DE1720646C3 - Process for the production of polycondensates with terminal amino groups - Google Patents

Description

2. The method according to claim 1, characterized in that the solvent is chlorobenzene or a mixture of the isomeric dichlorobenzene is used.

From US Pat. No. 2,888,439, it is known to prepare relatively high molecular weight aromatic diamines To produce dinitro compounds by catalytic hydrogenation with Raney-Nickei. It will «O process that either is hydrogenated without a solvent and the reaction product with a Solvent such as tetrahydrofuran is added to separate the catalyst or that in The presence of a solvent such as tetrahydrofuran is reduced. This solvent must as a result of The water of reaction formed during the hydrogenation must be miscible with water in all proportions.

When working without a solvent, such as Example 3 of US Pat. No. 2,888,439 and numerous follow-ups show, the conversion takes place at best only 96 to 97%. If you take the Catalytic hydrogenation in tetrahydrofuran is present

the implementation is uneconomical, since experience has shown that a considerable proportion of this valuable solvent is present get lost.

The imperfect hydrogenation and the inevitable use of one with water in every proportion Miscible solvents such as tetrahydrofuran for diluting or working up are real technical Disadvantage. On the other hand, it was now a particularly economical and smooth process found for the production of higher molecular weight aromatic polycondensates with terminal amino groups.

The invention therefore relates to a process for the production of polycondensates having terminal ends Aminoreslen by catalytic reduction of polynitro compounds from molecular weight 750 to 6000 of the general formula

O ₂ N - R - NH - COG 1 - O - C - NH-R - NOj

in which χ is an integer from 1 to 3, R is a (jc + 1) -valent aryl radical optionally substituted by halogen atoms and / or alkyl radicals and / or oxyalkyl radicals, and G is a divalent radical, as can be obtained by removing the terminal hydroxyl radicals Polyethers, polythioethers, polyesters, polycarbonates and polyacetals advanced with polyfunctional isocyanates and containing hydroxyl radicals are obtained, characterized in that the reduction is carried out with a supported nickel catalyst by adding inorganic salts or organic nitrogen bases to a pH of 5.9 to 7 , 2 adjusted solutions of the polynitro compounds in a water immiscible or only up to 0.2% miscible solvent at 20 to 140 ⁰ C and a hydrogen pressure of 5 to 300 atü is carried out with intensive stirring, the concentration of the polynitro compounds in the solvent being determined Quotient from the total reduction of the existing at the nitro groups occurring gram amount of water of reaction to the gram amount of solvent used is greater than 0.030 and less than 0.050.

The polynitro compounds used as starting compounds are due to the conversion of higher molecular weight Polyhydroxy compounds with nitroaryl isocyanate derivatives accessible in a simple manner.

Suitable nitroaryl isocyanate derivatives are in

U.S. Patent 2,888,439. In addition, products from hexanediol (1,6) and / or octane Derivatives such as diol- <2.6), decanediol- (1.10), decanedioH2.7) or - (2.8)

l-chloro-i-nitrophenyl ^isocyanate , ° ** βΓ "i ² » ⁹ ) as well as mixed polycarbonates from hexane

3-chloro-4-nitrophenyiisocyanate, dioHl, 6) and ^ -Hydroxyäthyi-hexanol-ether or from

!, S-dichloro ^ nitrophcnyUsocyanat, ⁵ hexanediol {1,6) and 4,4'-dihydroxydiphenyl-2 ^ -pro-

2,6-dichloro-4-nitrophenyl isocyanate, P ⁵ " ¹ · Condensation products come as polyacetals

^ Chlorine-l-nitrophenyüsocyanat, ' ^from dihydric aliphatic polyalcohols, such as

α-chloro-Z-nitropbenyl isocyanate, already mentioned above, or from butanediol {i, 3),

^ o-Dichlor ^ -nitrophenyÜsocyanat, ^Di "' ^Tri " ^oaer polyethylene glycols and bis-oxalky-

4-chloro-3-nitrophenyl ^isocyanate , 10 values of diphenols, e.g. B. of liydroquinone, resorcinol,

4-chloro-5-nitro-2-isocyanatotoluene 1,5-dihydroxynaphthalene, des 4,4'-dihydroxydiphe-

4-chloro-6-nitro-3-isocyanatotoluoU nylpropans, M'-dihydroxydiphenyl-sulfone, e.g. B.

S-nitro- ^ isocyanato-US-dimethylbenzoi ^nat aldehydes such as formaldehyde, acetaldehyde, benzene

6-nitro-4-isocyanato-1,3-dimethylbenzene aldehyde, crotonaldehyde, in question.

2- ^ socyanato-5-nitΓO-isopΓopylbenzol, ¹⁵ In addition, the higher molecular weight mentioned

2-isocyanato-5-nitΓO-ethylbenzene, 'hydroxyl-containing polyethers, polythioethers,

4-nitro-2-isocyanato-anisole polycarboxylic acid esters, polycarbonates or polyacetals

S-Nitro ^ -isocvanato-anisoli ^aucn ^ ⁰ * ¹ ^ " ⁰ ^ polyisocyanates to be extended,

4-Cblor-5-nitro-2-isocyanatoanisole ^where a maximum of λ moles of a diisocyanate with (n + 1)

4-chloro-6-nitro-isocyanatophenetoi and * ° ^{moles of the} compounds containing hydroxyl groups

^ Chlor-o-nitroO-isocyanatophenetol are reacted, but on the other hand the proportions are to be chosen so that the MoIe-

for the manufacture of the starting products for the notional weights of the end products are less than 5800. Proven with proper procedures. The use of polyfunctional isocyanates is said to be very advantageous in that the isocyanate component, based on the amount of isocyanate, should be dimensioned in such a way that the end-known processes by phosgenation of the end products are still easily soluble in chlorobenzene. The speaking amines in chlorobenzene or the mixture of reaction components, nitroaryl isocyanate derivative of the isomeric dichlorobenzene and without and higher molecular hydroxyl compound, isolation and purification with the higher molecular weight can be measured so that only some, but hydroxyl compounds in the chlorobenzene solution in 30 also all OH functions with the isoquantitative reaction at 20 to 130 ⁰ C to react as cyanate. On the other hand, a surplus starting material for the process according to the invention, nitroaryl isocyanate, can also be used. To convert the polyoxo compounds to be used of the specified after the reaction with the higher molecular weight Hybenen formula, the isocyanate solvent residue remaining in the same hydroxyl compound is then subjected to the reduction. 35 The derivative is then obtained by adding small amounts of higher molecular weight diol (1,2), propanediol (1,3), butanediol (1,4) that are suitable for reaction with the nitroaryl isocyanate on water or low molecular weight diols such as propane derivatives. Hexane-hydroxy compounds, which can have a molecular weight of diol (1.6), dipropylene glycol or tripropylene glycol of 500 to 5800 and which reacts, and the resulting mixture of poly at least two, but no more than four OH groups per 40 nitroderivate is then fed to the reduction. To carry out the process according to the invention, such as polyethylene glycol ether, polypropylene glycol, the higher molecular weight polyether (1,2), polypropylene glycol ether (1,3), stereo-nitro compound to be inhaled according to the invention (l , 2), Polybutylen- tende concentration brought. This concentration glycol ether- (1,2). Polybutylene glycol ether (1,4), poly 45 conditions are necessary to achieve over 99 ° _o Umpentanedioläther-U.SXPolyhexandioläther-O.oXMisch- settlements. As a solvent, before ether from, for example, polyethylene propylene glycol, the technically readily available chlorobenzene or ether or polypropylene-l ^ -butylene glycol ether, alk- the mixture of isomeric dichlorobenzene use products, which are derived from trimethylolpropane, is found. Furthermore, the solution to be hydrogenated, the solid glycerol, butanetriol, hexanetriol, decanetriol or from a concentration of 50, must be adjusted to the tetrahydroxyoctane or tetrahydroxycyclooctane from pH 5.9 to 7.2, which is in line and through Reaction with alkylene oxides in a technically simple manner by adding inorganic ethylene oxide or propylene oxide in a known manner, salts such as sodium hydrogen carbonate. Are potassium hydroavailable. Also polythioethers, which are made up of gencarbonate, alkali or alkaline earth carbonates or low molecular weight diols such as butanediol, hexanediol, 55 basic alkaline earth carbonates, as represented by the formula octanediol or decanediols and mercaptoglycols Me ¹ KOHXCOj) ₁ /, (Me "= divalent alkaline earth metal, such as dihydroxyether Dihydroxypropyl metal), or by adding orgathiomercaptan, bis - /? - bydroxyäthyl-diphenylsulfid- nischer nitrogen bases such as triethylamine, tributyl ether or from bis - ^ - hydroxypropyldibenzylsulfid-ether amine, dimethylbenzylamine, N-methylmorpholine, synthesize known way are suitable, 60 cyclo- (2,2,2) -diazaoctane in very small doses has the same effect as polyester, for example succinic acid % additives are carried out through acid ethylene glycol, adipic acid butylene glycol, adi. The additive is stirred substances at the space pinic acid hexylene glycol, adipic acid ethylene glycol temperature or slightly higher temperature, a few neopentyl glycol, adipic acid hexylene neopentyl gly- «5 minutes to several hours, controls the col-, adipic acid diethylene glycol, azelaic acid dipro- glycol pH value, and then adds the catalyst and then adds the catalyst - or azelaic acid triethylene glycol-poly- The catalyst according to the invention is a nickel ester. Suitable polycarbonates are the condensate supported catalyst, which is between 5 and 80% by weight

1 72CT646

Perzcnt nickel on a preferably neutral substrate weight 13SS) containing solution in technical precipitated contains- As substrates are kieselguhr, chlorobenzene with 1.0 kg sodium hydrogen carbonate, diatomaceous earth, activated carbon, bentonite, kaolin, silica 30 minutes at 60 ° C, add. 4.5 kg of a carrier contact acid gel, asbestos, quartz glass wool, building block, alumites containing 49.4% nickel on diatomite, and nium oxide, A Voran iwnh y dTosflkatc and neutral 5 presses the mixture with nitrogen into the autoclave. Barium sulfate suitable. The best results are achieved. At 65 to 68 ° C, printing is carried out with nickel on kieselguhr while stirring vigorously. The catalyst 20atü to hydrogen, wherein the reaction is to concentration rapidly, relative to the starts to be hydrogenated and the temperature to over 95 ⁰ C increases. Polynitro compound, in the first test batch It is kept at this temperature at a slower rate of about 3 percent by weight and the pressure can then be increased to 50 atmospheres H ₁ for 45 minutes. In the course of a repeated hydrogenation, generally successively, the reaction is then complete. Be restricted. The use of the poly advantageously but an additional 45 minutes at about AMINL & sung / _x leave solution of the polycondensates with the final 100 ° C 50 H atm. The solution standing above the sedimented amino residues, deposited old contact can th catalyst is repeated to 2 to 3 atm as often as desired. The re-expansion and use of a filter press under this pressure before old contact, which had been separated from the hot, brown and homogeneous substrate by filtration, succeeds if you become liquid by heating to 100 ° C the nickel-containing support catalyst is first in metal slightly reduced pressure water of reaction and THANOL, ethanol, tetrahydrofuran, dioxane or chlorobenzene separated product analysis, Beeinem touches similar solvent and with technical ao mood of the nitro group concentration by chlorobenzene nachwäscht the gradual lowering TiCl _a standard solution, showing at least 99.5% of the amount of fresh catalyst used and the amount of amino groups that Staudard perchloric acid solution has been used to make or renewed use of the catalyst make the hydrogenation process particularly economical, at least 99.5% of the theoretically calculated amount

The hydrogenation of the polynitro compounds according to "5 of amino groups of the formula will vary depending upon the catalyst Comparative ^ ver ^ uch activity at 20 to 140 ⁰ C under 5 to 300 atm Hj-pressure vcr ^ ciuK.vcii.uv.11 preferably at 70 to 110 ⁰ C under 20 to 70 atmospheres of water, the same experiment is carried out with a 32.5 material pressure propylene glycol ether- (1,2) (molecular weight 1355) around 100 ° C and leaves the containing solution in technical-grade chlorobenzene reaction usually for 15 to 60 mirutes without the pH itself according to the invention generally one is provided, the reaction stops at about 85 to intensive stirring of substrate and support - 90% conversion. The catalyst clumps to the catalyst, expediently at least 35 together and is deactivated on the bottom of the autoclave. 200 revolutions / minute can be applied. After the calculation gives a quotient of the end of the reaction, the supported catalyst water to chlorobenzene of 0.0255, that is lower in the substrate, is allowed to sedimentate and only then is the dissolved polycondensate with terminal amino radicals pressed as required according to the invention. . , “On a filter. 40 Example 2

Surprisingly in the process according to the invention, In the same apparatus as in Example 1 added

after which the catalytic ^ hydrogenation in the presence of 450 kg of 44.9 percent by weight bis (4-nitro-

one with water not or only to a maximum of 0.2% phenylcarbaminoyl) - polypropylene glycol ether - (1,2)

miscible solvent is carried out, the smooth (molecular weight 1355) containing solution is in tech-

Course and complete implementation of 45 niche chlorobenzene with 10 kg of sodium hydrogen Reduction reaction. Experience so far has shown carbonate, treated for 20 minutes at 50 ^° C., adds 4.5 kg

namely that with catalytic o 1 < ydration of the carrier contact mentioned in Example 1 to and

Polynitro compounds in with Wasoer not mixed hydrogenated under the conditions mentioned there. the

After a brief analysis of the water of reaction and chlorobenzene, the absorption of hydrogen is determined by the use of solvents

Time comes to a standstill because the water of reaction 50 freed bis- (4-aminophenylcarbaminoyl) -polypropy-

a second phase forms the catalyst of the reac- lenglykoläthers- (1,2) show 99.8% reduction, 99.9%

tion mixture only removes the working method according to the calculated amino groups and below 0.007%

Invention thus leads to success. Chloride content in the process product.

The manufacture according to the method according to the invention, higher molecular weight polyamines are valuable comparative tests Starting materials for pourable and sprayable poly- If the hydrogenation is carried out again according to Beiurethane-Polyurea-Kunststoffe. They are also game 1 on 450 kg of a 44.9% bis- (4-nitrophenylcarb suitable for curing epoxy resins and provide aminoyl) -polypropylene glycol ethers - (l, 2) (Molecular with diisocyanates fast drying lacquers and very weight 1355) containing chlorobenzene solution through hydrolysis-stable coating layers. In addition, if they do not use sodium pretreatment, they serve to build up emulsifiers and hydrogen carbonate, so 4.5 kg of carrier agents can be used. catalyst achieve only imperfect conversion.

Example 1 Example 3 In a 600-1 stirred tank to which a 900-1-65 in the same apparatus as in Example 1 is added High-pressure autoclave is connected, 450 kg are stirred, 450 kg of a 44.9 percent by weight bis- <4-nitro-

a 44.9 percent by weight bis (4-nitrophenyl-carbphenylcarbaminoyO-polypropylene glycol ether)

amino) -polypropylene glycol ether- (l, 2) (molecular-retaining solution in technical grade chlorobenzene with

7 8

0,201 tri-n-butylamine, stirred for 5 minutes at room chlorobenzene, 10 g of dry potassium carbonate are added at temperature, 4.5 kg of the substance mentioned in Example 1 is added and the mixture is stirred for 30 minutes. Then 70 g of supported nickel contact are added and hydrogenated under the same supported catalyst, the 64.8% nickel on diatomaceous conditions as there. After filtration, removing soil containing precipitated, too. This conversion of the water of reaction and the chlorobenzene remains 5 begins to react at 55 to 57 ° C under a hydrogen pressure of 10atü with a diamino polyether with 0.004% chloride content. The hydrogenation is quantitatively complete after 0.42 mol percent residual nitro content and a concentration of 99.6% theoretically calculated amino groups _{at 85 ° C./5O atm. H 1 for one hour.} The product shows after removal of the solution. · Ι λ by means of and the water of reaction over 99.5% of the B e ι s ρ ι e 1 4 ₁₀ theoretically calculated amino groups and below

100 kg of a solution of 45.0 kg of bis- (3-nitrophenyl- 0.3 mol percent NO _r groups on carbaminoyl) -polypropylene glycol ether- (1.2) (molecular weight 1315) in technical grade chlorobenzene are Example 6 with 1.0 kg anhydrous sodium carbonate was ^{stirred at 60 °} C. for half an hour. The pH is 6.4. 15 If you proceed as in Example 5, but with the

25 kg of this neutral chlorobenzene solution are applied to a supported catalyst which contains 34% nickel in a 40-1 VA steel autoclave with 310 g of a contact containing 50.2% nickel on diatomaceous earth, deposited on diatomaceous earth the reaction at 65 to 70 ⁰ C. the mixed hydrogenation catalyst and at from 90 to 100 ° C first requires about 2 hours at 110 to 115 ° C under 20 atm H "then 50 atm H ₁ analog examples 20 70 atm H _x . The process product contains more than 1 game hydrogenated. The main amount of 99% of the theoretically calculated amount of aminodes catalyst is then allowed to sediment and the overgroup and below 0.6 mol% unreacted solution, which is a polyvalent amine with nitro groups, a content of over 99.6% of calculated amino groups, is filtered and a ΝΟ, content of <0.3 mole percent «5 B ice ρ ie 1 7 and a content of 0.0041% chloride, from.

To the remainder of the process remaining in the autoclave, add product to a 1-1 V4A steel stirred autoclave and add 700 g of a 45 percent by weight solution of 25.0 kg of the above 45 percent by weight bis ( 4-nitrophenylcarbaminoyl) -polypropyleneglycoligen bis-P-mtrophenylcarbaminoylVpolypropylenengly- 30 ether- (l, 2) in technical chlorobenzene with 16 g of a koläther- (l, 2) -solution in chlorobenzene as well as 100 g 5% nickel on alumina containing carrier fresh nickel- Add carrier contact and hydrogenated contact and hydrogenated 90 minutes at 130 ^° C. under again as described. After sedimentation of the 50 atm. Hydrogen. The filtered reaction product old contact is separated, the higher molecular weight amine is freed from water and chlorobenzene by distillation, which in turn has 0.3 mol percent NO, -35 and then has the amine equivalent of 16.60 (calculated content, 0.0079% chloride and over 99.5% of the calculated 17.75). has neten ΝΗ, functions. Example 8

One adds again to the one remaining in the autoclave

The remainder of the process product as well as the sedimented. In a 10 l autoclave, 6.0 kg of an old contact (about 300 g) 25.0 kg of the above-mentioned 40% by weight solution of bis- (4-nitro-45% bis- 3- (nitrophenylcarbaminoyl) -polypropy- nylcarbaminoyl) - adipic acid ethylene - glycol polyester lenglykoläther- (1,2) solution in chlorobenzene and 75 g (molecular weight 2310) in technical chlorobenzene of the nickel carrier contact used and stirred with 60 g calcium carbonate for 20 minutes when hydrogenated and separated in the manner described. Also 40 ⁰ C and added 68 g of a 44% nickel on kieselguhr, this reaction product is 99.3% hydrogenated and 45 containing catalyst. The hydrogenation starts contains less than 0.45 mole percent ΝΟ, groups, and only at about 65 ⁰ C under 20 atm H ₁ and can be at 85 ⁰ C 0.0064% chloride. below 110 atü H, finish in an hour. The filtered 'in the fourth hydrogenation with 25.0 kg of the 45% reaction product contains 99.2% of the calculated bis (3 - nitrophenylcarbaminoyl) - polypropylene glycol amino groups and less than 0.4 mol percent of residual ether (l, 2) - Solution in chlorobenzene with a nitro content of about 360 g. Old contact and 75 g of fresh nickel carrier contact, Example 9, slowed but still complete hydrogen uptake by the substrate. This fourth batch is left in a 10 liter autoclave for 6.0 kg of a bis-iS-aminophenylcarbaininoyQ-polypropylene glycol- 36 weight percent solution of bis- {4-nitrophenylether- (1,2) contains less than 0.50 mol percent NO ₁ , more 55 carbaininoyl) -hexanediol- (1.6> porcarbonate in techals 99.4% of the calculated amino groups and only nical chlorobenzene 30 g potassium hydrogen carbonal 0.0079% chloride. Act for 20 minutes at 45 ° C, then add 65 g one

From this example it can be seen that 100 kg of a carrier containing 50.1% nickel on kieselguhr Chlorobenzene solution containing 45.0 kgs of bis (3-nitrophenyl catalyst are added and hydrogenated first at 8O ⁰ C, nact

carbaminoyl) polypropylene glycol ether (1,2), 60 to 20 minutes at 110 ° C under 70 atmospheric pressure up to

with only 560 g of a nickel carrier contact on silica-perfect hydrogen uptake. Reak's

gur with over 99.5% conversion into the corre- sponding water and carbon-benzene-freed process pro

corresponding diamine can be transferred. duct has 98.6% of the theoretically calculated amino

. . groups on and less than 0.35 mole percent ai

Example 5 _6s nitro groups. The deviation of the ΝΗ, -nippen One of them is contained in a 10-1 VA steel autoclave through a slight aminolysis reaction See solution of 3.25 kg of bis- (3-chloro-4-nitrophenyl- des hexanediol- (1,6> polycarbonate under the hydrogenation

rarbaminoyl) -polypropylene glycol ether- (l, 2) in 3.25 kg conditions conditional

1-5115

Example 10

In a 1-1 V4A steel autoclave, WOg of a 49.5 percent by weight chlorobenzene solution of bis (4-nitrophenylcarbaminoyl) polypropylene glycol ether (1.2) (molecular weight 1680) is mixed with 55 g of 11% nickel on aluminum oxide containing carrier contact and hydrogenated for 2 hours at 115 ° C, then 30 minutes at 125 ° C under 120 atm. hydrogen pressure. The filtered reaction product freed from the water of reaction and chlorobenzene has over 99.5% of the calculated amino group functions, 0.15 mol percent _{residual NO 2} content and 0.024% chloride content.

Example 11

600 g of the dinitro compound solution mentioned in Example 11 in chlorobenzene with 25 g of des

11% nickel on aluminum oxide containing carrier contact in the presence of 25 g sodium hydrogen carbonate hydrogenated. The diamine obtained has over 99.5% of the calculated amino groups in one Chloride content of 0.086%.

Example 12

2.51 kg are added to a 3 l stirred autoclave a 49.0 percent by weight solution of bis-

jo p-nitro ^ -chlorphenylcarbaminoyO-polypropylene glycol ether- (l, 2) (molecular weight 2395) in technical grade chlorobenzene with 75 g sodium hydrogen carbonate and 100 g of a 48% nickel on aluminum oxide containing carrier contact and hydrogenated l ^l / _t hours at 110 ⁰ C under 100 atü H ₂ . The reaction product has over 99.3% of the theoretically calculated amino groups, below 0.2 mol% NO ₂ content and a chloride content of 5.24% (calc. 5.23%).

1515

Claims (1)

Patent claims: 1. Process for the preparation of polycondensates with terminal amino groups by catalytic Reduction of Polyn'troverbindungen of molecular weight 750 to 6000 of the general formula O _t N — R —NH-C —O —G \ —O —C — NH- R - NoJ in which χ is an integer from 1 to 3, R is a divalent aryl radical optionally substituted by halogen atoms and / or alkyl radicals and / or oxyalkyl radicals, and G is an (x - + 1) -valent radical, as can be obtained by removing the terminal hydroxyl radicals, polyethers, polythioethers, polyesters, polycarbonates or polyacetals which have been pre-extended with polyfunctional isocyanates and have hydroxyl radicals, characterized in that the reduction is carried out with a supported nickel catalyst by adding inorganic salts or organic nitrogen bases to a pH of 5.9 to 7.2 adjusted solutions of the Polyoxoverbindungen in a water-miscible or only to a maximum of 0.2% solvent at 20 to 140 ⁰ C and eineiu hydrogen pressure of 5 to 300 atm is carried out under intensivei Durchrührung, wherein the concentration of the polynitro compounds in the solvent determining the quotient from the complete reduction of the existing nitro groups occurring gram amount of water of reaction to the gram amount of solvent used is greater than 0.030 and less than 0.050.