DE2603834A1 - CATALYSTS FOR ISOCYANATE POLYADDITIONAL REACTIONS - Google Patents

Description

Bayer Aktiengesellschaft

Central Patents Department. Trademarks and licenses

509 Leverkusen. Bayerwerk

Sft / bc

29

Catalysts for isocyanate polyaddition reactions

The present application relates to new catalyst combinations with improved catalytic effectiveness for isocyanate polyaddition reactions.

It has long been known that, on the one hand, there are many heavy metal compounds and on the other hand amines are also effective catalysts for addition reactions on isocyanates (See K.C. Frisch, L.P. Rennao, "Catalysis in Isocyanate Reactions "in J." lacromol.'Sei.-Revs. Macromol. Chem. C5 (1), 103-150 (197O)).

It is also known that combinations of metal compounds and amines act synergistically, one of which is generally used technically, especially in the reaction of polyisocyanates with polyols (cf. J.K. Saunders and K.C. Fresh, Polyurethanes, Part I, Interscience Publishers, New York - London - Sydney, 1962, pp. 231, 232).

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tertiary

The most catalytically active amines, which are usually tert contain bound nitrogen, e.g. 1,4-diazabicyclo- (2,2,2) -octane generally in concentrations of 0.04 to 0.5 parts by weight, based on the polyol used, be used, while with other amines, or when reactions of aliphatic isocyanates are catalyzed should, considerably larger quantities are required.

However, even the use of small amounts of amine catalysts has serious disadvantages. Since it is the industrially used catalysts are usually tertiary amines that do not enter the polyurethane are chemically incorporated, a disruptive phenomenon occurs long after the production of the polyurethane plastic Amine smell on. This is particularly uncomfortable with items of everyday use, such as upholstery, Automobile construction equipment, shoes, furniture, etc. The amines often lead to yellowing of light-colored leather or Plastic surfaces.

Bicyclic amidines as polyurethane catalysts are described in German Offenlegungsschrift 1 745 418, which also mentions the use of organometallic compounds. Free amidines as catalysts German Offenlegungsschrift 1 950 262 describes reactions of aliphatic isocyanates. However, this class of compounds has the disadvantage that they are easily removed from water is decomposed (cf. Houben-Weyl-Müller, methods of organic chemistry, published by G. Thieme, Stuttgart, Volume XI, p. 940).

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That includes the application for foam systems in which Water serves as a propellant, largely from. The traces of water that are always present in polyols are also sufficient to reduce the catalytic activity of free amidines within a few days. Storage of an amidine catalyst containing polyol mixture is therefore only possible to a limited extent.

Just like water, many halogenated hydrocarbons such as CH ₂ Cl ₂ , CHCl ₃ , CCl ₄ , HClC = CClH, HClC = CCl ₂ , H ₂ ClC-CClH ₂ , etc., severely limit the possible uses for amidines. They react very quickly with quaternization, the amidines being largely ineffective as catalysts.

The present invention relates to the use of the hydrazines defined in more detail below as cocatalysts for the isocyanate polyaddition reaction. Together with the metal compounds described below, they form excellent catalyst systems, which do not suffer from the disadvantages just mentioned and in particular have the following advantages:

1. Foams made using the new catalyst combinations produced, show no perceptible odor, since the hydrazines used with isocyanates react to semicarbazide.

2. In contrast to the amidines are those used according to the invention Hydrazino compounds stable in the presence of water and halogenated hydrocarbons.

3. The new catalyst systems make it easier to demold in the production of molded foamed plastics. This is where they differ in a particularly advantageous manner from those which have hitherto been preferably used as catalysts Combinations of 1,4-diazabicyclo- (2,2,2) -octane and organic tin (IV) compounds.

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The present invention relates to catalyst combinations, consisting of

A) 1 mol of a metal compound of the general formula

^{Me X} n ^Y m '

whereby

Me denotes a (n + m) valent metal, preferably from the I., II., VII. Or VIII. Subgroup or the IV. main group of the Periodic Table of the Elements,

X stands for an aliphatic hydrocarbon radical with 1 to 18 carbon atoms, an aromatic hydrocarbon rest with 6 to 10 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms,

Y for an optionally olefinic double bond and / or aliphatic carboxylate radical containing alcoholic hydroxyl groups and having 2 to 18 carbon atoms or an enolate radical with 5 to 18 carbon atoms,

η stands for an integer between 0 and 2 and m for an integer between 0 and 4 with the Restriction that the sum (n + m) is 2 to 4,

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B) 0.5 to 6 moles of an aromatic compound containing at least one tertiary nitrogen atom as a hetero atom, which at least one hydrazino group, preferably in ortho- or para position to the hetero atom, as a substituent.

In the TT electron-poor used as cocatalysts according to the invention, heterocyclic aromatics is due to the electronegatxvitat of the increased by the tertiary nitrogen atom aromatic nucleus weakened the reactivity of the hydrazino group- preferred cocatalysts according to the invention are:

1 . Hydrazines the Formulas l (D and (II): (II) R ¹ ^ N-NH " R ² R ² Ai H R ³ R ⁴ 'Si ^ N-NH ₉ H (I)

in which

12 3 4
R, R, R and R denote identical or different radicals and represent hydrogen, a hydroxyl, nitro or cyano group, an aliphatic hydrocarbon radical having 1 to 6 carbon atoms or an aromatic hydrocarbon radical

2 3 12 3 6-12 carbon atoms. R and R or R and R or R and

4th
R can also stand for a fused ring, so that corresponding bicyclic and tricyclic aromatic hydrocarbons are formed.

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Examples of such hydrazines are:

2-hydrazinopyrimidine, 4-hydroxy-2-hydrazino-6-methylpyrimidine, 2-hydrazinopurine, 2-hydrazinopyridine, 2-hydrazinoquinoline, 5-nitro-2-hydrazinopyrimidine and 2-hydrazino-6-methyl-pyrimidine.

2. Hydrazines of the formulas (III) and (IV) R ² NH-NH "

Π R

 TI 1?
"NH-NH ₂ R ^J ^ if ^ R

(Ill) (IV)

12 3

in which R, R and R have the meaning given under 1. Examples of such hydrazines are:

4-hydrazinopyrimidine, 4-hydrazino-6-methylpyrimidine, 4-hydrazino-6-phenyl-pyrimidine and 6-hydrazino-2,5-diphenylcyanopyrimidine.

3. Hydrazines of the formulas (V) and (VI)

NH-NH2 R

3'o λ '

R v "^ s ^ R ^z R ^J

R ⁴  ^ N ^ R ¹ R ⁴ ^ N ^ R ¹

(V) (VI)

1 2 ■} 4

in which R, R, R ^J and R have the meaning given under 1.

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Examples are:

3-hydrazinopyridine, 4-hydrazinopyridine, 4-hydrazinomethylquinoline 1-4 -ethyl-S-hydrazinopyridine and 4-hydrazinoquinoline.

4. Hydrazines of the formulas (VII), (VIII) and IX)

NH-NH ₂ NH-NH ₂ R ²

N IT R ^J  ^ N NH-NH ₃ H ₃ N-NHN NH-NH ₃

(VII) (VIII) (IX)

12 3
in which R, R and R have the meaning given under 1.

Examples are:

2/6-dihydrazinopyrimidine, 2,6-dihydrazinopurine, 2,6-dihydrazino-3,5-diphenylpyrimidine, 2,4-dihydrazinopyridine, 2,6-dihydrazinopyridine and the 2,4- and 2,6-dihydrazinopicolines.

Compounds of the general type are particularly preferred

Formulas (I) to (IX) in which R ¹ , R ² , R ³ , R ⁴ all represent

1 4 hydrogen or only one of the radicals R to R for methyl and the others for hydrogen or only two of the radicals R

4th
to R stand for a fused aromatic ring and the others stand for hydrogen.

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The dihydrazino compounds are of particular interest because they in the reaction mixture even at low temperatures (through reaction with polyisocyanates with the formation of bis-semicarbazides) act to lengthen the chain. In contrast to the corresponding amino compounds, however, those according to the invention also provide Monohydrazino derivatives to be used are not chain terminators because they are compared to at elevated temperatures Isocyanates are bifunctional.

That the cocatalysts according to the invention, at least each contain a primary, secondary and tertiary amino group, in combination with metal compounds a surprising catalytic one Have activity becomes clear when one considers the effectiveness of the hydrazino compounds described above Compare phenylhydrazine or nitrophenylhydrazine in combination with metal catalysts.

In the latter two cases, the mixtures examined do not already have any over that of the metal compound alone its own catalytic activity has a catalytic effect that goes well beyond it.

Preferably according to the invention in combination with the above-described amines metal compounds of trivalent iron, divalent nickel, divalent zinc, of divalent manganese, divalent tin and tetravalent tin. Examples of suitable metal compounds are:

Fe (III) acetate, Fe (III) oleate, Fe (III) stearate, Fe (III) acetylacetonate, Zn acetate, Zn oleate, Zn acetylacetonate, Mn (II) acetate, MndDacetylacetonat, Mn (II) palmitat, Mn (II) versatat, Mn (II) naphthenate, Sn (II) acetate, Sn (II) octoate, Sn (II) isooctoate, Sn (II) ricinoleate, Sn (II) naphthenate, dibutyl-Sn (IV) laurate, Dibutyl Sn (IV) octoate, diethyl Sn (IV) 2-methylhexoate, Diphenyl-Sn (IV) capronate, Ni (II) acetate, Ni (II) octoate, Ni (II) oleate, Ni (I) ricinoleate, Ni (II) acetylacetonate and Ni (II) salicylate.

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At

The described ^ hydrazines and the metal compounds are according to the invention in the molar ratio of hydrazine: metal compound from 0.5: 1 to 6: 1 are used.

In flexible foam formulations there are higher proportions of the hydrazino compound preferred (molar ratio approx. 3: 1 to 6: 1), while in the production of rigid and semi-rigid foams the components of the catalyst combinations according to the invention are used in approximately equal molar amounts. the Hydrazine compounds form an isolable complex with the metal compounds, in a molar ratio of 1: 1, which is thin-layer chromatography and can be detected by NMR and IR spectroscopy.

The complexes may, for example, by mixing the components in low molecular weight alcohols, such as tetraethylene glycol or trimethylolpropane are prepared at 50-10O ⁰ C. After cooling to room temperature, the complex, an oil, separates from the alcohol and can be isolated using a separating funnel.

It is of course also possible to dissolve the components in a low-boiling, inert organic solvent such as e.g. Acetone, diethyl ether, methanol, ethanol, toluene or xylene to mix and isolate the complex by evaporating the solvent.

The complexes can also be prepared directly in high molecular weight polyols, such as those used for isocyanate polyaddition reactions can be used. The complexes do not separate from these solutions. The solved complexes show one Catalytic activity analogous to the pure complexes.

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The catalyst systems of the invention can be the to be catalyzed Reaction mixtures in the form of the separate individual components, in the form of the pre-formed complex (if necessary mixed with additional hydrazine or metal compound) or preferably dissolved in higher molecular weight polyols be admitted.

When the new combinations are used according to the invention, those used to produce the polyurethane plastics are used Polyol component normally 0.001-4, preferably 0.01-0.8% by weight of the catalyst system is added.

The new catalyst combinations can be used both in the production of solid elastomers and for polyurethane foam distribution can be used to advantage. According to the invention, hard, Manufacture semi-hard or soft products. The volume weights are variable from approx. 15 kg / m up to approx. 1000 kg / m

Surprisingly, the semicarbazides formed by the reaction of the hydrazines with isocyanates show in combination with the organometallic compounds are also good catalytic ones Effectiveness.

In addition to their catalytic activity, the dihydrazino compounds are also of interest as hydrazine crosslinkers and are therefore advantageously used as chain extenders in concentrations greater than those described.

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The invention therefore also provides a method for Manufacture of polyurethane plastics by implementing Polyisocyanates, higher molecular weight compounds with at least 2 isocyanate-reactive hydrogen atoms and optionally chain extenders in the presence of catalyst combinations of an amine and an organometallic Compound which is characterized in that the mixtures according to the invention are used as catalysts will.

Starting components for the production of polyurethane plastics according to the invention under use of the novel catalyst combinations are any aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as r

z. B. von W. Siefken in Justus Liebig's Annals of Chemistry, 562, pages 75-136, for example Ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, Cyclohexane-1,3- and 1,4-diisocyanate as well as any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, U.S. Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate as well as any devices of these isomers, hexahydro-1,3- and / or -4,4-phenylene diisocyanate, Perhydro-2,4'- and / or ^^ '- diphenylmethane-dllsocyanat, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, as they are created by aniline-formaldehyde condensation and subsequent phosgenation

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$ 4

hold and are described, for example, in British patents 874 and 848 671, m- and p-isocyanatophenylsulfonyl isocyanates according to American patent 3 454 606, perchlorinated aryl polyisocyanates, as described, for example, in German Auslegeschrift 1 157 (American patent 3 277 138j Polyisocyanates containing carbodiimide groups, as described in German patent specification 1,092,007 (American patent specification 3,152,162), diisocyanates as described in American patent specification 3,492,330, polyisocyanates containing allophanate groups, as described 2.B. in US Pat British patent specification 994 890, Belgian patent specification 761 and published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, such as those described in American patent specification 3 001 973, in German patents 1 022 789, 1 222 067 and 1 027 394 as well as in the German Offenlegungsschriften n 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, as described in Belgian patent 752 261 or in American patent 3 394.164, polyisocyanates containing acylated urea groups according to German patent 1 230 778, polyisocyanates containing biuret groups, as described, for example, in German patent 1 101 394 (American patents 3 124 605 and 3 201 372) and in British patent 889, polyisocyanates produced by telomerization reactions, as described, for example, in American patent 3 654 106, Polyisocyanates containing ester groups, such as those described, for example, in British Patents 965,474 and

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709831/0864 BATH ORIGINAL

Are 1,072,956, referred to in United States Patent Specification 3,567,763 and in German Patent 1,231,688, reaction products of the abovementioned isocyanates with acetals according to German Patent 1,072,385, polymeric fatty acid radicals containing polyisocyanates according to the American patent 3,455,883.

It is also possible to use the isocyanate group-containing distillation residues obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates to be used. It is also possible to use any desired mixtures of the aforementioned polyisocyanates to use.

The technically easily accessible polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and are particularly preferred subsequent phosgenation are produced ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups and polyisocyanates containing biuret groups ("modified polyisocyanates").

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Starting components in the production of polyurethane plastics using the new catalyst combinations according to the invention are also compounds with at least two isocyanate-reactive hydrogen atoms and generally from 400-10,000 molecular weight. In addition to amino groups, thiol groups or compounds containing carboxyl groups, this is preferably polyhydroxy! compounds, especially compounds containing two to eight hydroxyl groups, especially those with a molecular weight of 800 to 10,000, preferably 1000 to 6000, for example at least two, usually 2 to 8, but preferably 2 to 4, hydroxyl groups, polyesters, polyethers, polythioethers, polyacetals , Polycarbonates, polyester amides, as are known per se for the production of homogeneous and cellular polyurethanes.

The possible polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated. Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrachlorophthalic anhydride, a mixture of trimachlorophthalic anhydride, a mixture of tri-chlorophthalic anhydride, a mixture of oleic, maleic anhydride, and with monomeric fatty acids, dimethyl terephthalate and

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Terephthalic acid bis-glycol ester. As polyhydric alcohols e.g. ethylene glycol, propylene glycol- (1,2) and - (1,3) »butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), Neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,

Glycerine, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methyl glycoside, also diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol Dipropylene glycol, polypropylene glycols, dibutylene glycol and Polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Also made of polyester Lactones, e.g. ε-caprolactone or hydroxycarboxylic acids, e.g. cj-hydroxycaproic acid can be used.

The polyethers which can be considered according to the invention, at least two, usually two to eight, preferably two to three, hydroxyl groups are those of the type known per se and are produced, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin with itself, for example in the presence of BF ,, or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols or amines, e.g. ethylene glycol, propylene glycol- (1,3) or - (1 , 2 ) , trimethylolpropane, 4,4'-dihydroaqrdiphenylpropane, aniline, ammonia, ethanolamine, ethylenediamine. Sucrose polyethers, as described, for example, in German Auslegeschriften 1,176,358 and 1,064,938, are also suitable according to the invention. In many cases, those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups. Also through vinyl poly

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merisate modified polyethers, such as those obtained by polymerization of styrene and acrylonitrile in the presence of polyethers arise (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German patent 1 152 536) are suitable, as are polybutadienes containing OH groups.

Among the polythioethers are in particular the condensation products of thiodiglycol with themselves and / or with others Glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components acts the products are polythio mixed ethers, polythioether esters or polythioether ester amides.

As polyacetals come e.g. those from glycols, such as diethylene glycol, Triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, Hexanediol and formaldehyde preparable compounds in question. Also let through the polymerization of cyclic acetals According to the invention, suitable polyacetals can be prepared.

Polycarbonates containing hydroxyl groups are those of the type known per se, which are produced, for example, by reacting Diols such as propanediol- (1,3), butanediol- (1,4) and / or hexanediol- (1,6), Diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. diphenyl carbonate, or phosgene can be produced.

The polyester amides and polyamides include, for example, those made of polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, Predominantly linear condensates obtained from diamines, polyamines and their mixtures.

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AFTER REPORT

Also polyhydroxy compounds already containing urethane or urea groups as well as optionally modified natural polyols such as castor oil, carbohydrates and starch usable. Addition products of alkylene oxides with phenol-formaldehyde resins or also with urea-formaldehyde resins can be used according to the invention.

Representatives of these compounds to be used according to the invention are, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology ", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44 - 54 and Volume II, 1964, pages 5-6 and 198 199, as well as in the Kunstsotff manual, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

Mixtures of the abovementioned compounds can of course be used with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400 - 10,000, e.g. mixtures of polyethers and polyesters, can be used.

As starting components optionally to be used according to the invention compounds with at least two isocyanate-reactive hydrogen atoms also come from one Molecular weight 32-400 in question. In this case too, this is understood to mean hydroxyl groups and / or amino groups and / or compounds containing thiol groups and / or carboxyl groups, preferably hydroxyl groups and / or amino groups comprising compounds which serve as chain extenders or crosslinking agents. These connections show usually 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive Hydrogen atoms. As examples of such compounds may be mentioned: ethylene glycol, propylene glycol- (1,2) and - (1,3),

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NAQH EEREIOHT

Butylene glycol (1,4) and - (2,3), pentanediol (1,5), hexanediol (1,6), octanediol (1, S) _f neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane , 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6), trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol , Polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with a molecular weight of up to 400, 4,4'-dihydroxy-diphenylpropane, di-hydroxymethy1-hydroquinone, ethanolamine, diethanolamine, triethanolamine, 3-aminopropanol, ethylene diamine, 1,3-diaminopropane 1-mercapto-3-aminopropane, 4-hydroxy- or -amino-phthalic acid, succinic acid, adipic acid, hydrazine, Ν, Ν'-dimethylhydrazine and 4,4'-diaminodiphenylmethane.

In this case too, mixtures of different compounds with at least two opposite isocyanates can be used reactive hydrogen atoms with a molecular weight of 32-400 can be used.

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GRiGiNAL INSPECTED

The production of polyurethane plastics under the invention The new catalyst combinations are often used with the use of water and / or lightly volatile organic substances as propellants. Organic blowing agents include acetone, ethyl acetate, Halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, Chlorodifluoromethane, dichlorodifluoromethane, also butane, Hexane, heptane or diethyl ether are possible. A blowing effect can also be achieved by adding at temperatures above room temperature with the elimination of gases, e.g. nitrogen, decomposing compounds, e.g. azo compounds such as azoisobutyronitrile, can be achieved. Further examples of propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.

Of course, in addition to the catalyst combinations according to the invention, further catalysts can be added, especially if it can be combined with special effects.

Catalysts to be used are those of the type known per se, for example tertiary amines, such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν ', N ¹ -tetramethyl-ethylenediamine , 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N ¹ -dimethylaminoethyl-piperazine, Ν, Ν-dimethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, Ν, Ν-diethylbenzylamine, pentamethyldiethylenetriamine, Ν, Ν-dimethylcyclohexylamine, Ν, Ν, Ν ', Ν ¹ -

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Tetramethyl-1,3-butanediamine, Ν, Ν-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole. As catalysts Mannich bases known per se from secondary amines, such as dimethylamine, and aldehydes, are also preferred Formaldehyde, or ketones such as acetone, methyl ethyl ketone, cyclohexanone and phenols such as phenol, nonylphenol or Bisphenol in question.

Hydrogen atoms active towards isocyanate groups tertiary amines as catalysts are e.g. triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, Ν, Ν-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or Ethylene oxide.

Silaamines with carbon-silicon bonds, such as those used in Germany, are also used as additional catalysts Patent specification 1,229,290 (corresponding to American patent specification 3,620,984) are in question, e.g. 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Nitrogen-containing bases such as tetraalkylammonium hydroxides and alkali metal hydroxides are also used as additional catalysts such as sodium hydroxide, alkali metal phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Even Hexahydrotriazines can be used as catalysts.

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Of course, it is also possible / mixtures of different inventive catalyst combinations a— add or add other organometallic components, if this also means reactions that are known per se be catalyzed, such as dimerization, trimerization or carbodiimide formation of the isocyanates or if it can be used to catalyze further reactions, such as allophanatization or biuret formation.

The additional catalysts are added in amounts of 0-90% of the total amount of catalyst, preferably in amounts from 0-50%.

The production of polyurethane plastics under the invention The new catalyst combinations can also be used with the use of surface-active additives (Emulsifiers and / or foam stabilizers).

The sodium salts of castor oil sulfonates, for example, are used as emulsifiers or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question. Also alkali or ammonium salts of Sulphonic acids such as of dodecylbenzenesulphonic acid or dinaphthylmethanedisulphonic acid or of fatty acids such as Ricinoleic acid or polymeric fatty acids can also be used as surface-active additives.

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Polyether siloxanes are mainly used as foam stabilizers, especially water-soluble representatives, in question. These connections are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide with a polydimethylsiloxane radical connected is. Such foam stabilizers are described, for example, in American patents 2,834,748 and 2,917 and 3,629,308.

According to the invention, reaction retarders, for example acid-reacting substances such as hydrochloric acid or organic acid halides, furthermore cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the type known per se, e.g. tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and - polyphosphate, also · stabilizers against aging and weathering influences, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, kieselguhr, soot or whiting chalk can also be used.

Further examples of optionally also to be used according to the invention surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, Stabilizers, flame-retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic Active substances as well as details about the use and mode of action of these additives are in Kunststoff-Handbuch, Volume VI, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on the Pages 103 to 113 described.

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REQUIRED

According to the invention, the reaction components are reacted by the one-step process known per se, the prepolymer process or the semiprepolymer process, often using mechanical devices, for example those described in US Pat. No. 2,764,565. Details about processing devices that can also be considered according to the invention are described in the Kunststoff-Handbuch, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 121 to 205.

In the case of foam production, according to the invention, foaming is often carried out in molds. The reaction mixture is introduced into a mold. Metal, for example aluminum, or plastic, for example aluminum, or plastic, for example epoxy resin, can be used as the molding material. The foamable reaction mixture foams up in the mold and forms the molded body. Foaming in the mold can be carried out in such a way that the molded part has a cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core. According to the invention, one can proceed in this connection in such a way that enough foamable reaction mixture is introduced into the mold that the foam formed just fills the mold. However, one can also work in such a way that more foamable reaction mixture is introduced into the mold than is necessary to fill the interior of the mold with foam. In the latter case, "overcharging" is used; Such a procedure is known, for example, from American patents 1,178,490 and 3,182,104 .

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in the case of foaming in the form, many are known per se "External release agents", such as silicone oils, are also used. But you can also use so-called "internal release agents", if appropriate in a mixture with external release agents, such as those from German Offenlegungsschriften 2 121 670 and P 307 589 have become known.

Cold-curing foams can also be produced in accordance with the invention (cf. British patent specification 1,162,517, German Disclosure document. 2 153 086).

Of course, foams can also be made by block foaming or by the double conveyor belt process known per se.

The following examples illustrate the present invention. Unless otherwise noted, figures are given as parts by weight or wt .-% to understand.

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Example 1:

11 g (0.1 mol) of 2-hydrazinopyrimidine are dissolved in 100 ml of tetraethylene glycol submitted and mixed with 63 g (0.1 mol) of dibutyltin dilaurate. The mixture is 10 minutes at 50-100 ° C stirred and then cooled. An oil separates from the solvent.

The oil is examined by thin layer chromatography (silica gel, ether eluent, staining with H ₂ SO ₄ ). The chromatogram contains only one spot. As a comparison, separate solutions of hydrazinopyrimidine and dibutyltin dilaurate are applied and treated analogously. After staining with H ₃ SO ₄ , 2 spots are obtained.

Example 2:

Semi-hard, free-foamed polyether foam of volume weight about 400 mg / cm.

It means:

T ₁ = start of the driving reaction,

T ₂ = end of the blowing reaction,
T ₃ = no tackiness,

T "= curing time (after this time it is done by hand 4

no longer possible to remove parts from the

To tear out foam).

Recipe: 70 g bifunctional, based on propylene glycol

'' started polyether made from 90% propylene oxide and 10% ethylene oxide (OH number = 27.5),

20 g of trifunctional polyether started on trimethylolpropane (OH number = 35.4) 90% propylene oxide and 10% ethylene oxide,

8 g of 1,4-butanediol
12 g trifluorochloromethane Le A 16 977 - 25 -

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0.06 g catalyst complex (2-hydrazinopyrimidine /

Dibutyltin dilaurate in a molar ratio of 1: 1)

The components are mixed carefully for 30 seconds a high-speed stirrer at room temperature, then 76.7 g of 4,4'-diisocyanatodiphenylmethane are added and stirring is continued Seconds.

T ₁ = 30 + 3 seconds T ₂ = 48 + 3 seconds T ₃ = 48 + 3 seconds T ₄ = 58 + 5 seconds

Example 3 (comparative experiment)

The analog foam formulation with triethylenediamine is used as a comparison and dibutyltin dilaurate catalyzed, 0.06 g of catalyst mixture (molar ratio 1: 1) also being used will.

T ₁ = 55 + 5 seconds

T ₃ = 100 ± 10 seconds

140 + 10 seconds

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Example 4:

If the procedure of Example 2 is used to process a mixture of
90 g of a polyester polyol (OH number 55) from adipic acid, Bu-

1,4-tanediol and ethylene glycol 14 g 1,4-butanediol 0.2 g 2-hydrazinopyrimidine / dibutyltin dilaurate (molar ratio 1: 1) and
0.4 g water,

this results in the following course of the reaction:

T. = 20 seconds

T ₂ = 32 seconds

Tο = 65 seconds

T. = 70 seconds

Example 5: (comparative experiment)

Example 4 is repeated using 1,4-diazabicyclo- (2,2,2) -octane (DABCO). To obtain comparable times, 0.55 g of DABCO must be used.

T = 20 seconds T ₂ = 47 seconds T- = 70 seconds T. = 90 seconds

Example 6;

Example 2 is repeated using 0.06 g of a catalyst complex composed of 2-hydrazinopurine / dibutyltin dilaurate (Molar ratio 1: 1). The following times are obtained:

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T ₁ = 29 seconds
T "= 45 seconds
T_ = 46 seconds
T ₄ = 60 seconds

Example 7;

74 g of 2-hydrazinopyrimidine / dibutyltin dilaurate catalyst complex (Molar ratio 1: 1) are reacted with 11.9 g of phenyl isocyanate in 37 ml of toluene. After 1 1/2 h the resulting Suspension of petroleum ether was added and the colorless precipitate was filtered off with suction. There are 22 g of N-2-pyrimidyl) -N'-phenylsemicarbazide isolated from mp 148 ° C.

The example shows that the cocomponents according to the invention react completely to form semicarbazides in the presence of polyisocyanates.

Example 8:

50 g of a polyether started on trimethylolpropane and composed of 90% propylene oxide and 10% ethylene oxide (OH number = 35.4), 0.25 g of a commercially available silicone stabilizer and 0.25 g of 2-hydrazinopyrimidine / dibutyltin dilaurate (molar ratio ' 4: 1) carefully with a high-speed stirrer, then add 18 g of toluene diisocyanate (80% 2,4-isomer, 20% 2,6-isomer) , stir the mixture for another 15 seconds and pour into a cardboard bowl. After 15 seconds the foaming starts, after about The process is completed in 120 seconds. Brief curing at 80 C completes the setting reaction. An open-pored one is obtained Foam that is very elastic. Volume weight approx. 35 kg / m.

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Example 9:

50 g of a polyether started on trimethylolpropane 75% propylene oxide and 25% ethylene oxide (OH number = 49) with 1.75 g of water, 0.25 g of a commercially available silicone stabilizer, 0.07 g of dimethylbenzylamine and 0.3 g of 2-hydrazinopyrimidine / dibutyltin dilaurate (Molar ratio 4: 1) as in Example 10 and mixed with 42 g of tolylene diisocyanate (8O% 2,4-isomer, 20% 2,6-isomer) added. The mix will Stirred for 25 seconds and poured into a tool. The foaming process starts after 30 seconds and is after 105 seconds closed. After 10 minutes of heating at 110 ° C., an elastic, open-pore foam is obtained.

Example 10:

A formulation analogous to that in Example 9 is foamed however, a polyether with an OH number of 56 made from 50% propylene oxide and 50% ethylene oxide.

With 41 g of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer) an open-cell foam with high elasticity is obtained obtained a rise time of 115 seconds.

Example 11:

Example 10 is repeated, but using the hydrazine component in the catalyst 4-hydrazino-6-methylpyrimidine. With 41 g Tolylene diisocyanate (80% 2,4-isomer content) becomes an open-cell foam with high elasticity after a rise time of 110 seconds.

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Example 12:

Example 2 is repeated using 0.06 q of a catalyst complex composed of 4-hydrazino-6-methylpyrimidine / dibutyltin dilaurate (Molar ratio 1: 1)

Ί '= - 29 seconds

T "= 45 seconds

Ί '= 48 seconds

T, = 57 seconds

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Claims (3)

Claims / ij) Catalyst inbinate ions for the isocyanate polyaddition reaction consisting of Λ) 1 mole of a metal prebinduna of the general formula Mo XY,
η m wöbe i Me a (n + ni) valued.s MeUaIl means, preferably from the I., II., VII. or VIII. subgroup or the IV. main group of the Periodic Table of the I am learning X for an aliphatic hydrocarbon residue irit 1 to 18 carbon atoms, an aromatic hydrocarbon radical with 6 to 10 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms, Y for an optionally olefinic double bond and / or aliphatic carboxylate radical containing alcoholic hydroxyl groups and having 2 to 18 carbon atoms or an enolate radical with 5 to 18 carbon atoms, η for an integer between 0 and 2 and m stand for an integer between 0 and 4 with the restriction that the sum (n + m) results in 2 to 4, and Le A 16 977 - 31 - 709831/0864 ORIGINAL INSPECTE9 B) 0.5 to 6 moles of an aromatic compound containing at least one tertiary nitrogen atom as a hetero atom, which has at least one hydrazino group as a substituent. 2) catalyst combination according to claim 1, characterized in that that as component B hydrazines of the general formulas (ID R - NH-NH ι 2 -ι
RN ^ W Rl NH-NH ₂ R ³ - ^ jf ^ R ² (III) (IV) NH-NH2 R ² ^ ^{r2 r3}  ^ -nh- (V) (VI) Le A 16 977 - 32 - 709831/0864 NH-NH ₂ NH-NH ₂ * ^D. H ₂ N-HN  IN R ²  R ³ ^ N NH-NH ₂ HjH-NH ^ /  NH-NH ₃ (VII) (VIII) (IX) in which R ₁ , R ", R., and R. are identical or different radicals and represent hydrogen, an aliphatic hydrocarbon radical with 1 to 6 carbon atoms or an aromatic hydrocarbon radical with 6 to 12 carbon atoms or two of the radicals R to R. stand for a fused aromatic ring, can be used, 3) Process for the production of polyurethane plastics by converting polyisocyanates, higher molecular ones Compounds with at least 2 isocyanate-reactive hydrogen atoms and optionally chain extenders in the presence of catalyst combinations of an amine and an organometallic Compound, characterized in that those according to Claims 1 and 2 are used as catalyst combinations will. Le A 16 977 - 33 - 709831 / m: iU