78, 860-861 shows that the hydrogenation of simple oximes over Raney cobalt or Raney nickel is less selective with respect to the ratio of primary to secondary amines. This is particularly critical for multifunctional oligomeric oximes since oligomer chains are linked upon the appearance of secondary amines, which can lead to an undesirable increase in molecular weight up to complete crosslinking. 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 multioxime functional oligomers. Hydrogenation of molecules containing two or more oxime groups to the corresponding primary amines has not previously been described.

It is known that carbon monoxide and olefins are polymerizable to polyketones. The radical copolymerization is in Progress of Polymer Science (1997) 22, 1547-1605 or in US6750278 . US6541586 . US6740718 or US6642328 described. The possibility of reacting polyketones obtainable by free radical polymerization with hydroxylamine to form polyoximes has been described in US Pat US2495286 mentioned.

The object of the present invention was to synthesize multi-amine-functional oligomers which have a low content of secondary amino groups and which are advanced as little as possible by formation of secondary amino groups.

Surprisingly, it has now been found that such products are accessible by hydrogenation of multioxime-functional oligomers. The oligomers to be hydrogenated can be obtained, for example, by free-radical copolymerization of carbon monoxide with olefins and subsequent reaction with hydroxylamine.

The invention relates to a process for the preparation of multi-amine-functional oligomers, characterized in that first
Carbon monoxide and at least one olefin are radically co-polymerized,
the carbonyl groups of the resulting co-polymers are then reacted with hydroxylamine to form multioxime-functional oligomers,
and subsequently reducing the multioxime-functional oligomers to multi-amine functional oligomers.

The invention also provides a process for the preparation of multi-amine-functional oligomers, characterized in that multioxime-functional oligomers are hydrogenated.

Another object of the invention are obtainable by the two methods described multiamine-functional oligomers.

wobei
R¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH₃C₆H₄ oder 4-CH₃C₆H₄,
R² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH₃C₆H₄ oder 4-CH₃C₆H₄,
R³ = H oder Me,
wobei m, n, o, p, q, r, s = 0 bis 400
und m + n + o + p + q + r +s = 1 bis 400
und t = 1 bis 100
und u = 2 bis 250
oder R¹ = R² = -[(CH²)_u(CHR³)_v(CR⁴ ₂)_w(CH₂)_x(CHR⁵)_y(CR⁶ ₂)_z]_a-,
wobei u, v, w, x, y, z 0 bis 6; u + v + w + x + y + z = 3 bis 6a = 3 bis 6
und R³ sowie m, n, o, p, q, r, s, t, u die oben genannte Bedeutung haben,
und die einzelnen Struktureinheiten t und u innerhalb der Oligomere sich hinsichtlich der Parameter m, n, o, p, q, r und/oder s unterscheiden können.The invention also provides a process corresponding to the latter process, wherein the multioxime-functional oligomers to be used are compounds of the following formula 1:

in which
R ¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ ,
R ² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ ,
R ³ = H or Me,
where m, n, o, p, q, r, s = 0 to 400
and m + n + o + p + q + r + s = 1 to 400
and t = 1 to 100
and u = 2 to 250
or R ¹ = R ² = - [(CH ² ) _u (CHR ³ ) _v (CR ⁴ ₂ ) _w (CH ₂ ) _x (CHR ⁵ ) _y (CR ⁶ ₂ ) _z ] _a -,
where u, v, w, x, y, z are 0 to 6; u + v + w + x + y + z = 3 to 6a = 3 to 6
and R ³ and m, n, o, p, q, r, s, t, u have the abovementioned meaning,
and the individual structural units t and u within the oligomers may differ with respect to the parameters m, n, o, p, q, r and / or s.

The term multioxime functional oligomers also includes mixtures of oligomers of formula 1.

wobei
R¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH₃C₆H₄ oder 4-CH₃C₆H₄,
R² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH₃C₆H₄ oder 4-CH₃C₆H₄,
R³ = H oder Me,
wobei m, n, o, p, q, r, s = 0 bis 400
und m + n + o + p + q + r + s = 1 bis 400
und t = 1 bis 100
und u = 2 bis 250
oder
R¹ = R² = -[(CH₂)_u(CHR³)_v(CR⁴ ₂)_w(CH₂)_x(CHR⁵)_y(CR⁶ ₂)_z]_a-,
wobei u, v, w, x, y, z = 0 bis 6; u + v + w + x + y + z = 3 bis 6; a = 3 bis 6 und R³ sowie m, n, o, p, q, r, s, t, u die oben genannte Bedeutung haben,
und die einzelnen Struktureinheiten t und u innerhalb der Oligomere sich hinsichtlich der Parameter m, n, o, p, q, r und/oder s unterscheiden können.Another object of the invention are multi-amine-functional oligomers of the formula 2:

in which
R ¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i-pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ ,
R ² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i -pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ ,
R ³ = H or Me,
where m, n, o, p, q, r, s = 0 to 400
and m + n + o + p + q + r + s = 1 to 400
and t = 1 to 100
and u = 2 to 250
or
R ¹ = R ² = - [(CH ₂ ) _u (CHR ³ ) _v (CR ⁴ ₂ ) _w (CH ₂ ) _x (CHR ⁵ ) _y (CR ⁶ ₂ ) _z ] _a -
where u, v, w, x, y, z = 0 to 6; u + v + w + x + y + z = 3 to 6; a = 3 to 6 and R ³ and m, n, o, p, q, r, s, t, u have the abovementioned meaning,
and the individual structural units t and u within the oligomers may differ with respect to the parameters m, n, o, p, q, r and / or s.

The term multi-amine functional oligomers also includes mixtures of oligomers of formula 2.

• A) ein Olefin, ausgewählt aus der Gruppe bestehend aus Ethylen und Propylen, oder eine Mischung aus Propylen und Ethylen und
• B) mindestens ein höheres terminales und/oder mindestens ein höheres internes Olefin

eingesetzt.In a preferred embodiment, olefin mixtures containing

• A) an olefin selected from the group consisting of ethylene and propylene, or a mixture of propylene and ethylene and
• B) at least one higher terminal and / or at least one higher internal olefin

used.

Higher terminal or internal olefins in the context of the invention are, for. 1-butene, 2-butene, butadiene, the isomers of pentene, hexene, hedge, octene, isooctene, nonene, decene, undecene, dodecene, higher terminal or internal alkenes, styrene, alpha-methylstyrene, 3- and 4- methylstyrene.

• A) Ethylen und
• B) mindestens ein höheres terminales und/oder mindestens ein höheres internes Olefin

eingesetzt.In a particularly preferred embodiment, olefin mixtures containing

• A) ethylene and
• B) at least one higher terminal and / or at least one higher internal olefin

used.

The copolymerization is initiated by radical initiators, such as azo compounds or peroxides, preferably azo compounds. There are used 0.01 to 50 wt .-%, preferably 0.1 to 30 wt .-%, particularly preferably 0.1 to 3 wt .-% radical initiator based on the monomers. The copolymerization takes place at temperatures such 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 50 to 250 ° C, preferably at 70 to 180 ° C. The reaction temperature depends on the decomposition temperature of the starter used and is at least above it. The temperatures are when using 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) preferably 30 to 140 ° C, with 2,2'-azobis (2.4-dimethyl valeronitrile) preferably 50 to 160 ° C, at 2,2'-azobis (2-methylbutyronitrile) preferably 70 to 180 ° C. In the azodiisobutyronitrile particularly preferably used, the temperatures are preferably 70 to 130 ° C. For gaseous or low-boiling monomers is operated under pressure. When using ethylene and / or propylene in the olefin mixture, the partial pressure of ethylene is preferably between 10 and 2000 bar, more preferably between 30 and 100 bar and the partial pressure of CO between 1 and 30% of the partial pressure of ethylene. The copolymerization can be carried out in the presence or absence, preferably in the absence of solvents. As solvents are u. a. Tetrahydrofuran, methylcyclohexane or pentane suitable.

The molecular weight can be adjusted by the amount of radical initiator used and / or by addition of a suitable regulator, such as hydrogen or mercaptans, and by suitable choice of reaction conditions, such as temperature and partial pressures.

For the formation of the multifunctional oximes hydroxylamine is used in one to ten times 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. Preference is given to a two-phase mixture consisting of 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. Furthermore, at least partially soluble in water, hydroxylamine-inert solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, dioxane, THF, DMF, NMP or dimethylacetamide can be used as a solubilizer. The reaction is carried out at temperatures of 0 to 100 ° C, preferably 15 to 40 ° C. Subsequently, the multifunctional oxime can be isolated by phase separation or / and distilling off the volatiles of the reaction mixture.

An object of the invention is also a process for the preparation of multioximfunktionieller oligomers, characterized in that by free radical copolymerization of carbon monoxide with ethylene and / or propylene and one or more higher terminal or internal olefins such as 1-butene, 2-butene, butadiene, pentene , Hexen, Hegten, Octen, Isoocten, Nonen, Decen, undecene, dodecene or higher terminal or internal alkenes, styrene, alpha-methylstyrene, 3- and 4-methylstyrene copolymers can be reacted with hydroxylamine to multioximfunktionellen oligomers.

An object of the invention are also the multioxime-functional oligomers obtainable by this process.

The reduction of the multioxime-functional oligomers is carried out using a suitable reducing agent, preferably molecular hydrogen, using a selective homogeneous or heterogeneous hydrogenation catalyst. The hydrogenation with hydrogen is carried out at temperatures of 20 to 200 ° C, preferably from 80 to 180 ° C, more preferably from 120 to 160 ° C, at pressures of 10 to 200 bar, preferably 10 to 100 bar, particularly preferably 10 to 50 in the presence of 0.1 to 20 wt .-% of hydrogenation catalysts, such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum. The catalysts can be used as Raney catalysts or on suitable supports. Preference is given to using Raney cobalt, Raney nickel, supported cobalt, nickel or ruthenium catalysts. As support materials are particularly suitable carbon and oxides, such as silica, alumina, mixed oxides of silica and alumina and titanium oxide. The hydrogenation is preferably carried out in the presence of ammonia, particularly preferably in equimolar amounts, based on oxime groups. The hydrogenation can be carried out in the presence or absence of solvents. Suitable solvents are THF, dioxane, or C 1 -C 4 alcohols. Other reducing agents are alkali metals or their hydrides, alanates or boranates.

If nitrile group-containing free-radical initiators, such as azodiisobutyronitrile, or 2,2'-azobis (4-methoxy-2,4-dimethyl valeronitrile) are used, incorporated into the polymer nitrile groups can also be reduced under the conditions of oxime reduction to primary amine groups, and contribute to the functionality of the inventive multi-amine oligomers.

If alkene groups or aryl groups are contained in the multioxime-functional oligomers, these can also be reduced under the conditions of oxime reduction.

The multiamine-functional oligomers according to the invention have a molecular weight M _n of 500 to 20,000, preferably of 800 to 8,000 g / mol. The multi-amine functional oligomers contain at least 2, and on average 3 to 20 amine groups, preferably 3 to 10 amine groups. The amine number, corresponding to the amount of KOH in mg equivalent to the amine content contained in one g substance, is 8 to 967, preferably 20 to 120. The ratio of primary to secondary amine groups is at least 7: 3, preferably at least 9: 1 , more preferably at least 19: 1.

The multifunctional oximes to be used have a molecular weight M _n of 500 to 20,000, preferably from 800 to 8,000 g / mol. The multioxime-functional oligomers contain at least 2, and on average 3 to 20 oxime groups, preferably 3 to 10 oxime groups. The oxime equivalent is 71 to 6700, preferably 500 to 2800 g / eq.

The novel multi-amine oligomers are particularly suitable as reactants for isocyanates and epoxides, as starting materials for the phosgenation to form multi-isocyanate-functional oligomers and for the production of elastic coatings or moldings. The secondary products with maleic acid diallyl esters (polyaspartates) and with ketones or aldehydes (polyketamines or polyaldimines) are particularly suitable as reactants for polyisocyanates.

The invention therefore also relates to the use of the inventive multi-amine-functional oligomers as reactants for isocyanates and epoxides, as starting materials for the phosgenation to form multi-isocyanate-functional oligomers and for the production of elastic coatings or moldings.

Examples

The determination of the CO content of the polyketones was carried out from 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).

-(CH₂)_>2, Interal B), 1.7 (CO-CH₂-C

-CH₂ +

₂CN + C-C

(C₄H₉)-C, Integral C), 1.2 ((CH₂)₂-(C

-(CH₂)₂, Integral D), 0.8

C(CH₂)₃, Integral E) ppm.The ¹ H NMR signals of the polyketones were assigned as follows: δ ≈ 2.6 (CO-C

- (CH ₂ ) _{> 2} , Interal B), 1.7 (CO-CH ₂ -C

-CH ₂ +

₂ CN + CC

(C ₄ H ₉ ) -C, integral C), 1.2 ((CH ₂ ) ₂ - (C

- (CH _{2) 2,} D integral), 0.8

C (CH ₂ ) ₃ , integral E) ppm.

The determination of the CO content of the polyketones with appropriate correction for the content of AIBN fragments C (CH ^AIBN ₃ ) ₂ CN and n-butyl side chains (of 1-hexene) from the integrals A, B, C, D and E. was made by the following calculations for the relative molar content n:
n (CO) = [n (CH ^α ₂ ) + n (CH ^{α '} ₂ )] / 2 = (A / 2 + B / 2) / 2 = (A + B) / 4
n (CH ^α ₂ ) = A / 2
n (CH ^{α '} ₂ ) = B / 2
n (CH ^β ₂ ) = n (CH ^{α '} ₂ ) = B / 2
n (CH ^Hex ) = n (H ₃ C (CH ₂ ) ₃ ) = E / 3
n (CH ^AIBN ₃ ) = (CBE / 3) / 6
n (CH ^ali ₂ ) = D / 2
n (CH ^{Hex '} ₃ ) = E / 3

After multiplying the relative molar content n of the individual groups by 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: CO content = 28 * n (CO) / {28 * n (CO) + 14 * Σ [n (CH ^α ₂ )] + 13 * n (CH ^Hex ) + 15 * n (CH ^{Hex '} ₃ ) + 68 N (CH ^AIBN ₃ )} = 7 (A + B) / [14A + 21B + 13E / 3 + 34 (CBE / 3) / 3 + 7D + 5F]

The nitrogen content was determined by CHN elemental analysis on a Vario EL.

M _n and M _w were determined by gel permeation chromatography (GPC) on a SECurity GPC system from PSS Polymer Service against polystyrene standards (THF as eluent for polyketones and polyoximes, 0.1% DEAEA in THF for polyamines, flow rate 1.0 ml / min, columns : 2 × PSS SDV linear S, 8 × 300 mm, 5 μm, RID detector, BHT as internal standard).

Viscosities were determined with a MCR 51 rheometer from Anton Paar (measuring system: cone-plate principle, heating range 23-60 ° C, heating rate 0.1 ° C / s, shear rate 250 / s (constant), measuring cone: CP 25.1 (25 mm diameter ), Angle of the cone: 1 °).

The glass transition temperatures (Tg) were determined using a DSC Pyris 6 from Perkin Elmer. Heating method: (-70) ° C (3 min) - (+10) ° C / min - (+180) ° C (-10) ° C / min - (-70) ° C (3 min) - (+ 10) ° C / min - (+180) ° C.

example 1

Preparation of an ethylene-hexene-carbon monoxide copolymer

In a 200 ml pressure reactor 50 ml of hexene, 50 ml of methylcyclohexane and 1 g of AIBN were submitted. 50 bar of ethylene, 10 bar of carbon monoxide and 20 bar of hydrogen were pressed in and the mixture was heated to 80 ° C. for 18 hours. The product was obtained after filtration and removal of the volatiles on a rotary evaporator as a colorless to yellow oil.

Experiment 1

• Yield: 5.3 g
• CO content = 7.1% by weight.
• Elemental analysis: nitrogen content = 2.91%.
• GPC analysis: M _n = 1301 g / mol, M _w = 2272 g / mol, D (M _w / M _f ) = 1.75

Experiment 2

• Yield: 3.4 g
• CO content = 9.9 wt .-%.
• Elemental analysis: nitrogen content = 4.49%.
• GPC analysis: M _n = 992 g / mol, M _w = 1559 g / mol, D (M _w / M _n ) = 1.57

Experiment 3

• Yield: 3.4 g
• CO content: 9.7% by weight.
• Elemental analysis: Nitrogen content = 3.5%.
• GPC analysis: M _n = 1106 g / mol, M _w = 1792 g / mol, D (M _w / M _n ) = 1.62.

Example 2

Preparation of Polyoxim of Polyketone According to Example 1

Experiment 1

4.3 g of the polyketone according to Example 1, Experiment 1 were mixed with 4.3 g of a 50 percent solution of hydroxylamine in water and 50 ml of THF and stirred for 4 h under reflux. The reaction mixture was combined with 30 ml of dichloromethane, shaken and the phases were separated. After drying over MgSO ₄ and clarification with activated carbon, the organic phase was evaporated. 4.1 g of polyoxime were obtained.
Elemental analysis: nitrogen content = 5.95%.
GPC analysis: M _n = 1339 g / mol, M _w = 2256 g / mol, D (M _w / M _n ) = 1.68

Experiment 2

2.1 g of the polyketone according to Example 1, Experiment 2 were mixed with 2.2 g of a 50 percent solution of hydroxylamine in water and 50 ml of THF and stirred for 4 h under reflux. The reaction mixture was combined with 30 ml of dichloromethane, shaken and the phases were separated. After drying over MgSO ₄ , the organic phase was evaporated. This gave 1.86 g of product. Since, according to NMR, unreacted keto groups were still present, 1.66 g of the product were again reacted under the same conditions with 1.7 g of a 50 percent solution of hydroxylamine in water. To
Work-up gave 1.2 g of polyoxime.
Elemental analysis: nitrogen content = 8.52%.
GPC analysis: M _n = 1008 g / mol, M _w = 1515 g / mol, D (M _w / M _n ) = 1.50

Experiment 3

3.4 g of the polyketone according to Example 1, Experiment 3 were added with 0.98 g of a 50 percent solution of hydroxylamine in water and 50 ml of THF and stirred for 4 h under reflux. The reaction mixture was combined with 30 ml of dichloromethane, shaken and the phases were separated. After drying over MgSO ₄ , the organic phase was evaporated. This gave 2.97 g of polyoxime.
Elemental analysis: nitrogen content = 7.1%.
GPC analysis: M _n = 1109 g / mol, M _w = 1749 g / mol, D (M _w / M _n ) = 1.58

Example 3

Preparation of the Polyamine from Polyoxime According to Example 2

Experiment 1

In a 200 ml pressure reactor 50 ml of a 0.5 N solution of ammonia in dioxane, 200 mg of Raney nickel and 3.5 g of polyoxime according to Example 2, Experiment 1 were submitted. 40 bar of hydrogen were pressed in and hydrogenated at 140 ° C. for 4 h. After filtering off the Raney nickel and washing with THF, the filtrate was evaporated. 3.4 g of polyamine were obtained. Elemental analysis: nitrogen content = 5.06%.
GPC analysis: M _n = 1363 g / mol, M _w = 2477 g / mol, D (M _w / M _n ) = 1.82
Viscosity (23 ° C): 20580 mPa · s
T _g <-70 ° C

Experiment 2a

30 ml of a 0.5 N solution of ammonia in dioxane, 40 mg of Raney nickel and 0.61 g of polyoxime according to Example 2, Experiment 2 were initially taken in a 200 ml pressure reactor. It was heated to 140 ° C, then pressed 40 bar of hydrogen and hydrogenated at 140 ° C for 4 h. After filtering off the Raney nickel and washing with THF, the filtrate was evaporated. 0.64 g of polyamine was obtained.
Elemental analysis: nitrogen content = 7.59%.
GPC analysis: M _n = 976 g / mol, M _w = 1580 g / mol, D (M _w / M _n ) = 1.62
Viscosity (23 ° C): 40320 mPa · s
T _g <-70 ° C

Experiment 2b

In a 200 ml pressure reactor, 30 ml of a 0.5 N solution of ammonia in dioxane, 40 mg of Raney nickel and 0.46 g of polyoxime according to Example 2, Experiment 2 were submitted. 40 bar of hydrogen were pressed in and hydrogenated at 140 ° C. for 4 h. After filtering off the Raney nickel and washing with THF, the filtrate was evaporated. 0.46 g of polyamine was obtained.
Elemental analysis: Nitrogen content = 7.30%.
GPC analysis: M _n = 967 g / mol, M _w = 1555 g / mol, D (M _w / M _n ) = 1.61
Viscosity (23 ° C): 34180 mPa · s
T _g <-70 ° C

A comparison of experiments 2a and 2b shows that it is irrelevant for the product properties, whether the additions of hydrogen at room temperature and the reaction mixture is then heated to reaction temperature, or the addition of hydrogen after reaching the reaction temperature.

Experiment 3

In a 200 ml pressure reactor 30 ml of a 0.5 N solution of ammonia in dioxane, 40 mg of Raney nickel and 0.87 g of polyoxime according to Example 2, Experiment 4 were submitted. 40 bar of hydrogen were pressed in and hydrogenated at 140 ° C. for 4 h. After filtering off the Raney nickel and washing with THF, the filtrate was evaporated. 0.71 g of polyamine was obtained. Elemental analysis: Nitrogen content = 6.1%.
GPC analysis: M _n = 1084 g / mol, M _w = 1814 g / mol, D (M _w / M _n ) = 1.67
Viscosity (23 ° C): mPa · s
T _g <-70 ° C

A comparison of the molecular weight of polyamine and polyoxime shows that the selectivity to primary amines in the oxime hydrogenation is very good, since the formation of secondary amines by linking polymer chains would lead to a considerable increase in the molecular weight.

Comparative Example 1

Preparation of an ethylene-carbon monoxide copolymer

100 ml of methylcyclohexane and 1 g of AIBN were placed in a 200 ml pressure reactor. There were 50 bar of ethylene, 10 bar carbon monoxide and 10 bar of hydrogen pressed and heated to 80 ° C for 8 h. After relaxing to atmospheric pressure, a solid-liquid mixture was obtained.

By filtration, 3.27 g of a waxy solid was isolated.
GPC analysis: M _n = 1800 g / mol, M _w = 2824 g / mol, D (M _w / M _n ) = 1.57

Removal of the volatile constituents of the filtrate on a rotary evaporator additionally gave 1.38 g of an oily liquid.
GPC analysis: M _n = 805 g / mol, M _w = 1191 g / mol, D (M _w / M _n ) = 1.48

The example shows that the copolymerization of ethylene and carbon monoxide compared to the copolymerization of ethylene, 1-hexene and carbon monoxide leads to a more inhomogeneous product with solid polymer components.

Comparative Example 2

Influence of steric demand on the selectivity of the hydrogenation of oximes A mixture of 7.5 g of the oxime according to Table 1, 175 ml of THF and 750 mg of Raney nickel was introduced into a 200 ml pressure reactor and 40 bar of hydrogen was injected at 140 ° C. After 135 minutes, the reactor was cooled to room temperature and vented. Raney nickel was filtered off and the filtrate was analyzed by gas chromatography. The results are summarized in Table 1.

Table 1: Model study for the hydrogenation of monofunctional oximes

From the experiments on model substrates it is clear that sterically demanding oximes are hydrogenated in higher selectivity to the primary amine. In addition, it is clear from the experiments that linear ketoximes are hydrogenated to the primary amine in a higher selectivity than linear aldoximes.

Comparative Example 3

Influence of ammonia on the selectivity of the hydrogenation of oximes

In a 200 ml pressure reactor, a mixture of 7.5 g of 2-Ethylbutanaldoxim, 175 ml of THF, 395 mg of a 28 percent aqueous ammonia solution and 750 mg Raney nickel submitted and pressed at 140 ° C 40 bar hydrogen. After 135 minutes, the reactor was cooled to room temperature and vented. Raney nickel was filtered off and the filtrate analyzed by GC. There was obtained 1-amino-2-ethylbutane as the only product.

From the comparison with the example of Table 1, entry 2, it is clear that the selectivity of the hydrogenation of oximes over Raney nickel to primary amines by the addition of 1 equivalent of ammonia is considerably increased from 79.4% to> 99%.

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 6750278 [0005]
• US 6541586 [0005]
• US 6740718 [0005]
• US 6642328 [0005]
• US 2495286 [0005]

Cited non-patent literature

• JACS (1956) 78, 860-861 [0004]
• Progress of Polymer Science (1997) 22, 1547-1605 [0005]

Claims (15)

A process for preparing multi-amine functional oligomers, characterized in that first carbon monoxide and at least one olefin are radically co-polymerized, the carbonyl groups of the resulting copolymers are then reacted with hydroxylamine to multioximfunktionellen oligomers, and the multioximfunktionellen oligomers are then reduced to multi-amine oligomers. Process according to Claim 1, characterized in that the olefin comprises an olefin mixture A) an olefin selected from the group consisting of ethylene and propylene, or a mixture of propylene and ethylene and B) at least one further, different from A), terminal and / or internal olefin is used. A method according to claim 2, wherein ethylene is used as component (A). Process according to claim 2 or 3, wherein as component (B) 1-butene, 2-butene, butadiene, the isomers of pentene, hexene, hedge, octene, isooctene, nonene, decene, undecene, dodecene, higher terminal or internal alkenes, styrene , alpha-methylstyrene, 3- and / or 4-methylstyrene. A process according to any one of claims 1 to 4 wherein the reduction is by hydrogenation with molecular hydrogen. Process for the preparation of multi-amine-functional oligomers, characterized in that multioxime-functional oligomers are hydrogenated. Process according to claim 5 or 6, wherein the hydrogenation is carried out in the presence of ammonia. Multiamine-functional oligomers obtainable by a process according to one of claims 1 to 7. A process according to claim 6, wherein the multioxime-functional oligomers to be hydrogenated are compounds of the following formula 1:

wherein R ¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i -pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ , R ² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i -pentyl, neopentyl, hexyl, heptyl, octyl , Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ , R ³ = H or Me, where m, n, o, p, q, r, s = 0 to 400 and m + n + o + p + q + r + s = 1 to 400 and t = 1 to 100 and u = 2 to 250 or R ¹ = R ² = - [(CH ₂ ) _u (CHR ³ ) _v (CR ⁴ ₂ ) _w (CH ₂ ) _x (CHR ⁵ ) _y (CR ⁶ ₂ ) _z ] _a -, where u, v, w, x, y, z = 0 to 6; u + v + w + x + y + z = 3 to 6; a = 3 to 6 and R ³ and m, n, o, p, q, r, s, t, u have the abovementioned meaning, and the individual structural units t and u within the oligomers with respect to the parameters m, n, o, p, q , r and / or s can differ. Process according to claim 9, wherein the hydrogenation is carried out using molecular hydrogen and in the presence of ammonia. Multiamine-functional oligomers of the formula 2:

wherein R ¹ = Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n-pentyl, i -pentyl, neopentyl, hexyl, heptyl, octyl, Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ , R ² = H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, n -pentyl, i -pentyl, neopentyl, hexyl, heptyl, octyl , Ph, 3-CH ₃ C ₆ H ₄ or 4-CH ₃ C ₆ H ₄ , R ³ = H or Me, where m, n, o, p, q, r, s = 0 to 400 and m + n + o + p + q + r + s = 1 to 400 and t = 1 to 100 and u = 2 to 250 or R ¹ = R ² = - [(CH ₂ ) _u (CHR ³ ) _v (CR ⁴ ₂ ) _w (CH ₂ ) _x (CHR ⁵ ) _y (CR ⁶ ₂ ) _z ] _a -, where u, v, w, x, y, z = 0 to 6; u + v + w + x + y + z = 3 to 6; a = 3 to 6 and R ³ and m, n, o, p, q, r, s, t, u have the abovementioned meaning, and the individual structural units t and u within the oligomers with respect to the parameters m, n, o, p, q, r and / or s can differ. Multiamine-functional oligomers according to claim 8 or 11, wherein the ratio of primary to secondary amino groups is at least 7: 3. Use of the inventive multi-amine-functional oligomers according to claim 8, 11 or 12 as reactants for isocyanates and epoxides, as starting materials for the phosgenation to multiisocyanate-functional oligomers and for the production of elastic coatings or moldings Process for the preparation of multioxime-functional oligomers, characterized in that by free-radical copolymerization of carbon monoxide with ethylene and / or propylene ((C)) and one or more of (C), terminal and / or internal olefins ((D)) available copolymers Hydroxylamine be converted to multioximfunktionellen oligomers. Multioxime-functional oligomers obtainable by a process according to claim 14.