AU4274489A - Aromatic polyhydroxylpolyamines, a process for their preparation, and their use for the preparation of polyurethane plastics - Google Patents

Abstract

The present invention relates to novel compounds of the general formula <IMAGE> containing terminal aminophenoxy and hydroxyl groups, a process for their preparation, and their use as starting materials in the preparation of cellular or non-cellular polyurethane plastics and foams.

Description

r

Our Ref 291870 FORM 1

AUSTRALIA Patents Act

APPLICATION FOR A STANDARD PATENT

Bayer Aktiengesellschaft, of D-5090 LEVERKUSEN, FEDERAL REPUBLIC OF GERMANY

hereby applies for the grant of a standard patent for an invention entitled

Aromatic polyhydroxylpolyamines, a process for their preparation, and their use for the preparation of polyurethane plastics

which is described in the accompanying complete specification.

Details of basic application(s): 99rl Baaic Application: Country: Date: P 38 34 749.0 FEDERAL REPUBLIC OF GERMANY 12 October 1988

9 9

I 9. The address for service is: ARTHUR S. CAVE CO. ea Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000

999 9

DATED this TENTH day of OCTOBER 1989 9 t 9

Bayer Aktiengesellschaft 9 9 By Its Patent Attorneys ARTHUR S. CAVE CO. It

J.G. SIELY, FIPAA IJ

TO: The Commissioner of Patents COMMONWEALTH OF AUSTRALIA

FEE: 318.00

S010653 10/10/-8

.4'

T I~ 7

(12) PATENT ABSTRACT (11) Document No. AU-A-42744/89 I (19) AUSTRALIAN PATENT OFFICE

(54) Title AROMATIC POLYHYDROXYLPOLYAMINES, A PROCESS FOR THEIR PREPARATION, AND THEIR USE FOR THE PREPARATION OF POLYURETHANE PLASTICS International Patent Classification(s) (51)4 C08G 065/32 C08G 018/50 (21) Application No. 42744/89 (22) Application Date 10.10.89 Priority Data (31) Number (32) Date (33) Country 3834749 12.10.88 DE FEDERAL REPUBLIC OF GERMANY (43) Publication Date :26.04.90 (71) Applicant(s) BAYER AKTIENGESELLSCHAFT (72) Inventor(s) NAME NOT GIVEN (74) Attorney or Agent ARTHUR S. CAVE CO. (57) Claim 1. A compound of the formula

2 R

HO rn-n -R1

NH2 n

wherein R1 is an m-functional residue of an m-functional polyhydroxyl compound having a molecular weight of about 400 to about 8000; R2 is hydrogen or methyl; m is an integer of from 2 to 4; and n is a positive number having an average value of from about 0.05m to about 0.73m.

(11)42744/89 -2- 7. A process for the preparation of a compound of the formula

1 HO- -nR m-n

NH2

wherein R1 is an m-functional residue of an m-functional polyhydroxyl compound having a molecular weight of 400 to about 8000; R2 is hydrogen or methyl; m is an integer of from 2 to 4; and n is a positive number having an average value of from about 0.05m to about 0.73m; comprising reacting, in the presence of an alkaline compound, an m-functional relatively high molecular weight polyhydroxyl compound of the formula

RI(OH)m

with (ii) an n-molar quantity of a compound of the formula

wherein R2 is as defined above and X is halogen, to form an (m-n)-hydroxy n-nitrophenoxy adduct of the

I11I1 ~l.li-L-IIIII~ L1

(11)42744/89

formula

-R 0-

wherein R1 R2 m, and n are as defined above; and hydrogenating said (m-n)-hydroxy n-nitrophenoxy adduct to form the product compound.

Our Ref: 291870

AUSTRALIA FORM Patents Act

COMPLETE SPECIFICATION (ORIGINAL)

Application Number: Lodged:

Complete Specification Lodged: Accepted: Published:

Priority: Related Art:

0@ t 000 Applicant(s): Bayer Aktiengesellschaft 0lr4

D-5090 LEVERKUSEN FEDERAL REPUBLIC OF GERMANY 0 r

0 t 0 Address for Service: ARTHUR S. CAVE CO. itt' Patent Trade Mark Attornerys *00 Level 10, 10 Barrack Street SYDNEY NSW 2000

Complete specification for the invention entitled

"Aromatic polyhydroxylpolyamines, a process for their preparation, and their use for the Stpreparation of polyurethane plastics".

r The following statement is a full description of this invention, including the citc best method of performing it known to me:-

ii

1 5020

I la

AROMATIC POLYHYDROXYPOLYAMINES, A PROCESS FOR THEIR PREPARATION, AND THEIR USE FOR THE PREPARATION OF POLYURETHANE PLASTICS

BACKGROUND OF THE INVENTION This invention relates to novel compounds terminated by aminophenoxy and hydroxy groups, to a process for their preparation, and to their use as a synthesis component in the preparation of optionally cellular polyurethane plastics and foams. Certain polyadducts terminated by aromatic amino groups are known. U.S. Patent 2,888,439 and German Offenlegungsschrift 1,720,646 describe the production of amino polyethers by reaction of nitroarylisocyanates with polyols and subsequent hydro- genation. German Offenlegungsschrift 1,257,427 describes the analogous reaction of azoarylisocyanates with polyols, which after reduction also gives aromatic amino polyethers, U.S. Patent 3,248,424 and German Offenlegungsschrift 1,694,152 describe a ot process in which isocyanate prepolymers are reacted with diamines containing amino groups of different reactivity.

The reactions of isocyanate prepolymers with sulfamic 20 acid in accordance with U.s. Patent 3,184,502, with 'formic acid in accordance with French Patent 1,415,317, or with enamines, aldimines, or ketimines containing hydroxyl groups in accordance with German Offenlegungsschriften 2,116,882 and 2,546,536 also produce, after hydrolysis or saponification, 25 aromatic amino polyethers. The thermal cleavage of urethanes from isocyanate prepolymers and secondary or tertiary carbinols in accordance with German Auslegeschrift 1,270,046 also produces aromatic amino polyethers. In addition, German Offen- L t legungsschriften 2,948,419, 3,223,397, 3,223,398, and 3,223,400 S. 30 describe various single-step or two-step processes for the

Le A 26 440

Li production of aromatic polyamines by hydrolysis of isocyanate prepolymers in the presence of var!ous solvent and catalyst systems. All the previously described processes involve isocyanate intermediate stages and, accordingly, always give products containing additional urethane or urea groups in addition to ether and aromatic amino groups. As a result, these products exhibit an undesirably high viscosity for many appli- cations. Another disadvantage of these additional urethane or urea groups is their relatively poor thermal stability, which adversely affects the heat resistance of corresponding polyurethane plastics, particularly elastomers, produced with these amino polyethers. The ring-opening reaction of isatoic anhydride with polyols provides another possible synthetic route to aromatic polyamines. Amines obtained in this way are described, for example, in German Offenlegungsschriften 2,019,432, 2,619,840, 2,648,774, and 2,648,825 and U.S. Patent 4.180,644. In addition, aromatic amino polyethers are obtained by reaction of polyoxy- alkylene polyols with p-aminobenzoic acid derivatives in Saccordance with Japanese patent applications 59/053,533, t %,I 59/089,322, and 59/199,715. However, the poor reactivity of the aromatic ester amines obtained in this way is not suitable for many applications. European Application 268,849 relates to polyphenoxy- f amines which have more favorable viscosities and, in some cases, exhibit good reactivity with isocyanates. However, in the production of the polyphenoxynitro compounds from which the amines are obtained by hydrogenation, unreacted nitrophenylating agent remains in the amines and must be removed at considerable expense because of serious interference with processing. Accordingly, the object of the present invention is to provide new polyhydroxypolyphenoxy amines under conditions that give complete reaction of the nitrophenylating agent and, in

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L.- particular, produce amines having even lower viscosities than the polyphenoxy amines mentioned above and, optionally, more favorable reactivities. The two-step reaction made possible by the presence of both rapidly reacting amino groups and more slowly reacting hydroxyl groups has a particularly favorable effect, for example, during reaction injection molding. The initially low viscosity permits thorough mixing in the mixing head. After the fast-reacting amino groups have reacted, viscosity increases to such an extent that there are no sealing problems in the mold, even though the product remains a thin liquid long enough to fill the mold completely. This object is achieved by using the compounds Saccording to the invention. SUMMARY OF THE INVENTION The present invention relates to novel aminophenoxy- and hydroxyl-terminated compounds of the general formula oft t 2 it. 20 HO- -R 1 -0- m-n

Goo* NH o NH2 n

wherein 1 R is an m-functional residue of an m-functional polyhydroxyl S,'compound having a molecular weight of 400 to about 8000; R is hydrogen or methyl; m is an integer of from 2 to 4; and n is a positive number having an average value of from about 0.05m to about 0.73m (preferably from 0.15m to 0.70m). *ol The present invention also relates to a process for the preparation of hydroxy- and aminophenoxy-terminated compounds of the general formula

Le A 26 440

yk

2 R

1 HO m-n -R

NH2 n

wherein R1 R2 m, and n are as defined above, comprising reacting, in the presence of alkaline compounds, m-functional relatively high molecular weight polyhydroxyl compounds of the general formula

R1(OH)m

09* with 0*40

*9*9 (ii) an n-molar quantity of compounds of the general formula 0 0040

09 2 00 9 9 t 0 #0

.9,9 X-

NO2

9. 0D 9 wherein R2 is as defined above and X is halogen 00 0 0 (preferably fluorine and more preferably chlorine), 00 09 0 to form (m-n)-hydroxy n-nitrophenoxy adducts of the general formula *09

9 -t

Le A 26 440

4 1

SO R2

HO- r-n -R1 HO m-n R L J NO2 n

wherein R1R2 m, and n are as defined above; and hydrogenating said (m-n)-hydroxy n-nitrophenoxy adducts to form the hydroxy- and aminophenoxy-terminated compounds. The invention further relates to the use of the hydroxy- and aminophenoxy-terminated compounds of the invention as synthesis component in the preparation of polyurethane plastics by the isocyanate polyaddition process. DETAILED DESCRIPTION OF THE INVENTION Starting materials for the process according to the 'invention are relatively high molecular weight polyhydroxyl compounds and (ii) optionally methyl-substituted halonitro- o, 20 benzenes. Suitable polyhydroxyl compounds include relatively high molecular weight compounds having an average molecular weight of from 400 to about 8000 and containing at least 2 to 4 reactive hydroxyl groups per mole (that is, wherein the number of hydroxyl groups is equal to the number Suitable polyhydroxyl icompounds include the polyacetals, polythioethers, poly- carbonates, polyamides, polysiloxanes, polybutadienes, polyesters, polylactones, and polyethers containing hydroxyl groups which are commonly encountered in polyurethane chemistry. Preferred polyhydroxyl compounds include polyethers containing hydroxyl groups, particularly polyalkylene polyethers Scontaining hydroxyl groups.

e A 26 440

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L.-

Suitable polyethers containing hydroxyl groups are known and can be obtained, for example, by polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, and epichlorohydrin, either by themselves or in the presence of a catalyst such as BF3 Suitable polyethers may also be obtained by the addition of such epoxides, either as mixtures or by sequential addition, onto starter components containing reactive hydrogen atoms, such as water, alcohols, or amines, for example, ethylene glycol, 1,3- or 1,2-propylene glycol, trimethylolpropane, 4,4'-dihydroxy- diphenylpropane, aniline, ammonia, ethanolamine, or ethylene diamine. Sucrose polyethers of the type described, for example, in German Auslegeschriften 1,176,358 and 1,064,938, may also be used in accordance with the invention. It is often preferable to use polyethers containing predominantly primary hydroxyl groups (up to 90% by weight, based on all the OH groups present in the ooo. polyether). Also suitable are polyethers modified by vinyl polymers of the type formed, for example, by polymerization of 0o6 styrene and acrylonitrile in the presence of polyethers. So,. 20 U.S. Patents 3,383,351, 3,304,273, 3,523,093, and 3,110,695 and o"a German Patentschrift 1,152,536, as are polybutadienes containing OH groups. 0000 Suitable polyacetals include compounds obtainable from glycols, such as diethylene or triethylene glycol, 4,4'-di- S 25 hydroxyethoxydiphenylmethane, and hexanediol, by reaction with o formaldehyde or by polymerization of cyclic acetals, such as 00 0

o. trioxane. Suitable polycarbonates containing hydroxyl groups are known and can be obtained, for example, by reaction of diols 64 30 (such as 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol), Sdi-, tri- or tetraethylene glycol, or thiodiglycol, with diaryl carbonates (such as diphenyl carbonate) or phosgene. German S Auslegeschrift 1,694,080, 1,915,908, and 2,221,751 and German Offenlegungsschrift 2,605,024.

Le A 26 440

V r pr~

-7-

Suitable polyesters of dicarboxylic acids and diols include those derived from adipic acid and isophthalic acid and linear and/or branched diols, as well as from lactone polyesters (preferably those based on caprolactone) and starter diols. Suitable polythioethers include condensation products of thiodiglycol, either by itself or with other glycols. Polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols 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 invention. It is also possible to introduce amide groups into the polyhydroxyl compounds, for example, in accordance with German Offen- legungsschrift 2,559,372. Polyhydroxyl compounds containing high molecular weight polyadducts or polycondensates or polymers in finely disperse or dissolved form may also be used in accordance with the invention. ,Polyhydroxyl compounds such as these are obtained, for example, 12 by allowing polyaddition reactions (for example, between l 20 polyisocyanates and aminofunctional compounds) or poly- Scondensation reactions (for example, between formaldehyde and phenols and/or amines) to take place in situ in the above-mentioned compounds containing hydroxyl groups. Such processes are described, for example, in German Auslegeschriften 1,168,075 and 1,260,142 and German Offenlegungsschriften ,,2,324,134,2,423,984, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833, 2,550,862, 2,633,293, and 2,639,254. However, in accordance with U.S. Patents 3,869,413 and 2,550,860, it is also possible to mix a prepared aqueous polymer dispersion with a 30 polyhydroxyl compound, followed by removal of the water from the mixture. Polyhydroxyl compounds modified by vinyl polymers of ao,, the type obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers Patents

Le A 26 440

3,383,351, 3,304,273, 3,523,093, and 3,110,695 and German Auslegeschrift 1,152,536) or polycarbonate polyols (German Patentschrift 1,769,795 and U.S. Patent 3,637,909) are also suitable for the process of the invention. Particularly flame-resistant plastics are obtained when polyether polyols that have been modified by graft polymerization with vinyl phosphonic acid esters and optionally (meth)acrylonitrile, (meth)acrylamide, or hydroxy-functional (meth)acrylates in accordance with German Offenlegungsschriften 2,442,101, 2,644,922, and 2,646,141 are used. When modified polyhydroxyl compounds of the type mentioned above are used as starting materials for the polyamines, the compounds thereby obtained often give polyurethane plastics having considerably improved mechanical properties when using the polyisocyanate polyaddition process. Other suitable, although less preferred, polyhydroxyl *r components include organofunctional polysiloxanes containing two terminal isocyanate-reactive groups and structural units of the formula -0-Si(R) 2 where R is CI-C 4 alkyl or phenyl, but 20 preferably methyl. Suitable starting materials for the invention include both the pure polysiloxanes terminated by organo- functional groups and the siloxane-polyoxyalkylene copolymers terminated by organofunctional groups. Particularly preferred organopolysiloxanes correspond to the general formula

SCH3 CH3 4 3 CI3 HO-CH2-Si- -CH2-OH

30 CH CH 3 3 p wherein p is from about 5 to about 29. Such organopolysiloxanes can be obtained in known manner by equilibration of 1,1,3,3-tetramethyl-l,3-hydroxymethyl disiloxane of formula

Le A 26 440 r 1.

-9-

CH3 CH3 HO-CH 2 -Si-0-Si-CH2-OH 1 1 CH3 CH3

with octamethylcyclotetrasiloxane in the presence of sulfuric acid or by the process according to German Auslegeschrift 1,236,505. Suitable starting materials (ii)include optionally methyl-substituted halonitrobenzenes having the general formula

2

X-

\M2

S 20 wherein 2 R is hydrogen or methyl (preferably hydrogen); X is halogen (preferably fluorine and more preferably chlorine). In the preferred halonitrobenzenes the halogen and nitro substituents are preferably arranged in the ortho- or para-position relative to each other. Suitable such starting materials include 2-nitrochlorobenzene, 2-nitrofluorobenzene, 4-nitrochlorobenzene, 4-nitrofluorobenzene, 1-methyl-2-nitro- 3-chlorobenzene, 1-methyl-2-nitro-3-fluorobenzene, 1-methyl- 4-nitro-5-chlorobenzene, 1-methyl-4-nitro-5-fluorobenzene, 1-methyl-2-nitro-6-chlorobenzene, and 1-methyl-2-nitro-6- fluorobenzene. Particularly preferred starting materials (ii) are 2-nitrochlorobenzene and 4-nltrochlorobenzene. Suitable alkaline compounds, which are required for the 35 reaction of polyhydroxyl compounds with the halonitrobentenes include metal hydrides, metal alkoxides, and, preferably,

Le A 26 440

T metal hydroxides. Sodium hydroxide and potassium hydroxide are particularly preferred, especially when used in powdered form. In step of the process of the invention, the halonitrobenzene starting materials (ii) are used in less than the quantity of the polyhydroxyl component In particular, an n-molar quantity of a halonitrobenzene relative to the polyhydroxyl compounds is used, where n is a positive number having an average value of from about 0.05-0.73 times the hydroxyl functionality m (preferably from 0.15-0.70m). Thus, hydroxyl groups will remain in the (m-n)-hydroxy n-nitrophenoxy adducts of the invention. The hydrogen halide released during the reaction of step (a) Smay be neutralized by the addition of metal hydrides, metal alkoxides, and metal hydroxides preferably sodium or potassium hydroxide in at least a stoichiometric quantity. In a particularly preferred embodiment, the alkaline compounds are used in a quantity such that aboutl to 3 molar equivalents of base are available per mole of components (ii). 0e4*

Step of the process of the invention is carried out oo,, 20 without solvent or, preferably, in an organic solvent and o° optionally in the presence of a phase transfer catalyst. The o reactants may be present in homogeneous phase or in two phases, in solution, in an emulsion, or in suspension. Suitable organic solvents include optionally substituted aromatic hydrocarbons, such as benzene, toluene, xyiene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ethers and cyclic ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetra- hydrofuran, dioxane, and othylene glycol dimethyl ether; (esters, such as ethyl acetate; ketones, such as acetone, and methyl ethyl ketone; and various other organic solvents known in the art, such as acetonitrile, furfurol, methylene chloride, chloroform, trichloroethylene, tetrachloroethylene, nitromethane, nitropropane, dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, tetramethyl urea, N-methylcaprolactam,

Le A 26 440

V r

-11- dimethylsulfoxide, tetramethylene sulfone, and hexamethylene phosphoric acid triamide. Preferred organic solvents are dimethylsulfoxide and aromatic hydrocarbons. It is, of course, also possible to use mixtures of such solvents. The quantity in which the solvent is used is generally selected so that the starting materials and (ii) clearly dissolve. In practice, the solvents are generally used in a quantity of from about 50 to about 1000 parts by weight (preferably in a quantity of from 100 to 500 parts by weight) of solvent per 100 parts by weight of the mixture of components and (ii). It can sometimes be advantageous to carry out the reaction of step in the presence of a phase transfer catalyst. Phase transfer catalysts are described, for example, by E.V. and S.S. Dehmlow in Phase Transfer Catalysis, 2nd Edition (Veriag Chemie 1983). Suitable catalysts include quaternary ammonium or phosphonium salts of the formula

R" R'-N-R A R""

wherein Z is nitrogen or phosphorus; R' is C1-C18 alkyl or C7 -C16 araliphatic; and are independently C1-C18 alkyl (with the total number of carbon atoms in and R"" preferably being about 12 to about 13); and A is a suitable counterion, such as halide (preferred, especially chloride or bromide) or a sulfate, ?uifonate, phosphate, or phosphonate group. r Suitable phase transfer catalysts include N-benzyl-N,N,N-triethylammonium chloride or bromide, N-benzyl-N-dodecyl-N,N-dimethylammonium chloride or bromide, N,N,N,N-tetrahexylammonium chloride or bromide,

Le A 26 440

J

-iar

-12- N-benzyl-N,N,N-trioctylammonijm chloride or bromide, and the phosphonium salts corresponding to these ammonium salts. The preferred phase transfer catalysts are N-benzyl-N,N,N-trimethyl- ammonium chloride or N-hexadecyl-N,N,N-trimethylammonium bromide. In the practical application of the process of the invention, the quaternary ammonium or phosphonium salts are preferably used as is or as aqueous solutions (for example, having a solids content of from about 30 to about 60 by weight), preferably in a quantity of from about 1 to about 10 mole-percent based on the moles of hydroxyl groups present. Step of the process of the invention is generally carried out at about iO to about 100 0C (preferably at 20 to 800C) under excess pressure, reduced pressure, or preferably sub- stantially under vacuum, and either continuously or dis- continuously. The residence time for the reaction is generally from about 0.5 to about 24 hours (preferably from 0.5 to 12 hours), *coo

oo* Step of the process of the invention may be carried out, for example, by initially adding the starting materials (and oo 20 optionally, the phase transfer catalyst) to the selected solvent and then adding the base in dissolved or suspended form (preferably in very finely ground solid form) in portions or oo* continuously with stirring and optionally with cooling. The reaction mixture is then stirred at room temperature or, optionally, at elevated temperature until the nitrophenylating agent (ii) is substantially completely reacted, as indicated, for example, by thin layer chromatography. o The nitrophenoxy adducts are worked up in known manner. 0 The reaction mixture is preferably diluted with a substantially 30 inert water-immiscible solvent, washed with water or saline solution until neutral, and concentrated by distilling off the volatiles (optionally in vacuo), and drying the reaction product 0 in vacuo. The reaction mixture may be also neutralized by o' o treatment, for example, with carbon dioxide. Suitable

Le A 26 440 substantially inert solvents include toluene, methylene chloride, chlorobenzene, dichlorobenzene, 1,2-dichloroethane, trichloro- ethylene, and other such solvents known in the art, The reaction product thus obtained may generally be subsequently processed without further purification. Another method of working up is to add water (of from 1 to to the reactive mixture, neutralizing with an acid, preferably hydrochloric acid or sulfuric acid, distilling off the water and filtering the mixture at 10 120 0 C. In another possible, although less preferred, procedure, the reaction mixture obtained in step is delivered directly to step without intermediate isolation, optionally after neutralization of the excess alkali hydroxide. In step the nitrophenoxy-terminated compounds obtained in step of the process of the invention are converted into the corresponding polyamines by reducting using methods known in the art with nascent hydrogen or hydrogen catalytically activated, for al 20 example, by known hydrogenation catalysts such as Raney nickel or ov r

01 palladium on carbon. The hydrogenation may be carried out in the 0 4 presence or absence of inert solvents at about 20 to 120 C under a pressure of about 20 to about 80 bar. Suitable solvents include methanol, ethanol, isopropyl alcohol, toluene, dimethylformamide, and other such solvents known in the art, preferably methanol or toluene, The diamines are obtained as distillation residue during i removal of the solvent by distillation and may be used without S' further purification for the production of polyurethane plastics. The polyhydroxypolyamines of the invention obtained after worked- up are generally light-yellow to brownish-colored products that are distinguished from the previously known aromatic amino polyethers by c t their lower viscosity. In addition to the functional groups already Spresent in the basic polyhydroxyl compounds (such as, ftr example, *4 ether, thioether, dialkylsiloxane, or carbonate groups or residues of 35 polybutadienes), the polyhydroxypolyamines of the invention contain only the number of ether groups and hydroxy groups corresponding to their functionality. The aromatic polyhydroxypolyamines of the invention are suitable as reactants for optionally blocked

Le A 26 440

Lb.

-14-

polyisocyanates in the preparation of polyurethanes (polyurethane ureas), optionally cellular polyurethane plastics, or poly- urethane foams, for which purpose they may optionally be combined with other low molecular weight compounds (that is, having a molecular weight of 32 to 399) and/or relatively high molecular weight compounds (that is, having a molecular weight of 400 to about 12,000) containing isocyanate-reactive groups. Suitable starting components for the production of polyurethane plastics are described, for example, in German Offenlegungsschriften 2,302,564, 2,432,764 (believed to be equivalent to U.S. Patent 3,903,679), 2,539,083, 2,512,385, 2,513,815, 2,550,796, 2,550,797, 2,550,833, 2,550,860, and 2,550,862, which also disclose auxiliaries and additives optionally used in the preparation of polyurethanes. The polyhydroxypolyamines of the invention are particularly suitable for use in combination with solid polyisocyanates. According to German Offenlegungsschrift 3,230,757, it is possible with these components to obtain O. reaction systems that can be stored indefinitely at room 20 temperature (or optionally at elevated temperature) and which o. harden only after fairly intensive heating. Systems such as 4, these are generally known as one-component systems. Suitable o solid polyisocyanates include dimeric 2,4-diisocyanatotoluene or 3,3'-dimethyl-4,4'-diisocyanatodiphenylurea ("TDIH"). The present invention also relates to the preparation of polyurethane ureas using the polyamines produced according to the invention. They may be used, for example, for elastomers, coatings, filaments, in which case they are applied from melts, ac°1 solutions, dispersions, or as a mixture of reactive components. b1" 30 The polyamines produced according to the invention may also be a used, for example, as coupling components for diazo dyes, as .sk hardeners for epoxy and phenolic resins, and in any other known reactions involving amines (such as amidation or imidation Sreactions, and the like).

Le A 26 440

L~

The following examples further illustrate details for the preparation of the compounds of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these compounds. Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight. DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples 1 to 9: Nitrophenylation Example 1 To 1000 g (0.17 mole) of a dehydrated trimethylolpropane (TMP) started polypropylene oxide ethylene cxide ether triol 15 (OH value 29) are added 26 g (0.1 mole) of 4-chloronitrobenzene, 14 g (0.25 mole) of powdered potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 12 hours at 700 C. After 200 ml of water are added at room temperature, the mixture is neutralized with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 800 g (79% theory) of polyhydroxypolynitro product. Viscosity: 1500 mPa.s (260C) i t OH value: 18 SGas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 2 A mixture of 1000 g (0.17 mole) of dehydrated poly- |i propylene oxide ether triol (OH value 29) of Example 1, 42 g (0.26 mole) §of 4-chloronitrobenzene, 22.4 g (0.40 mole) of potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium S .30 chloride are reacted as in Example 1 to yield 840 g (81% theory) Sof polyhydroxypolynitro product. Viscosity: 1600 mPa.s (26°C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene

Le A 26 440 m r-

-16-

Example 3 A mixture of 1000 g (0.17 mole) of dehydrated poly- propylene.oxide ether triol (OH value 29) of Example 1, 57.5 g (0.36 mole) of 4-chloronitrobenzene, 30.8 g (0.55 mole) of potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 1 to yield 820 g (78% theory) of polyhydroxypolynitro product. Viscosity: 1900 mPa.s (260 C) OH value: 9 Gas chromatogram: 0.0% 4-chloronitrobenzene Example 4 To a solution of 1000 g (0.17 mole) of a dehydrated poly- Spropylene oxide ether triol (OH value 29) of Example 1 in 1000 ml of toluene is added 26 g (0.16 mole) of 4-chloronitrobenzene, 14 g o¢il

15 (0.25 mole) of potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium chloride. The mixture is then stirred 0 for 12 hours at 70 C. After 200 ml of water are added at room temperature, the mixture is neutralized with 50% sulfuric acid, the solvent and water are distilled off, and the salts that precipitate are filtered off to yield 898 g (88% theory) of polyhydroxypolynitro product. Viscosity: 1500 mPa.s (200 C) OH value: 18 Gas chromatogram: 0.0% 4-chloronitrobenzene Example SA solution of 1000 g (0.17 mole) of dehydrated poly- propylene oxide ether triol (OH value 29) of Example 1 dissolved in 1000 ml of toluene, 42 g (0.26 mole) of 4-chloronitrobenzene, 22.4 g (0.40 mole) of potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 955 g (92% theory) of polyhydroxypolynitro product. Viscosity: 1400 mPa.s (270 C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene

Le A 26 440

il

I 77 -17-

Example 6 A solution of 1000 g (0.17 mole) of dehydrated poly- propylene oxide ether triol (OH value 29) of Example 1 dissolved in 1000 ml of toluene, 57.5 g (0.36 mole) of 4-chloronitrobenzene, 30.8 g (0.55 mole) of potassium hydroxide, and 9.25 g (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 1028 g (100% theory) of polyhydroxypolynitro product. Viscosity: 1700 mPa.s (200 C) OH value: 9 Gas chromatogram: 0.1% 4-chloronitrobenzene Example 7 To a solution of 1400 g (1 mole) of dehydrated polyethylene oxide ether diol (OH value 80) dissolved in 1500 ml of toluene are added 167 g (1.06 mole) of 4-chloronitrobenzene, 90 g (1.6 mole) of potassium hydroxide, and 11.1 g (0.06 mole) of o I trimethylbenzylammonium chloride. The mixture was then stirred Lt for 12 hours at 700 C. After 300 ml of water are added at room i temperature, the reaction mixture is neutralized with sulfuric acid, the solvent and water are distilled off, and the salts that precipitate are filtered off to yield 1440 g (94% theory) of polyhydroxypolynitro product. Viscosity: 140 mPa.s (700 C) OH value: Gas chromatogram: 0.0% 4-chloronitrobenzene Example 8 A mixture of 1000 g (0.17 mole) of a dehydrated poly- propylene oxide ether triol. (OH value 29) of Example 1, 57.5 g (0.36 mole) of 4-chloronitrobenzene, and 30.8 g (0.55 mole) of potassium hydroxide is stirred for 12 hours at 700 C while air is passed through. After 200 ml of water are added at room temperature, the reaction mixture is neutralized with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 756 g (74% theory) of polyhydroxypolynitro product.

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L.

Viscosity: 2000 mPa.s (260 C) OH value: Gas chromatogram: 0.0% 4-chloronitrobenzene Example 9 A mixture of 1000 g (0.17 mole) of a dehydrated polypropylene oxide ether triol (OH value 29) of Example 1, 42 g (0.26 mole) of 2-chloronitrobenzene, and 22.4 g (0.40 mole) of trimethylbenzylammonium chloride is stirred for 12 hours at 70 0 C while air is passed through. After 200 ml of water are added at room temperature, the reaction mixture is neutralized with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 770 g (75% theory) of polyhydroxypolynitro product. 0000 OH value: 16 S" Gas chromatogram: 0,0% 2-chloronitrobenzene. Example A mixture of 1000 g (0.21 mole) of a trimethylol- propane started polypropylenoxid ethylenoxide ether triol (OH value 35), 105 g (0,94 mole)of aqueous potassium hydroxide solution and 100 ml of toluene were destilled under vacuum (700C/20 mbar) in order to remove the toluene/water mixture. The dehydrated polyether was mixed with 69 g of p- chloronitrobenzene (0,44 mole) dissolved in 170 ml toluene and stirred under vacuum (20 mbar) for a period of 17 hours at 400C. 115 ml of water were added and neutralized with H 2 SO 4 The water was distilled off and the resulting salts filtered at 800 C.

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Yield: 940 g (88% theory) viscosity: 1600 mPas/240 C OH value: 12 Gel: 0,0% 4-chloronitrobenzene

Examples 11 to 18: Hydrogenation General procedure To a solution of 100 parts of polyhydroxypolynitro compound Examples 1 to 10) are dissolved in 100 parts of solvent are added 10 parts of Raney nickel. Hydrogenation is carried out in a pressure vessel under a hydrogen pressure of 60 bar at the beginning of the

reaction and at a temperature of 700C. The date of Examples 11 to 18 are shown in ,Table 1,

i

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C CCC 0 0 CC C C C C C 0 0~ C CCC 460

Table 1,

Polyhydi-oxy- Pa lyhydr-oxy- polynitro compound pa lyamine

Ex. MW f(-OH) f(N0 (AV~j 2 OH-No. I 1 'Ex. OH-N. f NH-Nt. viscosity mPas 250 C]

6121 2 1 1700 6191 1,4 1,6 2000 6266 0,8 2,2 2300 6193 1,4 1,6 1800 6266 0,8 2,2 2000 6266 0,8 2,2 2000 6193 1,4 1,6 1600 5054 0,9 2,1 1700

MW (AV) average melecular weight OH-no, and NH-no, in mg KOH/g compound

Example 19: Application Example The polyhydroxypolyamine (amine value 22) (200 g) described in Example 15 is degassed for 15 minutes at room temperature under an aspirator vacuum, followed by the addition of 19.0 g of finely ground dimeric 2,4-diisocyanatotoluene having an average particle size of 10 to 30 microns. A very finely divided suspension is prepared by brief intensive stirring (for approximately 1 minute) and then poured over a period of 2 to 3 minutes into a mold treated with release agents and preheated to 100C. After approximately 30 to 60 minutes at 120-1300C, the test specimen (which has hardened in the meantime) is removed from the mold and heated for another 3 to 4 hours at 04 S, the same temperature. o 20 Ultimate tensile strength: 6.0 kp/abs Elongation at break: 250% Modulus 100%: 3.16 mPa Tear propagation resistance: 81 N/cm i Shore A hardness: 74 Elasticity: 46% SExample 20: Comparison Example with Complete Nitrophenylation To 400 g (0.07 mole) of a dehydrated polypropylene Soxide ether triol (OH value 29) is added 30 g (0.19 mole) of

S .4

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r

22

4-chloronitrobenzene, 16.8 g (0.3 mole) of potassium hydroxide, and 3.7 g (0.02 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 22 hours at 70°C. After 100 ml of water are added at room temperature, the mixture is neutralized with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 383 g (91% theory) of the nitrophenylated product. Viscosity: 2000 mPa.s (260 C) OH value: Gas chromatogram: 1.0% 4-chloronitrobenzene Comparison Example 20 shows that, when u-ing slightly less than the equivalent quantity of nitrophenylating agent (4-chloronitrobenzene), a residue 4-chloronitrobenzene) remains. This residue must be removed by relatively costly 15 procedures before the subsequent reaction can be conducted. Example 21 Comparison Application Example After removal of the residual 4-chloronitrobenzene (amine value 26), the aminopolyether (200 g) obtained by hydrogenation of the nitro product of Example 20 is reacted as in Example 19 with 19.0 g of finely ground dimeric 2,4-diisocyanatotoluene (TT) having an average particle size of to 30 microns. Ultimate tensile strength: 5.9 kp/abs Elongation at break: 250% Modulus 100%: 5.2 mPa Tear propagation resistance: 78 N/cm Shore A hardness: 79 Elasticity: 47% Comparison application Example21 shows that, despite almost complete amination of the polyol, the property level of Sthe plastics produced therefrom is not significantly better.

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Claims (17)

1. n,

   -23

   The Claims defining the invention are as follows: 1. A compound of the formula
2. 2 R

   NH2 n

   wherein R is an m-functional residue of an m-functional polyhydroxyl compound having a molecular weight of about 400 to about 8000; 2 oa 15 R is hydrogen o methyl; m is an integer of from 2 to 4; and n is a positive number having an average value of from about 0.05m to about 0.73m. 2. A compound according to Claim 1 wherein the 20 polyhydroxyl compound is a polyalkylene polyether.
3. 3. A compound according to Claim 1 wherein R is hydrogen and the NH2 group is in an ortho or para position, having the formula

   Ho -r S m-n or

   n 4

   HOj r-n 0 -NH

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   7, 24
4. 4. A compound according to Claim 1 wherein n is a positive number having an average value of from 0.3m to 0.6m.
5. A compound according to Claim 1 wherein n is a positive number having an average value of from 0.15m to 0.70m.
6. 6. A compound according to Claim 1 wherein m is 2 or 3.
7. 7. A process for the preparation of a compound of the formula

   HO m-n -R

   NH2

   wherein R1 is an m-functional residue of an m-functional polyhydroxyl compound having a molecular weight of 400 to about 8000; R2 is hydrogen or methyl; m is an integer of from 2 to 4; and n is a positive number having an average value of from about 0.05m to about 0.73m; comprising reacting, in the presence of an alkaline compound, an m-functional relatively high molecular weight polyhydroxyl compound of the formula

   R1(OH)m

   with (ii) an n-molar quantity of a compound of the formula

   Le A 26 440 wherein R2 is as defined above and X is halogen, to form an (m-n)-hydroxy n-nitrophenoxy adduct of the formula

   -R1 -0-

   ~on o4 NO2 0dr 0 t rr n 00 o I 0 0 0 1 2 wherein R1 R2 m, and n are as defined above; and t0 hydrogenating said (m-n)-hydroxy n-nitrophenoxy adduct to form the product compound.
8. 8. A process according to Claim 7 wherein X is fluorine or chlorine.
9. 9. A process according to Claim 7 wherein the 0 0d
10. 0 0 alkaline compound is powdered sodium hydroxide or potassium 0 00 hydroxide in a quantity sufficient to neutralize hydrogen halide released during the reaction of step-(a). A process according to Claim 9 wherein about 1 to 3 molar equivalents of alkaline compound per mole of component (ii) is used in step
11. 11. A process according to Claim 7 wherein step is carried out in the absence of added solvent.
12. 12. A process according to Claim 7 wherein an organic solvent is used in step

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13. 13. A process according to Claim 12 wherein the organic solvent is dimethylsulfoxide or an aromatic hydrocarbon.
14. 14. A process according to Claim 7 wherein a phase transfer catalyst is used in step
15. 15. A process according to Claim 14 wherein the phase transfer catalyst is N-benzyl-N,N,N-trimethylammonium chloride, N-benzyl-N,N,N-triethylammonium chloride, or N-hexadecyl-N;N,N- trimethylammonium bromide.
16. 16. A method for preparing a polyurethane plastic comprising using a compound according to Claim 1 as a synthesis component in the isocyanate polyaddition process.
17. 17. Novel aminophenoxy- and hydroxyl-terminated compounds substantially as herein described with reference to any one of the Examples, excluding comparison examples.

    DATED the 10th day of October, 1989

    BAYER AKTIENGESELLSCHAFT By Its Patent Attorneys ARTHUR S. CAVE CO.

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