GB1588702A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1588702A – Process for the production of polyisocyanates polyaddition products
– Google Patents

GB1588702A – Process for the production of polyisocyanates polyaddition products
– Google Patents
Process for the production of polyisocyanates polyaddition products

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Publication number
GB1588702A

GB1588702A
GB14964/78A
GB1496478A
GB1588702A
GB 1588702 A
GB1588702 A
GB 1588702A
GB 14964/78 A
GB14964/78 A
GB 14964/78A
GB 1496478 A
GB1496478 A
GB 1496478A
GB 1588702 A
GB1588702 A
GB 1588702A
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United Kingdom
Prior art keywords
groups
organic
diamine
water
nco
Prior art date
1977-04-22
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Expired

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GB14964/78A
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Bayer AG

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Bayer AG
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1977-04-22
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1978-04-17
Publication date
1981-04-29

1978-04-17
Application filed by Bayer AG
filed
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Bayer AG

1981-04-29
Publication of GB1588702A
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patent/GB1588702A/en

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Classifications

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G18/00—Polymeric products of isocyanates or isothiocyanates

C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen

C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen

C08G18/30—Low-molecular-weight compounds

C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines

C08G18/3225—Polyamines

C08G18/3253—Polyamines being in latent form

C08G18/3256—Reaction products of polyamines with aldehydes or ketones

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G18/00—Polymeric products of isocyanates or isothiocyanates

C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen

C08G18/08—Processes

C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

C—CHEMISTRY; METALLURGY

C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON

C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

C08G2190/00—Compositions for sealing or packing joints

Description

PATENT SPECIFICATION ( 11) 1 588 702
et ( 21) Application No 14964/78 ( 22) Filed 17 April 1978 z: ( 31) Convention Application No 2718100 ( 19) ( 32) Filed 22 April 1977 in 0 ( 33) Federal Republic of Germany (DE) ( 44) Complete Specification published 29 April 1981 ( 51) INT CL 3 CO 8 G 18/32 ^ ( 52) Index at acceptance C 3 R 32 D 10 32 D 16 A 32 D 16 B 32 D 16 C 32 D 16 D 32 D 2 32 D 6 A 32 D 6 C 32 D 6 K 32 D 9 C 32 D 9 E 32 D 9 F 32 E 12 32 E 1 32 E 2 A 32 E 2 Y 32 E 3 A 32 E 3 D 32 E 3 E 32 E 3 F 32 E 3 Y 32 E 9 32 G 2 Y 32 G 5 32 H 5 AX 32 HSAY 32 H 5 B 2 32 H 5 BY 32 H 5 E 32 H 8 32 J 12 32 JIA 32 JIY 32 J 3 A 32 J 3 B 32 J 3 Y 32 J 5 32 J 9 A 32 J 9 E 32 KC 32 KH 32 S 32 T 2 C 33 C 33 K 33 P C 12 C 14 A C 22 C 25 C 29 C 6 AI C 6 B C 6 X C 8 P C 8 T C 9 A C 9 B L 2 X L 4 B L 5 X L 6 G SM C 2 C 1324 214 246 247 250 252 25 Y 28 X 305 30 Y 69 Y AA ZF C 3 Y B 230 B 240 B 245 B 248 F 530 ( 54) A PROCESS FOR THE PRODUCTION OF POLYISOCYANATES POLYADDITION PRODUCTS ( 71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Germany of 5090 Leverkusen Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following
statement: 5
This invention relates to a new process for the production of polyisocyanate polyaddition products by reacting organic polyisocyanates with certain moistureactivatable cross-linking agents described in more detail below and also with water, the organic compounds containing isocyanate-reactive hydrogen atoms known in polyurethane chemistry optionally being used in sub-equivalent quantities The 10 present invention also relates to a reaction mixture which is particularly suitable for carrying out the process according to the present invention.
It has surprisingly been found that certain condensation products of formaldehyde with diprimary aliphatic or cyclo-aliphatic diamines, which are described in more detail below, are particularly suitable for use as latent, moisture 15 activatable hardeners for polyisocyanates One particularly remarkable feature of these condensation products being that, on the one hand, they are largely stable with respect to water at room temperature in the absence of organic polyisocyanates and hydrolysis-accelerating catalysts and, on the other hand, show little or no reactivity with polyisocyanates in the absence of water at room 20 temperature Accordingly, the condensation products are sutiable for use both as latent hardeners for two-component polyurethane systems and as latent hardeners for single-component systems which are cross-linkable under the influence of atmospheric moisture and which contain NCO-prepolymers as the main binder component thereof The latent hardeners used in accordance with the present 25 invention are superior to conventional masked diamines, for example according to US-PS No 3,420,800, both in regard to the storability of the compositions in the absence of water and also in regard to the reactivity thereof in the presence of water and further in regard to the range of potential applications thereof.
The present invention relates to a process for the production of a 30 polyisocyanate polyaddition product by reacting an organic polyisocyanate with a compound which give off an organic diamine under the hydrolytic influence of water which compound is a polycyclic condensation product of formaldehyde with an aliphatic or cycloaliphatic diprimary 1,2-diamines and also with water, optionally in the presence of a sub-equivalent quantity based on the NCOgroups 35 present in the reaction mixture, of an organic polyhydroxyl compound, the amount of said condensation product being selected in such a way that, in the absence of an organic polyhydroxyl compound, from 0 4 to 2 0 potential amino groups are available per NCO-group, and, in the presence of an organic polyhydroxyl compound, the equivalent ratio of hydroxyl groups to amino groups of the diamine formed from the condensation product is from 4:1 to 3:2.
The present invention also relates to the mixtures preferably used for carrying out this process Thus, the present invention also relates to a mixture hardenable by the action of atmospheric moisture which comprises: 5 (a) an organic polyisocyanate; (b) a polycyclic condensation product of formaldehyde with an aliphatic or cycloaliphatic diprimary 1,2-diamine, said product containing no C=N double bonds and acting as a moisture-activatable hardener for component (a) and, optionally, 10 (c) a sub-equivalent amount, based on the NCO-groups present, of an organic polyhydroxyl compound; the amount of the condensation product being selected in such a way that, in the absence of an organic polyhydroxyl compound, from 0 4 to 2.0 potential amino groups are available per NCO-group and, in the presence of an organic polyhydroxyl compound, the equivalent ratio of hydroxyl groups to amino 15 groups of the diamine formed from the condensation product is from 4:1 to 3:2.
The production of the moisture-activatable cross-linking agents used in accordance with the present invention is known and is described, for example, by G Volpp in Ber Chem Ges 95 ( 1962), page 1493 (cf also Beilstein, Vol IV, page 250 and Ber Chem Ges 31, ( 1898), page 3254) and by Krassig in Makromol 20 Chem 17, page 77-130 ( 1955) The production of latent cross-linkers suitable for use in accordance with the present invention is also described in US-PS No.
3,156,658 According to this reference, however, the compounds described therein are merely used in catalytic quantities as accelerators for the isocyanate polyaddition reaction 25 To produce the moisture-activatable cross-linkers used in accordance with the present invention, from I to 5 moles, preferably from 1 to 3 moles, of formaldehyde are preferably reacted with I mole of an aliphatic or cycloaliphatic diprimary 1,2diamine Thus, for example, a polycyclic tetramine is formed from 2 moles of ethylene diamine and 4 moles of formaldehyde with elimination of 4 moles of water 30 in accordance with the following equation:
NH 2 2 + 4 CHO 20 4 H 20 LN w N H 2 Depending upon the nature of the diamine used, polycyclic condensates of different constitution, preferably without any C=N double bonds and preferably containing solely tertiary nitrogen atoms, are formed during the condensation 35 reaction with the formaldehyde.
Corresponding to the particularly preferred molar ratio of formaldehyde to diamine of 2:1 which is applied in the production thereof, the polycyclic condensation products predominantly contain tertiary nitrogen atoms and methylene bridges in a ratio of 1:1 40 The condensation reaction may be carried out in the absence or, preferably, in the presence of an inorganic or organic solvent It is particularly preferred to use water as solvent The presence of a basic catalyst, such as KOH or Na OH, accelerates the formation of the polycyclic condensation product.
The reaction may be carried out at a temperature of from -20 to + 150 C, 45 preferably from 0 to 100 C However, it is particularly preferred to carry out the reaction at room temperature.
Diamines preferably used for producing the moisture-activatable crosslinkers suitable for use in accordance with the present invention are diamines corresponding to the following general formula: 50 1.59 g 702 3 1,588,7023 R 2 2 X-NH 2 R H 2 4wherein R., R 2, R 3 and R 4, which may be the same or different, each represents hydrogen or an aliphatic hydrocarbon radical containing from 1 to 6 carbon atoms in addition to which the radicals R 2 and R 3 may together with the carbon atoms 5 attached to the amino groups complete a 5 or 7-membered cycloaliphatic ring and one of the radicals R, to R 4 may also represent a cyano group.
It is preferred to use diamines corresponding to the above general formula wherein at least two of the radicals R 1 to R 4 represent hydrogen and the remaining radicals represent a methyl group Examples of suitable diamines include: 1,2 10 ethylene diamine, 1,2-propylene diamine, 1,2-dimethyl 1,2 ethylene diamine, 1,2-butylene diamine, 1,2-diaminocyclohexane, 1 cyano 1,2 diamino ethane or 1,2-diaminohexane Ethylene diamine and 1,2-propylene diamine are the preferred diamines.
In many cases, it is advantageous to use mixtures of different 1,2diamines for 15 the reaction in order to obtain more readily processible liquid mixtures of polycyclic condensation products Particularly preferred mixtures are mixtures of 1,2-ethylene diamine and 1,2-propylene diamine in which the ethylene diamine may contain from 1 to 99 %, by weight, preferably from 30 to 70 %, by weight, based on ethylene diamine, of 1,2-propylene diamine 20 To produce the condensation products, the formaldehyde is preferably used in the form of an aqueous formaldehyde solution (formalin).
The process according to the present invention is particularly suitable for the production of coatings on substrates of many types and for the production of seals, for example in the form of gap-filling compounds The process according to the 25 present invention may be carried out in different ways, depending upon the required application.
In a first embodiment of the process according to the present invention, the latent hardener essential to the present invention is mixed with polyhydroxyl compounds of the type known in polyurethane chemistry and the resulting mixture 30 combined with a second component, the organic polyisocyanate, just before application A reactive system is thus obtained which hardens both by reaction of the hydroxyl groups with some of the isocyanate groups in the polyisocyanate component and also under the influence of atmospheric moisture after application and by the resulting formation of diamines from the latent hardener and the 35 subsequent reaction thereof with some more of the isocyanate groups of the polyisocyanate component.
In a second embodiment of the process according to the present invention, the water required for releasing the diamines from the latent hardeners is directly added to the mixture of polyhydroxyl compounds and latent hardener This is 40 possible because, in the presence of the polyisocyanate component, hydrolytic splitting of the latent hardener occurs only slowly and incompletely Following addition of the polyisocyanate component just before application of the twocomponent system, the diamine is completely released very rapidly and reacted with the isocyanate component so that it is possible with such systems to produce, 45 for example, two-component polyurethane lacquers which undergo very rapid initial hardening The lacquer films are then completely hardened by the relatively slow reaction of a second part of the isocyanate groups with the relatively slowly reacting hydroxyl groups The water required for releasing the diamine may also emanate, for example, from the fillers or pigments optionally used which, 50 therefore, do not have to be predried, or the water may be in the form of moisture contained in the reactants.
In the first and second embodiments of the process according to the present invention, it is, of course, also possible to use the auxiliaries and additives normally encountered in lacquers, such as the conventional lacquer solvents, catalysts for 55 1.588 702 the isocyanate polyaddition reaction fillers, pigments, anti-sedimenting agents or levelling agents These auxiliaries and additives are generally added to the component containing the latent hardener.
If polyhydroxyl compounds are used, the polyhydroxyl compounds and the latent hardeners essential to the present invention are used in such quantities that 5 the equivalent ratio (hydroxyl groups of the polyhydroxyl compounds) :(amino groups of the diamines formed from the latent hardeners) amounts to from 4:1 to 3:2 In the first and second embodiments, the quantity in which polyisocyanate component is used is preferably such that from 80 to 150, more preferably from 80 to 120, equivalent % of isocyanate groups are present, based on the sum of hydroxyl 10 groups and amino groups released by hydrolysis.
In a third embodiment of the process according to the present invention, which is particularly suitable for the production of thick-layer coatings or seals, the latent hardener is combined with a polyisocyanate component to form a onecomponent system which may be stored in the absence of atmospheric moisture 15 and which is hardenable under the influence of atmospheric moisture In this case, (that is, in the absence of a polyhydroxyl compound), the quantitative ratios between the reactants are selected in such a way that from 0 4 to 2 0, preferably from 0 8 to 1 2, potential amino groups are available per NCO-group.
The one-component systems according to the third embodiment of the process 20 according to the present invention may have the conventional auxiliaries and additives exemplified above added to them, although in this case it must be emphasised that, in cases where the systems are used for thick-layer coatings or seals, only small quantities of solvent should be used, preferably none at all.
In some cases, for example in the case of reactive aromatic polyisocyanates, it 25 may be advantageous, in order to improve stability in storage, to use polyisocyanates containing blocked NCO-groups rather than free NCO-groups.
Suitable blocking agents for this purpose are, for example, phenol, cresol, Ecaprolactam or malonic acid diethyl ester.
In all the embodiments of the process according to the present invention, the 30 formaldehyde which is released in addition to the diamines during the hydrolytic splitting of the latent hardeners essential to the present invention may have an additional cross-linking effect.
Polyisocyanates suitable for use in the process according to the present invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic 35 polyisocyanates of the type described, for example, by W Siefken in Justus Liebigs Annalen der Chemie 562, pages 75 to 136, for example 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3 diisocyanate, cyclohexane 1,3 and 1,4-diisocyanate, also mixtures of these isomers, I isocyanato 3,3,5 trimethyl 5 isocyanatomethyl cyclohexane (DAS No 40 1,202,785, 2,4 and 2,6 hexahydrotolylene diisocyanate, also mixtures of these isomers, hexahydro-l,3 and/or 1,4-phenylene diisocyanate, perhydro-2,4 ‘ and/or 4,4 ‘-diphenyl methane diisocyanate, 1,3 and 1,4-phenylene diisocyanate, 2,4 and 2,6-tolylene diisocyanate, also mixtures of these isomers, diphenyl methane-2,4 ‘and/or -4,4 ‘-diisocyanate, naphthylene-l,5-diisocyanate, triphenyl methane-4,4 ‘,4 » 45 triisocyanate, polyphenyl polymethylene polyisocyanates of the type which may be obtained by condensing aniline with formaldehyde, followed by phosgenation, and which are described, for example, in British Patent Nos 874,430 and 848, 671, perchlorinated aryl polyisocyanates of the type described, for example, in German Auslegeschrift No 1,157,601, polyisocyanates containing carbodiimide groups of 50 the type described in German Patent No 1,092,007, diisocyanates of the type described in US Patent No 3,492,330, polyisocyanates containing allophanate groups of the type described, for example, in British Patent No 994,890, Belgian Patent No 761,626 and published Dutch Patent Application No 7,102,524, polyisocyanates containing isocyanurate groups of the type described, for example, 55 in German Patent Nos 1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschrift Nos 1,929,034 and 2,004,048, polyisocyanates containing urethane groups of the type described, for example, in Belgian Patent No 752,261 or in US Patent No 3,394,164, polyisocyanates containing acylated urea groups according to German Patent No 1,230,778, polyisocyanates containing biuret 60 groups of the type described, for example, in German Patent No 1,101,394, in British Patent No 889,050 and in French Patent No 7,017,514, polyisocyanates obtained by telomerisation reactions of the type described, for example, in Belgian Patent No 723,640, polyisocyanates containing ester groups of the type described, for example, in British Patent Nos 965,474 and 1,072,956, in US Patent No 65 1,588,702 3,567,763 and in German Patent No 1,231,688, also reaction products of the abovementioned isocyanates with acetals according to German Patent No 1,072, 385.
It is also possible to use mixtures of the above-mentioned polyisocyanates.
In the first and second embodiments of the process according to the present invention, it is preferred to use organic polyisocyanates containing aliphatically or 5 cycloaliphatically bound isocyanate groups Preferred polyisocyanates for the first and second embodiments are, for example, 3,3,5 trimethyl 5 isocyanatomethyl cyclohexyl isocyanate, 1 methyl 2,4 diisocyanatocyclohexane, 1 methyl 2,6 diisocyanatocyclohexane, 4,4 ‘ diisocyanatodicyclohexyl methane, 2,4 ‘ diisocyanatodicylcohexyl methane and, 10 in particular, urethane group or biuret group-containing derivatives of these simple diisocyanates or of hexamethylene diisocyanate having a molecular weight below 1000, such as may be obtained in known manner by partially converting the isocyanate groups of the above-mentioned diisocyanates into biuret groups or by reacting the above-mentioned diisocyanates with sub-equivalent quantities of low 15 molecular weight polyols, such as trimethylol propane Trimerisation products, i e.
isocyanurate group-containing polyisocyanates having a molecular weight below 1000 produced from the above-mentioned diisocyanates, are also among the preferred polyisocyanates for the first and second embodiments of the process according to the present invention 20 In the third embodiment of the process according to the present invention, the polyisocyanate component preferably consists of NCO-prepolymers having an average NCO-functionality of from 2 to 4, preferably from 2 2 to 3, an NCOcontent of from 1 to 12, preferably from 1 to 5 / by weight, and an average molecular weight of from 500 to 10,000, preferably from 2000 to 5000, such as may 25 be obtained in known manner, for example, by reacting polyhydroxy polyethers of the type exemplified below having an average molecular weight of from 200 to less than 10,000, preferably from 500 to 5000, and an average OH-functionality of from 2 to 4, preferably from 2 2 to 3, with excess quantities of aliphatic and/or cycloaliphatic diisocyanates of the type exemplified above, the unreacted excess of 30 diisocyanate left over where a large excess of diisocyanate has been used preferably having been removed by distillation It is preferred to use NCOprepolymers based on aliphatic or cycloaliphatic diisocyanates containing isocyanate groups of different reactivity, such as those based on 3,3,5 trimethyl 5 isocyanatomethyl cyclohexyl isocyanate NCO-prepolymers having molecular weights in the above 35 mentioned range with excess quantities of triisocyanates, such as tris(isocyanatohexyl)biuret, are also suitable, although less preferred It is also possible to use NCO-prepolymers having molecular weights in the range defined above and also the abovementioned NCO-functionality of diisocyanates, polyhydroxy polyethers and up to 50 OH-equivalent / of low molecular weight 40 alkane polyols.
Other starting components suitable for use in accordance with the present invention are compounds containing at least two isocyanate-reactive hydrogen atoms and generally having a molecular weight of from 62 to 20,000 In addition to compounds containing amino groups, thiol groups or carboxyl groups, compounds 45 of this type are preferably polyhydroxyl compounds, more especially compounds containing from two to eight hydroxyl groups, for example polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyamides and polyester amides of the type commonly used for the production of non-cellular and cellular polyurethanes 50 Examples of suitable polyesters containing hydroxyl groups are reaction products of polyhydric, preferably dihydric, and, optionally, trihydric, alcohols with polybasic, preferably dibasic, carboxylic acids Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may 55 also be used for the production of the polyesters The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic, and may optionally be substituted, for example by one or more halogen atoms, and/or may be unsaturated Examples of these polycarboxylic acids and derivatives thereof include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic 60 acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, maleic acid, maleic acid anhydride, fumaric acid, dibasic and tribasic fatty acids, optionally in admixture with monobasic fatty acids, such as oleic acid, 65 1,588,702 terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester Examples of suitable polyhydric alcohols include: ethylene glycol, 1,2 and 1,3propylene glycol, 1,4 and 2,3-butylene glycol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, cyclohexane dimethanol(l,4 bis hydroxy methyl cyclohexane), 2 methyl 1,3 propane diol, glycerol, trimethylol propane, 1,2,6-hexane triol, 1,2, 4-butane 5 triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols, dipropylene glycol, higher polypropylene glycols, dibutylene glycol and higher polybutylene glycols The polyesters may contain terminal carboxyl groups Polyesters of lactones, for example E-caprolactone, or hydroxy 10 carboxylic acids, for example,-hydroxy caproic acid, may also be used.
The polyethers containing at least two, generally from 2 to 4, preferably (on average) from 2 5 to 3, hydroxyl groups which may be used in accordance with the present invention are also known and are obtained, for example, by the polymerisation of epoxides, such as ethylene oxide, propylene oxide, butylene 15 oxide, tetrahydrofuran, styrene oxide or epichlorhydrin, on their own, for example in the presence of BF 3, or by the chemical addition of these epoxides, optionally in admixture or in succession, with starter components containing reactive hydrogen atoms, such as water, ammonia, alcohols or amines, for example ethylene glycol, 1,3 or 1,2-propylene glycol, trimethylol propane, 4,4 ‘-dihydroxy diphenyl propane, 20 aniline, ethanolamine and ethylene diamine Sucrose polyethers of the type described, for example, in German Auslegeschrift Nos 1,176,358 and 1,064, 938 may also be used in accordance with the present invention In many cases, it is preferred to use polyethers of the type which predominantly contain primary OHgroups (up to 90 % by weight, based on all the OH-groups present in the polyether) 25 Polyethers modified by vinyl polymers of the type obtained, for example, by the polymerisation of styrene and acrylonitrile in the presence of polyethers (US Patent Nos 3,383,351; 3,304,273; 3,523,093 and 3,110,695, German Patent No.
1,152,536) are also suitable Polybutadienes containing OH-groups are also suitable 30
Among the polythioethers, particular reference is made to the condensation products of thiodiglycol with itself and/or with other glycols, dicarboxylic acids, formaldehyde, amino-carboxylic acids or amino alcohols Depending upon the cocomponents, these products include polythio mixed ethers, polythioether esters or polythioether ester amides 35 Suitable polyacetals are, for example, those compounds which may be obtained from the reaction of glycols, such as diethylene glycol, triethylene glycol, 4,4 ‘-dioxethoxy diphenyl dimethyl methane and hexane diol, with formaldehyde.
Polyacetals suitable for the purposes of the present invention may also be obtained by polymerising cyclic acetals 40 Suitable polycarbonates containing hydroxyl groups are those known compounds obtainable, for example, by reacting diols, such as 1,3-propane diol, 1,4-butane diol and/or 1,6-hexane diol, diethylene glycol, triethylene glycol and tetraethylene glycol, with diaryl carbonates, for example diphenyl carbonate, or with phosgene 45 Examples of the polyester amides and polyamides are the predominantly linear condensates obtained from polybasic, saturated and unsaturated carboxylic acids and the anhydrides thereof and polyfunctional saturated and unsaturated amino alcohols, diamines, higher polyamines and mixtures thereof.
Polyhydroxyl compounds already containing urethane or urea groups and 50 optionally modified natural polyols, such as castor oil, or carbohydrates, such as starch, may also be used Addition products of alkylene oxides with phenolformaldehyde resins or even with urea-formaldehyde resins may also be used in accordance with the present invention.
Representatives of these compounds used in accordance with the present 55 invention are described, for example, in High Polymers, Vol XVI, «Polyurethanes, Chemistry and Technology,» by Saunders-Frisch, Interscience Publishers, New York, London, Vol I, 1962, pages 32 to 42 and pages 44 to 54, and Vol II, 1964, pages 5-6 and 198-199, and in Kunststoff-Handbuch, Vol VII, ViewegHochtlen, Carl Hanser-Verlag, Munich, 1966, for example on pages 45 to 71 60 The first and second embodiments of the process according to the present invention may, in particular, be carried out using linear or branched polyhydroxy polyesters having molecular weights of from 500 to 3000, such as may be obtained from the exemplified starting materials, or using polyhydroxy polyacrylates having molecular weights of from 2000 to 20,000, preferably from 2000 to 10,000, of the 65 1.588702 type which may be obtained in known manner by copolymerising olefinically unsaturated compounds, such as acrylonitrile, acrylic acid, methacrylic acid, styrene, acrylic acid methyl ester, methacrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid ethyl ester, ethylene propylene and/or vinyl acetate, using hydroxyl group-containing unsaturated monomers, such as acrylic acid 5 hydroxyethyl ester, methacrylic acid hydroxyethyl ester, acrylic acid hydroxypropyl ester or methyacrylic acid hydroxypropyl ester Both the polyesters and also the polyacrylates generally contain from 1 to 10 %, by weight, preferably from 2 to 6 %, by weight, of hydroxyl groups.
It is also possible to add to these polyhydroxyl compounds which are 10 preferably used in accordance with the present invention up to at most 30 hydroxyl equivalent % of polyols having a molecular weight of from 62 to 500 Suitable such low molecular weight polyols are, for example, the polyhydroxyl compounds exemplified above as synthesis component for the polyhydroxy polyesters.
The polyhydroxy polyethers preferably used for producing the NCO 15 prepolymers used in accordance with the third embodiment of the process according to the present invention are polyhydroxy polyethers of the type mentioned above in the description of the NCO-prepolymers, such as may be obtained by known methods from the exemplified starting materials.
Solvents suitable for use in the process according to the present invention are, 20 in particular, alpihatic solvents, such as white spirit, aromatic solvents, such as toluene, xylene or relatively high boiling aromatic hydrocarbon solvents, ketones, such as methylethyl ketone or methylisobutyl ketone, or esters, such as acetic acid butyl ester.
Catalysts suitable for use in the process according to the present invention are, 25 in particular, the organometallic compounds known in polyurethane chemistry, more especially tin compounds, such as tin(II)salts of carboxylic acids, such as tin(II)acetate, tin(II)octoate, tin(II)ethylhexoate and tin(II)laurate, and the dialkyl tin salts of carboxylic acids, such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate 30Organic acids, such as benzene sulphonic acid or benzylic acid, may also be used as catalysts in accordance with the present invention In the first and second embodiments of the process according to the present invention, it has also proved to be best to use polyhydroxy polyacrylates still containing free carboxyl groups as the polyhydroxyl component because the free carboxyl group thereof take over the 35 role of a catalyst accelerating the diisocyanate addition reaction.
In many cases, there is no need to use catalysts However, if catalysts are employed, they are used in quantities of from 0 01 to 1 %, by weight, based on the polyhydroxyl component.
Suitable fillers which may also be used are, in particular, the fillers normally 40 used for coatings and lacquers, such as heavy spar, chalk powder, talcum, polymeric silicas, sand, organic polymer powders or organic granulates.
Other suitable auxiliaries and additives which may optionally be used are the pigments, antisedimenting agents or levelling agents normally encountered in lacquers 45 The process according to the present invention is particularly suitable for the production of films, lacquers or coatings on substrates of many types and also for the production of sealing materials, such as sealing compounds or gapfilling compounds.
The production of latent cross-linkers which may be used in accordance with 50 the present invention is described in Examples 1 to 3 below.
Unless otherwise indicated, all the percentages and parts quoted are used on a weight basis.
EXAMPLE 1
A mixture of 240 g of a 40 % aqueous formaldehyde solution in 150 g of water is 55 run slowly, at from 20 to 30 C, into 125 g of ethylene diamine and 25 g of Na OH in 1500 ml of water After a residence time of 20 hours at room temperature, most of the water is distilled off, the mixture filtered and the residue washed with cold dioxane.
Yield: 98 g of colourless crystals 60 M.p: 217-218 C.
EXAMPLE 2
226 8 g of a 37 % aqueous formaldehyde solution are added, at from 30 to 50 C, to 103 6 g of 1,2-diaminopropane and 24 4 g of Na OH in 400 ml of water 200 ml of 1,588,702 8 1,588,702 8 water are distilled off, the residue is extracted with chloroform and the chloroform phase is dried over anhydrous Na 2 SO Removal of the chloroform by distillation leaves 105 g of a pale yellow viscous oil.
EXAMPLE 3
226 8 g of a 37/ aqueous formaldehyde solution are added, at from 20 to 500 C, 5 to 42 g of ethylene diamine, 51 8 g of 1,2-diaminopropane and 24 4 g of Na OH in 400 ml of water After the mixture has reacted for 20 hours at room temperature, most of the water is distilled off The residue is extracted with chloroform and the chloroform phase is dried with anhydrous Na 2 SO Removal of the chloroform by distillation leaves 93 2 g of a pale yellowish oil 10 EXAMPLE 4
0 g of an NCO-prepolymer produced from a polyol mixture consisting of l mole of a linear polypropylene glycol having a molecular weight of 2000 and 0 4 mole of a propoxylated trimethylol propane having a molecular weight of 2000 and excess 3,3,5 trimethyl 5 isocyanatomethyl cyclohexyl isocyanate (NCO 15 content 4 0 o, viscosity at 20 C=approx 7500 m Pas) and 4 5 g of the cross-linker of Example 2 are mixed.
Coatings produced from the resulting mixture harden to a depth of from I to 2 mm in one day at room temperature/50 relative humidity The mixture is storable for more than 14 days at 500 C 20 EXAMPLE 5
Production of a moisture-hardening formulation for elastic coatings:
0 g of the NCO-prepolymer of-Example 4, 50.0 g of heavy spar, 10 0 g of titanium dioxide, 25 0.2 g of carbon black, 5.0 g of white spirit and 4.0 g of the cross-linker of Example 2 are mixed to form a ready-to-use coating composition The coating composition forms a skin after 8 hours in contact with atmospheric moisture ( 50 %/20 C) and 30 hardens to form elastic coatings Shore A hardness= 50.
EXAMPLE 6
0 g of the NCO-prepolymer of Example 4, 0 g of alkyl sulphonic acid ester (CH 3, SO 3-C 6 H,) 75 0 g of chalk powder, 25.0 g of highly disperse silica, 2.0 g of carbon black, 5.0 g of zeolite powder (molecular sieve) and 4.0 g of the cross-linker of Example 2, are mixed to form a ready-to-use sealing compound 40 Seals produced using this sealing compound form a skin after 12 hours in contact with atmospheric moisture ( 50 %) at a temperature of 200 C and harden at a rate of from I to 2 mm (depthwise) per day The material has a Shore A hardness of 30.
The following starting materials are used in following Examples 7 and 8: 45 Product 1: A polyester based on phthalic acid anhydride, a-ethyl hexanoic acid and trimethylol propane having an average molecular weight of 1500 and a hydroxyl content of 5 0 o, by weight.
Product 2: A polyacrylate resin based on styrene, butyl acrylate and 3hydroxypropylacrylate having a molecular weight of 3000 and a 50 hydroxyl content of 4 2 Yo, by weight.
Product 3: Cross-linker according to Example 1.
Product 4: The biuret polyisocyanate based on hexamethylene diisocyanate consisting essentially of tris-(isocyanatohexyl)-biuret, NCO-content 22 00, by weight 55 9 1,588,702 9 EXAMPLE 7
435 8 g of component (A) are mixed with 113 69 g of component (B) and the resulting mixture subsequently sprayed onto steel plates.
parts Composition of component (A): by weight 5 Product 1, 75 % in xylene 106 67 Product 3, 66 % in ethylene glycol monomethyl ether acetate 30 30 Standard commercial-grade titanium pigment having a water content of 0 3 %, by weight 170 95 10 Standard commercial-grade «anti-sedimenting agent» based on sodium aluminium silicate, 10 % in xylene/propylene carbonate ( 8:1) 17 10 Zinc octoate, 10 % in xylene 4 27 Standard commercial-grade levelling agent based on 15 polyacrylate, 10 % in ethylene glycol acetate 1 07 Standard commercial-grade silicone oil (levelling agent), % in xylene 2 14 Ethylene glycol acetate/butyl acetate ( 1:1) 103 30 435 80 20 parts Composition of component (B): by weight Product 4, 100 % 113 69 Drying at room temperature in accordance with DIN 53 150 (drying stage 1): approx 25 3.5 hours Pendulum hardness according to Konig (DIN 53 157), stoving conditions: 30 minutes at 80 C: approx.
seconds EXAMPLE 8 30
425 56 g of component (A) are mixed with 107 74 g of component (B) and the resulting mixture subsequently applied by spraying to steel plates.
parts Composition of component (A): by weight Product 2, 80 7 % in ethylene glycol acetate 99 13 35 Product 3, 66 % in ethylene glycol monomethyl ether acetate: 30 30 Standard commercial-grade titanium dioxide pigment ( 0.3 %, by weight of water) 166 19 Standard commercial-grade «anti-sedimenting agent» 40 based on sodium aluminium silicate, 10 % in xylene/propylene carbonate ( 8:1) 16 62 Zinc octoate, 10 % in xylene 4 14 Standard commercial-grade levelling agent based on polyacrylate, 10 % in ethylene glycol acetate 1 04 45 Standard commercial-grade silicone oil (levelling agent) % in xylene 2 08 Ethylene glycol acetate/butyl acetate ( 1:1) 106 06 425 56 parts 50 Composition of component (B): by weight Product 4, 100 % 107 74 Drying at room temperature in accordance with DIN 53 (drying stage 1): approx.
2 5 hours 55 Pendulum hardness according to Konig (DIN 53 157), stoving conditions 30 minutes at 80 C: approx.
seconds

Claims (9)

WHAT WE CLAIM IS:-

1 A process for the production of a polyisocyanate polyaddition product which comprises reacting an organic polyisocyanate with a compound which liberates an organic diamine under the hydrolytic influence of water, which compound is a polycyclic condensation product of formaldehyde with an aliphatic 5 or cycloaliphatic diprimary 1,2-diamine, and with water, optionally in the presence of a sub-equivalent quantity based on the NCO-group present in the reaction mixture of an organic polyhydroxyl compound, the amount of said condensation product being selected in such a way that, in the absence of an organic polyhydroxyl compound, from 0 4 to 2 0 potential amino groups are available per 10 NCO-group and in the presence of an organic polyhydroxyl compound, the equivalent ratio of hydroxyl groups to amino groups of the diamine formed from the condensation product is from 4:1 to 3:2.

2 A process as claimed in Claim 1 in which the said water is in the form of atmospheric moisture 15

3 A process as claimed in Claim 1 in which the said water is in liquid form.

4 A process as claimed in Claim 1 in which the said water is in the form of moisture contained in the reactants or in any fillers.

A process as claimed in Claim I substantially as herein described.

6 A process as claimed in Claim I substantially as herein described with 20 reference to any one of the Examples.

7 A polyisocyanate polyaddition product when produced by a process as claimed in any of Claims I to 6.

8 A mixture hardenable by the action of atmospheric moisture which comprises: 25 (a) an organic polyisocyanate; (b) a polycyclic condensation product of formaldehyde with an aliphatic or cycloaliphatic diprimary 1,2-diamine, said product containing no C=N double bonds and acting as a moisture-activatable hardener for component (a) and optionally, 30 (c) a sub-equivalent amount, based on the NCO-groups present, of an organic polyhydroxyl compound; the amount of the condensation product being selected in such a way that, in the absence of an organic polyhydroxyl compound, from 0 4 to 2.0 potential amino groups are available per NCO-group and, in the presence of an organic polyhydroxyl compound, the equivalent ratio of hydroxyl groups to amino 35 groups of the diamine formed from the condensation product is from 4:1 to 3:2.

9 A mixture as claimed in Claim 8 substantially as herein described.
A mixture as claimed in Claim 8 substantiallly as herein described with reference to any one of the Examples.
ELKINGTON AND FIFE, Chartered Patent Agents, High Holborn House, 52-54 High Holborn, London WCIV 65 H.
Agents for the Applicants.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
1,588,702 in

GB14964/78A
1977-04-22
1978-04-17
Process for the production of polyisocyanates polyaddition products

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METHOD FOR MANUFACTURING POLYISOCYANATE POLYADDITION PRODUCTS

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Process for the production of polyisocyanates polyaddition products

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GB2242907A
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1990-04-03
1991-10-16
Bostik Ltd
Two-component polyurethane composition and method of mixing thereof

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1975-10-17
1977-04-28
Bayer Ag

HIGH MOLECULAR POLYAMINE AND THE PROCESS FOR THEIR PRODUCTION

DE3063739D1
(en)

1979-04-10
1983-07-21
Akzo Nv
U.v.-curable coating composition

DE2922176C3
(en)

1979-05-31
1995-11-09
Akzo Gmbh

Water-curable polyisocyanate or polyepoxide mixtures

US5444117A
(en)

1994-02-09
1995-08-22
Bayer Corporation
Coating compositions containing polyisocyanates and aldimines which have improved storage stability

US5489704A
(en)

1994-08-29
1996-02-06
Bayer Corporation
Polyisocyanate/polyamine mixtures and their use for the production of polyurea coatings

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US3426097A
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1965-08-24
1969-02-04
Gen Motors Corp
Latent curing agents for epoxide polymers and polyurethanes

US3595839A
(en)

1969-02-05
1971-07-27
Gen Mills Inc
Curable compositions of improved versatility and process of preparing polyureas

1977

1977-04-22
DE
DE19772718100
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Withdrawn

1978

1978-04-07
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US05/894,230
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1990-04-03
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Two-component polyurethane composition and method of mixing thereof

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1978-04-20

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1978-10-26

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1979-04-17

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1978-10-23

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1978-11-20

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