CA1075397A - Process for the production of polyurethane resins - Google Patents
Process for the production of polyurethane resinsInfo
- Publication number
- CA1075397A CA1075397A CA262,098A CA262098A CA1075397A CA 1075397 A CA1075397 A CA 1075397A CA 262098 A CA262098 A CA 262098A CA 1075397 A CA1075397 A CA 1075397A
- Authority
- CA
- Canada
- Prior art keywords
- groups
- group
- alkylene
- carbon atoms
- isocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
- C08G18/832—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides by water acting as hydrolizing agent
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
The instant invention is directed to a process for the production of polyurethane resins, comprising reacting an isocyanate and polyamines of the formula:
The instant invention is directed to a process for the production of polyurethane resins, comprising reacting an isocyanate and polyamines of the formula:
Description
o-1650-Ca LeA 16,731-Ca ~L~7S~
A PROCESS FOR THE PRODUCTION
OF POLYURET~IANE RESINS
Background of the Invention - seside polyols, polyamines are the most important reactants for the isocyanate polyaddition process. The urea linkages formed when amino groups are added to isocyanates : result in high molecular weight compounds which have inter-esting commercial properties. Polyfunctional amines may also : be used as mixtures with other reactants for isocyanates, for example, polyols. The course of the reaction and the prop-erties of the end product ¢an be determined within wide - llmits by adjusting the proportions of the components in the mlxture.
Whereas low molecular weight polyamines are easily - 15 prepared on an industrial scale and a wide.choice is there-:~ ore available, the problem of preparing higher molecular weight diamines and polyamines has not hitherto been solved : satisfactorily. This is partl~ because the processes em-ployed in low molecular weight chemistry for synthesizing : 20 amines cannot easily be applied to higher molecular weight ~ compounds and partly because the preparation of suitable '. high molecular weight starting compounds also often leads .
~ - to d.ifficulties.
:, - It is therefore an ob]ect of the present invention . 25 -to provlde a simple and reproducibIe process for the prepara-. tion of higher molecular weight diamines and polyamines using steps of chemical.synthesis which are easily carried out in practice.
. ~
LeA 16,731-Ca.
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3~7~ 7 Description of the Invention This problem is solved by the process of the present invention since it has been found that the re-activity of the amiho group of amino alcohols towards S isocyanate groups can be reduced by suitable choice of protective groups to such an extent that the reaction cf the blocked amino alcohols with isocyanate prepolymers is virtually restricted to the hydroxyl group, resultiny in the formation of urethanes.~ The blockage of the amino group is subsequently removed in another reaction step to yield the desired high molecular weight polyamines~
The instant invention is dlrected to a process for the production of polyurethane resins, comprising reacting an isocyanate and polyamines of the formula:
O H H O R
~. , , " / 3 R(~~C~N~Rl~N~C~~R2~N \ )n (I) H
in which n represents an integer of between 2 and 10, R represents an n-valent organic group such as can be obtained by the removal of n hydroxyl groups from a polyhydroxyl compound which has an average molecular weight of between about - 200 and about 10,000 and may also contain urethane groups, Rl represents an alkylene, cycloalkylene, arylene or aralkylene group containing 2 to 15 carbon atoms, LeA 16j731-Ca.
~, ~5~7 R represents an alkylene, cycloalkylene, arylene or aralkylene group with from 2 to 15, preferably 6 to 12, carbon atoms which may contain an -O-or R3 group and -N-3 represents hydrogen, or an alkyl or cycloalkyl group with 1 to 9 carbon atoms, or an alkylene group which together with R2 and -NH- forms a 5- or 6-membered ring.
The polyamines may be prepared by reacting:
- 10- 1) ketimines, aldimines or enamines having a hydroxyl group with
A PROCESS FOR THE PRODUCTION
OF POLYURET~IANE RESINS
Background of the Invention - seside polyols, polyamines are the most important reactants for the isocyanate polyaddition process. The urea linkages formed when amino groups are added to isocyanates : result in high molecular weight compounds which have inter-esting commercial properties. Polyfunctional amines may also : be used as mixtures with other reactants for isocyanates, for example, polyols. The course of the reaction and the prop-erties of the end product ¢an be determined within wide - llmits by adjusting the proportions of the components in the mlxture.
Whereas low molecular weight polyamines are easily - 15 prepared on an industrial scale and a wide.choice is there-:~ ore available, the problem of preparing higher molecular weight diamines and polyamines has not hitherto been solved : satisfactorily. This is partl~ because the processes em-ployed in low molecular weight chemistry for synthesizing : 20 amines cannot easily be applied to higher molecular weight ~ compounds and partly because the preparation of suitable '. high molecular weight starting compounds also often leads .
~ - to d.ifficulties.
:, - It is therefore an ob]ect of the present invention . 25 -to provlde a simple and reproducibIe process for the prepara-. tion of higher molecular weight diamines and polyamines using steps of chemical.synthesis which are easily carried out in practice.
. ~
LeA 16,731-Ca.
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3~7~ 7 Description of the Invention This problem is solved by the process of the present invention since it has been found that the re-activity of the amiho group of amino alcohols towards S isocyanate groups can be reduced by suitable choice of protective groups to such an extent that the reaction cf the blocked amino alcohols with isocyanate prepolymers is virtually restricted to the hydroxyl group, resultiny in the formation of urethanes.~ The blockage of the amino group is subsequently removed in another reaction step to yield the desired high molecular weight polyamines~
The instant invention is dlrected to a process for the production of polyurethane resins, comprising reacting an isocyanate and polyamines of the formula:
O H H O R
~. , , " / 3 R(~~C~N~Rl~N~C~~R2~N \ )n (I) H
in which n represents an integer of between 2 and 10, R represents an n-valent organic group such as can be obtained by the removal of n hydroxyl groups from a polyhydroxyl compound which has an average molecular weight of between about - 200 and about 10,000 and may also contain urethane groups, Rl represents an alkylene, cycloalkylene, arylene or aralkylene group containing 2 to 15 carbon atoms, LeA 16j731-Ca.
~, ~5~7 R represents an alkylene, cycloalkylene, arylene or aralkylene group with from 2 to 15, preferably 6 to 12, carbon atoms which may contain an -O-or R3 group and -N-3 represents hydrogen, or an alkyl or cycloalkyl group with 1 to 9 carbon atoms, or an alkylene group which together with R2 and -NH- forms a 5- or 6-membered ring.
The polyamines may be prepared by reacting:
- 10- 1) ketimines, aldimines or enamines having a hydroxyl group with
2) isocyanate terminated prepolymers ~- prepared by reacting polyols having a molecular weight between about 200 and 10,000 with an excess of diisocyanates.
, ~
Following this reaction, the resulting polyketimines, aldimines or enamines are hydrolytically decomposed.
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Following this reaction, the resulting polyketimines, aldimines or enamines are hydrolytically decomposed.
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-3 LeA 16,731-Ca.
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The polyamines of the general formula (I) are obtained by hydrolysis of compounds of the general formulae (II a) R(-o-c-N~Rl-N-c-o-R2-N=c ~ )n (II a) or (II b~
O H H O ,3,6 / R7 R(.-O-C-N-Rl-N-C-O-R2-N-C=C \ ~n (II b) : in which n, R, Rl, R2 and R3 have the meanings specified above. The groups R4 to R8 r=present alkyl, cycloalkyl, .
LeA 16,731-Ca. - 3a -,.'' ' ' ~' ' ' .' " , , .
.
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aryl and aralkyl groups with from 1 to 15 and preferably 1 to 7 carbon atoms or R4 and R5 together or~6 ~nd~-R8~t'ogether form a 5- to-1,2-membered ring and/or R4,tR6 and/or R7 ~
represqnt hydrogen atoms.
..
' 5 Thç polyaldimines, polyketimines or polyenamines requir~ed for the process according to the inventio~ ~re obtained by reaction of isocyanate prepolymers of-the general formula ;~ O H
R~O~C-N-Rl-N=C=O)n (IXI) .. ~
with ~-hydroxymonoaldimines, -ketimines or -enamines of ?
the general formula ~ ~ .
` ,3 ~ / ~ R4 t HO-R2 N-C=C or ~-R2-N=C \
. ' , .
, wherein R2 to R8 have the meanings specified above.
The isocyanate prepolymers (III) used fo~ the pro- ' " . ~ .
15 cess according to the invention are prepared by ba~ically known methods of reacting polyhydroxyl compounds with diiso cyanates.
.', ' " , Suitable polyhydroxyl compounds are in p~rticular polyethers with a molecular weight of from about 200 to 20 about 10,000, preferably 1000 to 6000, containing at least 2, generally 2 to 8 and preferably 2 to 3 hydroxyl groups.
The hydroxyl polyethers which may be used in the invention are known per se and may be prepared, for example, by polymerization of epoxides such as ethylene oxide, propyl-LeA 16,731 ~4-. . .
~5~
ene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlarohydrin. The polymerization may be of the oxides themselves, for example, in the presence of boron trifluoride, or by addition reactions of these epoxides, either as mix-tures or successively, to starting components containing reactive hydrogen atomsD Such starting compounds include water~ alcohols or amines, e.g. ethylene glycol, propylene-1,3- or -1,2-glycol, trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ammonia, e-thanolamine or ethylene-- 10 diamine. Sucrose polyethers such as those described, for example, in German Auslegeschriften 1,176,358 and 1,064,938 may also be used. It is in many cases preferred to use polyethers which contain predominantly primary hydroxyl groups (up to.90~ by weight, based on all the hydroxyl ; 15 groups present in tpe polyether). Polyethers which have been modified,with vinyl polymers, Eor example, the compounds obtained by the polymeri2ation of styrene and acrylonitrile in the presence of polyethers as described in U.S. Patents 3,383,351; 3,304,273; 3,523,093 and 3,110,695 and German Patent 1,152,536 are also suitable. Polybutadienes con-taining hydroxyl groups may also be used.
Polythioethers and polyacetals are also $uitable for the process of the invention. Polyesters may also be used if the polyamines which are the subject o~ the present ~; 25 invention carry secondary amino groups.
Suitable polyesters with hydroxyl groups include, for example, the reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added, with polybasic, preferably dibasic carboxylic acids. If desired~ the corresponding polycarboxylic acid anhydrides LeA 16,731 -5-~75~5~7 or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may be used instead of the free poly-carboxylic acids for preparing the polyesters. The polycar-boxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heteroe~yclic and they may be substituted, ~or example, by h~,Llogen atoms, and/or may be unsaturated. The following are examples of suitable polycarboxylic acids:
Succinc acid; adipic acid; azelaic acid; sebacic acid;
phthalic acid; isophthalic acid; trimellitic acid; phthalic ,, acid anhydride; tetrahydrophthalic acid anhydride; hexa-hydrophthaliq acid anhydride; endomethylene tetrah~dro-phthalic acid anhydride; glutaric acid anhydride; ~aleic acid; maleic acid anhydride; fumaric acid; dimethylterephtha-' late and b,is~g,lycol terephthalate. ~uitable polyhydric alcohols include, f~or example, ethylene glycol; propylene-1,2- and -1,3-~glycol; butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol; neopenty:L glycol; cyclohexane : dimetha~ol (1,4-bis-hydroxymethylcyclohexane); 2-m~thyl-1,3-pro~anediol; glycerol; trimethylolpropane; he~ane-1,2,6-triol; butane-1,2,~-triol; trimethylolethane; pentaerythritol;
quinitol; mannitol and sorbitol; methyl glycoside; di-ethylene glycol; triethylene glycol; tetraethylene glycol;
polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol and polybutylene glycols. Poly- -esters of lactones such as s-caprolactone or hydroxycar-boxylic acids such as ~-hydroxycaproic acid, may also be , used.
~- Among the polythioethers which should be particu-larly mentioned are the condensation products obtained by reacting thiodiglycol on its own and/or with other glycols, ~ LeA 16,731 -6-~7~7 dicarbo~ylic acids, formaldèhyde, aminocarboxylic ~cids or amino alcohols. The products obtained are polythi~ mixed ethers, polythioether esters or polythioether ester amides, dependipg on the co-components.
, ~
Suitable polyacetals include, for example, the compounds which can be prepared from glycols such as diethylene y~ycol, triethylene glycol, 3,4'-dioxethoxy-diphenyldimethyl methane, hexanediol and formaldehyde.
Suitabl~ polyacetals may also be obtained by the polymeri-æation pf eyelic acetals.
Sultable polycarbonates with hydroxyl grpups include thosç known per se which ean be obtained, ~or example, by t~e reaction o~ diols such as propane-1,3-diol, butane-1,4-diol and~or hexane-1,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates such as diphenylcarbonate or phosgene~
The isocyanates used as starting compone~ts for the pre~aration of the isocyanate prepolymers required accordipg to the invention may be any number of known iso-cyanates but are preferably bifunctional aliphatic, cyclo-aliphatic, araliphatic, aromatic or heterocyclic isocyanates of the kind which have been described, for example, by W.
Sie~ken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. The following are specific examples: Ethylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; eyclohexane-1,3- and -1,4-diisoeyanate and any mixtures of these isomers; l-isoeyanato-3,3,5-trime~hyl-5-isoeyanatomethyl-cyclohexane as described in Ger~an LeA 16,731 -7-Auslegeschrift 1,202,785 and U.S. Patent 3,401,190; hexa-hydrotolylene-2,4- and -2,6-diisocyanate and any mixtures ; of these isomers; hexahydro-1,3- and/or 1,4-phenylene - diisocyanate; perhydro 2,4'- and/or 4,4'-diphenylmethane diisocyanate; phenylene-1,3- and -1,4-diisocyanate;
tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers; diphenylmethane-2,4'- and/or 4,4'-diisocyanate and naphthyl~ene-1,5-diisocyanate.
The following are examples of hydroxy~mineS
r which are sultable for the process of the present invention~
2-aminoethanpl; 2-methylaminoethanol; 1-amino-2-propanol;
3~amino-1-propanol; 4-amino-1-butanol; 4-amino-2-butanol;
2-amino-2-methyl-propanol; 5-amino-1-pentanol and 6-amino-l-hexanol.
Particularly suitable, however, are those hydroxy-amines in which the two functional groups are separated by at least 6 atoms or by a ring. These include 7-amino-1-heptanol; 10-amino-1 decanol; 12-amino-1-dodecanol; 4-(2-aminoethyl)-(2-hydroxyethyl)-benzene; 4-~-hydroxyethyl-aminobe~zene and N-~-hydroxyethyl-piperazine. Hydroxya~ineS
having hetero atoms as represented by the following formulae may also be used , . .
HO-(CH2)2-O-(CH2)3 NH2 HO (CH ) -O-(CH ) -NH
HO-(CH2)5-O-(CH2)3 NH2 HO-(CH2)6-O-(CH2)3 NH2 HO-(CH2)2-O-(cH2)2 (C~l2)3 2 LeA 16,731 -8 ~' ~, .
HO-CH2 ~ CH2-0 (CH2)3 2 Ho-(cH2)2-N-(cH2)3 NH2 These are prei~erably obtained by the monoaddition of acrylo-nitril~ to glycols or to N-substituted hydroxyamineS fol-lowed ~y reduction.
.
The followin~ aldehydes, for example, may be used for blocking the NH functional group: Acetaldehyde;
propio~aldehyde; n-butyraldehyde; isobutyraldehydq; n-valeraldehyd~; isovaleraldehyde; caproic aldehyde; heptenal;
3-formyl-heptane; formylcyclohexane; l- and 2-met~yl-4-formyl-cyclohexane-(1), phenyl acetaldehyde; 3-phenylpro-pionaldehyde;'benzaldehyde; chlorobenzaldehydes; ~ethylbenz-aldehy~es and cinn~aldehyde.
The follo~ing are examples o~ suit;able ketonss: Acetone;
methy~ ethyl ketone; methyl n-propyl ketone, methyl-isobutyl ^- ketone; diethyl-ketone; methyl-n-amylketone; diiso';;lutyl ketone;
~methyl--t-butyl-ketone; methyl-n-heptyl ketone; acetony-~ acetone;
.:
acetophenone; propionphenone; cyclopentanone; cyclohexa-none; l-methylcyclohexanone-(2), l-cyclohexyl cyclohexanone-(2); cyclohexadione-(1,4); cyclododecanone; hydrindone and tetralone.
:
~' Using the above mentioned reactants ketimines aldimines and/or enamines are obtained according to processes kno~n in the art (compare Robert WO Layer, The Chemistry of Imines~ Chemical Reviews, page 489 and following, vol 63 (1963); ~lonographie "Enamines: Synthesis, Structure and Reactions, edited by A. Gilbert Cook, published'by Marcel Dekker, New York and London, 1969).
., .
~ Le A 16 731 - 9 ~
-, " . . . .
: . . .
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The isocyanate prepolymer~ are prepared by methods known per se, preferably employing ~emperatures of between about 10C and about 140~C. The NCO/OH equivalent ratio of the reactants employed is generally between abcut 1.5:1 and about 6:1, preferably between 2:1 and 4:1. The OH/NCO
reactianmaybe accelerated if desired by the addition of suitable cat~lysts for this reaction. The excess of mono-., , ~ .
' ' .
. . , .' ~ .
.~' ' .
` '` ' .
", , ` Le A 16 731 _ 9 a -... . . . . . . . . .. .. . . ....
~o?75~
- meric diisocyanate is preferably subsequently remored partly or completely in known manner.
The subsequent reaction of the resulting isocya-nate prepolymers with the N-blocked amino alcohols is also carried out by methods conventionally employed in isocya-nate chemistry. One preferred method, in which all unwanted side reactions are substantially suppressed, consists of continuously adding the isocyanate prepolymer to the ~
hydroxyamine~ with blocked amino group at temperatures of between about 20C and about 120C, preferably between 20C
and 60C, with vigorous stirring. Catalys~s may also be ;~ used for this reactîon if desired. The two reactants are -~ pxeferably employed in a stoichiometric ratio of 1:1 (based on isocyanate and hydroxyl). A slight excess of hydroxyl compound may be used if desired.
. . .
~' .
~he resulting blocked polyamines are converted into the free polyamines according to the invention by ~` hydrolysis. Removal of the carbonyl compounds may be - ; carried out, for example, by treating ~he blocked polyamine ~- 20 with water or with a water/solvent mixture at temperatures between 20C and 120C and then distilling off the carbonyl -~ compound and excess water and, if necessary, solvent at a reduced pressure and elevated temperature.
~he preferred method, however, consists of injecting steam at elevated temperatuxe (about 100 to 130C) into the ~ blocked polyamine and then freeing the resulting polyamine - ~ from residual water at reduced pressure when the reaction i ~ ~
has been completed.
- LeA 16,731 10-ii39~7 , The re~ulting prepolymers with amino end groups can then be used for the isocyanate polyaddition process either alone or as mixtures with polyol~ and/or other active ~ hydrogen containing compounds.
: S The compounds according to the invention may also be used for various condensatio~l reactions, for example, with polycarboxylic acids or polycarboxylic acid derivatives ` or formaldehyde, e.g~ for the preparation of polyamides, ;~ polyester amides and cross-linked polyhexahydrotriazines.
~':
The preferred field of application of the poly-amines according to the invention lies in the production of polyurethane resins, in particular foams. For this purpose;
~- they may, if desired, be used in col~ination with higher molecular weight polyhydroxyl compounds, for example, of . ~ ~
`. 15 the kind already described above, and/or with low molecular :`~ weight chain lengthening agents,in the reaotion with polyisocy-~,. ana~e~.
The chain lengthening agents which may be used are compounds with a molecular weight of from about 32 to ` about 4Q0 which contain at least two hydrogen atoms capable - 20 of reacting with isocyanates. The following are examples of such compounds: Ethylene glycol; propylene~ and , .~ .;
1,3-glycol; butylene-1,4- and 2,3-glycol; pentane-1,5-~:- diol; hexane-lt6-diol; octane-1,8-diol; neopentyl glycol;
~ , ~
... ~ 1,4-bis-hydroxymethyl-cyclohexane; 2-methyl-propane-1,3-~ 25 diol: glycerol; trimethylolpropane; hexane-1,2,6-triol;
;`;^.~ trimethylolethane; pentaerythritol; quinitol; mannitol and :; sorbitol; diethylene glycol; triethylene glycol; tetraethyl-:~ ene glycol; polyethylene glycols with a molecular weight of . ~ up to 400; dipropylene glycol; polypropylene glycol~ with LeA 16,731 11 , , ~)'75~9~7 a molecular weight of up to 400; dibutylene glycol; poly-butylene glycols with a molecular weight of up to 400; 4,4'-dihydroxydiphenylpropane; dihydroxymethyl hydroquinone;
ethanolamine; diethanolamine; triethanolamine; 3-amino-S propanol; ethylene diamine; 1,3-diaminopropane; l-mercapto-3-aminopropane; 4-hydroxy- or 4-amino-phthalic acid;
~uccinic acid; adipic acid; hydrazine; N,N'-dimethylhydra-zine and 4,4'-diaminodiphenylmethane.
Suitable reactants for the polyamines of the inven-tion, apart from the diisocyanates already mentioned above, .
include the followingo Triphenylmethane-4,4',4"-triisocya-nate, polyphenyl-polymethylene-polyisocyanatPs of the kind described, for example, in British Patents 874,430 and 848,671 which can be obtained by aniline-formaldehyde con-densation followed by phosgenation; m- and p-isocyanatophenyl-sulphonylisocyanates according to U.S. Patent 3,454,606;
~ perchlorinated aryl polyisocyanates such as those described, :~ ~ for example, in German Auslegeschrift 1,157,601 (U.S. Patent 3,277,138); polyisocyanates hav.ing carbodiimide groups as described in German Patent 1,092,007 ~U.S. Patent 3,152,162);
~: the diisocyanates described in U.S. Patent 3,492,330; poly-, .
`~ isocyanates with allophanate groups as described e.g. in British Patent 994,890; Belgian Patent 761,626 and published Dutch Patent Application 7,102,524; polyisocyanates with : 25 isocyanurate groups as described e.g. in U.S. Patent 3,001,973; German Patents 1,022,789; 1,222,067 and 1,027,394 and German Offenlegungsschriften 1,929,034 and 2,004,048;
polyisocyanates with urethane groups hS described e.g. in Belgian Patent 752,261 and U.S. Patent 3,394,164; polyiso-cyanates having acylated urea groups according to German Le~ 16,731 -12-, .. ..... .. .
Patent 1,230,778; polyisocyanates with biuret groups as described e~g. in German Patent 1,101,394 (U.S. Patents 3,124,605 and 3,201,372) and British Patent 889,050; poly-isocyanates prepared by telomerization reactions as described e.g. in U.S. Patent 3,654,106; polyisocyanates having ester groups, for example, hose mentioned in British Paten~s 965,474 and 1,072,956; U.S. Patent 3,567,763 ~ and German Patent 1,2317688; reaction products of the above--~ mentioned isocyanates with acetals in accordance with German ~i 10 Patent 1,072,385 and polyisocyanates containing polymeric fatty acid groups according to U.S. Patent 3,455,883.
The distillation residues still containing isocya-~; nate groups from the commercial production of isocyanates may also be used, if desired as solutions in one or more of the above-mentioned polyisocyanates. Any mixtures of the above-mentioned polyisocyanates may also be used.
When producing foams from the polyamines of the present invention, water and/or readily volatile organic ~'!,`,~ substances are used as blowing agents. The following are `~ 20 examples of suitable organic blowing agents: Acetone; ethyl .
~i acetate;halogenated alkanes such as methylene chloride;
~, . . .
chloroform; ethylidene chloride; vinylidene chloride; mono~
~`~ fluorotrichloromethane; chlorodifluoxomethane; and dichloro-difluoromethane; also butane, hexane, heptane and diethyl-;
ether. The effect of a blowing agent can also be obtained by the addition o~ compounds which decompose at temperatures above room temperature with the liberation of gases such as nitrogen, e.g. azo compounds such as azoisobutyric acid nitrile. Other examples of blowing agents and details con-cerning the u~e of blowing agents may be found in Kunststoff-LeA 16,731 -13-' ~5~'7 Handbuch, Volume VII, published by Vieweg and ~ochtlen, Carl~Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
Catalysts may often be advantageously used. Suit able catalysts are known per se, for example, tertiary amines such as triethylamine; tributylamine; N-methylmorpholine;
~ N-ethylmorpholine; N-cocomorpholine, N,N,N',N'-tetramethyl-;~ ethylenediamine; 1,4diaz~bicyclo-(2 t 2,2)-octane; N-methyl-N'-dimethyl-aminoethyl-piperazine; N,N-dimethylbenzylamine;
bis-(N,N-diethylaminoethyl)-adipate; N,N-diethylbenzylamine;
pentamethyldiethylena triamine; N,N-dimethylcyclohexylamine; :~
~ N,N,N',N'-tetramethyl-1,3-butanediamine; N,N-dimethyl~
:~ phenylethylaminet 1,2-dimethylimidazole and 2-methylimida-zole. The known Mannich bases obtained ~rom secondary amines such as dimethylamine, and aldehydes, preferably . formaldehyde; or ketones such as ac~tone, methyl ethyl ketone or cyclohexanone; and phenols such as phenol, nonyl-phenol or bis-phenol may also be used as catalysts.
The following are example~ of tertiary amines having isocyanate-reacti~e hydrogen atoms which may be used as catalysts: Trie~hanolamine; triisopropanolamine; N-methyl-diethanolamine; N-ethyl-diethanolamine; N,N-dimethyl-ethanolamine and their reaction products with alkylene .. ~`; oxides such as propylene oxide and/or ethylene oxide.
; ~..................................................................... .
~,, .
Silaamines having carbon-silicon bonds may also be used as catalysts, for example, compounds described in Ger-~ man Patent 1,229,290 (corresponding to U.S. Patent 3,620,984), :- such as 2,2,4-trimethyl-2-silamorpholine or 1,3-diethylamino-methyl-tetramethyl disiloxane.
LeA 16,731 -14-~7S397 Other suitable catalysts include basic nitrogen compounds such as tetraalkylammonium hydroxides; alkali metal hydroxides such as sodium hydroxide; alkali metal phenolates such as sodium phenolate and alkali metal alcohols such as sodium methylate. Hexahydrotriazines may also be used a~ catalysts.
;
Organic metal compounds may also be used as cata-lysts according to the invention. ~hese particularly include organic tin compounds.
The organic tin compounds used are preferably di-valent tin salts of carboxylic acids, such as tin(II) ace--~ tate; tin(II) octoate; tin(II) ethyl hexoate and tin(II) ; laurate, and the tetravalent tin compounds such as dibutyl ~; tin oxide; dibutyl tin dichloride, dibutyl tin diacetate;
dibutyl tin dilaurate; dibutyl tin maleate or dioctyl tin diacetate. The above mentioned catalysts may, of course, also be used as mixtures.
.~, i~ Other examples of catalysts which may be used according to the invention and the action of the catalysts have been described in Xunststoff-Handbucht Volume VII, pub-lished by Vieweg and Hochtlen, Carl-Hanser-~erlag, Munich ~i' 1966, e.g. on pages 96 to 10~
The catalysts are generally used in a quantity of .. .
~- between about 0.001 and 10% by weight, based on the polyamine according to the invention.
' "`
Surface active additives such as emulsifiers and foam stabilizers may also be used. Sodium salts of ricino-lei~ sulphonates or salts of fatty acids with amines such as LeA 16,731 -15-.
~75~
oleic acid diethylamine or stearic acid diethanolamine, for example, ar~ suitable emulsifiers. Alkali metal or ammonium salts of sulphonic acids such as dodecylbenzene sulphonic acid or dinaphthylmethane disulphonic acid or of fatty acids such as ricinoleic acid or of polymeric fa ~y acids may also be used as surface-active additives.
:
The most important foam stabilizers are polyether ;~ siloxanes, especially those which are water-soluble. These ~ compounds generally have a polydimethylsiloxane group -~ 10 attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this kind have been described~
~- for example, in U.S. Patents 2,~34~748, 2,917,480 and 3,629,308.
Reaction retarders may also be used according to the -~ 15 invention, for example, compounds which are acidic in reac-tion such as hydrochloric acid or organic acid halides.
~; Other additives which may be used include cell regulators ~.
;` of the kind known ~ se such as paraffins or fatty alcohols . ............................ -- . .
or dimethylpolysiloxanes; pigments; dyes; flame-retarding agents known per se such as tris-chloroethyl phosphate, tricresyl phosphate, ammonium phosphate and ammonium poly-phosphate; stabilizers against ageing and weathering; plas-ticizers; fungistatic and bacteriostatic substances and fillers such as barium sulphate, kieselguhr, carbon black -~ 25 or whiting.
~ Other examples of surface active additives and foam ~. .
stabilizers which may be used according to the invention and .., ~
~, of cell regulators, reaction retarders, stabilizers, fl~me LeA 16,731 -16-. ~ ~
3~
retardants, plasticiæers, dyes, fillers and fungistatic and bacteriostatic Rubstances and the use and mode of action of these additives have been descxibed in Kunststoff-Handbuch, Volume VII, published by Viewey and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.gO on payes 103 to 113.
When using the polyamines according to the inven~
: tion in the isocyanate polyaddition process, the components ~: are reacted together by the known one-shot, prepolymer or ~ semiprepolymer process, in many cases using mechanical devices such as those described in U.S. Patent 2,764,565.
Processing apparatus of the kind which may be used according to the invention have been described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-~: . Verlag, Munich 1966, e.g. on pages 121 to 205.
When producing foams according to the invention, ~- the foaming reaction is often carried out in molds. The ~ reaction mixture is introduced into a mold which may be ;~; made of a metal such as aluminum or a plastics material ~; such as an epoxide resin and it foams up inside the mold .:; 20 to give rise to the molded article. This foaming process .
. may be carried out so that the molded product has a cellu-~` lar structure on its surface or it may be carried out to produce a product with a non-cellular skin and cellular ~-~ core. According to the invention, the quantity of foamable ~, .
. 25 reaction mixture introduced into the mold may be just ; ~ sufficient to fill the mold with foam or if desired, a :~ larger quantity of foamable reaction mixture may be used, in which case the foaming process is said to be carried out under conditions of "overcharging". This procedure has already been described~ for example, in ~.S. Paten~s LeA 16,731 -17-:, 3,178,490 and 3,132,104.
. .
When foaming is carried out inside molds, so-called external mold release agents known per se, such as silicone oils, are frequently used. Alternatively, so-S called internal mold release agents may be used, optionally in combina~ion with external mold release agents,for example, as disclosed in Gexman Offenlegungsschriften 2,121,670 and 2,307,589.
. Cold setting foams may also be produced according to the invention as described in see British Patent 1,162,517 and German Offenlegungsschrift 2,153,086.
~ .
Fo~ns may, of course, also be produced by the ~ prooess of block foaming or by the laminator process known : ~ per se~
The following Examples serve to explain the process of the invention. The figures given refer to parts by , ~: weight or percentages by weight unless otherwise indicated~
, :
,~,................................................................... . .
. . ,. ~ .
, ....
"~
~ ~.', .
.'~`.' .
;. ~`~'. .
. j .
LeA 16,731 -18-' Example 1 A solution of 234 g of l-aminohexanol (CH2)6 NH2 in 400 ml of methyl isobutyl ketone is boiled under reflux using a water separator until about 36 ml of water have been removed. The excess ketone is then distilled off at reduced pressureO The resulting hydroxy ketimine 0- (CH2 ) 6-N=C
:, \
-~ ~CH2~CH(~H3)~
~ is slowly added at ~emperatures of between 20C and 30C to ;~ 10 2340 g o~ an isoc~anate prepolymer having an isocyanate con!~ent ~ o~ 3.5 % (the i~ocyanate prepolymer was prepared by known .
methods from a bifunctional polypropylene glycol (OH number 56) and hexamethylene diisocya~ate). The OH/NCO reaction is catalyzed by the addition of 1 g of tin-(II) octoate.
. .
When the addition reaction has been completed, as indicated by IR spectroscopy, the reaction mixturP is heated to a temperature of between 110C and 120C and steam dis-,.. .
tilled until no ketone can be detected in the distillateO
The residue is then rapidly hea~ed to 130C and the slight ~ /
'i~ 20 residue of water is distilled off, using an oil pump vacuum.
,, ~
~; After about 30 minutes, the reaction mixture left behind ,i. . .
~ contains less than 0.1% of water. The resulting product i~ is a higher molecular weigh diamine which has mainly the following end groups:
, ~1 :, LeA 16,731 -19-;' ~ ` ~
~7~ 97 H O
-N-C-O-(CH ) -NH
Example 2 230 g of the hydroxyaldLmine of the following formula ;~ 5 HO~ 2)6-O-(CH2)3-N=C-CH \
C~l are added over a period of one hour at temperatures of about ~ 40C to 1200 g of an isocyanate prepolymer having an isocya-,~ nate content of 3.5% which has been prepared by known methods ~ of reacting a polypropylene glycol (having a hydroxyl num-: :.
ber of 56 and a molecular weight of 2900 which had been prepared from trimethylolpropane and propylene glycol) with ::
isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane.
The hydroxyaldimine was obtained by the intro-; duction of 175 g of 1,6-hexanediol-1(-3-aminopropyle~her) :
into 150 ml of isobu~yraldehyde, followed by boiling under reflux a~d ~epara~o~ o~ water. The exc~s8 aldehyde wa then di~tlll~d off ~t reduc~d pre~ure.
,, ~ ~ . .
The reaction of the hydroxyaldimine with the iso--;~ cyanate prepolymer is catalyzed with 0.8 g of tin-(II) octoate. The resulting prepol~mex which has aldimine end -~ groups 1~ treated as described in Example 1. A prepolymer '~ with the following end groups is obtained:
H O
,........................... , -N-C-O-(CH2)6-O-(c~2)3 N~2 ..~
~ LeA 16,731 -20-, .. . .
~` ~
~75i3~ 17 243 g of the following ke~imine HO-(CH2)2-O-(c~2)2-o (CH2~3 O
are slowly added at temperatures below 40C to 1900 g of an : S isocyanate prepolymer (2.2% NCO) which has been obtained by known methods of reacting a copolymer of propylene oxide and ethylene oxide which has been started on trLmethylol , : propane and has a hydroxyl number of 35 with tolylene ~: diisocyanate.
; 10 The ketimine was obtained by introducing 163 g of ~, diethylene glycol-(3-propylamine)-ether . .
.:.:
;~ HO-(CH2)2-O-(CH2)2 (CH2)3 2 ., i ~ into a mixture of 105 g of cyclohexanone and 200 ml o tolu-. ~, .
~ ene and then boiling the reaction product, using a water .
- 15 separator. When about 18 ml of water had been removed in . . . ~
;~: this way, the carrier agen~ and excess ketone were removed under vacuum.
~. The reaction between isocyanate prepolymer and -~ hydroxyketimine is catalyzed by the addition of 2 g of 20 dibutyltin dilaurate. The ketimine prepolymer i~ then decom-posed as in Examplip 1.
` ,i A polyfunctional amino prepolymer haviny the fol~
lowing end group~
(CH2)2 O-(CH~)2 (CH2)3 ~; 25 is obtained.
- LeA 16,731 -21--~7S;397 ~,~
186 g of the hydroxyaldimine of the formula -(CH2)2-N-(CH2)3-N=C-C~(CH3)2 are added at room temperature, together with 2 g of tin~
; 5 octoat~, to 2450 g of an isocyanate prepolymer which has an isocyanate content of 3.4% and which was obtained by known methods from a bifunctional polypropylene glycol (hydroxyl ~`` number 56) and hexamethylene diisocyanate.
~` The blocked amine of the above formula was -` 10 obtained by introducing 132 g of N-methyl-N-(3-aminopropyl) , :
ethanolamine or the ~ormula HO-(CH2)2-N-(CH2)3 NH2 into a mixture of 150 ml of isobutyraldehyde and 150 ml of , ~ cyclohexane and then boiling under reflux, using a water separator. When condensation had been completed, all the readily volatile constituents were distilled off and the hydroxyaldimine was used as described.
!',' The reaction of the i~ocyanate prepolymer with the masked a~ine is followed by IR spectroscopy. When the iso-cyanate band has disappeared, the reaction mixture is heated , ~
to a temperature of from 105C to 115C and steam treated ~ with vigorous stirring until no more aldehyde can be detected -~; in the distillate. The residue is then heated to 130C for '~ 30 minutes in an oil pump vacuum. A prepolymer having the following end groups is obtained:
LeA 16,731 -22-....
~.~7S~
, C~3 -o-(cH2)~-N-(cH2)3 NH2 Example S
132 g of N-methyl-N-(3-aminopropyl)-ethanolamine HO-tCH2)2-N-(CH2)3 NH2 ~ 5 are slowly added dropwise with stirring to a mixture of 106 g `~ of freshly distilled benzaldehyde and 200 ml of toluene. When all the ethanolamine has been added, the mixture is boiled under reflux, using a water separator, until about 18 ml of ~`~ water have bee~ removed. When condensation has been com-pleted, the carrier agent is removecl by means of a rotary evaporator.
~` The ~rude hydroxybenzaldimine of the formula , ~(CH2)2-N-(CH2)3-N=CH ~
is introduced into a reaction vessel and 1200 g of the isocya-~15 nate prepolymer used in Example 2 is slowly added at room temperature with vigorous stirring together with 2 g of , ~:
dibutyl tin dilaurate. When the isocyanate band in the IR
spectrum has disappeared, the product is æteam distilled and ~;~ dried as described i~ Example lo A polyfunctional prepoly-.,~
~ 20 mer having the following end groups '`''': C~H :
;~ , 3 is thus obtained.
, ';~.
LeA 16,731 23 xample 6 130 g of N-~-hydroxyethylpiperazine are slowly added dropwise to a mixture of 80 g of isobutyraldehyde and 200 ml of cyclohexane. The xeaction mixture is then boiled : 5 under reflux, using a water separator, until about 18 ml of water have been remo~ed. The carrier agent and excess alde-hyde are distilled off at reduced pressure.
~ .
184 ~ of the resulting hydroxyenamin~ of the form--~ ula ~.~
HO (CH2)2 N~---~N-cH=c \
are slowly added dropwise at temperatures of between 30C and 40C to 1900 g of the isocyanate prepolymer used in Example 3, to which 2 g of tin octoate have been added. When the addition reaction has been completecl, hydrolytic decomposi-~- 15 tion of the polyenamine and dehydration are carried out as indicated in Example 1.
. .
The product obtained is a higher molecular weight polyamine having the following end groups:
. -O-(CH2)2-N N-H
~,',' ~ .
~ 20 Example 7 .:"' ' ~i 80 parts by weight of a polypropylene-polyethylene ~;: oxide which has been started on trimethylolpropane and has the hydroxyl number 35 are mixed with 20 parts by weight of the polyamine prepared in Example 4 and the mixture is foamed up in an open cardboard box with 51 g of tol~ler~ediisocyanate (65~ 2,4-isomer9 35~
Le A 16 731 - 24 -107S~7 2,6-isomer) with the addition of 4.5 parts of water, 1.2 parts of a polyether siloxane and 0.15 parts of tin octoate.
An open celled polyurethane-polyurea foam having the fol-lowing properties is obtained:
Density 35 kg/m3 . (DIN 53 420) Tensile strength 125 k Pa (DIN 53 571) Elongation at break 165% (DIN 53 571) Compression strength 5.3 k Pa (DIN 53 577) ~; .
-;
:, , ' Y~
.:
':
.' ;
~ .
., ~
:
~, ...
~"', I
LeA 16,731 -25-.~ :
. .
'- !~ I .
~753~
The polyamines of the general formula (I) are obtained by hydrolysis of compounds of the general formulae (II a) R(-o-c-N~Rl-N-c-o-R2-N=c ~ )n (II a) or (II b~
O H H O ,3,6 / R7 R(.-O-C-N-Rl-N-C-O-R2-N-C=C \ ~n (II b) : in which n, R, Rl, R2 and R3 have the meanings specified above. The groups R4 to R8 r=present alkyl, cycloalkyl, .
LeA 16,731-Ca. - 3a -,.'' ' ' ~' ' ' .' " , , .
.
9~
aryl and aralkyl groups with from 1 to 15 and preferably 1 to 7 carbon atoms or R4 and R5 together or~6 ~nd~-R8~t'ogether form a 5- to-1,2-membered ring and/or R4,tR6 and/or R7 ~
represqnt hydrogen atoms.
..
' 5 Thç polyaldimines, polyketimines or polyenamines requir~ed for the process according to the inventio~ ~re obtained by reaction of isocyanate prepolymers of-the general formula ;~ O H
R~O~C-N-Rl-N=C=O)n (IXI) .. ~
with ~-hydroxymonoaldimines, -ketimines or -enamines of ?
the general formula ~ ~ .
` ,3 ~ / ~ R4 t HO-R2 N-C=C or ~-R2-N=C \
. ' , .
, wherein R2 to R8 have the meanings specified above.
The isocyanate prepolymers (III) used fo~ the pro- ' " . ~ .
15 cess according to the invention are prepared by ba~ically known methods of reacting polyhydroxyl compounds with diiso cyanates.
.', ' " , Suitable polyhydroxyl compounds are in p~rticular polyethers with a molecular weight of from about 200 to 20 about 10,000, preferably 1000 to 6000, containing at least 2, generally 2 to 8 and preferably 2 to 3 hydroxyl groups.
The hydroxyl polyethers which may be used in the invention are known per se and may be prepared, for example, by polymerization of epoxides such as ethylene oxide, propyl-LeA 16,731 ~4-. . .
~5~
ene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlarohydrin. The polymerization may be of the oxides themselves, for example, in the presence of boron trifluoride, or by addition reactions of these epoxides, either as mix-tures or successively, to starting components containing reactive hydrogen atomsD Such starting compounds include water~ alcohols or amines, e.g. ethylene glycol, propylene-1,3- or -1,2-glycol, trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ammonia, e-thanolamine or ethylene-- 10 diamine. Sucrose polyethers such as those described, for example, in German Auslegeschriften 1,176,358 and 1,064,938 may also be used. It is in many cases preferred to use polyethers which contain predominantly primary hydroxyl groups (up to.90~ by weight, based on all the hydroxyl ; 15 groups present in tpe polyether). Polyethers which have been modified,with vinyl polymers, Eor example, the compounds obtained by the polymeri2ation of styrene and acrylonitrile in the presence of polyethers as described in U.S. Patents 3,383,351; 3,304,273; 3,523,093 and 3,110,695 and German Patent 1,152,536 are also suitable. Polybutadienes con-taining hydroxyl groups may also be used.
Polythioethers and polyacetals are also $uitable for the process of the invention. Polyesters may also be used if the polyamines which are the subject o~ the present ~; 25 invention carry secondary amino groups.
Suitable polyesters with hydroxyl groups include, for example, the reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added, with polybasic, preferably dibasic carboxylic acids. If desired~ the corresponding polycarboxylic acid anhydrides LeA 16,731 -5-~75~5~7 or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof may be used instead of the free poly-carboxylic acids for preparing the polyesters. The polycar-boxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heteroe~yclic and they may be substituted, ~or example, by h~,Llogen atoms, and/or may be unsaturated. The following are examples of suitable polycarboxylic acids:
Succinc acid; adipic acid; azelaic acid; sebacic acid;
phthalic acid; isophthalic acid; trimellitic acid; phthalic ,, acid anhydride; tetrahydrophthalic acid anhydride; hexa-hydrophthaliq acid anhydride; endomethylene tetrah~dro-phthalic acid anhydride; glutaric acid anhydride; ~aleic acid; maleic acid anhydride; fumaric acid; dimethylterephtha-' late and b,is~g,lycol terephthalate. ~uitable polyhydric alcohols include, f~or example, ethylene glycol; propylene-1,2- and -1,3-~glycol; butylene-1,4- and -2,3-glycol; hexane-1,6-diol; octane-1,8-diol; neopenty:L glycol; cyclohexane : dimetha~ol (1,4-bis-hydroxymethylcyclohexane); 2-m~thyl-1,3-pro~anediol; glycerol; trimethylolpropane; he~ane-1,2,6-triol; butane-1,2,~-triol; trimethylolethane; pentaerythritol;
quinitol; mannitol and sorbitol; methyl glycoside; di-ethylene glycol; triethylene glycol; tetraethylene glycol;
polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol and polybutylene glycols. Poly- -esters of lactones such as s-caprolactone or hydroxycar-boxylic acids such as ~-hydroxycaproic acid, may also be , used.
~- Among the polythioethers which should be particu-larly mentioned are the condensation products obtained by reacting thiodiglycol on its own and/or with other glycols, ~ LeA 16,731 -6-~7~7 dicarbo~ylic acids, formaldèhyde, aminocarboxylic ~cids or amino alcohols. The products obtained are polythi~ mixed ethers, polythioether esters or polythioether ester amides, dependipg on the co-components.
, ~
Suitable polyacetals include, for example, the compounds which can be prepared from glycols such as diethylene y~ycol, triethylene glycol, 3,4'-dioxethoxy-diphenyldimethyl methane, hexanediol and formaldehyde.
Suitabl~ polyacetals may also be obtained by the polymeri-æation pf eyelic acetals.
Sultable polycarbonates with hydroxyl grpups include thosç known per se which ean be obtained, ~or example, by t~e reaction o~ diols such as propane-1,3-diol, butane-1,4-diol and~or hexane-1,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates such as diphenylcarbonate or phosgene~
The isocyanates used as starting compone~ts for the pre~aration of the isocyanate prepolymers required accordipg to the invention may be any number of known iso-cyanates but are preferably bifunctional aliphatic, cyclo-aliphatic, araliphatic, aromatic or heterocyclic isocyanates of the kind which have been described, for example, by W.
Sie~ken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. The following are specific examples: Ethylene diisocyanate; tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate; dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate; eyclohexane-1,3- and -1,4-diisoeyanate and any mixtures of these isomers; l-isoeyanato-3,3,5-trime~hyl-5-isoeyanatomethyl-cyclohexane as described in Ger~an LeA 16,731 -7-Auslegeschrift 1,202,785 and U.S. Patent 3,401,190; hexa-hydrotolylene-2,4- and -2,6-diisocyanate and any mixtures ; of these isomers; hexahydro-1,3- and/or 1,4-phenylene - diisocyanate; perhydro 2,4'- and/or 4,4'-diphenylmethane diisocyanate; phenylene-1,3- and -1,4-diisocyanate;
tolylene-2,4- and -2,6-diisocyanate and any mixtures of these isomers; diphenylmethane-2,4'- and/or 4,4'-diisocyanate and naphthyl~ene-1,5-diisocyanate.
The following are examples of hydroxy~mineS
r which are sultable for the process of the present invention~
2-aminoethanpl; 2-methylaminoethanol; 1-amino-2-propanol;
3~amino-1-propanol; 4-amino-1-butanol; 4-amino-2-butanol;
2-amino-2-methyl-propanol; 5-amino-1-pentanol and 6-amino-l-hexanol.
Particularly suitable, however, are those hydroxy-amines in which the two functional groups are separated by at least 6 atoms or by a ring. These include 7-amino-1-heptanol; 10-amino-1 decanol; 12-amino-1-dodecanol; 4-(2-aminoethyl)-(2-hydroxyethyl)-benzene; 4-~-hydroxyethyl-aminobe~zene and N-~-hydroxyethyl-piperazine. Hydroxya~ineS
having hetero atoms as represented by the following formulae may also be used , . .
HO-(CH2)2-O-(CH2)3 NH2 HO (CH ) -O-(CH ) -NH
HO-(CH2)5-O-(CH2)3 NH2 HO-(CH2)6-O-(CH2)3 NH2 HO-(CH2)2-O-(cH2)2 (C~l2)3 2 LeA 16,731 -8 ~' ~, .
HO-CH2 ~ CH2-0 (CH2)3 2 Ho-(cH2)2-N-(cH2)3 NH2 These are prei~erably obtained by the monoaddition of acrylo-nitril~ to glycols or to N-substituted hydroxyamineS fol-lowed ~y reduction.
.
The followin~ aldehydes, for example, may be used for blocking the NH functional group: Acetaldehyde;
propio~aldehyde; n-butyraldehyde; isobutyraldehydq; n-valeraldehyd~; isovaleraldehyde; caproic aldehyde; heptenal;
3-formyl-heptane; formylcyclohexane; l- and 2-met~yl-4-formyl-cyclohexane-(1), phenyl acetaldehyde; 3-phenylpro-pionaldehyde;'benzaldehyde; chlorobenzaldehydes; ~ethylbenz-aldehy~es and cinn~aldehyde.
The follo~ing are examples o~ suit;able ketonss: Acetone;
methy~ ethyl ketone; methyl n-propyl ketone, methyl-isobutyl ^- ketone; diethyl-ketone; methyl-n-amylketone; diiso';;lutyl ketone;
~methyl--t-butyl-ketone; methyl-n-heptyl ketone; acetony-~ acetone;
.:
acetophenone; propionphenone; cyclopentanone; cyclohexa-none; l-methylcyclohexanone-(2), l-cyclohexyl cyclohexanone-(2); cyclohexadione-(1,4); cyclododecanone; hydrindone and tetralone.
:
~' Using the above mentioned reactants ketimines aldimines and/or enamines are obtained according to processes kno~n in the art (compare Robert WO Layer, The Chemistry of Imines~ Chemical Reviews, page 489 and following, vol 63 (1963); ~lonographie "Enamines: Synthesis, Structure and Reactions, edited by A. Gilbert Cook, published'by Marcel Dekker, New York and London, 1969).
., .
~ Le A 16 731 - 9 ~
-, " . . . .
: . . .
`
The isocyanate prepolymer~ are prepared by methods known per se, preferably employing ~emperatures of between about 10C and about 140~C. The NCO/OH equivalent ratio of the reactants employed is generally between abcut 1.5:1 and about 6:1, preferably between 2:1 and 4:1. The OH/NCO
reactianmaybe accelerated if desired by the addition of suitable cat~lysts for this reaction. The excess of mono-., , ~ .
' ' .
. . , .' ~ .
.~' ' .
` '` ' .
", , ` Le A 16 731 _ 9 a -... . . . . . . . . .. .. . . ....
~o?75~
- meric diisocyanate is preferably subsequently remored partly or completely in known manner.
The subsequent reaction of the resulting isocya-nate prepolymers with the N-blocked amino alcohols is also carried out by methods conventionally employed in isocya-nate chemistry. One preferred method, in which all unwanted side reactions are substantially suppressed, consists of continuously adding the isocyanate prepolymer to the ~
hydroxyamine~ with blocked amino group at temperatures of between about 20C and about 120C, preferably between 20C
and 60C, with vigorous stirring. Catalys~s may also be ;~ used for this reactîon if desired. The two reactants are -~ pxeferably employed in a stoichiometric ratio of 1:1 (based on isocyanate and hydroxyl). A slight excess of hydroxyl compound may be used if desired.
. . .
~' .
~he resulting blocked polyamines are converted into the free polyamines according to the invention by ~` hydrolysis. Removal of the carbonyl compounds may be - ; carried out, for example, by treating ~he blocked polyamine ~- 20 with water or with a water/solvent mixture at temperatures between 20C and 120C and then distilling off the carbonyl -~ compound and excess water and, if necessary, solvent at a reduced pressure and elevated temperature.
~he preferred method, however, consists of injecting steam at elevated temperatuxe (about 100 to 130C) into the ~ blocked polyamine and then freeing the resulting polyamine - ~ from residual water at reduced pressure when the reaction i ~ ~
has been completed.
- LeA 16,731 10-ii39~7 , The re~ulting prepolymers with amino end groups can then be used for the isocyanate polyaddition process either alone or as mixtures with polyol~ and/or other active ~ hydrogen containing compounds.
: S The compounds according to the invention may also be used for various condensatio~l reactions, for example, with polycarboxylic acids or polycarboxylic acid derivatives ` or formaldehyde, e.g~ for the preparation of polyamides, ;~ polyester amides and cross-linked polyhexahydrotriazines.
~':
The preferred field of application of the poly-amines according to the invention lies in the production of polyurethane resins, in particular foams. For this purpose;
~- they may, if desired, be used in col~ination with higher molecular weight polyhydroxyl compounds, for example, of . ~ ~
`. 15 the kind already described above, and/or with low molecular :`~ weight chain lengthening agents,in the reaotion with polyisocy-~,. ana~e~.
The chain lengthening agents which may be used are compounds with a molecular weight of from about 32 to ` about 4Q0 which contain at least two hydrogen atoms capable - 20 of reacting with isocyanates. The following are examples of such compounds: Ethylene glycol; propylene~ and , .~ .;
1,3-glycol; butylene-1,4- and 2,3-glycol; pentane-1,5-~:- diol; hexane-lt6-diol; octane-1,8-diol; neopentyl glycol;
~ , ~
... ~ 1,4-bis-hydroxymethyl-cyclohexane; 2-methyl-propane-1,3-~ 25 diol: glycerol; trimethylolpropane; hexane-1,2,6-triol;
;`;^.~ trimethylolethane; pentaerythritol; quinitol; mannitol and :; sorbitol; diethylene glycol; triethylene glycol; tetraethyl-:~ ene glycol; polyethylene glycols with a molecular weight of . ~ up to 400; dipropylene glycol; polypropylene glycol~ with LeA 16,731 11 , , ~)'75~9~7 a molecular weight of up to 400; dibutylene glycol; poly-butylene glycols with a molecular weight of up to 400; 4,4'-dihydroxydiphenylpropane; dihydroxymethyl hydroquinone;
ethanolamine; diethanolamine; triethanolamine; 3-amino-S propanol; ethylene diamine; 1,3-diaminopropane; l-mercapto-3-aminopropane; 4-hydroxy- or 4-amino-phthalic acid;
~uccinic acid; adipic acid; hydrazine; N,N'-dimethylhydra-zine and 4,4'-diaminodiphenylmethane.
Suitable reactants for the polyamines of the inven-tion, apart from the diisocyanates already mentioned above, .
include the followingo Triphenylmethane-4,4',4"-triisocya-nate, polyphenyl-polymethylene-polyisocyanatPs of the kind described, for example, in British Patents 874,430 and 848,671 which can be obtained by aniline-formaldehyde con-densation followed by phosgenation; m- and p-isocyanatophenyl-sulphonylisocyanates according to U.S. Patent 3,454,606;
~ perchlorinated aryl polyisocyanates such as those described, :~ ~ for example, in German Auslegeschrift 1,157,601 (U.S. Patent 3,277,138); polyisocyanates hav.ing carbodiimide groups as described in German Patent 1,092,007 ~U.S. Patent 3,152,162);
~: the diisocyanates described in U.S. Patent 3,492,330; poly-, .
`~ isocyanates with allophanate groups as described e.g. in British Patent 994,890; Belgian Patent 761,626 and published Dutch Patent Application 7,102,524; polyisocyanates with : 25 isocyanurate groups as described e.g. in U.S. Patent 3,001,973; German Patents 1,022,789; 1,222,067 and 1,027,394 and German Offenlegungsschriften 1,929,034 and 2,004,048;
polyisocyanates with urethane groups hS described e.g. in Belgian Patent 752,261 and U.S. Patent 3,394,164; polyiso-cyanates having acylated urea groups according to German Le~ 16,731 -12-, .. ..... .. .
Patent 1,230,778; polyisocyanates with biuret groups as described e~g. in German Patent 1,101,394 (U.S. Patents 3,124,605 and 3,201,372) and British Patent 889,050; poly-isocyanates prepared by telomerization reactions as described e.g. in U.S. Patent 3,654,106; polyisocyanates having ester groups, for example, hose mentioned in British Paten~s 965,474 and 1,072,956; U.S. Patent 3,567,763 ~ and German Patent 1,2317688; reaction products of the above--~ mentioned isocyanates with acetals in accordance with German ~i 10 Patent 1,072,385 and polyisocyanates containing polymeric fatty acid groups according to U.S. Patent 3,455,883.
The distillation residues still containing isocya-~; nate groups from the commercial production of isocyanates may also be used, if desired as solutions in one or more of the above-mentioned polyisocyanates. Any mixtures of the above-mentioned polyisocyanates may also be used.
When producing foams from the polyamines of the present invention, water and/or readily volatile organic ~'!,`,~ substances are used as blowing agents. The following are `~ 20 examples of suitable organic blowing agents: Acetone; ethyl .
~i acetate;halogenated alkanes such as methylene chloride;
~, . . .
chloroform; ethylidene chloride; vinylidene chloride; mono~
~`~ fluorotrichloromethane; chlorodifluoxomethane; and dichloro-difluoromethane; also butane, hexane, heptane and diethyl-;
ether. The effect of a blowing agent can also be obtained by the addition o~ compounds which decompose at temperatures above room temperature with the liberation of gases such as nitrogen, e.g. azo compounds such as azoisobutyric acid nitrile. Other examples of blowing agents and details con-cerning the u~e of blowing agents may be found in Kunststoff-LeA 16,731 -13-' ~5~'7 Handbuch, Volume VII, published by Vieweg and ~ochtlen, Carl~Hanser-Verlag, Munich 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
Catalysts may often be advantageously used. Suit able catalysts are known per se, for example, tertiary amines such as triethylamine; tributylamine; N-methylmorpholine;
~ N-ethylmorpholine; N-cocomorpholine, N,N,N',N'-tetramethyl-;~ ethylenediamine; 1,4diaz~bicyclo-(2 t 2,2)-octane; N-methyl-N'-dimethyl-aminoethyl-piperazine; N,N-dimethylbenzylamine;
bis-(N,N-diethylaminoethyl)-adipate; N,N-diethylbenzylamine;
pentamethyldiethylena triamine; N,N-dimethylcyclohexylamine; :~
~ N,N,N',N'-tetramethyl-1,3-butanediamine; N,N-dimethyl~
:~ phenylethylaminet 1,2-dimethylimidazole and 2-methylimida-zole. The known Mannich bases obtained ~rom secondary amines such as dimethylamine, and aldehydes, preferably . formaldehyde; or ketones such as ac~tone, methyl ethyl ketone or cyclohexanone; and phenols such as phenol, nonyl-phenol or bis-phenol may also be used as catalysts.
The following are example~ of tertiary amines having isocyanate-reacti~e hydrogen atoms which may be used as catalysts: Trie~hanolamine; triisopropanolamine; N-methyl-diethanolamine; N-ethyl-diethanolamine; N,N-dimethyl-ethanolamine and their reaction products with alkylene .. ~`; oxides such as propylene oxide and/or ethylene oxide.
; ~..................................................................... .
~,, .
Silaamines having carbon-silicon bonds may also be used as catalysts, for example, compounds described in Ger-~ man Patent 1,229,290 (corresponding to U.S. Patent 3,620,984), :- such as 2,2,4-trimethyl-2-silamorpholine or 1,3-diethylamino-methyl-tetramethyl disiloxane.
LeA 16,731 -14-~7S397 Other suitable catalysts include basic nitrogen compounds such as tetraalkylammonium hydroxides; alkali metal hydroxides such as sodium hydroxide; alkali metal phenolates such as sodium phenolate and alkali metal alcohols such as sodium methylate. Hexahydrotriazines may also be used a~ catalysts.
;
Organic metal compounds may also be used as cata-lysts according to the invention. ~hese particularly include organic tin compounds.
The organic tin compounds used are preferably di-valent tin salts of carboxylic acids, such as tin(II) ace--~ tate; tin(II) octoate; tin(II) ethyl hexoate and tin(II) ; laurate, and the tetravalent tin compounds such as dibutyl ~; tin oxide; dibutyl tin dichloride, dibutyl tin diacetate;
dibutyl tin dilaurate; dibutyl tin maleate or dioctyl tin diacetate. The above mentioned catalysts may, of course, also be used as mixtures.
.~, i~ Other examples of catalysts which may be used according to the invention and the action of the catalysts have been described in Xunststoff-Handbucht Volume VII, pub-lished by Vieweg and Hochtlen, Carl-Hanser-~erlag, Munich ~i' 1966, e.g. on pages 96 to 10~
The catalysts are generally used in a quantity of .. .
~- between about 0.001 and 10% by weight, based on the polyamine according to the invention.
' "`
Surface active additives such as emulsifiers and foam stabilizers may also be used. Sodium salts of ricino-lei~ sulphonates or salts of fatty acids with amines such as LeA 16,731 -15-.
~75~
oleic acid diethylamine or stearic acid diethanolamine, for example, ar~ suitable emulsifiers. Alkali metal or ammonium salts of sulphonic acids such as dodecylbenzene sulphonic acid or dinaphthylmethane disulphonic acid or of fatty acids such as ricinoleic acid or of polymeric fa ~y acids may also be used as surface-active additives.
:
The most important foam stabilizers are polyether ;~ siloxanes, especially those which are water-soluble. These ~ compounds generally have a polydimethylsiloxane group -~ 10 attached to a copolymer of ethylene oxide and propylene oxide. Foam stabilizers of this kind have been described~
~- for example, in U.S. Patents 2,~34~748, 2,917,480 and 3,629,308.
Reaction retarders may also be used according to the -~ 15 invention, for example, compounds which are acidic in reac-tion such as hydrochloric acid or organic acid halides.
~; Other additives which may be used include cell regulators ~.
;` of the kind known ~ se such as paraffins or fatty alcohols . ............................ -- . .
or dimethylpolysiloxanes; pigments; dyes; flame-retarding agents known per se such as tris-chloroethyl phosphate, tricresyl phosphate, ammonium phosphate and ammonium poly-phosphate; stabilizers against ageing and weathering; plas-ticizers; fungistatic and bacteriostatic substances and fillers such as barium sulphate, kieselguhr, carbon black -~ 25 or whiting.
~ Other examples of surface active additives and foam ~. .
stabilizers which may be used according to the invention and .., ~
~, of cell regulators, reaction retarders, stabilizers, fl~me LeA 16,731 -16-. ~ ~
3~
retardants, plasticiæers, dyes, fillers and fungistatic and bacteriostatic Rubstances and the use and mode of action of these additives have been descxibed in Kunststoff-Handbuch, Volume VII, published by Viewey and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.gO on payes 103 to 113.
When using the polyamines according to the inven~
: tion in the isocyanate polyaddition process, the components ~: are reacted together by the known one-shot, prepolymer or ~ semiprepolymer process, in many cases using mechanical devices such as those described in U.S. Patent 2,764,565.
Processing apparatus of the kind which may be used according to the invention have been described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-~: . Verlag, Munich 1966, e.g. on pages 121 to 205.
When producing foams according to the invention, ~- the foaming reaction is often carried out in molds. The ~ reaction mixture is introduced into a mold which may be ;~; made of a metal such as aluminum or a plastics material ~; such as an epoxide resin and it foams up inside the mold .:; 20 to give rise to the molded article. This foaming process .
. may be carried out so that the molded product has a cellu-~` lar structure on its surface or it may be carried out to produce a product with a non-cellular skin and cellular ~-~ core. According to the invention, the quantity of foamable ~, .
. 25 reaction mixture introduced into the mold may be just ; ~ sufficient to fill the mold with foam or if desired, a :~ larger quantity of foamable reaction mixture may be used, in which case the foaming process is said to be carried out under conditions of "overcharging". This procedure has already been described~ for example, in ~.S. Paten~s LeA 16,731 -17-:, 3,178,490 and 3,132,104.
. .
When foaming is carried out inside molds, so-called external mold release agents known per se, such as silicone oils, are frequently used. Alternatively, so-S called internal mold release agents may be used, optionally in combina~ion with external mold release agents,for example, as disclosed in Gexman Offenlegungsschriften 2,121,670 and 2,307,589.
. Cold setting foams may also be produced according to the invention as described in see British Patent 1,162,517 and German Offenlegungsschrift 2,153,086.
~ .
Fo~ns may, of course, also be produced by the ~ prooess of block foaming or by the laminator process known : ~ per se~
The following Examples serve to explain the process of the invention. The figures given refer to parts by , ~: weight or percentages by weight unless otherwise indicated~
, :
,~,................................................................... . .
. . ,. ~ .
, ....
"~
~ ~.', .
.'~`.' .
;. ~`~'. .
. j .
LeA 16,731 -18-' Example 1 A solution of 234 g of l-aminohexanol (CH2)6 NH2 in 400 ml of methyl isobutyl ketone is boiled under reflux using a water separator until about 36 ml of water have been removed. The excess ketone is then distilled off at reduced pressureO The resulting hydroxy ketimine 0- (CH2 ) 6-N=C
:, \
-~ ~CH2~CH(~H3)~
~ is slowly added at ~emperatures of between 20C and 30C to ;~ 10 2340 g o~ an isoc~anate prepolymer having an isocyanate con!~ent ~ o~ 3.5 % (the i~ocyanate prepolymer was prepared by known .
methods from a bifunctional polypropylene glycol (OH number 56) and hexamethylene diisocya~ate). The OH/NCO reaction is catalyzed by the addition of 1 g of tin-(II) octoate.
. .
When the addition reaction has been completed, as indicated by IR spectroscopy, the reaction mixturP is heated to a temperature of between 110C and 120C and steam dis-,.. .
tilled until no ketone can be detected in the distillateO
The residue is then rapidly hea~ed to 130C and the slight ~ /
'i~ 20 residue of water is distilled off, using an oil pump vacuum.
,, ~
~; After about 30 minutes, the reaction mixture left behind ,i. . .
~ contains less than 0.1% of water. The resulting product i~ is a higher molecular weigh diamine which has mainly the following end groups:
, ~1 :, LeA 16,731 -19-;' ~ ` ~
~7~ 97 H O
-N-C-O-(CH ) -NH
Example 2 230 g of the hydroxyaldLmine of the following formula ;~ 5 HO~ 2)6-O-(CH2)3-N=C-CH \
C~l are added over a period of one hour at temperatures of about ~ 40C to 1200 g of an isocyanate prepolymer having an isocya-,~ nate content of 3.5% which has been prepared by known methods ~ of reacting a polypropylene glycol (having a hydroxyl num-: :.
ber of 56 and a molecular weight of 2900 which had been prepared from trimethylolpropane and propylene glycol) with ::
isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane.
The hydroxyaldimine was obtained by the intro-; duction of 175 g of 1,6-hexanediol-1(-3-aminopropyle~her) :
into 150 ml of isobu~yraldehyde, followed by boiling under reflux a~d ~epara~o~ o~ water. The exc~s8 aldehyde wa then di~tlll~d off ~t reduc~d pre~ure.
,, ~ ~ . .
The reaction of the hydroxyaldimine with the iso--;~ cyanate prepolymer is catalyzed with 0.8 g of tin-(II) octoate. The resulting prepol~mex which has aldimine end -~ groups 1~ treated as described in Example 1. A prepolymer '~ with the following end groups is obtained:
H O
,........................... , -N-C-O-(CH2)6-O-(c~2)3 N~2 ..~
~ LeA 16,731 -20-, .. . .
~` ~
~75i3~ 17 243 g of the following ke~imine HO-(CH2)2-O-(c~2)2-o (CH2~3 O
are slowly added at temperatures below 40C to 1900 g of an : S isocyanate prepolymer (2.2% NCO) which has been obtained by known methods of reacting a copolymer of propylene oxide and ethylene oxide which has been started on trLmethylol , : propane and has a hydroxyl number of 35 with tolylene ~: diisocyanate.
; 10 The ketimine was obtained by introducing 163 g of ~, diethylene glycol-(3-propylamine)-ether . .
.:.:
;~ HO-(CH2)2-O-(CH2)2 (CH2)3 2 ., i ~ into a mixture of 105 g of cyclohexanone and 200 ml o tolu-. ~, .
~ ene and then boiling the reaction product, using a water .
- 15 separator. When about 18 ml of water had been removed in . . . ~
;~: this way, the carrier agen~ and excess ketone were removed under vacuum.
~. The reaction between isocyanate prepolymer and -~ hydroxyketimine is catalyzed by the addition of 2 g of 20 dibutyltin dilaurate. The ketimine prepolymer i~ then decom-posed as in Examplip 1.
` ,i A polyfunctional amino prepolymer haviny the fol~
lowing end group~
(CH2)2 O-(CH~)2 (CH2)3 ~; 25 is obtained.
- LeA 16,731 -21--~7S;397 ~,~
186 g of the hydroxyaldimine of the formula -(CH2)2-N-(CH2)3-N=C-C~(CH3)2 are added at room temperature, together with 2 g of tin~
; 5 octoat~, to 2450 g of an isocyanate prepolymer which has an isocyanate content of 3.4% and which was obtained by known methods from a bifunctional polypropylene glycol (hydroxyl ~`` number 56) and hexamethylene diisocyanate.
~` The blocked amine of the above formula was -` 10 obtained by introducing 132 g of N-methyl-N-(3-aminopropyl) , :
ethanolamine or the ~ormula HO-(CH2)2-N-(CH2)3 NH2 into a mixture of 150 ml of isobutyraldehyde and 150 ml of , ~ cyclohexane and then boiling under reflux, using a water separator. When condensation had been completed, all the readily volatile constituents were distilled off and the hydroxyaldimine was used as described.
!',' The reaction of the i~ocyanate prepolymer with the masked a~ine is followed by IR spectroscopy. When the iso-cyanate band has disappeared, the reaction mixture is heated , ~
to a temperature of from 105C to 115C and steam treated ~ with vigorous stirring until no more aldehyde can be detected -~; in the distillate. The residue is then heated to 130C for '~ 30 minutes in an oil pump vacuum. A prepolymer having the following end groups is obtained:
LeA 16,731 -22-....
~.~7S~
, C~3 -o-(cH2)~-N-(cH2)3 NH2 Example S
132 g of N-methyl-N-(3-aminopropyl)-ethanolamine HO-tCH2)2-N-(CH2)3 NH2 ~ 5 are slowly added dropwise with stirring to a mixture of 106 g `~ of freshly distilled benzaldehyde and 200 ml of toluene. When all the ethanolamine has been added, the mixture is boiled under reflux, using a water separator, until about 18 ml of ~`~ water have bee~ removed. When condensation has been com-pleted, the carrier agent is removecl by means of a rotary evaporator.
~` The ~rude hydroxybenzaldimine of the formula , ~(CH2)2-N-(CH2)3-N=CH ~
is introduced into a reaction vessel and 1200 g of the isocya-~15 nate prepolymer used in Example 2 is slowly added at room temperature with vigorous stirring together with 2 g of , ~:
dibutyl tin dilaurate. When the isocyanate band in the IR
spectrum has disappeared, the product is æteam distilled and ~;~ dried as described i~ Example lo A polyfunctional prepoly-.,~
~ 20 mer having the following end groups '`''': C~H :
;~ , 3 is thus obtained.
, ';~.
LeA 16,731 23 xample 6 130 g of N-~-hydroxyethylpiperazine are slowly added dropwise to a mixture of 80 g of isobutyraldehyde and 200 ml of cyclohexane. The xeaction mixture is then boiled : 5 under reflux, using a water separator, until about 18 ml of water have been remo~ed. The carrier agent and excess alde-hyde are distilled off at reduced pressure.
~ .
184 ~ of the resulting hydroxyenamin~ of the form--~ ula ~.~
HO (CH2)2 N~---~N-cH=c \
are slowly added dropwise at temperatures of between 30C and 40C to 1900 g of the isocyanate prepolymer used in Example 3, to which 2 g of tin octoate have been added. When the addition reaction has been completecl, hydrolytic decomposi-~- 15 tion of the polyenamine and dehydration are carried out as indicated in Example 1.
. .
The product obtained is a higher molecular weight polyamine having the following end groups:
. -O-(CH2)2-N N-H
~,',' ~ .
~ 20 Example 7 .:"' ' ~i 80 parts by weight of a polypropylene-polyethylene ~;: oxide which has been started on trimethylolpropane and has the hydroxyl number 35 are mixed with 20 parts by weight of the polyamine prepared in Example 4 and the mixture is foamed up in an open cardboard box with 51 g of tol~ler~ediisocyanate (65~ 2,4-isomer9 35~
Le A 16 731 - 24 -107S~7 2,6-isomer) with the addition of 4.5 parts of water, 1.2 parts of a polyether siloxane and 0.15 parts of tin octoate.
An open celled polyurethane-polyurea foam having the fol-lowing properties is obtained:
Density 35 kg/m3 . (DIN 53 420) Tensile strength 125 k Pa (DIN 53 571) Elongation at break 165% (DIN 53 571) Compression strength 5.3 k Pa (DIN 53 577) ~; .
-;
:, , ' Y~
.:
':
.' ;
~ .
., ~
:
~, ...
~"', I
LeA 16,731 -25-.~ :
. .
Claims (3)
1. A process for the production of polyurethane resins, comprising reacting an isocyanate and polyamines of the formula:
in which n represents an integer of between 2 and 10, R represents an n-valent organic group such as can be obtained by the removal of n hydroxyl groups from a polyhydroxyl compound which has an average molecular weight of between about 200 and about 10,000 and which may contain urethane groups, R1 represents an alkylene, cycloalkylene, arylene or aralkylene group having 2 to 15 carbon atoms and R2 represents an alkylene, cycloalkylene, arylene or aralkylene group having from 2 to 15 carbon atoms and R3 represents hydrogen or an alkyl or cycloalkyl group having from 1 to 9 carbon atoms or it represents an alkylene group which together with R2 and -NH- forms a 5-membered or 6-membered ring.
in which n represents an integer of between 2 and 10, R represents an n-valent organic group such as can be obtained by the removal of n hydroxyl groups from a polyhydroxyl compound which has an average molecular weight of between about 200 and about 10,000 and which may contain urethane groups, R1 represents an alkylene, cycloalkylene, arylene or aralkylene group having 2 to 15 carbon atoms and R2 represents an alkylene, cycloalkylene, arylene or aralkylene group having from 2 to 15 carbon atoms and R3 represents hydrogen or an alkyl or cycloalkyl group having from 1 to 9 carbon atoms or it represents an alkylene group which together with R2 and -NH- forms a 5-membered or 6-membered ring.
2. The process of Claim 1 wherein R2 represents an alkylene, cycloalkylene, arylene or aralkylene group having from 6 to 12 carbon atoms.
3. The process of Claim 1 wherein said R2 groups optionally contain -O- or R3 groups.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752546536 DE2546536A1 (en) | 1975-10-17 | 1975-10-17 | HIGH MOLECULAR POLYAMINE AND THE PROCESS FOR THEIR PRODUCTION |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1075397A true CA1075397A (en) | 1980-04-08 |
Family
ID=5959389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA262,098A Expired CA1075397A (en) | 1975-10-17 | 1976-09-27 | Process for the production of polyurethane resins |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4224417A (en) |
| JP (2) | JPS5250396A (en) |
| AT (1) | AT353009B (en) |
| AU (1) | AU504102B2 (en) |
| BE (1) | BE847333A (en) |
| CA (1) | CA1075397A (en) |
| DE (1) | DE2546536A1 (en) |
| ES (1) | ES452450A1 (en) |
| FR (1) | FR2328006A1 (en) |
| GB (1) | GB1531578A (en) |
| IT (1) | IT1069070B (en) |
| SE (1) | SE7611420L (en) |
Families Citing this family (74)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3112118A1 (en) * | 1981-03-27 | 1982-10-07 | Bayer Ag, 5090 Leverkusen | POLYETHERPOLYAMINES CONTAINING POLYMERISATE, METHOD FOR PRODUCING THESE POLYAMINES AND THE USE THEREOF AS CONSTRUCTION COMPONENT FOR PRODUCING POLYURETHANES |
| US4525590A (en) * | 1981-07-29 | 1985-06-25 | Bayer Aktiengesellschaft | Simplified process for the production of polyamines by the alkaline hydrolysis of compounds containing NCO-groups |
| CA1221383A (en) * | 1981-08-07 | 1987-05-05 | Werner Rasshofer | Polyamines, a process for the production of polyamines and their use in the production of polyurethanes |
| US4723032A (en) * | 1981-11-12 | 1988-02-02 | Bayer Aktiengesellschaft | Modified polyamines and a process for their production |
| DE3144874A1 (en) * | 1981-11-12 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYAMINES FROM N-MONOARYL-N ', N'-DIALKYL UREA COMPOUNDS AND THE USE THEREOF FOR BUILDING POLYURETHANES |
| DE3223395A1 (en) * | 1982-06-23 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | PRIMARY AROMATIC AMINO GROUPS, URETHANE GROUPS AND COMPOUNDS WITH POLYESTER GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A BUILDING COMPONENT OF POLYURETHANES |
| DE3223400A1 (en) * | 1982-06-23 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | POLYAMINES, METHOD FOR PRODUCING POLYAMINES AND THE USE THEREOF FOR PRODUCING POLYURETHANES |
| DE3223397A1 (en) * | 1982-06-23 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | ONE-STEP PROCESS FOR PRODUCING POLYAMINES FROM NCO-PREPOLYMERS, POLYAMINS AND THE USE THEREOF FOR PRODUCING POLYURETHANES |
| DE3223398A1 (en) * | 1982-06-23 | 1983-12-29 | Bayer Ag, 5090 Leverkusen | POLYAMINES, METHOD FOR PRODUCING POLYAMINES AND THE USE THEREOF FOR PRODUCING POLYURETHANES |
| DE3227219A1 (en) * | 1982-07-21 | 1984-02-02 | Bayer Ag, 5090 Leverkusen | ONE-STEP PROCESS FOR PRODUCING POLYAMINES FROM NCO-PRAEPOLYMERS, POLYAMINS AND THE USE THEREOF FOR PRODUCING POLYURETHANES |
| EP0103996B1 (en) * | 1982-09-17 | 1988-09-21 | Imperial Chemical Industries Plc | Polyurea dispersions in organic isocyanates |
| DE3244913A1 (en) * | 1982-12-04 | 1984-06-07 | Bayer Ag, 5090 Leverkusen | REACTION COMPONENTS CONTAINING AMINO GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE |
| DE3401753A1 (en) * | 1984-01-19 | 1985-08-01 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF POLYURETHANES, POLYURETHANES WITH AROMATIC AMINO END GROUPS AND THE USE THEREOF |
| DE3446921A1 (en) * | 1984-12-21 | 1986-07-03 | Bayer Ag, 5090 Leverkusen | NEW ALKOXYLATED AMINOPOLYETHER, METHOD FOR THE PRODUCTION THEREOF, AND COAL-WATER SLAVES CONTAINING THE SAME |
| DE3517333A1 (en) * | 1985-05-14 | 1986-11-20 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING STABLE DISPERSIONS OF FINE PARTICULATE POLYISOCYANATES AND THE USE THEREOF |
| DE3530476A1 (en) * | 1985-08-27 | 1987-03-05 | Bayer Ag | POLYAMINES, METHOD FOR THE PRODUCTION THEREOF FROM NCO PREPOLYMERS AND THEIR USE IN THE PRODUCTION OF POLYURETHANES |
| DE3534947A1 (en) * | 1985-10-01 | 1987-04-09 | Bayer Ag | METHOD FOR PRODUCING POLYAMINES, POLYAMINS AND THE USE THEREOF FOR PRODUCING POLYURETHANES |
| US5283364A (en) * | 1985-10-18 | 1994-02-01 | Bayer Aktiengesellschaft | Hydrolysis process for polyamines |
| JPS63105753A (en) * | 1986-10-21 | 1988-05-11 | 株式会社 日本メデイカル・サプライ | Packing method and material for medical product |
| US4935460A (en) * | 1987-03-11 | 1990-06-19 | Ici Americas Inc. | Reaction injection molding compositions |
| DE3713858A1 (en) * | 1987-04-25 | 1988-11-17 | Bayer Ag | AROMATIC POLYAMINE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYURETHANE PLASTICS |
| GB8821183D0 (en) * | 1988-09-09 | 1988-10-12 | Ici America Inc | Composition of matter |
| DE4311922A1 (en) * | 1993-04-10 | 1994-10-13 | Huels Chemische Werke Ag | New polyamines, a process for their preparation and their use |
| DE4311901A1 (en) * | 1993-04-10 | 1994-10-13 | Huels Chemische Werke Ag | New azeomethines, a process for their preparation and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3635908A (en) * | 1969-11-10 | 1972-01-18 | Basf Wyandotte Corp | Process of preparing polyurethane-urea thermoplastic products base on a polyamine carbamate as chain extender |
| DE2166502C3 (en) * | 1971-04-06 | 1982-01-14 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Process for the preparation of new prepolymers containing enamine groups and their use |
| DE2356213C2 (en) * | 1973-11-10 | 1986-11-13 | Schering AG, 1000 Berlin und 4709 Bergkamen | Prepolymers terminated by ketimine groups and processes for their preparation |
| US3941753A (en) * | 1971-04-06 | 1976-03-02 | Schering Aktiengesellschaft | Prepolymers of polyisocyanates with hydroxy-enamines or hydroxy-ketimines |
| DE2325824A1 (en) * | 1973-05-22 | 1974-12-19 | Veba Chemie Ag | POLYURETHANE TWO-COMPONENT VARNISHES |
| DE2418041C3 (en) * | 1974-04-13 | 1982-04-29 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Process for the production of elasticized molded parts according to flat structures |
| DE2637115C3 (en) * | 1976-08-18 | 1980-10-09 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethane ureas |
| DE2718100A1 (en) * | 1977-04-22 | 1978-10-26 | Bayer Ag | METHOD FOR MANUFACTURING POLYISOCYANATE POLYADDITION PRODUCTS |
-
1975
- 1975-10-17 DE DE19752546536 patent/DE2546536A1/en not_active Ceased
-
1976
- 1976-09-27 CA CA262,098A patent/CA1075397A/en not_active Expired
- 1976-10-14 SE SE7611420A patent/SE7611420L/en unknown
- 1976-10-14 GB GB42701/76A patent/GB1531578A/en not_active Expired
- 1976-10-15 IT IT51758/76A patent/IT1069070B/en active
- 1976-10-15 BE BE171543A patent/BE847333A/en not_active IP Right Cessation
- 1976-10-15 JP JP51123031A patent/JPS5250396A/en active Granted
- 1976-10-15 AT AT768576A patent/AT353009B/en not_active IP Right Cessation
- 1976-10-15 FR FR7631163A patent/FR2328006A1/en active Granted
- 1976-10-16 ES ES452450A patent/ES452450A1/en not_active Expired
- 1976-10-18 AU AU18764/76A patent/AU504102B2/en not_active Expired
-
1979
- 1979-01-02 US US06/000,052 patent/US4224417A/en not_active Expired - Lifetime
-
1982
- 1982-04-30 JP JP57071669A patent/JPS5830329B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA768576A (en) | 1979-03-15 |
| JPS5830329B2 (en) | 1983-06-28 |
| US4224417A (en) | 1980-09-23 |
| FR2328006B1 (en) | 1983-01-14 |
| AU504102B2 (en) | 1979-10-04 |
| BE847333A (en) | 1977-04-15 |
| JPS5757051B2 (en) | 1982-12-02 |
| DE2546536A1 (en) | 1977-04-28 |
| JPS57185312A (en) | 1982-11-15 |
| AU1876476A (en) | 1978-04-27 |
| GB1531578A (en) | 1978-11-08 |
| SE7611420L (en) | 1977-04-18 |
| ES452450A1 (en) | 1977-11-01 |
| IT1069070B (en) | 1985-03-25 |
| FR2328006A1 (en) | 1977-05-13 |
| JPS5250396A (en) | 1977-04-22 |
| AT353009B (en) | 1979-10-25 |
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