CA2037082A1 - Stable dispersions of polyureas and/or polyhydrazodicarbonamides in relatively high molecular weight compounds containing at least one hydroxyl group, a process for production andtheir use for the production of polyurethane plastics - Google Patents
Stable dispersions of polyureas and/or polyhydrazodicarbonamides in relatively high molecular weight compounds containing at least one hydroxyl group, a process for production andtheir use for the production of polyurethane plasticsInfo
- Publication number
- CA2037082A1 CA2037082A1 CA002037082A CA2037082A CA2037082A1 CA 2037082 A1 CA2037082 A1 CA 2037082A1 CA 002037082 A CA002037082 A CA 002037082A CA 2037082 A CA2037082 A CA 2037082A CA 2037082 A1 CA2037082 A1 CA 2037082A1
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- Prior art keywords
- weight
- molecular weight
- diphenyl methane
- relatively high
- methane diisocyanate
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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
- C08G18/409—Dispersions of polymers of C08G in organic compounds having active hydrogen
-
- 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
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0871—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
- C08G18/0876—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic the dispersing or dispersed phase being a polyol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
Mo-3539 LeA 27,530 STABLE DISPERSIONS OF POLYUREAS AND/OR
POLYHYDRAZODICARBONAMIDES IN RELATIVELY HIGH MOLECULAR WEIGHT
COMPOUNDS CONTAINING AT LEAST ONE HYDROXYL GROUP, A PROCESS FOR
THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF
POLYURETHANE PLASTICS
ABSTRACT OF THE DISCLOSURE
This invention relates to a stable dispersion of polyurea and/or polyhydrazodicarbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group,the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene polyisocyanate.
POLYHYDRAZODICARBONAMIDES IN RELATIVELY HIGH MOLECULAR WEIGHT
COMPOUNDS CONTAINING AT LEAST ONE HYDROXYL GROUP, A PROCESS FOR
THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF
POLYURETHANE PLASTICS
ABSTRACT OF THE DISCLOSURE
This invention relates to a stable dispersion of polyurea and/or polyhydrazodicarbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group,the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene polyisocyanate.
Description
2~)37~ ;2 Mo-3539 LeA 27,530 STABLE DISPERSIONS OF POLYUREAS AND/OR
POLYHYDRAZODICARBONAMIDES IN RELATIVELY HIGH MOLECULAR WEIGHT
COMPOUNDS CONTAINING AT LEAST ONE HYDROXYL GROUP, A PROCESS FOR
THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF
BACKGROUND OF LHE I VEl~2 Field of the Invention The present invention relates to stable dispersions of polyureas and/or polyhydrazodicarbonamides in polyethers (so-called ~PHD polyols~). More specifically, the present invention relates to low viscosity PHD polyols which are employed through the proper selection of starting materials.
Brief DescriDtion of the Prior Art PHD polyols have acquired worldwide significance as starting materials in the production of polyurethane plastics, more particularly flexible polyurethane foams. In the automobile industry and in the automobile supply industry in the USA in particular, solid seats are made from PHD polyols.
The use of PHD polyols provides for increased safety of foaming and for a more favorable hardness-to-density ratio of the cold-cure molded foams.
According to DE-PS 2,513,815, DE-PS 2,550,833 and DE-PS
2,550,862, low-viscosity stable dispersions of polyureas and/or polyhydrazodicarbonamides are prepared in situ by carrying out the reaction of organic polyisocyanates with polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides in relatively high molecular weight polyols continuously in a flow mixer and after-reactlng the product leaving the flow mixer in a receiver. Any water that is present is removed in vacuo either at the same time or afterwards. Polyurea dispersions can also be produced discontinuously by other methods which are described in DE-OS
2,550,796 and DE-OS 2,550,797. Low viscosities are again obtained by the use of water as part of the reaction medium.
2 ~ 2 The isocyanates preferably used in the patents cited above are tolylene diisocyanate isomer mixtures, particularly isomer mixtures of 80% by weight 2,4- and 20% by weight 2,6-tolylene diisocyanate. If mixtures o~ diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates ~crude MDI") are used, the products obtained cannot be processed on account of their viscosity.
DE-OS 3,500,339 describes PHD polyols of high filler content for which addition products of ethylenediamine and acrylonitrile are reacted with a polyisocyanate, including for example crude MDI. The particular advantage of this process lies in the low viscosity of the products obtained and in the excellent processability of the polyols to form polyurethane plastics. However, these PHD polyol types are not lS toxicologically safe. At very high temperatures, they can be split back to a slight extent, so that acrylonitrile is released.
Another method of reducing the viscosity of PHD polyols for the same filler content is to add materials containing hydroxyl groups, particularly water, during the mixing process, as described in EP-OS 187 333. The disadvantage of this process lies in the additional process step which distinctly increases the production costs.
As would be realized, there has been a continuous effort to improve on the PHD polyols and the processes for preparing the same without the disadvantages described hereinabove. The present invention provides such a low viscosity PHD polyol.
S~MMARY OF THE INVENTIQN
In accordance with the foregoing, the present invention 3~ encompasses an improved stable dispersion of polyurea and/or polyhydrazodicarbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a Mo-3539 ~ ~ t~ J ~3 ~ ~
hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of 5 diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60Xo by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene pol yi socyanate .
According to the invention, polyethers are preferably used as the relatively high molecular weight compounds.
Also, in accordance with the invention, alkanolamines can 15 be employed. In one preferred embodiment, polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide is employed in combination with up to 40 mol -% of an al kanol ami ne .
Further, encompassed by the invention is a process for 20 preparing the claimed composition of matter and products made therewi th .
DETAILED DESCRIPTION OF THE INVENTION
It has now surprisingly been found that by the appropriate selection of polyisocyanates, low-viscosity PHD polyols can be ~5 produced even by using diphenyl methane diisocyanate ~MDI) if special MDI types are used instead of the usual "crude MDI"
with its low 2,4'-isomer content and its high oligomer content.
These special MDI types are characterized by the relat~vely high content of monomeric isomers, more particularly the 30 2,4'-MDI isomer. Processable dispersions containing up to 30%
solids and having a viscosi~ of 2000 to 15000 and preferably 2500 to 8000 mPas/25C can be produced in this way. The dispersions are said to be stable in that they do not sediment even after a prolonged storage over a period of, say, > 180 days and even after storage at elevated temperatures.
Mo-3539 ~, ~i3 .j ~ ", ~
POLYHYDRAZODICARBONAMIDES IN RELATIVELY HIGH MOLECULAR WEIGHT
COMPOUNDS CONTAINING AT LEAST ONE HYDROXYL GROUP, A PROCESS FOR
THEIR PRODUCTION AND THEIR USE FOR THE PRODUCTION OF
BACKGROUND OF LHE I VEl~2 Field of the Invention The present invention relates to stable dispersions of polyureas and/or polyhydrazodicarbonamides in polyethers (so-called ~PHD polyols~). More specifically, the present invention relates to low viscosity PHD polyols which are employed through the proper selection of starting materials.
Brief DescriDtion of the Prior Art PHD polyols have acquired worldwide significance as starting materials in the production of polyurethane plastics, more particularly flexible polyurethane foams. In the automobile industry and in the automobile supply industry in the USA in particular, solid seats are made from PHD polyols.
The use of PHD polyols provides for increased safety of foaming and for a more favorable hardness-to-density ratio of the cold-cure molded foams.
According to DE-PS 2,513,815, DE-PS 2,550,833 and DE-PS
2,550,862, low-viscosity stable dispersions of polyureas and/or polyhydrazodicarbonamides are prepared in situ by carrying out the reaction of organic polyisocyanates with polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides in relatively high molecular weight polyols continuously in a flow mixer and after-reactlng the product leaving the flow mixer in a receiver. Any water that is present is removed in vacuo either at the same time or afterwards. Polyurea dispersions can also be produced discontinuously by other methods which are described in DE-OS
2,550,796 and DE-OS 2,550,797. Low viscosities are again obtained by the use of water as part of the reaction medium.
2 ~ 2 The isocyanates preferably used in the patents cited above are tolylene diisocyanate isomer mixtures, particularly isomer mixtures of 80% by weight 2,4- and 20% by weight 2,6-tolylene diisocyanate. If mixtures o~ diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates ~crude MDI") are used, the products obtained cannot be processed on account of their viscosity.
DE-OS 3,500,339 describes PHD polyols of high filler content for which addition products of ethylenediamine and acrylonitrile are reacted with a polyisocyanate, including for example crude MDI. The particular advantage of this process lies in the low viscosity of the products obtained and in the excellent processability of the polyols to form polyurethane plastics. However, these PHD polyol types are not lS toxicologically safe. At very high temperatures, they can be split back to a slight extent, so that acrylonitrile is released.
Another method of reducing the viscosity of PHD polyols for the same filler content is to add materials containing hydroxyl groups, particularly water, during the mixing process, as described in EP-OS 187 333. The disadvantage of this process lies in the additional process step which distinctly increases the production costs.
As would be realized, there has been a continuous effort to improve on the PHD polyols and the processes for preparing the same without the disadvantages described hereinabove. The present invention provides such a low viscosity PHD polyol.
S~MMARY OF THE INVENTIQN
In accordance with the foregoing, the present invention 3~ encompasses an improved stable dispersion of polyurea and/or polyhydrazodicarbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a Mo-3539 ~ ~ t~ J ~3 ~ ~
hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of 5 diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60Xo by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene pol yi socyanate .
According to the invention, polyethers are preferably used as the relatively high molecular weight compounds.
Also, in accordance with the invention, alkanolamines can 15 be employed. In one preferred embodiment, polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide is employed in combination with up to 40 mol -% of an al kanol ami ne .
Further, encompassed by the invention is a process for 20 preparing the claimed composition of matter and products made therewi th .
DETAILED DESCRIPTION OF THE INVENTION
It has now surprisingly been found that by the appropriate selection of polyisocyanates, low-viscosity PHD polyols can be ~5 produced even by using diphenyl methane diisocyanate ~MDI) if special MDI types are used instead of the usual "crude MDI"
with its low 2,4'-isomer content and its high oligomer content.
These special MDI types are characterized by the relat~vely high content of monomeric isomers, more particularly the 30 2,4'-MDI isomer. Processable dispersions containing up to 30%
solids and having a viscosi~ of 2000 to 15000 and preferably 2500 to 8000 mPas/25C can be produced in this way. The dispersions are said to be stable in that they do not sediment even after a prolonged storage over a period of, say, > 180 days and even after storage at elevated temperatures.
Mo-3539 ~, ~i3 .j ~ ", ~
In addition, flexible polyurethane foams produced with the dispersions according to the ;nvention are distinguished by improved flame behavior compared with foams produced with toluene diisocyanates (TDI)-based PHD polyols, as described in DE-OS 2,519,004. The advantages described in this DE-OS, such as greater hardness, elasticity and favorable mechanical properties of the foams obtained, are also achieved where the dispersions according to the invention are used.
Another advantage of the polyurethane foams produced by the process according to the invention lies in their better resistance to humid heat. It has been found that, after storage in a steam autoclave, a distinctly improved compression set and relatively little change in compression hardness are obtained where the dispersions according to the invention are used.
As set forth above, the present invention relates to stable dispersions of polyureas and/or polyhydrazodicarbon-amides in relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight of 200 to 16,000, obtainable by reaction of a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate (4,4'-MDI) 5 to 60% by weight 2,4'-diphenyl methane diisocyanate (2,4'-MDI~
O to 4% by weight 2,2'-diphenyl methane diisocyanate (2,2'-MDI) and O to 3~% by weight polyphenyl polymethylene 3G polyisocyanates (oligomeric isomers) with b) polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides, in the Mo-3~39 ~ S~ '3 c) relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight in the range from 200 to 16,000.
The present invention also relates to a process for the production of stable dispersions of polyurPas and/or polyhydrazodicarbonamides in relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight of 200 to 16,000, characterized in that a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate and 0 to 30% by weight polyphenyl polymethylene polyisocyanates are reacted with b) polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides, in c) relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight in the range from 200 to 16,~00.
The present invention also relates to a process for the production of optionally foamed polyurethane plastics, more particularly flexible foams, by reaction of polyisocyanates with relatively high molecular weight hydroxyl compounds, optionally in the presence of water and/or readily volatile organic substances as blowing agents and optionally using catalysts, foam auxiliaries and additives and chain-extending and/or crosslinking agents, characterized in that the dispersions according to the invention are exclusively or partly used as the relatively high molecular weight hydroxyl compounds.
~ ;i t ~
The following starting compounds are used for the production of the dispersions according to the invention: a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate and O to 30% by weight polyphenyl polymethylene polyisocyanates.
This mixture preferably consists of 50 to 75% by weight 4,4'-diphenyl methane diisocyanate 10 to 25% by weight 2,4'-diphenyl methane diisocyanate 0 to 3% b~ weight 2,2'-diphenyl methane d;isocyanate and 10 to 30% by weight polyphenyl polymethylene polyisocyanates.
The following are mentioned as examples of component b):
primary and/or secondary, aliphatic, araliphatic, cycloaliphatic and aromatic polyamines, for example ethylenediamine, 1,2- and 1,3-propylenediamine, tetramethylene-diamine, hexamethylenediamine, dodecamethylenediamine, trimethyl diaminohexane, N,N'-dimethyl ethylenediamine, 2,2'-bis-aminopropyl methylamine, higher homologs of ethylenediamine, such as diethylenetriamine, triethylene tetramine and tetraethylene pentamine, homologs of propylenediamine, such as dipropylenetrlamine, piperazine, N,N'-bis-aminoethyl piperazine, triazine, 4-aminobenzylamine, 4-aminophenyl ethylamine, 1-amino-3,3,5-trimethyl-5-aminomethyl 3~ cyclohexane, 4,4'-diaminodicyclohexyl methane and propane, 1,4-diaminocyclohexane, phenylenediamines, naphthylenediamines, condensates of aniline and formaldehyde, tolylenediamines, bis-aminomethyl benzenes and derivatives of the aromatic amines mentioned monoalkylated at one or both nitrogen atoms. The Mo-3539 polyamines generally have a molecular weight in the range from ~0 to 1,000 and preferably in the range from 60 to 3~0.
Suitable hydrazines are hydrazine and mono- or N,N'-disubstituted hydrazines, the substituents being alkyl yroups, cyclohexyl groups or phenyl groups. The hydrazines generally have a molecular weight of 32 to 500.
Hydrazine itself is preferably used.
Su;table hydrazides are the hydrazides of dibasic or polybasic carboxylic acids, such as carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid; the esters of hydrazine monocarboxylic acid with dihydric or polyhydric alcohols and phenols, such as for example ethanediol, propane-1,2-diol, butane-1,2-, -1,3-and -1,4-diol, hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and hydroquinone, and also the amides of hydra~ine monocarboxylic acid (semicarbazides), for example with the diamines and polyamines mentioned above. The hydrazides generally have a molecular weight in the range from 90 to 3,000 and preferably in the range from 90 to 1,00Q.
The amines and hydrazines mentioned above are optionally used in the form of commercially available aqueous solutions.
Ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine and dibutanolamine are mentioned as examples of alkanolamines which may optionally be used. In one preferred embodiment, up to 40 mol-% of an alkanolamine is employed in combination with the polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide.
Starting component c) can be relatively high molecular weight compounds containing at least 1, generally 2 to 8 and preferably 2 to 6 hydroxyl groups, such as polyethers, polyesters, polyesteramides, polythioethers or polycarbonates having an average molecular weight in the range from 200 to Mo-3539 16,000 and preferably in the range from 500 to 12tO00.
According to the invention, polyethers are preferred.
The preferred hydroxyl polyethers are those known Per se and are obtained, for example, by polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, on their own, for example in the presence of Lewis catalysts, such as BF3, or by addition of these epoxides, preferably ethylene oxide and propylene oxide, optionally in admixture or successively, onto starter components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol, 1,3-or 1,2-propylene glycol, trimethylol propane, glycerol, sorbitol, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine and ethylenediamine. Sucrose polyethers, for example of the type described in DE-AS 1,176,358 and 1,064,938, and formitol or formose started polyethers IDE-OS 2,639,083 and 2,737,951 may also be used in accordance with the invention. In many cases, it is preferred to use polyethers predominantly containing primary OH ~roups (up to 90% by weight, based on all the OH groups present in the polyether. According to the invention, polybutadienes containing OH groups are also suitable, as are hydroxyfunctional polymers of tetrahydrofuran.
According to the invention, amines, hydrazines or ~ydrazides having a functionality of more than 2 may also be exclusively or partly used. It may be regarded as surprising that the reaction of more than difunctional compounds in the hydroxyl compounds in accordance with the invention does not lead to solid or at least very high viscosity reaction products. Instead, there are obtained finely divided dispersions of low viscosity. The particle size of the dispersed products can be from 0,3to 2,5 and preferably 0,6tol,2~rn.
The polyaddition products prepared in accordance with the invention and dispersed in the hydroxyl compounds may even be Mo-3539 modified by the partial use of monofunctional isocyanates, amines, hydrazine derivatives or ammonia.
For example9 the average molecular weight of the polyaddition products may be adjusted as required through the incorporation of such monofunctional compounds. ~here alkanolamines containing primary or secondary amino groups are used, polyureas and/or polyhydrazodicarbonamides containing $ree hydroxyl groups may be synthesized. Other groups, for example ester groups, relatively long aliphatic radicals, 1~ tertiary amino groups, active double bonds, etc., may also be introduced provided that the correspondingly substituted mono-or diamines or isocyanates are used.
According to the invention, the monofunctional compounds may be used in quantities of up to 40 mol-% and preferably in quantities of up to 25 mol-% (based on total isocyanate or amine, hydrazine or hydrazide).
Suitable monofunctional isocyanates are, for example, alkyl isocyanates, such as methyl, ethyl, isopropyl, isobutyl, hexyl, lauryl and stearyl isocyanate, chlorohexyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, 4-chlorophenyl isocyanate and diisopropyl phenyl isocyanate.
Suitable monoamines are, for example, alkyl and dialkylamines containing Cl 18 alkyl groups, cycloaliphatic amines, such as cyclohexylamine and homologs, aniline and N-alkylanilines and also aniline derivatives substituted at the benzene ring, alkanolamines, such as ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanol amine and dibutanolamine, and also diamines containing one tertiary amino group and one primary or secondary amino group, such as for example N,N-dimethyl ethylenediamine and N-methyl piperazine. Suitable monofunctional hydrazine derivatives and hydrazides are, for example, N,N-dialkyl hydrazines, the hydrazides of monocarboxylic acids, hydrazine monocarboxylic acid esters of monofunctional alcohols or phenols and also semicarbazides such as, for example, methyl, ethyl, propyl, Mo-3539 butyl, hexyl, dodecyl, stearyl, phenyl and cyclohexyl semicarbazide.
The dispersions according to the ;nvention are prepared discontinuously or (preferably) cont;nuously by methods known per se.
The concentration of the polyaddition products in the hydroxyl compound may vary within wide limits, but is generally between 1 and 35% by we;ght and preferably between 5 and 25% by weight. The quantity of dispersed polyaddit;on product required for foams having opt;mal propert;es is generally from about 5 to 15% by weight. According to the invention, these 5 to 15~O by weight d;spers;ons may of course be directly produced. ~or econom;c reasons, ;t ;s often preferred to produce a d;spers;on hav;ng a high content of polyadd;tion products (approx. 20 to 35% by we;ght) and subsequently d;lute it to the desired concentration w;th a relatively high molecular we;ght hydroxyl compound.
~ he dispersions obtained by the process according to the ;nvent;on may be processed, for example, to flex;ble, sem;rigid and r;gid polyurethane foams having improved properties, such as increased tensile strength and hardness. The dispersions are also suitable for the production of, for example, polyurethane-based elastomers and coatings.
The following starting components are used for the production of the optionally foamed polyurethane plastics:
1. Aliphatic, cycloaliphatic, aral;phatic, aromatic and heterocycl;c polyisocyanates of the type descr;bed for example by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those corresponding to the formula Q(NCO)n in which n = 2-4, and preferably 2;
Mo-35~9 ~ ~J '' J '~
Q represents an aliphatic hydrocarbon radical containing from 2 to 18 carbon atoms and preferably from 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical containing from 4 to 15 and preferably from 5 to l0 carbon atoms, an aromatic hydrocarbon radical containing from 6 to 15 carbon atoms and preferably 6 to 13 carbon atoms, or an araliphatic hydrocarbon radical containing from 8 to 15 carbon atoms and preferably from 8 to 13 carbon atoms. Example of the useful polyisocyanates are described in DE-OS 2,832,253, pages 10-11. In general, it is particularly preferred to use the commercially readily available polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate, also any mixtures of these isomers ("TDI"~, polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation ("crude MDI") and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), particularly modified polyisocyanates of the type derived from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
2. Other starting components are the dispersions according to the invention and, optionally in part (up to 80%
by weight), other compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of generally 200 to 10,000. In addition to compounds containing amino groups, thiol groups or carboxyl groups, compounds such as these are preferably compounds containing hydroxyl groups, particularly compounds containing from 2 to 8 hydroxyl groups, above all those having molecular weights of 1,000 to 6,000 and preferably 2,000 to 6,000, for example polyethers and polyesters containing at least 2, generally 2 to 8, but preferably 2 to 6 hydroxyl groups and also polycarbonates and polyester amides of the type known per se for the product;on of homogeneous and cellular polyurethanes and described, for example, in DE-OS 2,832,253, pages 11-18.
Mo-3539 ~b ~ ., 3"
3. Other starting components are optionally compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of ~rom 32 to 199. In this case, too, the compounds in question are compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl sroups and/or amino groups which serve as cha;n extenders or crosslinkers. These compounds generally contain 2 to 8 and preferably 2 to 4 isocyanate-reactive hydrogen atoms. Examples thereof can be found in DE-OS 2,832,253, pages 19-20.
4. Auxiliaries and additives are optionally usedt including a) water and/or readily volatile organic compounds as blowing agents, b) additional catalysts known per se in quantities of up to 10% by weight, based on the quantities of component 2, c) surface-active additives, such as emulsifiers and foam stabilizers, d) reaction retarders, for example acid-reacting substances such as hydrochloric acid or organic acid halides, also cell regulators known per se, such as paraffins or fatty alcohols or dimethyl polysiloxanes and also pigments or dyes and other flameproofing agents known per se for example trischloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, also stabilizers against the effects of aging and weather, plastic~zers and fungistatic and bacteriostatic substances as well as fillers such as barium sulfate, kieselguhr, carbon black or whiting.
These optional auxiliaries and additives are described, for example, in ~E-OS 2,732,292, pages 21-24. Further examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flameproofing agents, plasticizers, dyes, fillers, fungistatic and bacteriostatic substances which may optionally be used in Mo-3539 ~J ~ ! J
accordance with the invention and information on the way in which these additives are used and on their respective modes of action can be found in Kunststoff-Handbuch by Vieweg and Hochtlen, Vol. VII, Carl-Hanser-Verlag, Munchen 1966, for example on pages 103 to 113.
The foams are produced by methods known per se.
The process for the production of polyurethane plastics is carried out as follows: The reaction components are reacted by the one-shot process known per se, by the prepolymer process or by the semiprepolymer process, in many cases using machines, for example of the type described in US-PS 2,764,565.
Particulars of processing machines which may also be used in accordance with the invention can be found in Kunststoff Handbuch by Vieweg and Hochtlen~ Vol. VII, Carl-Hanser Verlag, Munchen, 1966, for example on pages l2l to 205.
According to the invention, it is also possible to produce cold-cure foams (cf. GB-PS 1,162,517 and DE-OS 2,153,086).
However, it is of course also possible to produce foams by slabstock foaming or by the laminator process known per se.
The rigid foams obtainable in accordance with the invention are used, for example, as roof insulation panels.
The flex;ble polyurethane foams preferably obtainable in accordance with the invention are used, for example, as arm rests (for example in automobiles) and as cushions for furniture and seats in public transportation.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Examp~le 1 a) Preparation of the dispersion 4,000 g/min. of a polyether prepared f`rom propylene oxide(83%~
ethylene oxide (17%)and ~imethylo1 propane (hydloxyl v~ue 35, approx. 80% primary OH groups), 890 g/min. of a mixture of 60%
by weight 4,4'-MDI, 23% by weight 2,4'-MDI, 2% by weight Mo-3539 5, 2,2'-MDI and 15% by weight polyphenyl polymethylene polyisocyanates (oligomeric isomers) and 175 g/min. hydrazine hydrate are continuously introduced at room temperature into a toothed stirrer (chamber volume 0.5 l, rotational speed 5,000 r.p.m.). The polyether is introduced from the storage tank by a gear pump while two thinly liquid components are introduced from separate storage vessels by piston metering pumps. The exothermic polyaddition reaction takes place in the toothed stirrer. By cooling the toothed stirrer, the reaction temperature is kept at 100C. After a residence tlme of approximately 6 seconds, an almost completely reacted dispersion leaves the toothed stirrer. The dispersion formed, which has still not completely reacted off, is transferred to a holding vessel where it is stirred at 80 to 100~C.
After stirring, the water emanating from the hydrazine hydrate is distilled off in vacuo at 100C. A stable, finely divided 20% by weight dispersion having an OH value of 28 and a viscosity of 3,600 mPas/25~C is obtained.
b) Production of a flexible wlYurethane foam A component 60 parts by weight of the dispersion of example la 40 parts by weight of a polyether polyol having an OH value of 28 prepared by propoxyla~on (83%) of trimethylol propane and subsequent ethoxyla~on (17%) 3.3 parts by weight water 0.12 part by weight bis-dimethylaminoethyl ether (catalyst) 0.50 part by weight of a 33% solution of diazabicyclo(2,2,2)-octane in dipropylene glycol (catalyst) 0.20 part by weight of a commercially available foam stabilizer (B 4617, a product of Goldschmidt AG, Essen) 0.80 part by weight of a commercially available foam stabilizer (KS 43, a product of Bayer AG).
~o-3539 '~J r~
B component Mixture of B0% by weight TDI 80 and 20% by weight of a mixture of diphenyl methane diisocyanates and polyphenylene polymethylene polyisocyanates having the composition:
50% by weight 4,4'-MDI, 3% by weight 2,4'-MDI and 47% by weight oligomeric isomers.
100 Parts by weight of the A component are mixed with 38 parts by weight of the B component in 2 high-pressure ~achine.
The reaction mixture is introduced into a 40 liter box mold heated to approximately 50C. The mold is closed and the flexible foam molding is removed from the mold after about 6 minutes. The filled weight is 1.88 kg. Mechanical testing produces the following results:
Test results Density (kg/m3) DIN 53 420 42.4 Compression hardness 50% ~KPa) DIN 53 577 5.1 Tensile strength (KPa) DIN 53 571 186 Elongation at break (%) DIN 53 571 148 Compression set 50%, Cd value (%) GME 60 283 7.5 Storage in a steam autoclave ~ME 60 283 Compression hardness after stortge (KP~3 5.2 Compression set 50%, Cd value after storage (%) 24.2 Example 2 (Comparison Example) a) Preparation of the dispersion The polyether dispersion is prepared in the same way as in Example la) except that the isocyanate used and the quantities used are different. 4,000 9 of the same polyether as in Example la) are reacted with 845 9 of a mixture oF 80% by weight 2,4- and 20% by weight 2,6-tolylene diisocyanate and 245 9 hydrazine hydrate in the same way as in Example la) A
stable, white, finely divided 2~% by weight dispersion having Mo-3539 tr'J ,) ;J : 3 j `
an OH value of ~8 and a viscosity of 3,000 mpas/25C is obtained.
b) Production of a flexible polYurethane foam A component 60 Parts by weight of the same dispersion as in Example 2a).
All the other constituents of the A component are the same as in Example la).
B component Identical with Example lb) 100 Parts by weight of the A component are mixed with 38 parts by weight of the B component in a high-pressure machine.
The reaction mixture is introduced into a 40 liter box mold heated to approximately 50C. The mold is closed and the flexible foam molding is removed from the mold after about 6 minutes. The filled weight is 1.88 kg. Mechanical testing produces the following results:
lest results Density (kg/m3) DIN 53 420 42.0 Compression hardness 50% (KPa) DIN 53 577 4.3 Tensile strength (KPa) DIN 53 571 166 Elongation at break (%) DIN 53 571 151 Compression set 50/Q, Cd value GME 60 283 9.1 Storage in a steam autoclave GME 60 283 Compression hardness after storage (KPa) 5.0 Compression set 5000, Cd value after storage (%) 32.6 Comparison of Examples 1 and 2 shows that aging in a steam autoclave causes distinctly less damage to the foams according to the invention. Overall, the properties of the foam according to the invention are improved over those of the conventional foam produced in accordance with Example 2.
Mo-3539 Example 3 (Comparison Example) The dispersion is again prepared in the same way as in Example Ia) using an isocyanate typically known as "crude MDI".
The MDI used in this case has the following composition:
49% by weight 4,4'-MDI
2% by weight 2,4'-MDI
~0.5YO by weight 2,2/-MDI
49% by weight oligomeric isomers.
A white-brown paste is obtained but cannot be processed on account of its viscosity.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variation can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-3539
Another advantage of the polyurethane foams produced by the process according to the invention lies in their better resistance to humid heat. It has been found that, after storage in a steam autoclave, a distinctly improved compression set and relatively little change in compression hardness are obtained where the dispersions according to the invention are used.
As set forth above, the present invention relates to stable dispersions of polyureas and/or polyhydrazodicarbon-amides in relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight of 200 to 16,000, obtainable by reaction of a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate (4,4'-MDI) 5 to 60% by weight 2,4'-diphenyl methane diisocyanate (2,4'-MDI~
O to 4% by weight 2,2'-diphenyl methane diisocyanate (2,2'-MDI) and O to 3~% by weight polyphenyl polymethylene 3G polyisocyanates (oligomeric isomers) with b) polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides, in the Mo-3~39 ~ S~ '3 c) relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight in the range from 200 to 16,000.
The present invention also relates to a process for the production of stable dispersions of polyurPas and/or polyhydrazodicarbonamides in relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight of 200 to 16,000, characterized in that a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate and 0 to 30% by weight polyphenyl polymethylene polyisocyanates are reacted with b) polyamines containing primary and/or secondary amino groups and/or hydrazines and/or hydrazides, in c) relatively high molecular weight compounds containing at least one hydroxyl group and having a molecular weight in the range from 200 to 16,~00.
The present invention also relates to a process for the production of optionally foamed polyurethane plastics, more particularly flexible foams, by reaction of polyisocyanates with relatively high molecular weight hydroxyl compounds, optionally in the presence of water and/or readily volatile organic substances as blowing agents and optionally using catalysts, foam auxiliaries and additives and chain-extending and/or crosslinking agents, characterized in that the dispersions according to the invention are exclusively or partly used as the relatively high molecular weight hydroxyl compounds.
~ ;i t ~
The following starting compounds are used for the production of the dispersions according to the invention: a) a mixture of diphenyl methane diisocyanates and polyphenyl polymethylene polyisocyanates consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate and O to 30% by weight polyphenyl polymethylene polyisocyanates.
This mixture preferably consists of 50 to 75% by weight 4,4'-diphenyl methane diisocyanate 10 to 25% by weight 2,4'-diphenyl methane diisocyanate 0 to 3% b~ weight 2,2'-diphenyl methane d;isocyanate and 10 to 30% by weight polyphenyl polymethylene polyisocyanates.
The following are mentioned as examples of component b):
primary and/or secondary, aliphatic, araliphatic, cycloaliphatic and aromatic polyamines, for example ethylenediamine, 1,2- and 1,3-propylenediamine, tetramethylene-diamine, hexamethylenediamine, dodecamethylenediamine, trimethyl diaminohexane, N,N'-dimethyl ethylenediamine, 2,2'-bis-aminopropyl methylamine, higher homologs of ethylenediamine, such as diethylenetriamine, triethylene tetramine and tetraethylene pentamine, homologs of propylenediamine, such as dipropylenetrlamine, piperazine, N,N'-bis-aminoethyl piperazine, triazine, 4-aminobenzylamine, 4-aminophenyl ethylamine, 1-amino-3,3,5-trimethyl-5-aminomethyl 3~ cyclohexane, 4,4'-diaminodicyclohexyl methane and propane, 1,4-diaminocyclohexane, phenylenediamines, naphthylenediamines, condensates of aniline and formaldehyde, tolylenediamines, bis-aminomethyl benzenes and derivatives of the aromatic amines mentioned monoalkylated at one or both nitrogen atoms. The Mo-3539 polyamines generally have a molecular weight in the range from ~0 to 1,000 and preferably in the range from 60 to 3~0.
Suitable hydrazines are hydrazine and mono- or N,N'-disubstituted hydrazines, the substituents being alkyl yroups, cyclohexyl groups or phenyl groups. The hydrazines generally have a molecular weight of 32 to 500.
Hydrazine itself is preferably used.
Su;table hydrazides are the hydrazides of dibasic or polybasic carboxylic acids, such as carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid; the esters of hydrazine monocarboxylic acid with dihydric or polyhydric alcohols and phenols, such as for example ethanediol, propane-1,2-diol, butane-1,2-, -1,3-and -1,4-diol, hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and hydroquinone, and also the amides of hydra~ine monocarboxylic acid (semicarbazides), for example with the diamines and polyamines mentioned above. The hydrazides generally have a molecular weight in the range from 90 to 3,000 and preferably in the range from 90 to 1,00Q.
The amines and hydrazines mentioned above are optionally used in the form of commercially available aqueous solutions.
Ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine and dibutanolamine are mentioned as examples of alkanolamines which may optionally be used. In one preferred embodiment, up to 40 mol-% of an alkanolamine is employed in combination with the polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide.
Starting component c) can be relatively high molecular weight compounds containing at least 1, generally 2 to 8 and preferably 2 to 6 hydroxyl groups, such as polyethers, polyesters, polyesteramides, polythioethers or polycarbonates having an average molecular weight in the range from 200 to Mo-3539 16,000 and preferably in the range from 500 to 12tO00.
According to the invention, polyethers are preferred.
The preferred hydroxyl polyethers are those known Per se and are obtained, for example, by polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, on their own, for example in the presence of Lewis catalysts, such as BF3, or by addition of these epoxides, preferably ethylene oxide and propylene oxide, optionally in admixture or successively, onto starter components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol, 1,3-or 1,2-propylene glycol, trimethylol propane, glycerol, sorbitol, 4,4'-dihydroxydiphenyl propane, aniline, ethanolamine and ethylenediamine. Sucrose polyethers, for example of the type described in DE-AS 1,176,358 and 1,064,938, and formitol or formose started polyethers IDE-OS 2,639,083 and 2,737,951 may also be used in accordance with the invention. In many cases, it is preferred to use polyethers predominantly containing primary OH ~roups (up to 90% by weight, based on all the OH groups present in the polyether. According to the invention, polybutadienes containing OH groups are also suitable, as are hydroxyfunctional polymers of tetrahydrofuran.
According to the invention, amines, hydrazines or ~ydrazides having a functionality of more than 2 may also be exclusively or partly used. It may be regarded as surprising that the reaction of more than difunctional compounds in the hydroxyl compounds in accordance with the invention does not lead to solid or at least very high viscosity reaction products. Instead, there are obtained finely divided dispersions of low viscosity. The particle size of the dispersed products can be from 0,3to 2,5 and preferably 0,6tol,2~rn.
The polyaddition products prepared in accordance with the invention and dispersed in the hydroxyl compounds may even be Mo-3539 modified by the partial use of monofunctional isocyanates, amines, hydrazine derivatives or ammonia.
For example9 the average molecular weight of the polyaddition products may be adjusted as required through the incorporation of such monofunctional compounds. ~here alkanolamines containing primary or secondary amino groups are used, polyureas and/or polyhydrazodicarbonamides containing $ree hydroxyl groups may be synthesized. Other groups, for example ester groups, relatively long aliphatic radicals, 1~ tertiary amino groups, active double bonds, etc., may also be introduced provided that the correspondingly substituted mono-or diamines or isocyanates are used.
According to the invention, the monofunctional compounds may be used in quantities of up to 40 mol-% and preferably in quantities of up to 25 mol-% (based on total isocyanate or amine, hydrazine or hydrazide).
Suitable monofunctional isocyanates are, for example, alkyl isocyanates, such as methyl, ethyl, isopropyl, isobutyl, hexyl, lauryl and stearyl isocyanate, chlorohexyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, tolyl isocyanate, 4-chlorophenyl isocyanate and diisopropyl phenyl isocyanate.
Suitable monoamines are, for example, alkyl and dialkylamines containing Cl 18 alkyl groups, cycloaliphatic amines, such as cyclohexylamine and homologs, aniline and N-alkylanilines and also aniline derivatives substituted at the benzene ring, alkanolamines, such as ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanol amine and dibutanolamine, and also diamines containing one tertiary amino group and one primary or secondary amino group, such as for example N,N-dimethyl ethylenediamine and N-methyl piperazine. Suitable monofunctional hydrazine derivatives and hydrazides are, for example, N,N-dialkyl hydrazines, the hydrazides of monocarboxylic acids, hydrazine monocarboxylic acid esters of monofunctional alcohols or phenols and also semicarbazides such as, for example, methyl, ethyl, propyl, Mo-3539 butyl, hexyl, dodecyl, stearyl, phenyl and cyclohexyl semicarbazide.
The dispersions according to the ;nvention are prepared discontinuously or (preferably) cont;nuously by methods known per se.
The concentration of the polyaddition products in the hydroxyl compound may vary within wide limits, but is generally between 1 and 35% by we;ght and preferably between 5 and 25% by weight. The quantity of dispersed polyaddit;on product required for foams having opt;mal propert;es is generally from about 5 to 15% by weight. According to the invention, these 5 to 15~O by weight d;spers;ons may of course be directly produced. ~or econom;c reasons, ;t ;s often preferred to produce a d;spers;on hav;ng a high content of polyadd;tion products (approx. 20 to 35% by we;ght) and subsequently d;lute it to the desired concentration w;th a relatively high molecular we;ght hydroxyl compound.
~ he dispersions obtained by the process according to the ;nvent;on may be processed, for example, to flex;ble, sem;rigid and r;gid polyurethane foams having improved properties, such as increased tensile strength and hardness. The dispersions are also suitable for the production of, for example, polyurethane-based elastomers and coatings.
The following starting components are used for the production of the optionally foamed polyurethane plastics:
1. Aliphatic, cycloaliphatic, aral;phatic, aromatic and heterocycl;c polyisocyanates of the type descr;bed for example by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those corresponding to the formula Q(NCO)n in which n = 2-4, and preferably 2;
Mo-35~9 ~ ~J '' J '~
Q represents an aliphatic hydrocarbon radical containing from 2 to 18 carbon atoms and preferably from 6 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical containing from 4 to 15 and preferably from 5 to l0 carbon atoms, an aromatic hydrocarbon radical containing from 6 to 15 carbon atoms and preferably 6 to 13 carbon atoms, or an araliphatic hydrocarbon radical containing from 8 to 15 carbon atoms and preferably from 8 to 13 carbon atoms. Example of the useful polyisocyanates are described in DE-OS 2,832,253, pages 10-11. In general, it is particularly preferred to use the commercially readily available polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate, also any mixtures of these isomers ("TDI"~, polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation ("crude MDI") and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), particularly modified polyisocyanates of the type derived from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
2. Other starting components are the dispersions according to the invention and, optionally in part (up to 80%
by weight), other compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of generally 200 to 10,000. In addition to compounds containing amino groups, thiol groups or carboxyl groups, compounds such as these are preferably compounds containing hydroxyl groups, particularly compounds containing from 2 to 8 hydroxyl groups, above all those having molecular weights of 1,000 to 6,000 and preferably 2,000 to 6,000, for example polyethers and polyesters containing at least 2, generally 2 to 8, but preferably 2 to 6 hydroxyl groups and also polycarbonates and polyester amides of the type known per se for the product;on of homogeneous and cellular polyurethanes and described, for example, in DE-OS 2,832,253, pages 11-18.
Mo-3539 ~b ~ ., 3"
3. Other starting components are optionally compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of ~rom 32 to 199. In this case, too, the compounds in question are compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl sroups and/or amino groups which serve as cha;n extenders or crosslinkers. These compounds generally contain 2 to 8 and preferably 2 to 4 isocyanate-reactive hydrogen atoms. Examples thereof can be found in DE-OS 2,832,253, pages 19-20.
4. Auxiliaries and additives are optionally usedt including a) water and/or readily volatile organic compounds as blowing agents, b) additional catalysts known per se in quantities of up to 10% by weight, based on the quantities of component 2, c) surface-active additives, such as emulsifiers and foam stabilizers, d) reaction retarders, for example acid-reacting substances such as hydrochloric acid or organic acid halides, also cell regulators known per se, such as paraffins or fatty alcohols or dimethyl polysiloxanes and also pigments or dyes and other flameproofing agents known per se for example trischloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, also stabilizers against the effects of aging and weather, plastic~zers and fungistatic and bacteriostatic substances as well as fillers such as barium sulfate, kieselguhr, carbon black or whiting.
These optional auxiliaries and additives are described, for example, in ~E-OS 2,732,292, pages 21-24. Further examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flameproofing agents, plasticizers, dyes, fillers, fungistatic and bacteriostatic substances which may optionally be used in Mo-3539 ~J ~ ! J
accordance with the invention and information on the way in which these additives are used and on their respective modes of action can be found in Kunststoff-Handbuch by Vieweg and Hochtlen, Vol. VII, Carl-Hanser-Verlag, Munchen 1966, for example on pages 103 to 113.
The foams are produced by methods known per se.
The process for the production of polyurethane plastics is carried out as follows: The reaction components are reacted by the one-shot process known per se, by the prepolymer process or by the semiprepolymer process, in many cases using machines, for example of the type described in US-PS 2,764,565.
Particulars of processing machines which may also be used in accordance with the invention can be found in Kunststoff Handbuch by Vieweg and Hochtlen~ Vol. VII, Carl-Hanser Verlag, Munchen, 1966, for example on pages l2l to 205.
According to the invention, it is also possible to produce cold-cure foams (cf. GB-PS 1,162,517 and DE-OS 2,153,086).
However, it is of course also possible to produce foams by slabstock foaming or by the laminator process known per se.
The rigid foams obtainable in accordance with the invention are used, for example, as roof insulation panels.
The flex;ble polyurethane foams preferably obtainable in accordance with the invention are used, for example, as arm rests (for example in automobiles) and as cushions for furniture and seats in public transportation.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Examp~le 1 a) Preparation of the dispersion 4,000 g/min. of a polyether prepared f`rom propylene oxide(83%~
ethylene oxide (17%)and ~imethylo1 propane (hydloxyl v~ue 35, approx. 80% primary OH groups), 890 g/min. of a mixture of 60%
by weight 4,4'-MDI, 23% by weight 2,4'-MDI, 2% by weight Mo-3539 5, 2,2'-MDI and 15% by weight polyphenyl polymethylene polyisocyanates (oligomeric isomers) and 175 g/min. hydrazine hydrate are continuously introduced at room temperature into a toothed stirrer (chamber volume 0.5 l, rotational speed 5,000 r.p.m.). The polyether is introduced from the storage tank by a gear pump while two thinly liquid components are introduced from separate storage vessels by piston metering pumps. The exothermic polyaddition reaction takes place in the toothed stirrer. By cooling the toothed stirrer, the reaction temperature is kept at 100C. After a residence tlme of approximately 6 seconds, an almost completely reacted dispersion leaves the toothed stirrer. The dispersion formed, which has still not completely reacted off, is transferred to a holding vessel where it is stirred at 80 to 100~C.
After stirring, the water emanating from the hydrazine hydrate is distilled off in vacuo at 100C. A stable, finely divided 20% by weight dispersion having an OH value of 28 and a viscosity of 3,600 mPas/25~C is obtained.
b) Production of a flexible wlYurethane foam A component 60 parts by weight of the dispersion of example la 40 parts by weight of a polyether polyol having an OH value of 28 prepared by propoxyla~on (83%) of trimethylol propane and subsequent ethoxyla~on (17%) 3.3 parts by weight water 0.12 part by weight bis-dimethylaminoethyl ether (catalyst) 0.50 part by weight of a 33% solution of diazabicyclo(2,2,2)-octane in dipropylene glycol (catalyst) 0.20 part by weight of a commercially available foam stabilizer (B 4617, a product of Goldschmidt AG, Essen) 0.80 part by weight of a commercially available foam stabilizer (KS 43, a product of Bayer AG).
~o-3539 '~J r~
B component Mixture of B0% by weight TDI 80 and 20% by weight of a mixture of diphenyl methane diisocyanates and polyphenylene polymethylene polyisocyanates having the composition:
50% by weight 4,4'-MDI, 3% by weight 2,4'-MDI and 47% by weight oligomeric isomers.
100 Parts by weight of the A component are mixed with 38 parts by weight of the B component in 2 high-pressure ~achine.
The reaction mixture is introduced into a 40 liter box mold heated to approximately 50C. The mold is closed and the flexible foam molding is removed from the mold after about 6 minutes. The filled weight is 1.88 kg. Mechanical testing produces the following results:
Test results Density (kg/m3) DIN 53 420 42.4 Compression hardness 50% ~KPa) DIN 53 577 5.1 Tensile strength (KPa) DIN 53 571 186 Elongation at break (%) DIN 53 571 148 Compression set 50%, Cd value (%) GME 60 283 7.5 Storage in a steam autoclave ~ME 60 283 Compression hardness after stortge (KP~3 5.2 Compression set 50%, Cd value after storage (%) 24.2 Example 2 (Comparison Example) a) Preparation of the dispersion The polyether dispersion is prepared in the same way as in Example la) except that the isocyanate used and the quantities used are different. 4,000 9 of the same polyether as in Example la) are reacted with 845 9 of a mixture oF 80% by weight 2,4- and 20% by weight 2,6-tolylene diisocyanate and 245 9 hydrazine hydrate in the same way as in Example la) A
stable, white, finely divided 2~% by weight dispersion having Mo-3539 tr'J ,) ;J : 3 j `
an OH value of ~8 and a viscosity of 3,000 mpas/25C is obtained.
b) Production of a flexible polYurethane foam A component 60 Parts by weight of the same dispersion as in Example 2a).
All the other constituents of the A component are the same as in Example la).
B component Identical with Example lb) 100 Parts by weight of the A component are mixed with 38 parts by weight of the B component in a high-pressure machine.
The reaction mixture is introduced into a 40 liter box mold heated to approximately 50C. The mold is closed and the flexible foam molding is removed from the mold after about 6 minutes. The filled weight is 1.88 kg. Mechanical testing produces the following results:
lest results Density (kg/m3) DIN 53 420 42.0 Compression hardness 50% (KPa) DIN 53 577 4.3 Tensile strength (KPa) DIN 53 571 166 Elongation at break (%) DIN 53 571 151 Compression set 50/Q, Cd value GME 60 283 9.1 Storage in a steam autoclave GME 60 283 Compression hardness after storage (KPa) 5.0 Compression set 5000, Cd value after storage (%) 32.6 Comparison of Examples 1 and 2 shows that aging in a steam autoclave causes distinctly less damage to the foams according to the invention. Overall, the properties of the foam according to the invention are improved over those of the conventional foam produced in accordance with Example 2.
Mo-3539 Example 3 (Comparison Example) The dispersion is again prepared in the same way as in Example Ia) using an isocyanate typically known as "crude MDI".
The MDI used in this case has the following composition:
49% by weight 4,4'-MDI
2% by weight 2,4'-MDI
~0.5YO by weight 2,2/-MDI
49% by weight oligomeric isomers.
A white-brown paste is obtained but cannot be processed on account of its viscosity.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variation can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-3539
Claims (5)
1. In an improved stable dispersion of polyurea and/or polyhydrazodicarbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene polyisocyanate.
2. A stable dispersion as recited in Claim 1 wherein the relatively high molecular compound is a polyether.
3. A stable dispersion as recited in Claim 1 wherein the polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide is in combination with up to 40 mol-% an alkanolamine.
4. In an improved process for preparing a stable low viscosity dispersion of a polyurea and/or a polyhydrazodi-carbonamide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group comprising reacting a polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane Mo-3539 diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate
5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate and 0 to 30% by weight a polyphenyl polymethylene polyisocyanate.
5. In an improved process for the production of optionally foamed polyurethane plastics, more particularly flexible foams, by reacting a polyisocyanate with an active hydrogen containing material and additives and auxiliaries, the improvement comprising the active hydrogen material which is a stable dispersion of a polyurea and/or a polyhydrazodicarbon-amide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene polyisocyanate.
Mo-3539
5. In an improved process for the production of optionally foamed polyurethane plastics, more particularly flexible foams, by reacting a polyisocyanate with an active hydrogen containing material and additives and auxiliaries, the improvement comprising the active hydrogen material which is a stable dispersion of a polyurea and/or a polyhydrazodicarbon-amide in a relatively high molecular weight compound having a molecular weight of 200 to 16,000, and containing at least one hydroxyl group which is a reaction product of polyisocyanate with a polyamine containing primary, and/or secondary amino groups and/or a hydrazine and/or a hydrazide in a relatively high molecular weight compound containing at least one hydroxyl group, the improvement comprising the stable dispersion of low viscosity wherein the polyisocyanate is characterized in that it is a mixture of diphenyl methane diisocyanate and a polyphenyl polymethylene polyisocyanate consisting of 50 to 95% by weight 4,4'-diphenyl methane diisocyanate 5 to 60% by weight 2,4'-diphenyl methane diisocyanate 0 to 4% by weight 2,2'-diphenyl methane diisocyanate, and 0 to 30% by weight of a polyphenyl polymethylene polyisocyanate.
Mo-3539
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4007063A DE4007063A1 (en) | 1990-03-07 | 1990-03-07 | STABLE DISPERSIONS OF POLYHANE SUBSTANCES AND / OR POLYHYDRAZODICARBONAMIDES IN HIGHER MOLECULAR COMPOUNDS AT LEAST ONE HYDROXYL GROUP, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE OF THE PRODUCTION THEREOF |
| DEP4007063.8 | 1990-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2037082A1 true CA2037082A1 (en) | 1991-09-08 |
Family
ID=6401556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037082A Abandoned CA2037082A1 (en) | 1990-03-07 | 1991-02-26 | Stable dispersions of polyureas and/or polyhydrazodicarbonamides in relatively high molecular weight compounds containing at least one hydroxyl group, a process for production andtheir use for the production of polyurethane plastics |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0448813B1 (en) |
| KR (1) | KR930007351B1 (en) |
| CA (1) | CA2037082A1 (en) |
| DE (2) | DE4007063A1 (en) |
| ES (1) | ES2059978T3 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037382A (en) * | 1997-03-25 | 2000-03-14 | Imperial Chemical Industries Plc | Process for preparing a flexible polyurethane foam |
| US6660783B2 (en) | 2001-06-15 | 2003-12-09 | Basf Aktiengesellschaft | Preparation of highly resilient polyurethane foams |
| US7622542B2 (en) | 2004-12-17 | 2009-11-24 | Bayer Materialscience Ag | Plastic moldings from optionally filled polyurethanes and their use |
| US10273325B2 (en) | 2013-12-19 | 2019-04-30 | Dow Global Technologies Llc | Polymer dispersions having nanosized polyurea particles dispersed in a polyether |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229427A (en) * | 1992-06-02 | 1993-07-20 | Miles Inc. | Flexible, combustion-modified, polyurethane foams |
| US5258417A (en) * | 1992-12-28 | 1993-11-02 | Basf Corporation | Low viscosity polymeric MDI |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2513815C3 (en) * | 1975-03-27 | 1979-05-23 | Bayer Ag, 5090 Leverkusen | Process for the production of stable dispersions |
| GB2102825A (en) * | 1981-07-31 | 1983-02-09 | Ici Plc | Polymer-modified polyols |
-
1990
- 1990-03-07 DE DE4007063A patent/DE4007063A1/en not_active Withdrawn
- 1990-12-19 EP EP90124683A patent/EP0448813B1/en not_active Expired - Lifetime
- 1990-12-19 DE DE90124683T patent/DE59003363D1/en not_active Expired - Fee Related
- 1990-12-19 ES ES90124683T patent/ES2059978T3/en not_active Expired - Lifetime
-
1991
- 1991-02-26 CA CA002037082A patent/CA2037082A1/en not_active Abandoned
- 1991-03-05 KR KR8501619A patent/KR930007351B1/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037382A (en) * | 1997-03-25 | 2000-03-14 | Imperial Chemical Industries Plc | Process for preparing a flexible polyurethane foam |
| US6660783B2 (en) | 2001-06-15 | 2003-12-09 | Basf Aktiengesellschaft | Preparation of highly resilient polyurethane foams |
| US7622542B2 (en) | 2004-12-17 | 2009-11-24 | Bayer Materialscience Ag | Plastic moldings from optionally filled polyurethanes and their use |
| US10273325B2 (en) | 2013-12-19 | 2019-04-30 | Dow Global Technologies Llc | Polymer dispersions having nanosized polyurea particles dispersed in a polyether |
Also Published As
| Publication number | Publication date |
|---|---|
| KR910016798A (en) | 1991-11-05 |
| EP0448813B1 (en) | 1993-11-03 |
| DE59003363D1 (en) | 1993-12-09 |
| EP0448813A1 (en) | 1991-10-02 |
| KR930007351B1 (en) | 1993-10-25 |
| DE4007063A1 (en) | 1991-09-12 |
| ES2059978T3 (en) | 1994-11-16 |
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