CA1334104C - Aromatic polyhydroxypolyamines, a process for their preparation, and their use for the preparation of polyurethane plastics - Google Patents
Aromatic polyhydroxypolyamines, a process for their preparation, and their use for the preparation of polyurethane plasticsInfo
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- CA1334104C CA1334104C CA000613904A CA613904A CA1334104C CA 1334104 C CA1334104 C CA 1334104C CA 000613904 A CA000613904 A CA 000613904A CA 613904 A CA613904 A CA 613904A CA 1334104 C CA1334104 C CA 1334104C
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/329—Hydroxyamines containing aromatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33379—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group
- C08G65/33386—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic
- C08G65/33389—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing nitro group cyclic aromatic
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- 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
- C08G2101/00—Manufacture of cellular products
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention relates to novel aminophenoxy-and hydroxyl-terminated compounds of the general formula wherein R1 is the residue of an m-functional polyhydroxyl compound;
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.
The present invention also relates to a process for the preparation of such compounds comprising reacting in the presence of an alkaline compound (i) an m-functional relatively high molecular weight polyhydroxyl compound with (ii) an n-molar quantity of a halonitrobenzene to form a hydroxy nitrophenoxy adduct, which is then hydrogenated to the corresponding amine.
The invention further relates to the use of the compounds of the invention as synthesis component in the preparation of polyurethane plastics by the isocyanate polyaddition process.
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.
The present invention also relates to a process for the preparation of such compounds comprising reacting in the presence of an alkaline compound (i) an m-functional relatively high molecular weight polyhydroxyl compound with (ii) an n-molar quantity of a halonitrobenzene to form a hydroxy nitrophenoxy adduct, which is then hydrogenated to the corresponding amine.
The invention further relates to the use of the compounds of the invention as synthesis component in the preparation of polyurethane plastics by the isocyanate polyaddition process.
Description
3 3 4 1 ~ 4 AROMATIC POLYHYDROXYPOLYAMINES, A PROCESS FOR THEIR PREPARATION, AND THEIR USE FOR THE PREPARATION OF POLYURETHANE PLASTICS
BACKGROUND OF THE INVENT$0N
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 ~150 gives aromatic amino polyethers. U.S. Patent ~,248,424 and German Offenlegungsschrift 1,694,152 describe a pro~ess in which is~cyanate prepolymers are reacted with ~iamines containing amino groups of different reactivity.
The reactions of isocyanate prepolymers with sulfamic 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, 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-legungsschriften 2,948,419, 3,223,397, 3,223,398, and 3,223,400 describe various single-step or two-step processes for the Le A 26 440 2 l 334 1 04 production of aromatic polyamines by hydrolysis of isocyanate prepolymers in the presence of various solvent and catalyst systems.
All the previously described processes involve 5 isocyanate intermediate stages and, accord;ngly, 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 10 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 15 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-20 alkylene polyols with p-aminobenzoic acid derivatives in accordance with Japanese patent applications 59/053,533, 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-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 30 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 Le A 26 440 ~ 1 334 1 04 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 5 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 10 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 according to the invention.
SUMMARY OF THE INVENTION
The present invention relates to novel aminophenoxy-and hydroxyl-terminated compounds of the general formula _ _ R2 HO- m n ~R1~ -- ~
_ n 25 wherein R1 is an m-functional residue of an m-functional polyhydroxyl 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 30 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).
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 _4_ l 3341 04 H0 R1 0 ~ ~
_ _ NH2 n wherein Rl, R2, m, and n are as defined above, 10 comprising (a) reacting, in the presence of alkaline compounds, (i) m-functional relatively high molecular weight polyhydroxyl compounds of the general formula R1(OH)m with (ii) an n-molar quantity of compounds of the general formula , ~ ~2 \
wherein R2 is as defined above and X is halogen (preferably fluorine and more preferably chlorine), to form (m-n)-hydroxy n-nitrophenoxy adducts of the general formula Le A 26 440 _ _5 l 3 3 4 1 0 4 HO- m n _p1_ ~~ ~
_ n wherein R1, R2, m, and n are as defined above, and 10 (b) 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 15 plastics by the isocyanate polyaddition process.
DETAILED DESCRIPTION OF THE INVENTION
Starting materials for the process according to the invention are (i) relatively high molecular weight polyhydroxyl compounds and (ii) optionally methyl-substituted halonitro-20 benzenes.
Suitable polyhydroxyl compounds (i) include relativelyhigh molecular we;ght 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 25 hydroxyl groups is equal to the number m). Suitable polyhydroxyl compounds include the polyacetals, polythioethers, poly-carbonates, polyamides, polysiloxanes, polybutadienes, polyesters, polylactones, and polyethers containing hydroxyl groups which are commonly encountered in polyurethane chemistry.
30 Preferred polyhydroxyl compounds (i) include polyethers containing hydroxyl groups, particularly polyalkylene polyethers containing hydroxyl groups.
Le A 26 440 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, 5 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 10 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 15 use polyethers containing predominantly primary hydroxyl groups (up to 90% by weight, based on all the OH groups present in the polyether). Also suitable are polyethers modified by vinyl polymers of the type formed, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers.
20 U.S. Patents 3,383,351, 3,304,273, 3,523,093, and 3,110,695 and German Patentschrift 1,152,536, as are polybutadienes containing OH groups.
Suitable polyacetals include compounds obtainable from glycols, such as diethylene or triethylene glycol, 4,4'-di-25 hydroxyethoxydiphenylmethane, and hexanediol, by reaction withformaldehyde or by polymerization of cyclic acetals, such as trioxane.
Suitable polycarbonates containing hydroxyl groups are known and can be obtained, for example, by reaction of diols 30 (such as 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol), di-, tri- or tetraethylene glycol, or thiodiglycol, with diaryl carbonates (such as diphenyl carbonate) or phosgene. German Auslegeschrift 1,694,080, 1,915,908, and 2,221,751 and German Offenlegungsschrift 2,605,024.
Le A 26 440 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-10 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, by allowing polyaddition reactions (for example, between 20 polyisocyanates and aminofunctional compounds) or poly-condensation 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 25 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 the type obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. 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 5 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 10 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 15 properties when using the polyisocyanate polyaddition process.
Other suitable, although less preferred, polyhydroxyl components (i) include organofunctional polysiloxanes containing two terminal isocyanate-reactive groups and structural units of the formula -O-Si(R)2-, where R is Cl-C4 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 CH ~ CH-HO-CH2-Si - -O-Si - -CH2-OH
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-1,3-hydroxymethyl disiloxane of formula Le A 26 440 . _ g HO-CH2-Si -O-Si -CH2-OH
~CH3 CH3 with octamethylcyclotetrasiloxane in the presence of sulfuric acid or by the process according to German Auslegeschrift 10 1,236,505.
Suitable starting materials (ii) include optionally methyl-substituted halonitrobenzenes having the general formula ~R
X-~/ ~
~N02 20 wherein R2 is hydrogen or methyl (preferably hydrogen);
X is halogen (preferably fluorine and more preferably chlorine).
In the preferred halonitrobenzenes (ii), the halogen and nitro 25 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-30 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-nitrochlorobenzene.
Suitable alkaline compounds, which are required for the 35 reaction of polyhydroxyl compounds (i~ with the halonitrobenzenes (ii), include metal hydrides, metal alkoxides, and, preferably, Le A 26 440 o- 1 3341 04 metal hydroxides. Sodium hydroxide and potassium hydroxide are particularly preferred, especially when used in powdered form.
In step (a) of the process of the invention, the halonitrobenzene starting materials (ii) are used in less than 5 the quantity of the polyhydroxyl component (i). 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, 10 (m-n) hydroxyl groups will remain in the (m-n)-hydroxy n-nitrophenoxy adducts of the invention.
The hydrogen halide released during the rea~tion o~ step (a) may be neutralized by the addition of metal hydrides, metal alkoxides, and metal hydroxides preferably sodium or potassium 15 ~ydroxide in at least a stoi~hiometric quantity. In a particularly preferred em~odiment, the alkaline compounds are used in a quantity such that aboutl to 3 molar equivalents of base are a~ailable per mole of components (ii).
Step (a) of the process of the invention is carried out 20 without solvent or, preferably, in an organic solvent and optionally in the presence of a phase transfer catalyst. The 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, 25 such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ethers and cyclic ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetra-hydrofuran, dioxane, and ethylene glycol dimethyl ether, esters, such as ethyl acetate; ketones, such as acetone, and methyl ethyl 30 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 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 5 which the solvent is used is generally selected so that the starting materials (i) 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 10 mixture of components (i) and (ii).
It can sometimes be advantageous to carry out the reaction of step (a) 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 15 (Verlag Chemie 1983). Suitable catalysts include quaternary ammonium or phosphonium salts of the formula R" (+) R'-N-R"' A( ) I
R""
wherein 25 Z is nitrogen or phosphorus;
s C1 C18 alkyl or C7-C16 araliphatic;
R", R"', and R"" are independently C1-C18 alkyl (with the total number of carbon atoms in R', R", R"', and R""
preferably being about 12 to about 13), and 30 A( ) is a suitable counterion, such as halide (preferred, especially chloride or bromide) or a sulfate, sulfonate, phosphate, or phosphonate group.
Suitable phase transfer catalysts include N-benzyl-N,N,N-triethylammonium chloride or bromide, 35 N-benzyl-N-dodecy~-N,N-dimethylammonium chloride or bromide, N,N,N,N-tetrahexylammonium chloride or bromide, Le A 26 440 N-benzyl-N,N,N-trioctylammonium 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.
5 In the practical application of the process of the invention, t~e`
quaternary ammonium or phosphonium salts are preferably used as is or as aqueous solutions (for example, having a solids conten of from about 30 to about 60 by weight), preferably in a quanti~
of from about 1 to about 10 mole-percent based on the moles of 10 hydroxyl groups present.
Step (a) of the process of the invention is generally carried out at about 10 to about 100C (preferably at 20 to 80C
under excess pressure, reduced pressure, or preferably sub-stantially under vacuum, and either continuously or dis-15 continuously. The residence time for the reaction is generallyfrom about 0.5 to about 24 hours (preferably from 0.5 to 12 hours).
Step (a) of the process of the invention may be carri~
out, for example, by initially adding the starting materials (a 20 optionally, the phase transfer catalyst) to the selected solven and then adding the base in dissolved or suspended form (preferably in very finely ground solid form) in portions or continuously with stirring and optionally with cooling. The reaction mixture is then stirred at room temperature or, 25 optionally, at elevated temperature until the nitrophenylatin~
agent (ii) is substantially completely reacted, as indicated, example, by thin layer chromatography.
The nitrophenoxy adducts are worked up in known mar'er.
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 in vacuo. The reaction mixture may be also neutralized by 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 sol~ents known in the art, The reactionproduct thus obtained may generally be subsequently processed without further purification.
Another method of working up is to add water (of from 1 to 20%) to the reactive mixture, neutralizing with an acid, preferably hydrochloric acid or sulfuric acid, distilling off the water and filtering the mixture at 10 - 12~ C.
In another possible, although less preferred, procedure, the reaction mixture obtained in step (a) is delivered directly to step (b) without intermediate isolation, optionally after neutralization of the excess alkali hydroxide.
In step (b) the nitrophenoxy-terminated compounds obtained in step (a) 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 acti~ated, for example, by known hJlrogenation catalysts such as Raney nickel or palladium on carbon. The hydrogenation may be carried out in the presence or absence of inert sol~ents at about 20 to 120C 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 removal of the sol~ent by distillation and may be used without 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 pre~iously known aromatic amino polyethers by their lower ~iscosity. In addition to the functional groups already present in the basic polyhydroxyl compounds (sucb as, for example, ether, thioether, dialkylsiloxane, or carbonate groups or residues of ~5 polybutadienes), the polyh~dr~a~olyamines of the invention contain only the number of ether groups and h~d. GA~ groups corresponding to their functionality. The aromatic polyhydroxypolyamines of the invention are suitable as reactants for optionally blocked Le A 26 440 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 5 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 10 2,302,564, 2,432,764 (believed to be equivalent to U.S. Patent 3,903,679), 2,639,083, 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 reaction systems that can be stored indefinitely at room 20 temperature (or optionally at elevated temperature) and which harden only after fairly intensive heating. Systems such as these are generally known as one-component systems. Suitable solid polyisocyanates include dimeric 2,4-diisocyanatotoluene ("TT") 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, solutions, dispersions, or as a mixture of reactive components.
30 The polyamines produced according to the invention may also be used, for example, as coupling components for diazo dyes, as hardeners for epoxy and phenolic resins, and in any other known reactions involving amines (such as amidation or imidation reactions, and the like).
Le A 26 440 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 5 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 9 (0.17 mole) of a dehydraLed trimethylolpropane (TMP) started polypropylene oxide (82,5X) ethylene oxide (17,5Y.) ether t riol 15 (OH value 29) are added 26 g (0.1 mole) of 4-c~loronitrobenzene, 14 g (0.25 mole) of powdered po~assium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride. The mix~ure is then s~irred for 12 hours at 7~ C. Af~er 200 ml of water are added a~ room ~empera~ure, the mixture is neutralized with 50% sulfuric acid, the water is distilled 20 off, and the salts that precipitate are filtered off to yield 800 g (79Y.
~heory) of polyhydroxypolynitro product.
Yiscosity: 1500 mPa.s (26C~
OH value: 18 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 2 A mixture of 1000 9 (0.17 mole) of dehydrated poly-pr~lene oxide et~r t~iol (-~ value 29) of E~ple 1, 42 g (-0.26 ~le) of 4-chloronitrobenzene, 22.4 9 (0.40 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium 30 chloride are reacted as in Example 1 to yield 840 9 (81% theory) of polyhydroxypolynitro product.
Viscosity: 1600 mPa.s (26C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene Le A 26 440 --16- l 3341 04 Example 3 A mixture of 1000 9 (0.17 mole) of dehydrated poly-propylene.oxide ether triol (O~ value 29) of Example 1, 57.5 g (0.36 m~le) of 4-chloronitrobenzene, 30.8 9 (0.55 mole) of potassium 5 hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 1 to yield 820 9 (78% theory) of polyhydroxypolynitro product.
Viscosity: 1900 mPa.s (26C) OH value: 9 10 Gas chromatogram: 0.0% 4-chloronitrobenzene Example 4 To a solution of 1000 9 (0.17 mole) of a dehydrated poly-propylene c~ide ether triol (OH value 29) of Example 1 in 1000 ml of toluene is added 26 9 (0.16 mole) of 4-chloronitrobenzene, 14 9 15 (0.25 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 12 hours at 70C. 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 20 precipitate are filtered off to yield 898 9 (88% theory) of polyhydroxypolynitro product.
Viscosity: 1500 mPa.s (20C) OH value: 18 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 5 A solution of 1000 9 (0.17 mole) of dehydrated poly-propylene oxide ether triol (O~-value 29) of Fx~pl~ 1 dissolved in 1000 ml of toluene, 42 9 (0.26 mole) of 4-chloronitrobenzene, 22.4 9 (0.40 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) 30 of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 955 9 (92~ theory) of polyhydroxypolynitro product.
Viscosity: 1400 mPa.s (27C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene Le A 26 44~
Example 6 A solution of 1000 9 (0.17 mole) of dehydrated poly-p~ylene oxide ether triol (CH value 29) of Exa~le 1 dissolved in 1000 ml of toluene, 57.5 9 (0.36 mole) of 4-chloronitrobenzene, 5 30.8 9 (0.55 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 1028 9 (100% theory) of polyhydroxypolynitro product.
Viscosity: 1700 mPa.s (20C) OH value: 9 10 Gas chromatogram: 0.1% 4-chloronitrobenzene Example 7 To a solution of 1400 9 (1 mole) of dehydrated polyethylene oxide ether diol (OH value 80) dissolved in 1500 ml of toluene are added 167 9 (1.06 mole) of 4-chloronitrobenzene, 15 90 9 (1.6 mole) of potassium hydroxide, and 11.1 9 (0.06 mole) of trimethylbenzylammonium chloride. The mixture was then stirred for 12 hours at 70C. After 300 ml of water are added at room temperature, the reaction mixture is neutralized with 50~
sulfuric acid, the solvent and water are distilled off, and the 20 salts that precipitate are filtered off to yield 1440 9 (94% theory) of polyhydroxypolynitro product.
Viscosity: 140 mPa.s (70C) OH value: 35 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 8 A mixture of 1000 9 (0.17 mole) of a dehydrated poly-~pylene oxide ether triol~ value 29) of Exa~ple 1, 57.5 g (0.36 le) of 4-chloronitrobenzene, and 30.8 9 (0.55 mole) of potassium hydroxide is stirred for 12 hours at 70C while air is passed 30 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 9 ~74X theory) of polyhydroxypolynitro product.
Le A 26 440 Viscosity: 2000 mPa.s (26C) OH value: 10 Gas chromatogram: 0.0% 4-chloronitrobenzene ExamPle 9 A mixture of 1000 g tO.17 mole) of a dehydrated polypropylene oxide ether triol (OH value 29) of Example 1, 42 9 (0.26 mole) of 2-chloronitrobenzene, and 22.4 9 (0.40 mole) of trimethylbenzylammonium chloride is stirred for 12 hours at 70C 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.
OH value: 16 Gas chromatogram: 0.0% 2-chloronitrobenzene.
ExamPle 10 A mixture of 1000 9 (0.21 mole) of a trimethylol-propane started polypropylenoxid (82,5%) ethylenoxide (17,2%) ether triol (OH value 35), 105 9 (0,94 mole)of 50% aqueous potassium hydroxide solution and 100 ml of toluene were destilled under vacuum (70CI20 mbar) in order to remove the toluenelwater mixture.
The dehydrated polyether was mixed with 69 9 of p-chloronitrobenzene (0,44 mole) dissolved in 170 ml toluene and stirred under vacuum (20 mbar) for a period of 17 hours at 40C. 115 ml of water were added and neutralized with H2S04 (50%). The water was distilled off and the resulting salts filtered at 80C.
Le A 26 440 - 19 _ 1334104 Yield: 940 g (88% ~heory) viscosity: 1600 mPasl24C
OH value: 12 Gel: 0,0% 4-chloronitrobenzene ExamDles 11 to 18: Hydrogena~ion General Procedure To a solu~ion of 100 parts of polyhydroxypolyni~ro compound (e.g., Examples 1 to 10) are dissolved in 100 parts of solven~ are added 10 parts of Raney nickel.
Hydrogenation is carried ou~ in a pressure vessel under a hydrogen pressure of 60 bar at the beginning of ~he reaction and at a ~emperature of 70C.
The data of Examples 11 ~o 18 are shown in Table 1.
Le A 26 440 ~o O O o o o o o o ~ U~ o o o o o o o o ~ N t` O t'') 0 0 0 ~ t~
Ul -- ~ N N --I N N
O ~1 U
In ~L
~rl E
X 0~ ~r ~ 0 N N ~ ~
Z -- N _I N N --IN
O
O O O O ~ ~ O U~
C X t~l t~ t`lt~lN N t~
~rl O
. E
O O X --I N ~ ~ 0 O ~
z 0 ~ ~ O ~ON C
~ ~ 3 O O
~ U
O `D N ~0 N N'D--~ --~ ~L X
-- ~-1 N _1 N N ~ N 111 0 --I Y
u 10 c 111 E
~ O ~ 0 ~r 0 0 ~ ~ C
E~ I N
I O -- --~ O --I O O ~ O
U ~ C
O . I
L ~ ~
_ Z
I N --I N N_1 o 0 D. X ' ' ~ O
_~ -- C
.0 .
N t`~ o 0 ~ _I ~ o Le A 26 440 s Example 19: Application Example The polyhydroxypolyamine (amine value 22) (200 9) 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 ("TT") 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 120-130C, the test specimen (which has hardened in the meantime) is removed from the mold and heated for another 3 to 4 hours at the same temperature.
20 Ultimate tensile strength: 6.0 kp/abs Elongation at break: 250Yo Modulus 100%: 3.16 mPa Tear propagation resistance: 81 N/cm , Shore A hardness: 74 25 Elasticity: 46%
Example 20: Comparison Example with Complete Nitrophenylation To 400 9 (0.07 mole) of a dehydrated polypropylene oxide ether triol (OH value 29) is added 30 g (0.19 mole) of Le A 26 440 - 22 - l 334 1 04 4-chloronitrobenzene, 16.8 9 (0.3 mole) of potassium hydroxide, and 3.7 9 (0.02 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 22 hours at 70C. After 100 ml of water are added at room temperature, the mixture is neutralized 5 with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 383 9 (91% theory) of the nitrophenylated product.
Viscosity: 2000 mPa.s (26C) OH value: 5 10 Gas chromatogram: 1.0% 4-chloronitrobenzene Comparison Example 20 shows that, when using slightly less than the equivalent quantity of nitrophenylating agent (4-chloronitrobenzene), a residue (1.0% 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 9) obtained by hydrogenation of the nitro product of Example 20 is reacted as in 20 Example 19 with 19.0 9 of finely ground dimeric 2,4-diisocyanatotoluene (TT) having an average particle size of 10 to 30 microns.
Ultimate tensile strength: 6.9 kp/abs Elongation at break: 250%
25 Modulus 100%: 5.2 mPa Tear propagation resistance: 78 N/cm Shore A hardness: 79 Elasticity: 47%
Comparison application Example21 shows that, despite 30 almost complete amination of the polyol, the property level of the plastics produced therefrom is not significantly better.
Le A 26 440
BACKGROUND OF THE INVENT$0N
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 ~150 gives aromatic amino polyethers. U.S. Patent ~,248,424 and German Offenlegungsschrift 1,694,152 describe a pro~ess in which is~cyanate prepolymers are reacted with ~iamines containing amino groups of different reactivity.
The reactions of isocyanate prepolymers with sulfamic 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, 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-legungsschriften 2,948,419, 3,223,397, 3,223,398, and 3,223,400 describe various single-step or two-step processes for the Le A 26 440 2 l 334 1 04 production of aromatic polyamines by hydrolysis of isocyanate prepolymers in the presence of various solvent and catalyst systems.
All the previously described processes involve 5 isocyanate intermediate stages and, accord;ngly, 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 10 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 15 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-20 alkylene polyols with p-aminobenzoic acid derivatives in accordance with Japanese patent applications 59/053,533, 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-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 30 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 Le A 26 440 ~ 1 334 1 04 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 5 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 10 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 according to the invention.
SUMMARY OF THE INVENTION
The present invention relates to novel aminophenoxy-and hydroxyl-terminated compounds of the general formula _ _ R2 HO- m n ~R1~ -- ~
_ n 25 wherein R1 is an m-functional residue of an m-functional polyhydroxyl 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 30 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).
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 _4_ l 3341 04 H0 R1 0 ~ ~
_ _ NH2 n wherein Rl, R2, m, and n are as defined above, 10 comprising (a) reacting, in the presence of alkaline compounds, (i) m-functional relatively high molecular weight polyhydroxyl compounds of the general formula R1(OH)m with (ii) an n-molar quantity of compounds of the general formula , ~ ~2 \
wherein R2 is as defined above and X is halogen (preferably fluorine and more preferably chlorine), to form (m-n)-hydroxy n-nitrophenoxy adducts of the general formula Le A 26 440 _ _5 l 3 3 4 1 0 4 HO- m n _p1_ ~~ ~
_ n wherein R1, R2, m, and n are as defined above, and 10 (b) 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 15 plastics by the isocyanate polyaddition process.
DETAILED DESCRIPTION OF THE INVENTION
Starting materials for the process according to the invention are (i) relatively high molecular weight polyhydroxyl compounds and (ii) optionally methyl-substituted halonitro-20 benzenes.
Suitable polyhydroxyl compounds (i) include relativelyhigh molecular we;ght 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 25 hydroxyl groups is equal to the number m). Suitable polyhydroxyl compounds include the polyacetals, polythioethers, poly-carbonates, polyamides, polysiloxanes, polybutadienes, polyesters, polylactones, and polyethers containing hydroxyl groups which are commonly encountered in polyurethane chemistry.
30 Preferred polyhydroxyl compounds (i) include polyethers containing hydroxyl groups, particularly polyalkylene polyethers containing hydroxyl groups.
Le A 26 440 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, 5 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 10 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 15 use polyethers containing predominantly primary hydroxyl groups (up to 90% by weight, based on all the OH groups present in the polyether). Also suitable are polyethers modified by vinyl polymers of the type formed, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers.
20 U.S. Patents 3,383,351, 3,304,273, 3,523,093, and 3,110,695 and German Patentschrift 1,152,536, as are polybutadienes containing OH groups.
Suitable polyacetals include compounds obtainable from glycols, such as diethylene or triethylene glycol, 4,4'-di-25 hydroxyethoxydiphenylmethane, and hexanediol, by reaction withformaldehyde or by polymerization of cyclic acetals, such as trioxane.
Suitable polycarbonates containing hydroxyl groups are known and can be obtained, for example, by reaction of diols 30 (such as 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol), di-, tri- or tetraethylene glycol, or thiodiglycol, with diaryl carbonates (such as diphenyl carbonate) or phosgene. German Auslegeschrift 1,694,080, 1,915,908, and 2,221,751 and German Offenlegungsschrift 2,605,024.
Le A 26 440 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-10 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, by allowing polyaddition reactions (for example, between 20 polyisocyanates and aminofunctional compounds) or poly-condensation 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 25 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 the type obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. 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 5 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 10 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 15 properties when using the polyisocyanate polyaddition process.
Other suitable, although less preferred, polyhydroxyl components (i) include organofunctional polysiloxanes containing two terminal isocyanate-reactive groups and structural units of the formula -O-Si(R)2-, where R is Cl-C4 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 CH ~ CH-HO-CH2-Si - -O-Si - -CH2-OH
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-1,3-hydroxymethyl disiloxane of formula Le A 26 440 . _ g HO-CH2-Si -O-Si -CH2-OH
~CH3 CH3 with octamethylcyclotetrasiloxane in the presence of sulfuric acid or by the process according to German Auslegeschrift 10 1,236,505.
Suitable starting materials (ii) include optionally methyl-substituted halonitrobenzenes having the general formula ~R
X-~/ ~
~N02 20 wherein R2 is hydrogen or methyl (preferably hydrogen);
X is halogen (preferably fluorine and more preferably chlorine).
In the preferred halonitrobenzenes (ii), the halogen and nitro 25 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-30 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-nitrochlorobenzene.
Suitable alkaline compounds, which are required for the 35 reaction of polyhydroxyl compounds (i~ with the halonitrobenzenes (ii), include metal hydrides, metal alkoxides, and, preferably, Le A 26 440 o- 1 3341 04 metal hydroxides. Sodium hydroxide and potassium hydroxide are particularly preferred, especially when used in powdered form.
In step (a) of the process of the invention, the halonitrobenzene starting materials (ii) are used in less than 5 the quantity of the polyhydroxyl component (i). 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, 10 (m-n) hydroxyl groups will remain in the (m-n)-hydroxy n-nitrophenoxy adducts of the invention.
The hydrogen halide released during the rea~tion o~ step (a) may be neutralized by the addition of metal hydrides, metal alkoxides, and metal hydroxides preferably sodium or potassium 15 ~ydroxide in at least a stoi~hiometric quantity. In a particularly preferred em~odiment, the alkaline compounds are used in a quantity such that aboutl to 3 molar equivalents of base are a~ailable per mole of components (ii).
Step (a) of the process of the invention is carried out 20 without solvent or, preferably, in an organic solvent and optionally in the presence of a phase transfer catalyst. The 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, 25 such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and trichlorobenzene; ethers and cyclic ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetra-hydrofuran, dioxane, and ethylene glycol dimethyl ether, esters, such as ethyl acetate; ketones, such as acetone, and methyl ethyl 30 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 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 5 which the solvent is used is generally selected so that the starting materials (i) 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 10 mixture of components (i) and (ii).
It can sometimes be advantageous to carry out the reaction of step (a) 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 15 (Verlag Chemie 1983). Suitable catalysts include quaternary ammonium or phosphonium salts of the formula R" (+) R'-N-R"' A( ) I
R""
wherein 25 Z is nitrogen or phosphorus;
s C1 C18 alkyl or C7-C16 araliphatic;
R", R"', and R"" are independently C1-C18 alkyl (with the total number of carbon atoms in R', R", R"', and R""
preferably being about 12 to about 13), and 30 A( ) is a suitable counterion, such as halide (preferred, especially chloride or bromide) or a sulfate, sulfonate, phosphate, or phosphonate group.
Suitable phase transfer catalysts include N-benzyl-N,N,N-triethylammonium chloride or bromide, 35 N-benzyl-N-dodecy~-N,N-dimethylammonium chloride or bromide, N,N,N,N-tetrahexylammonium chloride or bromide, Le A 26 440 N-benzyl-N,N,N-trioctylammonium 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.
5 In the practical application of the process of the invention, t~e`
quaternary ammonium or phosphonium salts are preferably used as is or as aqueous solutions (for example, having a solids conten of from about 30 to about 60 by weight), preferably in a quanti~
of from about 1 to about 10 mole-percent based on the moles of 10 hydroxyl groups present.
Step (a) of the process of the invention is generally carried out at about 10 to about 100C (preferably at 20 to 80C
under excess pressure, reduced pressure, or preferably sub-stantially under vacuum, and either continuously or dis-15 continuously. The residence time for the reaction is generallyfrom about 0.5 to about 24 hours (preferably from 0.5 to 12 hours).
Step (a) of the process of the invention may be carri~
out, for example, by initially adding the starting materials (a 20 optionally, the phase transfer catalyst) to the selected solven and then adding the base in dissolved or suspended form (preferably in very finely ground solid form) in portions or continuously with stirring and optionally with cooling. The reaction mixture is then stirred at room temperature or, 25 optionally, at elevated temperature until the nitrophenylatin~
agent (ii) is substantially completely reacted, as indicated, example, by thin layer chromatography.
The nitrophenoxy adducts are worked up in known mar'er.
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 in vacuo. The reaction mixture may be also neutralized by 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 sol~ents known in the art, The reactionproduct thus obtained may generally be subsequently processed without further purification.
Another method of working up is to add water (of from 1 to 20%) to the reactive mixture, neutralizing with an acid, preferably hydrochloric acid or sulfuric acid, distilling off the water and filtering the mixture at 10 - 12~ C.
In another possible, although less preferred, procedure, the reaction mixture obtained in step (a) is delivered directly to step (b) without intermediate isolation, optionally after neutralization of the excess alkali hydroxide.
In step (b) the nitrophenoxy-terminated compounds obtained in step (a) 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 acti~ated, for example, by known hJlrogenation catalysts such as Raney nickel or palladium on carbon. The hydrogenation may be carried out in the presence or absence of inert sol~ents at about 20 to 120C 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 removal of the sol~ent by distillation and may be used without 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 pre~iously known aromatic amino polyethers by their lower ~iscosity. In addition to the functional groups already present in the basic polyhydroxyl compounds (sucb as, for example, ether, thioether, dialkylsiloxane, or carbonate groups or residues of ~5 polybutadienes), the polyh~dr~a~olyamines of the invention contain only the number of ether groups and h~d. GA~ groups corresponding to their functionality. The aromatic polyhydroxypolyamines of the invention are suitable as reactants for optionally blocked Le A 26 440 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 5 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 10 2,302,564, 2,432,764 (believed to be equivalent to U.S. Patent 3,903,679), 2,639,083, 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 reaction systems that can be stored indefinitely at room 20 temperature (or optionally at elevated temperature) and which harden only after fairly intensive heating. Systems such as these are generally known as one-component systems. Suitable solid polyisocyanates include dimeric 2,4-diisocyanatotoluene ("TT") 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, solutions, dispersions, or as a mixture of reactive components.
30 The polyamines produced according to the invention may also be used, for example, as coupling components for diazo dyes, as hardeners for epoxy and phenolic resins, and in any other known reactions involving amines (such as amidation or imidation reactions, and the like).
Le A 26 440 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 5 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 9 (0.17 mole) of a dehydraLed trimethylolpropane (TMP) started polypropylene oxide (82,5X) ethylene oxide (17,5Y.) ether t riol 15 (OH value 29) are added 26 g (0.1 mole) of 4-c~loronitrobenzene, 14 g (0.25 mole) of powdered po~assium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride. The mix~ure is then s~irred for 12 hours at 7~ C. Af~er 200 ml of water are added a~ room ~empera~ure, the mixture is neutralized with 50% sulfuric acid, the water is distilled 20 off, and the salts that precipitate are filtered off to yield 800 g (79Y.
~heory) of polyhydroxypolynitro product.
Yiscosity: 1500 mPa.s (26C~
OH value: 18 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 2 A mixture of 1000 9 (0.17 mole) of dehydrated poly-pr~lene oxide et~r t~iol (-~ value 29) of E~ple 1, 42 g (-0.26 ~le) of 4-chloronitrobenzene, 22.4 9 (0.40 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium 30 chloride are reacted as in Example 1 to yield 840 9 (81% theory) of polyhydroxypolynitro product.
Viscosity: 1600 mPa.s (26C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene Le A 26 440 --16- l 3341 04 Example 3 A mixture of 1000 9 (0.17 mole) of dehydrated poly-propylene.oxide ether triol (O~ value 29) of Example 1, 57.5 g (0.36 m~le) of 4-chloronitrobenzene, 30.8 9 (0.55 mole) of potassium 5 hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 1 to yield 820 9 (78% theory) of polyhydroxypolynitro product.
Viscosity: 1900 mPa.s (26C) OH value: 9 10 Gas chromatogram: 0.0% 4-chloronitrobenzene Example 4 To a solution of 1000 9 (0.17 mole) of a dehydrated poly-propylene c~ide ether triol (OH value 29) of Example 1 in 1000 ml of toluene is added 26 9 (0.16 mole) of 4-chloronitrobenzene, 14 9 15 (0.25 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 12 hours at 70C. 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 20 precipitate are filtered off to yield 898 9 (88% theory) of polyhydroxypolynitro product.
Viscosity: 1500 mPa.s (20C) OH value: 18 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 5 A solution of 1000 9 (0.17 mole) of dehydrated poly-propylene oxide ether triol (O~-value 29) of Fx~pl~ 1 dissolved in 1000 ml of toluene, 42 9 (0.26 mole) of 4-chloronitrobenzene, 22.4 9 (0.40 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) 30 of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 955 9 (92~ theory) of polyhydroxypolynitro product.
Viscosity: 1400 mPa.s (27C) OH value: 14 Gas chromatogram: 0.0% 4-chloronitrobenzene Le A 26 44~
Example 6 A solution of 1000 9 (0.17 mole) of dehydrated poly-p~ylene oxide ether triol (CH value 29) of Exa~le 1 dissolved in 1000 ml of toluene, 57.5 9 (0.36 mole) of 4-chloronitrobenzene, 5 30.8 9 (0.55 mole) of potassium hydroxide, and 9.25 9 (0.05 mole) of trimethylbenzylammonium chloride are reacted as in Example 4 to yield 1028 9 (100% theory) of polyhydroxypolynitro product.
Viscosity: 1700 mPa.s (20C) OH value: 9 10 Gas chromatogram: 0.1% 4-chloronitrobenzene Example 7 To a solution of 1400 9 (1 mole) of dehydrated polyethylene oxide ether diol (OH value 80) dissolved in 1500 ml of toluene are added 167 9 (1.06 mole) of 4-chloronitrobenzene, 15 90 9 (1.6 mole) of potassium hydroxide, and 11.1 9 (0.06 mole) of trimethylbenzylammonium chloride. The mixture was then stirred for 12 hours at 70C. After 300 ml of water are added at room temperature, the reaction mixture is neutralized with 50~
sulfuric acid, the solvent and water are distilled off, and the 20 salts that precipitate are filtered off to yield 1440 9 (94% theory) of polyhydroxypolynitro product.
Viscosity: 140 mPa.s (70C) OH value: 35 Gas chromatogram: 0.0% 4-chloronitrobenzene 25 Example 8 A mixture of 1000 9 (0.17 mole) of a dehydrated poly-~pylene oxide ether triol~ value 29) of Exa~ple 1, 57.5 g (0.36 le) of 4-chloronitrobenzene, and 30.8 9 (0.55 mole) of potassium hydroxide is stirred for 12 hours at 70C while air is passed 30 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 9 ~74X theory) of polyhydroxypolynitro product.
Le A 26 440 Viscosity: 2000 mPa.s (26C) OH value: 10 Gas chromatogram: 0.0% 4-chloronitrobenzene ExamPle 9 A mixture of 1000 g tO.17 mole) of a dehydrated polypropylene oxide ether triol (OH value 29) of Example 1, 42 9 (0.26 mole) of 2-chloronitrobenzene, and 22.4 9 (0.40 mole) of trimethylbenzylammonium chloride is stirred for 12 hours at 70C 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.
OH value: 16 Gas chromatogram: 0.0% 2-chloronitrobenzene.
ExamPle 10 A mixture of 1000 9 (0.21 mole) of a trimethylol-propane started polypropylenoxid (82,5%) ethylenoxide (17,2%) ether triol (OH value 35), 105 9 (0,94 mole)of 50% aqueous potassium hydroxide solution and 100 ml of toluene were destilled under vacuum (70CI20 mbar) in order to remove the toluenelwater mixture.
The dehydrated polyether was mixed with 69 9 of p-chloronitrobenzene (0,44 mole) dissolved in 170 ml toluene and stirred under vacuum (20 mbar) for a period of 17 hours at 40C. 115 ml of water were added and neutralized with H2S04 (50%). The water was distilled off and the resulting salts filtered at 80C.
Le A 26 440 - 19 _ 1334104 Yield: 940 g (88% ~heory) viscosity: 1600 mPasl24C
OH value: 12 Gel: 0,0% 4-chloronitrobenzene ExamDles 11 to 18: Hydrogena~ion General Procedure To a solu~ion of 100 parts of polyhydroxypolyni~ro compound (e.g., Examples 1 to 10) are dissolved in 100 parts of solven~ are added 10 parts of Raney nickel.
Hydrogenation is carried ou~ in a pressure vessel under a hydrogen pressure of 60 bar at the beginning of ~he reaction and at a ~emperature of 70C.
The data of Examples 11 ~o 18 are shown in Table 1.
Le A 26 440 ~o O O o o o o o o ~ U~ o o o o o o o o ~ N t` O t'') 0 0 0 ~ t~
Ul -- ~ N N --I N N
O ~1 U
In ~L
~rl E
X 0~ ~r ~ 0 N N ~ ~
Z -- N _I N N --IN
O
O O O O ~ ~ O U~
C X t~l t~ t`lt~lN N t~
~rl O
. E
O O X --I N ~ ~ 0 O ~
z 0 ~ ~ O ~ON C
~ ~ 3 O O
~ U
O `D N ~0 N N'D--~ --~ ~L X
-- ~-1 N _1 N N ~ N 111 0 --I Y
u 10 c 111 E
~ O ~ 0 ~r 0 0 ~ ~ C
E~ I N
I O -- --~ O --I O O ~ O
U ~ C
O . I
L ~ ~
_ Z
I N --I N N_1 o 0 D. X ' ' ~ O
_~ -- C
.0 .
N t`~ o 0 ~ _I ~ o Le A 26 440 s Example 19: Application Example The polyhydroxypolyamine (amine value 22) (200 9) 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 ("TT") 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 120-130C, the test specimen (which has hardened in the meantime) is removed from the mold and heated for another 3 to 4 hours at the same temperature.
20 Ultimate tensile strength: 6.0 kp/abs Elongation at break: 250Yo Modulus 100%: 3.16 mPa Tear propagation resistance: 81 N/cm , Shore A hardness: 74 25 Elasticity: 46%
Example 20: Comparison Example with Complete Nitrophenylation To 400 9 (0.07 mole) of a dehydrated polypropylene oxide ether triol (OH value 29) is added 30 g (0.19 mole) of Le A 26 440 - 22 - l 334 1 04 4-chloronitrobenzene, 16.8 9 (0.3 mole) of potassium hydroxide, and 3.7 9 (0.02 mole) of trimethylbenzylammonium chloride. The mixture is then stirred for 22 hours at 70C. After 100 ml of water are added at room temperature, the mixture is neutralized 5 with 50% sulfuric acid, the water is distilled off, and the salts that precipitate are filtered off to yield 383 9 (91% theory) of the nitrophenylated product.
Viscosity: 2000 mPa.s (26C) OH value: 5 10 Gas chromatogram: 1.0% 4-chloronitrobenzene Comparison Example 20 shows that, when using slightly less than the equivalent quantity of nitrophenylating agent (4-chloronitrobenzene), a residue (1.0% 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 9) obtained by hydrogenation of the nitro product of Example 20 is reacted as in 20 Example 19 with 19.0 9 of finely ground dimeric 2,4-diisocyanatotoluene (TT) having an average particle size of 10 to 30 microns.
Ultimate tensile strength: 6.9 kp/abs Elongation at break: 250%
25 Modulus 100%: 5.2 mPa Tear propagation resistance: 78 N/cm Shore A hardness: 79 Elasticity: 47%
Comparison application Example21 shows that, despite 30 almost complete amination of the polyol, the property level of the plastics produced therefrom is not significantly better.
Le A 26 440
Claims (16)
1. A compound of the formula 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.
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.
2. A compound according to Claim 1 wherein the polyhydroxyl compound is a polyalkylene polyether.
3. A compound according to Claim 1 wherein R2 is hydrogen and the NH2 group is in an ortho or para position, having the formula or
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. A compound according to Claim l wherein m is 2 or 3.
7. A process for the preparation of a compound of the formula 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 (a) reacting, in the presence of an alkaline compound, (i) 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 wherein R2 is as defined above and X is halogen, to form an (m-n)-hydroxy n-nitrophenoxy adduct of the formula wherein R1, R2, m, and n are as defined above, and (b) hydrogenating said (m-n)-hydroxy n-nitrophenoxy adduct to form the product compound.
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 (a) reacting, in the presence of an alkaline compound, (i) 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 wherein R2 is as defined above and X is halogen, to form an (m-n)-hydroxy n-nitrophenoxy adduct of the formula wherein R1, R2, m, and n are as defined above, and (b) hydrogenating said (m-n)-hydroxy n-nitrophenoxy adduct to form the product compound.
8. A process according to Claim 7 wherein X is fluorine or chlorine.
9. A process according to Claim 7 wherein the alkaline compound is powdered sodium hydroxide or potassium hydroxide in a quantity sufficient to neutralize hydrogen halide released during the reaction of step (a).
10. 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 (a).
11. A process according to Claim 7 wherein step (a) is carried out in the absence of added solvent.
12. A process according to Claim 7 wherein an organic solvent is used in step (a).
13. A process according to Claim 12 wherein the organic solvent is dimethylsulfoxide or an aromatic hydrocarbon.
14. A process according to Claim 7 wherein a phase transfer catalyst is used in step (a).
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. A method for preparing a polyurethane plastic comprising using a compound according to Claim 1 as a synthesis component in the isocyanate polyaddition process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3834749.0 | 1988-10-12 | ||
| DE3834749A DE3834749A1 (en) | 1988-10-12 | 1988-10-12 | AROMATIC POLY-HYDROXYPOLYAMINES, A PROCESS FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF POLYURETHANE-PLASTICS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334104C true CA1334104C (en) | 1995-01-24 |
Family
ID=6364958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000613904A Expired - Fee Related CA1334104C (en) | 1988-10-12 | 1989-09-28 | Aromatic polyhydroxypolyamines, a process for their preparation, and their use for the preparation of polyurethane plastics |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0363758B1 (en) |
| JP (1) | JPH02169614A (en) |
| KR (1) | KR900006400A (en) |
| AT (1) | ATE83231T1 (en) |
| AU (1) | AU619903B2 (en) |
| BR (1) | BR8905157A (en) |
| CA (1) | CA1334104C (en) |
| DD (1) | DD288385A5 (en) |
| DE (2) | DE3834749A1 (en) |
| ES (1) | ES2053901T3 (en) |
| ZA (1) | ZA897690B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4022931A1 (en) * | 1990-07-19 | 1992-01-23 | Bayer Ag | METHOD FOR PRODUCING POLYETHERS HAVING AMINOPHENOXY GROUPS, THE COMPOUNDS OBTAINED BY THIS METHOD AND THE USE THEREOF AS A REACTION PARTNER FOR ORGANIC POLYISOCYANATES |
| JPH05156002A (en) * | 1991-06-04 | 1993-06-22 | Natl Starch & Chem Investment Holding Corp | Polyether amine compound and epoxy adhesive |
| US5637119A (en) * | 1995-12-29 | 1997-06-10 | Chevron Chemical Company | Substituted aromatic polyalkyl ethers and fuel compositions containing the same |
| US5849048A (en) * | 1997-09-30 | 1998-12-15 | Chevron Chemical Company Llc | Substituted biphenyl poly (oxyalkylene) ethers and fuel compositions containing the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6038412B2 (en) * | 1982-09-21 | 1985-08-31 | 東洋ゴム工業株式会社 | Polyether polyol derivative and its manufacturing method |
| DE3622784A1 (en) * | 1986-07-07 | 1988-01-21 | Wella Ag | NEW 5-ALKOXY-2,4-DIAMINO-ALKYLBENZOLES AND HAIR-COLORING AGENTS WITH 5-ALKOXY-2,4-DIAMINO-ALKYL-BENZOLES |
| US4847416A (en) * | 1986-10-27 | 1989-07-11 | The Dow Chemical Company | Capping of polyols with aromatic amines |
| 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 |
| EP0371248A1 (en) * | 1988-11-03 | 1990-06-06 | Miles Inc. | Polyurea rim systems |
-
1988
- 1988-10-12 DE DE3834749A patent/DE3834749A1/en not_active Withdrawn
-
1989
- 1989-09-28 CA CA000613904A patent/CA1334104C/en not_active Expired - Fee Related
- 1989-09-29 ES ES89118111T patent/ES2053901T3/en not_active Expired - Lifetime
- 1989-09-29 AT AT89118111T patent/ATE83231T1/en not_active IP Right Cessation
- 1989-09-29 DE DE8989118111T patent/DE58902962D1/en not_active Expired - Fee Related
- 1989-09-29 EP EP89118111A patent/EP0363758B1/en not_active Expired - Lifetime
- 1989-10-09 JP JP1262315A patent/JPH02169614A/en active Pending
- 1989-10-10 DD DD89333472A patent/DD288385A5/en not_active IP Right Cessation
- 1989-10-10 AU AU42744/89A patent/AU619903B2/en not_active Ceased
- 1989-10-10 KR KR1019890014461A patent/KR900006400A/en not_active Application Discontinuation
- 1989-10-11 BR BR898905157A patent/BR8905157A/en unknown
- 1989-10-11 ZA ZA897690A patent/ZA897690B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ATE83231T1 (en) | 1992-12-15 |
| JPH02169614A (en) | 1990-06-29 |
| DD288385A5 (en) | 1991-03-28 |
| AU619903B2 (en) | 1992-02-06 |
| ES2053901T3 (en) | 1994-08-01 |
| ZA897690B (en) | 1990-07-25 |
| DE58902962D1 (en) | 1993-01-21 |
| EP0363758A2 (en) | 1990-04-18 |
| EP0363758A3 (en) | 1991-05-02 |
| AU4274489A (en) | 1990-04-26 |
| DE3834749A1 (en) | 1990-04-19 |
| EP0363758B1 (en) | 1992-12-09 |
| BR8905157A (en) | 1990-05-15 |
| KR900006400A (en) | 1990-05-08 |
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