GB1569248A - Creación de Inventos y Patentes con Inteligencia Artificial

GB1569248A – Polyhydroxyl compounds containing acyl urea groups
– Google Patents

GB1569248A – Polyhydroxyl compounds containing acyl urea groups
– Google Patents
Polyhydroxyl compounds containing acyl urea groups

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Publication number
GB1569248A

GB1569248A
GB12024/78A
GB1202478A
GB1569248A
GB 1569248 A
GB1569248 A
GB 1569248A
GB 12024/78 A
GB12024/78 A
GB 12024/78A
GB 1202478 A
GB1202478 A
GB 1202478A
GB 1569248 A
GB1569248 A
GB 1569248A
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United Kingdom
Prior art keywords
groups
acid
compound
mole
carbodiimide
Prior art date
1977-03-31
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GB12024/78A
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Bayer AG

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Bayer AG
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1977-03-31
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1978-03-28
Publication date
1980-06-11

1978-03-28
Application filed by Bayer AG
filed
Critical
Bayer AG

1980-06-11
Publication of GB1569248A
publication
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patent/GB1569248A/en

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legal-status
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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

C08G18/40—High-molecular-weight compounds

C08G18/48—Polyethers

C08G18/50—Polyethers having heteroatoms other than oxygen

C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen

C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups

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

C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen

C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen

C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups

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

C08G18/40—High-molecular-weight compounds

C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain

C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen

C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen

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

C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used

C08G18/72—Polyisocyanates or polyisothiocyanates

C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur

C08G18/78—Nitrogen

C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates

C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups

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

C08G18/83—Chemically modified polymers

C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides

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

C08G18/83—Chemically modified polymers

C08G18/833—Chemically modified polymers by nitrogen containing compounds

Description

PATENT SPECIFICATION
( 11) 1 569 248 Application No 12024/78 ( 22) Filed 28 March 1978 Convention Application No 2714293 Filed 31 March 1977 in Federal Republic of Germany (DE)
Complete Specification published 11 June 1980
INT CL 3 C 08 G 18/06 C 07 C 127/22 Index at acceptance C 3 R 27 K 2 E 27 K 8 E 32 DIIA 32 D 12 32 D 16 A 32 D 16 B 32 D 16 C 32 D 16 D 32 D 17 32 D 1 32 D 6 A 32 D 6 B 32 D 6 C 32 D 6 D 32 D 6 G 32 D 6 H 32 D 6 J 32 D 6 K 32 D 9 B 1 32 Ell 32 E 6 32 GIY 32 G 2 X 32 G 2 Y 32 G 3 B 32 G 3 X 32 G 4 32 JIY 32 J 2 C 32 J 2 F 32 J 2 X 32 J 2 Y 32 J 3 A 32 J 3 Y 32 J 7 X 32 J 7 Y 32 J 9 B 32 KA 32 KB 32 KJ 32 S 32 T 2 X 33 K 33 P ( 54) POLYHYDROXYL COMPOUNDS CONTAINING ACYL UREA GROUPS ( 71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of Germany, of 509 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:-
This invention relates to new polyols modified by acyl urea groups, to a process for the preparation thereof and to the use thereof as starting component for the preparation of preferably foamed polyurethane plastics.
More particularly, the present invention relates to compounds containing at least two, preferably from 2 to 8 and, with particular preference, from 2 to 4, terminal hydroxyl groups, having a molecular weight of from 400 to 20,000, preferably from 600 to 15,000 and, with particular preference, from 2000 to 10,000 and containing segments corresponding to the following general formulae:
-R 2-NHI-C-NI I X C-Y I RI and lR 2 NH C -O 1 OH)t wherein Xand Y, which may be the same or different, each represents oxygen or sulphur, preferably oxygen; R’ represents hydrogen or a monofunctional or-in the form of a bridge to other acyl urea groups-a polyfunctional (preferably difunctional) C,-C,8, preferably C,-C 8, aliphatic, C 4-C 15, preferably Ce-C 1,, cycloaliphatic, C 8-Cs, preferably C 8C 10, araliphatic or aromatic radical which may contain one or more aliphatic double bonds and/or one or more branches and which may be substituted one or more times by hydroxyl, mercapto, secondary amino, sulphonic acid ester, phosphonic acid ester, carboxylic, carboxylic ester, phenoxy, siloxane or trifluoromethyl groups or by fluorine, chlorine, bromine or iodine; R 2 represents a divalent aliphatic, cycloaliphatic aromatic or araliphatic radical having from 4 to 25, preferably from 6 to 15 carbon atoms obtained by removing the isocyanate groups from a diisocyanate; A represents an n-valent radical obtained by removing n-hydroxyl groups from a polyhydroxyl compound having a molecular weight of from 62 to 6000; n represents an integer of from 2 to 8, preferably from 2 to 4, and with particular preference, 2 or 3; and I represents zero or an integer having a value of from I to (n-1 l).
The present invention also relates to a process for the preparation of the polyhydroxyl compounds containing acyl urea groups, wherein, in a first step, a diisocyanatocarbodiimide corresponding to the following general formula:
OCN (-R 2-N=C=N)m-R 2-NCO is reacted at a temperature of from about 25 to 130 C, preferably from 90 to 120 C, optionally in the presence of an inert solvent, with a polyhydroxyl compound corresponding to the following general formula:
A-(OH), in an OH/NCO-ratio of from 1 2:1 to 30:1, preferably from 1 5:1 to 15:1 and, with ( 21) ( 31) ( 32) ( 33) ( 44) ( 51) ( 52) ( 1 1,569,248 particular preference, about 2:1, to form a polyhydroxyl compound containing carbodiimide groups and, in a second step, the carbodiimide groups are completely or only partly reacted at a temperature of from to 100 C, preferably from 60 to 90 C, optionally in the presence of an inert solvent, with a carboxylic acid corresponding to the following general formula:
RI-C YH) X to form at least some acyl urea groups, after which the solvent used, if any, is distilled off; wherein m represents an integer of from 1 to 10, preferably 1 or 2; and s represents an integer of from 1 to 3, preferably 1 or 2; and R’, R 2, A, X, Y and N are as defined above.
The preparation of diisocyanatocarbodiimides corresponding to the following general formula:
OCN-(-R 2 N=C=N-)m R 2 NCO is known and is described, for example, in US Patent Nos 2,840,589 and 2,941,966 and by P W Campbell and K C Smeltz in «Journal of Organic Chemistry», 28, 2069 ( 1963) Diisocyanatocarbodiimides may also be obtained in a particularly mild manner and free from secondary products by heterogeneous catalysis in accordance with German Offenlegungsschrift Nos 2,504,400 and 2,552,350 The conversion of diisocyanates into carbodiimides in the presence of very small quantities of phospholine oxide, followed by blocking of the catalyst with acid chlorides, is described in DOS No 2,653,120.
Starting components suitable for producing the diisocyanatocarbodiimides are aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates of the type described, for example, by W Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example 1,4 tetramethylene diisocyanate, 1,6 hexamethylene diisocyanate, 1,12 dodecane diisocyanate, cyclobutane 1,3 diisocyanate, cyclohexane 1,3 and 1,4 diisocyanate and mixtures of these isomers, 1 isocyanato 3,3,5 trimethyl isocyanatomethyl cyclohexane (DAS No 1,202,785; US Patent No 3,401,190), 2,4 and 2,6 hexahydrotolylene diisocyanate and mixtures of these isomers, hexahydro 1,3 and/or 1,4 phenylene diisocyanate, perhydro 2,4 ‘ and/or4,4 ‘ diphenyl methane diisocyanate, 1,3 and 1,4 phenylene diisocyanate, 2,4 and 2,6 tolylene diisocyanate and mixtures of these isomers, diphenyl methane 2,4 ‘ and/or 4,4 ‘ diisocyanate, naphthylene 1,5 diisocyanate, m and p isocyanatophenyl sulphonyl isocyanates according to US Patent No 3,454,606, perchlorinated aryl polyisocyanates of the type described, for example, in German Auslegeschrift No 1,157,601 (US Patent No.
3,277,138), polyisocyanates containing carbodiimide groups of the type described in German Patent No 1,092,007 (US Patent No 3,152,162), 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, in Belgian Patent No 761,626 and in Published Dutch Patent Application No 7,102,524, 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 groups of the type described, for example, in German Patent No 1,101,394 (US Patent Nos 3,124,605 and 3,201,372) and in British Patent No 889,050, polyisocyanates produced by telomerisation reactions of the type described, for example, in US Patent No 3,654,106, polyisocyanates containing ester groups of the type described, for example, in British Patent Nos 965,474 and 1,072,956, in US Patent No 3,567,763 and in German Patent No 1,231,688, reaction products of the abovementioned isocyanates with acetals according to German Patent No 1,072,385 and polyisocyanates containing polymeric fatty acid residues according to US Patent No 3,455,883.
It is particularly preferred to use diisocyanates of the type in which one isocyanate group has a greater tendency towards carbodiimide formation than the other Examples of such diisocyanates include: 2,4 tolylene diisocyanate, 1 methoxy 2,4 phenylene diisocyanate, 1 chlorophenyl 2,4 diisocyanate, p (I isocyanatoethyl) phenyl isocyanate, m( 3 isocyanatobutyl) phenyl isocyanate and 4 ( 2 isocyanatocyclohexyl methyl) phenyl isocyanate.
According to the present invention, polyhydroxyl compounds corresponding to the following general formula:
A-(OH).
may be, on the one hand, polyhydric alcohols having a molecular weight of from 62 to approximately 250 and, on the other hand, polythioether, polyacetal, polycarbonate, polyester-amide, polyamide, polyester and polyether polyols having a 1,569,248 molecular weight of from 150 to 6000, preferably from 500 to 5000 and, with particular preference, from 1000 to 4000, of the type known for the preparation of noncellular and cellular polyurethane plastics.
Examples of such compounds include:
ethylene glycol, 1,2 and 1,3 propylene glycol, 1,4 and 2,3 butylene glycol, 1,5 pentane diol, 1,6 hexane diol, 1,8 octane diol, neopentyl glycol, 1,4 bis hydroxymethyl cyclohexane, 2 methyl1,3 propane diol, glycerol, trimethylol propane, 1,2,6 hexane triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethvlene glycol, tetraethylene glycol, higher polyethylene glycols having a molecular weight of up to 400, dipropylene glycol, higher polypropylene glycols having a molecular weight of up to 400, dibutylene glycol, higher polybutylene glycols having a molecular weight of up to 400, methyl glycoside, diethanolamino N methyl ohosphonic acid ester, castor oil, diethanolamine, and triethanolamine.
Suitable polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and, optionally, even trihydric, alcohols with polybasic, preferably dibasic, carboxylic acids Instead of using 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 for producing the polyesters The .1 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 usaturated.
Examples of such compounds include:
succinic acid, adipic acid, suberic acid, azelaic acid, sebacic ucid, phthalic 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 mionobasic fatty acids, such as oleic acid terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester Suitable polyhydric alcohols are, for example, ethylene glycol, 1,2 and 1,3 propylene glycol, 1,4 and 2,3 butylene glycol 1,6 hexane diol, 1,8 octane diol, neopentyl glycol, cyclohexane dimethanol ( 1,4 bis hydroxymethylcyclohexane), 2 methyl1,3 propane diol, glycerol, trimethylol propane, 1,2,6-hexane triol, 1,2,4 butane triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, methyl glycoside, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols, dipropylene glycol, higher polypropylene glycols, dibutylene glycol and higher polybutylene glycols The polyesters may also contain terminal carboxyl groups Polyesters of lactones, for example E-caprolactone, or hydroxy carboxylic acids, for example ohydroxycaproic acid, may also be used.
The polyethers containing at least two, generally from two to eight, preferably 2 or 3, hydroxyl groups which may be used in accordance with the present invention are also known and are obtained, for example, by polymerising epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorhydrin, on their own, for example in the presence of BF 3, or by adding these epoxides, optionally in admixture or successively, with starter components containing reactive hydrogen atoms, such as water, ammonia, alcohols or amines, for example ethylene glycol, 1,3 or 1,2propylene glycol, trimethylol propane, 4,4 ‘ dihydroxydiphenyl propane, aniline, ethanolamine or 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 OH-groups (up to 90 %, by weight, based on all the OH-groups present in the polyether) Polyethers modified by vinyl polymers of the type obtained, for example, by polymerising 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 may also be used.
Among the polythioethers, particular reference is made to the condensation products of thiodiglycol on its own and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols Depending upon the cocomponents, the products include polythio mixed ethers, polythioether esters or polythioether ester amides.
Suitable polyacetals are, for example, the compounds obtainable 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 use in accordance with the present invention may also be obtained by the polymerisation of cyclic acetals.
Polycarbonates containing hydroxyl groups suitable for use in accordance with 1,569,248 the present invention are those known compounds which may be prepared, 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 or tetraethylene glycol, with diaryl carbonates, for example diphenyl carbonate, or with phosgene.
The polyester amides and polyamides include, for example, the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxylic acids or the anhydrides thereof and polyfunctional saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof.
Polyhydroxyl compounds already containing urethane or urea groups an optionally modified natural polyols, such as castor oil, or carbohydrates such as starch, may also be used Addition products of alkylene oxides with phenol formaldehyde resins or even with urea formaldehyde resins may also be used in accordance with the present invention.
Representatives of these compounds which may be used in accordance with the present 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 Kunstst 6 ff-Handbuch, Vol VII, Vieweg-Hochtlen, Carl-Hanser Verlag, Munich, 1966, for example on pages to 71.
According to the present invention, however, it is also possible to use polyhydroxyl compounds which contain high molecular weight polyadducts or polycondensates in finely disperse or dissolved form Such modified polyhydroxyl compounds are obtained by carrying out polyaddition reactions (for example reactions between polyisocyanates and amino-function compounds) or polycondensation reactions (for example between formaldehyde and phenols and/or amines) in situ in the above-mentioned compounds containing hydroxyl groups.
Such processes are described, for example, in German Auslegeschrift Nos 1,168,075 and 1,260,142 and in German Offelegungsschrift Nos 2,324,134; 2,423,984; 2,512,385: 2,513,815; 2,550,796; 2,550,797; 2,550,833 and 2,550,862.
However, it is also possible, in accordance with US Patent No 3,869,413 or German Offenlegungsschrift No 2,550,860, to mix a prepared aqueous polymer dispersion with a polyhydroxyl compound and then to remove the water from the mixture.
According to the present invention, preferred polyols are polypropylene glycols, trimethylol propane-or glycerol-started copolymers of propylene oxide and ethylene oxide and also polyesters based on adipic acid, 1,4 butane diol, diethylene glycol, 1,6 hexane diol and/or neopentyl glycol.
In the first step of the process according to the present invention, the diisocyanatocarbodiimide corresponding to the following general formula:
OCN-(-R 2-N=C=N-)m-R 2 NCO is reacted with the polyhydroxyl compound corresponding to the following general formula:
in an OH/NCO-ratio of from 1 2:1 to 30:1, preferably from 1 5:1 to 15:1 and, with particular preference, about 2:1, at temperatures of from 25 to 130 C, preferably from 90 to 120 C The progress of the reaction may readily be followed by IR-spectroscopy from the disappearance of the isocyanate band at 2220 cm-‘.
After all the isocyanate groups have reacted, a carboxylic acid corresponding to the following general formula:
R’-(-C-YH), X is added at a temperature of from 25 to C, preferably from 60 to 90 C A quantity of carboxylic acid groups substantially equivalent to the carbodiimide groups is preferably used However, it is also possible, in order to keep some of the carbodiimide groups, unreacted to add a less than equivalent amount of carboxylic acid (e g from 25 to 95 % of the equivalent quantity) The free carbodiimide groups which are still present in that case may optionally be reacted with other reactants, for example with amines or water In the case of polycarboxylic acids, it is also possible to use more than equivalent quantities In that case, modified polyols containing free carboxy groups are formed.
In the above general formula, R’ preferably represents a C 1-C,, aliphatic hydrocarbon radical which may optionally contain double bonds and/or branches and which may be substituted by chlorine, hydroxyl groups or secondary alkylamino groups.
Examples of such compounds include:
formic acid, acetic acid, thioacetic acid, propionic acid, lactic acid, lauric acid, stearic acid, acrylic acid, methacrylic acid, oleic acid, undecylenic acid, sorbic acid, linoleic acid, crotonic acid, cyclohexane carboxylic acid, 1 cyclohexene carboxylic 1,569,248 acid, caproic acid, chloroacetic acid, phenoxy acetic acid, 2-chlorophenoxy acetic acid, N,N dimethyl 6 aminocaproic acid, linolenic acid, adipic acid and sebacic acid.
The process according to the present invention may optionally be carried out in the presence of inert solvents, for example benzene, toluene, xylene, chlorobenzene, dichlorobenzene and mixtures thereof with sterically hindered alcohols, such as tert butanol; methylene chloride, chloroform, dimethyl formamide or dioxane In order to isolate the pure product, the solvent used, if any, may be subsequently removed.
It is known from the literature that carbodiimides react with alcohols to form isourea compounds Accordingly, it may be regarded as surprising that virtually no addition of hydroxyl groups with the carbodiimide groups to form cross-linked, insoluble products occurs in the first step of the process according to the present invention, instead an intermediate product which is relatively stable in storage is formed It may also be regarded as surprising that, in the second step of the process according to the present invention, there is no ester formation between the carboxylic acid and the free hydroxyl groups because it also known from the literature that carbodiimides greatly accelerate the esterification reaction The fact that virtually no esterification occurs in the process according to the present invention is proved by the absence of the urea band at 1675 cm-‘ in qhe IR-spectrum of the end product which, after an esterification reaction, should appear automatically through the addition of water with the carbodiimide group.
The modified polyhydroxyl compounds according to the present invention are valuable starting components for the preparation of polyurethane plastics, preferably foams Polyurethane foams prepared from them show greatly improved fire resistance and excellent mechanical properties.
Accordingly, the present invention also relates to a process for the preparation of optionally cellular polyurethane plastics by reacting:
(a) a polyisocyanate, with (b) a polyhydroxyl compound; and, optionally, (c) other compounds containing isocyanate-reactive groups; optionally in the presence of (d) a blowing agent, a catalyst and other known additives; wherein the polyol according to the present invention modified by acyl urea groups is used as component (b).
Suitable isocyanates are any of the abovementioned diisocyanates and also the distillation residues containing isocyanate groups obtained in the commercial production of isocyanates, optionally in solution in one or more monomeric polyisocyanates, as well as polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation In addition to the polyhydroxyl compounds according to the present invention, it is also possible to use the above-mentioned unmodified polyols and the conventional diamine chain-extending agents.
Aliphatic and diamines cyclaliphatic suitable for use in accordance with the present invention are, for example, ethylene diamine, 1,4 tetramethylene diamine, 1,1 1-undecamethylene diamine, 1,12dodecamethylene diamine and mixtures thereof, 1 amino 3,3,5 trimethyl 5 aminomethyl cyclohexane, 2,4 and 2,6 hexahydrotolylene diamine and mixtures thereof, perhydro 2,4 ‘ and 4,4 ‘diamino diphenyl methane, p xylylene diamine, bis ( 3 aminopropyl) methylamine According to the present invention, it is also possible to use hydrazine and substituted hydrazines, for example methyl hydrazine, N,N’ dimethyl hydrazine and homologues thereof, as well as acid dihydrazides, for example carbodihydrazide, oxalic acid dihydrazide, the dihydrazides of malonic acid, succinic acid, glutaric acid, adipic acid, /3 methyl adipic acid, sebacic acid, hydracrylic acid and terephthalic acid, semicarbazidoalkylene hydrazides, such as /3 semicarbazido propionic acid hydrazide (DOS No 1,770,591), semicarbazido alkylene carbazinic esters, such as 2semicarbazidoethyl carbazinic ester (DOS 1,918,504) or even aminosemicarbazide compounds, such as /3 aminoethyl semicarbazidocarbonate (DOS No.
1,902,931).
Examples of aromatic diamines are bis anthranilic acid esters according to German Offenlegungsschrift Nos, 2,040,644 and 2,160,590, 3,5 and 2,4 diaminobenzoic acid esters according to Dos No.
2,025,900, the diamines containing ester groups described in German Offenlegungsschrift Nos 1,803,635; 2,040,650 and 2,160,589 and also 3,3 ‘dichloro 4,4 ‘ diaminodiphenyl methane, tolylene diamine, 4,4 ‘ diaminodiphenyl methane and 4,4 ‘ diaminodiphenyl disulphide.
According to the present invention, other suitable chain-extenders are compounds such as 1 mercapto 3 amino propane, optionally substituted amino acids, for example glycine, analine, valine, serine and lycine, and optionally substituted 6 1569248 6 dicarboxylic acids, for example succinic acid, adipic acid, phthalic acid, 4 hydroxyphthalic acid and 4 aminophthalic acid.
It is also possible to use compounds which are mono-functional with respect to isocyanates in proportions of from 0 01 to %, by weight, based on the polyurethane solids, as so-called «chain-terminators».
Such monofunctional compounds are, for example, monoamines, such as butyl and dibutyl amine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine and cyclohexylamine, monohydric alcohols, such as butanol, 2 ethyl hexanol, octanol, dodecanol, the various amyl alcohols, cyclohexanol, and ethylene glycol monoethyl ether.
According to the present invention water and/or readily volatile organic substances may be used as blowing agents Suitable organic blowing agents are, for example, acetone, ethyl acetate, vinylidene chloride, halogen-substituted alkanes, such as methylene chloride, chloroform, ethylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether A blowing effect may also be obtained by adding compounds which decompose at temperatures above room temperature giving off gases, for example nitrogen, for example azo compounds, such as azoisobutyronitrile Other examples of blowing agents and information on the use of blowing agents may be found in Kunststoff-Handbuch, Vol VII, by Vieweg and H 6 chtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 108 and 109, 453 to 455 and 507 to 510.
According to the present invention, catalysts are also frequently used Examples of suitable known catalysts are, for example tertiary amines, such as triethylamine, tributylamine, N methyl morpholine, N ethyl morpholine, N cocomorpholine, NN,N’,N’ tetramethyl ethylene diamine, 1,4 diazabicyclo ( 2,2,2) octane, N methyl N’ dimethylaminoethyl piperazine, N,N-dimethyl benzylamine, bis (N,N diethylaminoethyl) adipate, N,N diethyl benzylamine, pentamethyl diethylene triamine, N,N dimethyl cyclohexylamine, N,N,N’,N’ tetramethyl 1,3 butane diamine, N,N dimethyl 3 phenylethylamine, 1,2dimethylimidazole and 2 methylimidazole Other suitable catalysts are known Mannich bases of secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones such as acetone, methylethyl ketone or cyclohexanone, and phenols, such as phenol, nonylphenol or bisphenol.
Examples of tertiary amine catalysts containing isocyanate-reactive hydrogen atoms include: triethanolamine, triisopropanol amine, N methyl diethanolamine, N ethyl diethanolamine, N,N dimethyl ethanolamine, also the reaction products thereof with alkylene oxides, such as propylene oxide and/or ethylene oxide.
Other suitable catalysts are silaamines having carbon-silicon bonds of the type described, for example, in German Patent No 1,229,290 (corresponding to US Patent No 3,620,984), for example 2,2,4 trimethyl 2 silamorpholine and 1,3 diethyl aminomethyl tetramethyl disiloxane.
Other suitable catalysts are nitrogencontaining bases, such as tetraalkyl ammonium hydroxides, also alkali metal hydroxides, such as sodium hydroxide, alkali metal phenolates, such as sodium phenolate, or alkali metal alcoholates, such as sodium methylate, Hexahydrotriazines may also be used as catalysts.
According to the present invention, organometallic compounds, especially organo-tin compounds, may also be used as catalysts.
Preferred organo-tin compounds are tin(II)salts of carboxylic acids, such as tin(II)acetate, tin(II)octoate, tin(II)ethyl hexoate and tin(II)laurate, and the tin(IV) compounds, for example dibutyl tin oxide, dibutyl tin dichloride, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate It is, of course, possible to use the above-mentioned catalysts in the form of mixtures.
Further representatives of catalysts suitable for use in accordance with the present invention and details on the way in which the catalysts work may be found in Kunststoff-Handbuch, Vol VII, by Vieweg and H 6 chtlen, Carl-Hanser-Verlag, Munich, 1966, for example on pages 96 to 102.
The catalysts are generally used in quantities of from about 0 001 to 10 %, by weight, based on the quantity of compounds containing at least two terminal hydroxy groups and having a molecular weight of from 400 to 20,000.
According to the present invention, surface-active additives, such as emulsifiers and foam stabilisers, may also be used.
Examples of emulsifiers are the sodium salts of castor oil sulphonates or salts of fatty acids with amines, such as diethyl amine/oleic acid or diethanolamine/stearic acid Alkali metal or ammonium salts of sulphonic acids, such as those of dodecyl benzene sulphonic acid or dinaphthyl methane disulphonic acid, or of fatty acids, such as ricinoleic acid, or of polymeric fatty acids, may also be used as surface-active additives.
1.569248 1,569,248 Suitable foam stabilisers are above all polyether siloxanes, especially watersoluble types These compounds generally have a structure in which a copolymer of ethylene oxide and propylene oxide is attached to a polydimethyl siloxane radical.
Foam stabilisers of this type are described, for example, in US Patent Nos 2,834,748; 2,917,480 and 3,629,308.
According to the present invention, it is also possible to use reaction retarders, for example substances, which are acid in reaction, such as hydrochloric acid ororganic acid halides, also known cell regulators, such as paraffins or fatty alcohols or dimethyl polysiloxanes, as well as pigments or dyes, known flameproofing agents, for example trischlorethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, stabilisers against the effects of ageing and weathering, plasticisers, substances having fungistatic and bacteriostatic effects and fillers such as barium sulphate, kieselguhr, carbon black or prepared chalk.
Other examples of the surface-active additives and foam stabilisers optionally used in accordance with the present invention and of cell regulators, reaction retarders, stabilisers, flameproofing substances, plasticisers, dyes and fillers, substances having fungistatic and bacteriostatic effects and also details on the way in which these additives are to be used and how they work, may be found in Kunststoff-Handbuch, Vol VII, published by Vieweg and H 6 chtlen, Carl-HanserVerlag, Munich, 1966, for example on pages 103 to 113.
According to the present invention, the reaction components may be reacted by the known one-shot process, by the prepolymer process or by the semi-prepolymer process, in many cases using machines of the type described, for example, in US-PS No.
2,764,565 Particulars of processing equipment suitable for use in accordance with the present invention may be found, for example, on pages 121 and 205 of Kunststoff-Handbuch, Vol VII, published by Vieweg and H 6 chtlen, Carl-HanserVerlag, Munich 1966.
In the production of foams, the foaming reaction is preferably carried out in moulds in accordance with the present invention.
To this end, the reaction mixture is introduced into a mould Suitable mould materials are metals, for example aluminium, or plastics, for example epoxide resins Inside the mould the foamable reaction mixture foams and forms the moulding In-mould foaming may be carried out in such a way that the moulding has a cellular structure at its surface, or even in such a way that the moulding has compact skin and a cellular core According to the present invention, it is possible in this connection to introduce such a quantity of foamable reaction mixture into the mould that the foam formed just fills the mould.
However, it is also possible to introduce into the mould more foamable reaction mixture than is required for filling the mould with foam This technique is known as «overcharging» and is known, for example, from US Patent Nos 3,178,490 and 3,182,104.
Known «external release agents», such as silicone oils, are frequently used for inmould foaming However, it is also possible to use so-called «internal release agents», optionally in admixture with external release agensts, such as are known, for example, from German Offenlegungsschrift Nos 2,121,670 and 2,307,589.
According to the present invention, coldhardening foams may also be produced (cf.
British Patent No 1,162,517, German Offenlegungsschrift No 2,153,086).
However, it is, of course, also possible to produce foams by block foaming or by the known laminator process.
Example 1
2400 g ( 0 5 mole) of a polyether from trimethylol propane, propylene oxide and ethylene oxide having an OH-number of are dehydrated by heating to 120 C in a vacuum of 12 Torr and then combined, at C, with 76 g ( 0 25 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide dissolved in 300 ml of xylene.
After all the isocyanate groups have reacted, which takes about 2 hours, 18 g ( 0 3 mole) of acetic acid are added at 80 C.
Following removal of the solvent (at from 90 to 100 C/0 15 Torr), the product which contains acetyloyl urea groups has a viscosity 1124 of 7400 c P and an OH-number of 24 (molecular weight approximately 10,000).
Example 2
172 g ( 0 1 mole) of a polyester from adipic acid, 1,6 hexane diol and neopentyl glycol having an OH-number of 66 are dried by heating to 120 C in a vacuum of 12 Torr and subsequently combined with 15 2 g ( 0 05 mole) of bis ( 3 isocyanato 4methylphenyl) carbodiimide After the isocyanate groups have reacted at from 110 to 120 C, 3 g ( 0 05 mole) of acetic acid are added at from 80 to 90 C, being attached to the carbodiimide groups to form acyl urea groups The thus-formed product has viscosity /24 of 9280 c P and an OH-number of 30 (molecular weight approximately 4000).
1,569,248 Example 3
2400 g ( 0 5 mole) of a polyether from trimethylol propane, propylene oxide and ethylene oxide having an OH-number of 35 are dehydrated over a period of 30 minutes at 120 C in a vacuum of 12 Torr and subsequently combined, at 120 C, with 76 g ( 0.25 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide.
After the isocyanate groups have reacted, g ( 0 25 mole) of lauric acid are stirred in at from 80 to 90 C, the carbodiimide groups reacting to form the corresponding acyl urea groups The product has a viscosity at 24 C of 7200 c P and an OH-number of 24 (molecular weight approximately 10,000).
Example 4
480 g ( 0 1 mole of a polyether from trimethylol propane, propylene oxide and ethylene oxide having an OH-number of 35 are dried by heating for 30 minutes to 120 C in a vacuum of 12 Torr and subsequently reacted with 15 2 g ( 0 05 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide.
After the isocyanate groups had reacted at from 110 to 120 C, 3 6 g ( 0 05 mole) of acrylic acid are added at from 80 to 90 C.
The polyhydroxy polyether formed, which is modified with acryloyl urea groups, has a viscosity /24 of 8520 c P and an OH-number of 24 (molecular weight approximately 10,000) after thin-layer distillation at from to 100 C/0 15 Torr.
Example 5
2400 g ( 0 5 mole) of a polyether from trimethylol propane, propylene oxide and ethylene oxide having an OH-number of 35 are dehydrated by heating to 120 C in a vacuum of 12 Torr and subsequently combined, at 120 C, with 76 g ( 0 25 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide After all the isocyanate groups have reacted, which takes about 2 hours, 21 5 g ( 0 25 mole) of methacrylic acid are added The product which contains methacryloyl urea groups has a viscosity at 24 C of 13320 c P and an OH-number of 23 (molecular weight approximately 10,000).
Example 6 g ( 0 1 mole) of a polypropylene glycol having an OH-number of 56 are dehydrated for 30 minutes at 120 C in a vacuum of 12 Torr 15 2 g ( 0 05 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide are then added at from 110 to C.
After the isocyanate groups have reacted, 5.05 g ( 0 025 mole) of sebacic acid are stirred in at from 80 to 90 C The polyhyhydroxy polyether modified with acyl urea groups has a viscosity 124 of 34400 c P (molecular weight approximately 9000).
Example 7
480 g ( 0 1 mole) of polyether from trimethylol propane, propylene oxide and ethylene oxide having an OH-number of 35 are dehydrated for 30 minutes at 120 C/12 Torr and subsequently reacted with 15 2 g ( 0.05 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide.
After the isocyanate groups have reacted at from 110 to 120 C, 1 5 g ( 0 025 mole) of acetic acid are stirred in at from 80 to 90 C.
Thereafter, the product still shows a strong carbodiimide band in its IR-spectrum The remaining carbodiimide bands are converted into guanidine groups by introducing 1 1 g ( 0 025 mole) of dimethylamine The pale reddish product formed has a viscosity /24 of 7400 c P (molecular weight approximately 10,000).
Example 8 g ( 0 4 mole) of 4,4 ‘ diisocyanatodiphenyl methane dissolved in g of xylene are subjected to carbodiimide formation at 120 C in the presence of 8 g of the insoluble catalyst containing phosphine oxide groups according to Example Ila of DOS No.
2,552,350 until 3 5 litres of carbon dioxide have formed The catalyst is separated off by filtration and 70 g ( 0 2 equivalents of isocyanate groups, as determined by titration) of the filtrate are reacted with 400 g ( 0 2 mole) of a polypropylene glycol having an OH-number of 56 which was dried by heating to 120 C/12 Torr.
After the isocyanate groups have reacted at from 110 to 120 O C, the reaction mixture is cooled to from 80 to 90 C and 3 2 g ( 0 055 mole) of acetic acid are added Following removal of the solvent, the polyhydroxy polyether formed, which is modified with acyl urea groups, has viscosity /24 of 8730 c P and an OH-number of 28 (molecular weight approximately 4600).
Example 9 g ( 0 1 mole) of a polypropylene glycol having an OH-number of 56 are dehydrated 110 at 120 C in a vacuum of 12 Torr and reacted with 15 2 g ( 0 05 mole) of bis 3 isocyanato 4 methylphenyl) carbodiimide.
After the isocyanate groups have reacted 115 at from 110 to 120 C, 10 1 g ( 0 05 mole) of sebacic acid are stirred in at from 80 to C The polyhydroxy polyether which is modified both with acyl urea groups and also with carboxyl groups has a viscosity /24 of 120 39800 c P and an acid number of 15.
1.569 248 Example 10
111 g ( 0 5 mole) of I isocyanato 3,3,5 trimethyl 5 isocyanatomethyl cyclohexane are subjected to carbodiimide formation at 150 C in the presence of 0 3 ml of a mixture of 1 methyl I phospha 2 cyclopentene 1 oxide and 1 methyl 1 phospha 3 cyclopentene I oxide until 6 liters of carbon dioxide have formed.
g ( 0 05 mole) of the reaction product are reacted with 200 g ( 0 1 mole) of a polypropylene glycol having an OH-number of 56 which was dried by heating to 120 C in a vacuum of 12 Torr.
After the isocyanate groups have reacted at from 110 to 120 C, the reaction mixture is cooled to from 80 to 90 C and 8 g ( 0 05 mole) of N,N dimethyl 6 aminocaproic acid are added The polyhydroxy polyether formed, which is modified with acyl urea groups, has a viscosity 124 of 10700 and an OH-number of 26 (molecular weight approximately 4600).
Example 11
15.2 g ( 0 2 mole) of 1,2 propane diol dissolved in 60 ml of N,N dimethyl formamide are reacted at 80 C with 30 4 g ( 0.1 mole) of bis ( 3 isocyanato 4methylphenyl) carbodiimide dissolved in 250 ml of toluene.
After the isocyanate groups have reacted, 6.6 g ( 0 11 mole) of acetic acid are added at from 80 to 90 C and the solvent is subsequently removed A product containing acetyloyl groups and having a melting point of 85 C is obtained.
Example 12
172 g ( 0 1 mole) of a polyester from adipic acid, 1,6 hexane diol and neopentyl glycol having an OH-number of 66 are dried by heating to 120 C in a vacuum of 12 Torr and subsequently mixed with 15 2 g ( 0 05 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide After the isocyanate groups have reacted at from 110 to 120 C, 3 3 g of acetic acid are added at C A wax-like polyol containing acetyloyl groups is obtained (molecular weight approximately 3800).
Example 13 g ( 0 1 mole) of a polyether from propylene glycol and propylene oxide having an OH-number of 56 are dehydrated by heating to 120 C in a vacuum of 12 Torr and subsequently reacted at 120 C, with 15.2 g ( 0 05 mole) of bis ( 3 isocyanato 4 methylphenyl) carbodiimide After all the isocyanate groups have reacted, which takes about 2 hours, 3 8 g ( 0 05 mole) of thioacetic acid are added at 120 C The polyol formed, which is modified with acetylol thiourea groups, has a viscosity 1724 of 2050 c P (molecular weight approximately 4400).

Claims (9)

WHAT WE CLAIM IS:-

1 A compound which has a molecular weight of from 400 to 20,000 contains at least two terminal hydroxyl groups and contains segments corresponding to the following general formulae:
-R 2-NH-C-N I l and z NH C OH)t X C-Y & 1 O RI _Jwherein X and Y, which may be the same or different, each represents oxygen or sulphur; RI represents hydrogen or a monovalent, or in the form of a bridge to other acyl urea groups, a polyvalent C,-C,8 aliphatic, C 4-C 15 cycloaliphatic, C 6C,5 araliphatic or aromatic radical which may contain one or more aliphatic double bonds and/or one or more branches and which may be substituted one or more times by hydroxyl, mercapto, secondary amino, sulphonic acid ester, phosphonic acid ester carboxylic, carboxylic ester, phenoxy, siloxane or trifluoromethyl groups, fluorine, chlorine, bromine or iodine; R 2 represents a divalent aliphatic, cycloaliphatic aromatic, or araliphatic radical containing from 4 to 25 carbon atoms obtained by removing the isocyanate groups from a diisocyanate; A represents an n-valent radical obtained by removing N hydroxyl groups from a polyhydroxyl compound having a molecular weight of from 62 to 6000; n represents an integer of from 2 to 8; and I represents zero or an integer having a value of from 1 to (n-1).

2 A compound as claimed in claim 1 substantially as herein described.

3 A compound as claimed in claim 1 substantially as herein described with reference to any one of the Examples.

4 A process for the preparation of a compound as claimed in claim 1 which comprises reacting, in a first step, a diisocyanatocarbodiimide corresponding to the following general formula:
OCN-(R 2-N=C=N)m R 2 NCO wherein m represents an integer of from 1 to 10; with a polyhydroxyl compound corresponding to the following general formula:
A-(-OH)n v 6 281 at a temperature of from 25 to 1300 C in an OH/NCO ratio of from 1 2:1 to 30:1 to form a carbodiimide group-containing polyhydroxyl compound; and, in a second step, reacting at least some of the carbodiimide groups of the said carbodiimide group-containing polyhydroxyl compound with a carboxylic acid corresponding to the following general formula:
RW-(C-YH)S X wherein s represents an integer of from 1 to 3; at a temperature of from 25 to 1000 C to form at least some acyl urea groups.

A process as claimed in claim 4 substantially as herein described.

6 A process as claimed in claim 4 substantially as herein described with reference to any one of the Examples.

7 A compound when prepared by a process as claimed in any of claims 4 to 6.

8 A process for the preparation of a polyurethane which comprises reacting a polyisocyanate with a compound as claimed in any of claims 1 to 3 or 7.

9 A process as claimed in claim 8 substantially as herein described.
A polyurethane when prepared by a process as claimed in claim 8 or claim 9.
ELKINGTON & FIFE Chartered Patent Agents, High Holborn House, 52/54 High Holborn, London WC 1 V 65 H Agents for the Applicants.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa, 1980 Published by The Patent Office, 25 Southampton Buildings London, WC 2 A l AY, from which copies may be obtained.
1,569,248 in

GB12024/78A
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AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE ADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A COATING OR SIZING AGENT FOR PAPER

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AQUEOUS SOLUTIONS OR DISPERSIONS OF POLYISOCYANATE ADDITION PRODUCTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE AS A COATING OR SIZING AGENT FOR PAPER

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Italiane Vernici Ind

QUICK-SETTING COATING COMPOSITION.

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Bayer Ag

METHOD FOR STABILIZING PLASTICS CONTAINING ESTER GROUPS

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Sherwin Williams Co
Dispersing polymers.

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