CA1129598A - Process for the manufacture of flexible polyurethane foams with high load-bearing and high energy-absorption capacity - Google Patents
Process for the manufacture of flexible polyurethane foams with high load-bearing and high energy-absorption capacityInfo
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- CA1129598A CA1129598A CA325,400A CA325400A CA1129598A CA 1129598 A CA1129598 A CA 1129598A CA 325400 A CA325400 A CA 325400A CA 1129598 A CA1129598 A CA 1129598A
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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
- C08G18/70—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
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
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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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
-
- 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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
Abstract of the Disclosure The invention concerns a process for the manufacture of flexible polyurethane foams by reaction of a mixture consisting of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyantes having a functionality greater than 2 containing 55 to 85 percent by weight diphenylmethane diisocyanate based on the total weight of the isocyanate mixture with polyester polyols or mixtures of polyester polyols and polyether polyols having a polyester polyol content of more than 60 percent by weight based on the weight of the polyol mixture, and optionally chain extenders, auxiliaries, and additives, in the presence of catalysts and, in particular, water as a blowing agent. The special selec-tion of starting compounds results in the production of flexible polyurethane foams having a high resistance to hydrolysis, high load-bearing capacity, and high energy absorption upon impact.
Description
The invention concerns a process for the manufacture of flexible polyurethane foams consisting of a mixture o~
diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates (crude MDIJ having a functionality greater than 2 containing 55 to 85 percent by weight diphenylme-thane diisocyanate, polyester polyols or mixtures of polyester polyols and polyether polyols and auxiliaries and addirives having a high resistance to hydrolysis, high load-bearing capacity, and high energy absorption upon impact.
The manufacture of flexible polyurethane foam is a known process. Toluene diisocyanate and particularly, the commercially available toluene diisocyanate isomer mixtures are commonly used as polyisocyanates. The disadvantage is that toluene diisocyanates, due to their high vapor pressure, are relatively strongly toxic and therefore, special pre-cautionary measures must be taken and observed during processing.
In order to reduce the toxicity hazard and increase the rèactivity, it has been suggested to replace the toluene `
diisocyanates with mixtures of toluene diisocyanates and a mixture of homologous polyarylene polyalkylene polyisocyanates for the manufacture of polyurethane plastics, including foams.
According to sritish Patent 874,430, flexible polyurethane foams are also produced by reaction of polyether -polyols with at least two hydroxyl groups and a polyisocyanate mixture consisting of diarylmethane diisocyanates and 5 to 10 percent be weight of a polyisocyanate having a functionality greater than 2 in the presence of water. According to German Published Application, No. 24 25 657, diphenylmethane di-isocyanate mixtures having an average isocyanate fwlctionality of less than 2.4 and not containing more than 60 percent by weight of 4,4'-diphenylmethane diisocyanate, with at least 15 "~ 1 ~ ' '' ' : : , percent by weight of the diphenylmethane diisocyanate isomer mixture consisting of 2,4'-diphenylmethane diisocyanate, are suited for themanufacture of integral skin foams.
All of these polyurethane foams, which are of great elasticity, have in common one drawback which prohibits their use in certain areas of application. This is their unsuf-ficient load-bearing capacity and their deficient energy absorption upon impact, particularly in the case of flexible foams of low densities. In order to lessen this drawback, it has been suggested to increase the density. This measure, however, only resulted in increasing the cost per piece. A
satisfactory improvement of the above-mentioned mechanical properties could not be achieved with these measures.
This invention concerns a process for the manu-facture of flexible polyurethane foams by the reaction of a mixture consisting of diphenylmethane diisocyanates and polyphenyle polymethylene polyisocyanates having a function-ality greater than 2 containing 55 to 85 percent by weight of diphenylmethane diisocyanate based on the total weight of the isocyanate mixture with polyester polyols or mixtures of polyester polyols and polyether polyols having a polyester polyol content of more than 60 percent by weight relative to the weight of the polyol mixture, and optionally chain extenders, auxiliaries, and additives, in the presence of catalysts and, in particular, water as a blowing agent.
The special selection of starting compounds results in the production of flexible polyurethane foams having a high resistance to hydrolysis, high load-bearing capacity, and high energy absorption upon impact.
It is the purpose of this invention to produce, based on polyisocyanates with little or no toxicity, flexible polyurethane foams having a high load-bearing capacity
diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates (crude MDIJ having a functionality greater than 2 containing 55 to 85 percent by weight diphenylme-thane diisocyanate, polyester polyols or mixtures of polyester polyols and polyether polyols and auxiliaries and addirives having a high resistance to hydrolysis, high load-bearing capacity, and high energy absorption upon impact.
The manufacture of flexible polyurethane foam is a known process. Toluene diisocyanate and particularly, the commercially available toluene diisocyanate isomer mixtures are commonly used as polyisocyanates. The disadvantage is that toluene diisocyanates, due to their high vapor pressure, are relatively strongly toxic and therefore, special pre-cautionary measures must be taken and observed during processing.
In order to reduce the toxicity hazard and increase the rèactivity, it has been suggested to replace the toluene `
diisocyanates with mixtures of toluene diisocyanates and a mixture of homologous polyarylene polyalkylene polyisocyanates for the manufacture of polyurethane plastics, including foams.
According to sritish Patent 874,430, flexible polyurethane foams are also produced by reaction of polyether -polyols with at least two hydroxyl groups and a polyisocyanate mixture consisting of diarylmethane diisocyanates and 5 to 10 percent be weight of a polyisocyanate having a functionality greater than 2 in the presence of water. According to German Published Application, No. 24 25 657, diphenylmethane di-isocyanate mixtures having an average isocyanate fwlctionality of less than 2.4 and not containing more than 60 percent by weight of 4,4'-diphenylmethane diisocyanate, with at least 15 "~ 1 ~ ' '' ' : : , percent by weight of the diphenylmethane diisocyanate isomer mixture consisting of 2,4'-diphenylmethane diisocyanate, are suited for themanufacture of integral skin foams.
All of these polyurethane foams, which are of great elasticity, have in common one drawback which prohibits their use in certain areas of application. This is their unsuf-ficient load-bearing capacity and their deficient energy absorption upon impact, particularly in the case of flexible foams of low densities. In order to lessen this drawback, it has been suggested to increase the density. This measure, however, only resulted in increasing the cost per piece. A
satisfactory improvement of the above-mentioned mechanical properties could not be achieved with these measures.
This invention concerns a process for the manu-facture of flexible polyurethane foams by the reaction of a mixture consisting of diphenylmethane diisocyanates and polyphenyle polymethylene polyisocyanates having a function-ality greater than 2 containing 55 to 85 percent by weight of diphenylmethane diisocyanate based on the total weight of the isocyanate mixture with polyester polyols or mixtures of polyester polyols and polyether polyols having a polyester polyol content of more than 60 percent by weight relative to the weight of the polyol mixture, and optionally chain extenders, auxiliaries, and additives, in the presence of catalysts and, in particular, water as a blowing agent.
The special selection of starting compounds results in the production of flexible polyurethane foams having a high resistance to hydrolysis, high load-bearing capacity, and high energy absorption upon impact.
It is the purpose of this invention to produce, based on polyisocyanates with little or no toxicity, flexible polyurethane foams having a high load-bearing capacity
- 2 -. ~lZ~9~
and a large energy-absorption capacity upon impact.
This purpose is met by a process Eor the manu-facture of flexible polyurethane foams of organic poly-isocyanates, polyols, catalysts, blowing agents and possibly chain extenders, auxiliaries and additives, characterized in that a mixture of diphenylmethane diisocyanates and poly-phenylene polymethylene polyisocyanates having a diphenyl-methane diisocyanate content of 55 to 85 percent by weight, is used as organic polyisocyanates, that polyester polyols or mixtures of polyester polyols and polyether polyols having a polyester polyol conten-t of 60 to approximately 100 percent /
/' /
/ ~i, _ 5~313 weight relative -to the to-tal weight of the polyol mixture are used as polyols, and that water or mixtures of water and low-boiling, posslbly halogenated hydrocargons, are used as blowing agents.
Surprinsingly, it was found that the selection of the polyisocyanate mixture to be used according to this inven tion from the multitude of known and commercially available polyisocyanates in combination with polyester polyols or mixtures of polyester and polyether polyols consisting pre-dominantly of polyester polyols as well as water or mix-tures of water and low-boiling, possibly halogenated hydrocarbons as blowing agents, results in flexible polyurethane foams having a high load-bearing and energy-absorption capacity.
Also, especially remarkable is the high resistance to hydro-lysis of the polyurethane foams manufactured according to this invention.
For the manufacture of flexible polyurethane foams according to the process of this invention, mixtures of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates having a dipheny~methane diisocyanate content of 55 to 85 percent by weight, preferably of 60 to 80 percent by weight, based on the total weight of the mixture, are used as organic polyisocyanates. It is basically unimportant in which quantity ratios the isomeric 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates are present in the mixture.
According to the invention, it ls of primary importance that the total content of diphenylmethane diisocyanate isomers in the mixture corresponds with the above-referenced concentra-tion conditions. Preferably, however, there are used such mixtures with a 2,4'-diphenylmethane diisocyanate content r~
below 10 percent by weight, and particularly below 3 percen-t by weight, based on the total weight of diphenylmethane 1~29~;9~
diisocyanate. Instead of the pure polyisocyanate mix-tures, it is also possible to use ones which are modified with small quantities of an alkylene diol or polyoxyalkylene diol, such as propylene glycol, diethylene glycol and butylene glycol, in order to reduce the tendency toward crystallization, and which have an NC0 content of 20 to 34 percent by weight, preferably of 25 to 30 percent by weight, based on the total weight of the urethane-modified mixture. The manufacture of such possibly urethane-modified polyisocyanate mixtures with the corresponding content of diphenylmethane diisocyanate isomers is described, for instance, in German Published Applications 24 25 658, 25 13 793, and 25 13 796. r Polyester polyols with a molecular weight of 750 to 5000, preferably 1500 to 3000, and a functionality of 2 to
and a large energy-absorption capacity upon impact.
This purpose is met by a process Eor the manu-facture of flexible polyurethane foams of organic poly-isocyanates, polyols, catalysts, blowing agents and possibly chain extenders, auxiliaries and additives, characterized in that a mixture of diphenylmethane diisocyanates and poly-phenylene polymethylene polyisocyanates having a diphenyl-methane diisocyanate content of 55 to 85 percent by weight, is used as organic polyisocyanates, that polyester polyols or mixtures of polyester polyols and polyether polyols having a polyester polyol conten-t of 60 to approximately 100 percent /
/' /
/ ~i, _ 5~313 weight relative -to the to-tal weight of the polyol mixture are used as polyols, and that water or mixtures of water and low-boiling, posslbly halogenated hydrocargons, are used as blowing agents.
Surprinsingly, it was found that the selection of the polyisocyanate mixture to be used according to this inven tion from the multitude of known and commercially available polyisocyanates in combination with polyester polyols or mixtures of polyester and polyether polyols consisting pre-dominantly of polyester polyols as well as water or mix-tures of water and low-boiling, possibly halogenated hydrocarbons as blowing agents, results in flexible polyurethane foams having a high load-bearing and energy-absorption capacity.
Also, especially remarkable is the high resistance to hydro-lysis of the polyurethane foams manufactured according to this invention.
For the manufacture of flexible polyurethane foams according to the process of this invention, mixtures of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates having a dipheny~methane diisocyanate content of 55 to 85 percent by weight, preferably of 60 to 80 percent by weight, based on the total weight of the mixture, are used as organic polyisocyanates. It is basically unimportant in which quantity ratios the isomeric 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanates are present in the mixture.
According to the invention, it ls of primary importance that the total content of diphenylmethane diisocyanate isomers in the mixture corresponds with the above-referenced concentra-tion conditions. Preferably, however, there are used such mixtures with a 2,4'-diphenylmethane diisocyanate content r~
below 10 percent by weight, and particularly below 3 percen-t by weight, based on the total weight of diphenylmethane 1~29~;9~
diisocyanate. Instead of the pure polyisocyanate mix-tures, it is also possible to use ones which are modified with small quantities of an alkylene diol or polyoxyalkylene diol, such as propylene glycol, diethylene glycol and butylene glycol, in order to reduce the tendency toward crystallization, and which have an NC0 content of 20 to 34 percent by weight, preferably of 25 to 30 percent by weight, based on the total weight of the urethane-modified mixture. The manufacture of such possibly urethane-modified polyisocyanate mixtures with the corresponding content of diphenylmethane diisocyanate isomers is described, for instance, in German Published Applications 24 25 658, 25 13 793, and 25 13 796. r Polyester polyols with a molecular weight of 750 to 5000, preferably 1500 to 3000, and a functionality of 2 to
3.5, preferably 2 to 2.8, are preferably used as polyols.
For some areas of application, it has proven to be advanta- r geous,to replace the pure polyester polyols with mixtures of polyester polyols and polyether polyols having a polyester r content of 60 to approximately lO0 percent by weight, preferably of 75 to 99.5 percent by weight.
Suitable polyester polyols may be produced, for instance, from dicarboxylic acids, preferably aliphatic dicarboxylic acids having 2 to 12, preferably ~ to 8, carbon atoms in the alkylene radical and polyvalent alcohols, prefer-ably diols. These acids include, for instance, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimelic acid, undecanedioic acid, dodecanedioic, acid and preferably adipic acid, cyclic dicarboxylic acids, such as 1,3- and l,~-cyclohexane dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid. Examples of di- and multifunctional, particularly difunctional, alcohols are: propylene glycol, trimethylene _ 5 _ X - ,,~
"
. : ~ , ~Z9598 glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, l,10-decanediol, glycerine, trimethylolpropane, and preferably ethylene glycol and diethylene glycol. Alkanolamines such as triethanolamine and triisopropanoiamine can also be used as multifunctional alcohols. If trilfunctional compounds are used in the manufacture of the polyester polyols, their content must be chosen in such a manner that the functionality of the obtained polyester polyol is a maximum of 2.8,~ preferably 2 to 2.8.
Proven to have worked particular;y well and there-. fore preferably used are those polyester polyols which are produced by polycondensation of a dicarboxylic acid mixture r which, based on the total weight of the named dicarboxylic acids, contains: 20 to 35 percent by weight, preferably 28 to 33 percent by weight, succinic acid, 35 to 50 percent by weight, preferably 40 to 45 percent by weight, glutaric acid, and 20 to 32 percent by weight, preferably 24 to 28 percent by weight, adipic acid, and alcohol mixtures from ethylene glycol/diethylene glycol, ethylene glycol/trimethylolpropane, diethylene glycol/trimethylolpropane, ethylene glycol/trilso-propanolamine, and diethylene glycol/triisopropanolamine. In addition to the named dicarboxylic acids, the dicarboxylic acid mixture may contain up to 5 percent by weight, prefer-ably approximately 2 to 3 percent by weight, relative to the total weight, of impurities, which consist primarily of imides of the succinic and glutaric acids.
Dicarboxyli.c acid mixtures of the indicated type may, for instance, be obtained as by-products during the manufac.ture of adipic acid by oxidation of cyclohexanol or cyclohexanone with nitric acid. According to the inventioh, r the polyester polyols may be used as such or in the form of mixtures.
.: ; .
~ ;. ` - .. ' , . . ' 1~l%~598 As already stated, mixtures of polyester polyols and polyether polyols can also be used instead of the polyester polyols if the mixtures consist at least to 60 percent byweight of polyester polyols. Polyether polyols suitable for mixing have molecular weights of 400 to 7000, preferably 2000 to 5000, and functionalities of 2 to 3, preferably of 2 to 2.3, and particularly of approximately 2. t~
The preferably primarily linear polyether polyols are produced aeeording to known methods from one or more alkylene oxides with 2 to 4 earbon atoms in the alkylene radical and a starter molecule eontaining 2 to 3, preferably 2, bound ~
aetive hydrogen atoms. Suitable alkylene oxides are, for p instanee, 1,2- or 2,3- butylene oxide, styrene oxide, and preferably ethylene oxide and 1,2-propylene oxide. Comprable produets prepared from tetrahydrofuran and oxetane can also be employed. The above monomeric compounds may be used individually, alternatingly in sequence, or as mixtures.
Possible starter molecules include: water, dicarboxylic acids sueh as succinie aeid, adipie acid, phthalic acid, and terephthalie aeid, N,N'-dialkyl-substituted diamines with 1 to 4 ea~bon atoms in the alkyl radical, such as dialkyl-substituted ethylenediamine, 1,2- or 1j3-propanediamine, 1,4-butanediamine, hexamethylenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenyl methane, as well as N-alkyldiethanolamine, and preferably, multifunctional, particularly difunctional, alco- 5 hols sueh as ethylene glyeol, propylene glycol, trimethylene glyeol, diethylene glycol, dipropylene glycol, 1,4-butanediol, hexamethylene glyeol, and trifunctional alcohols such as glyeerine and trimethylolpropane.
It may, under eertain eireumstanees, be appropriate to also use, in addition to the polyester polyols or mixtures of polyester and polyether polyols chain extenders for the - . .: .
: . : :: . . :. .
: . - . - . ;,, .
13l29591~
manufacture of the flexible polyure-thane foams. Possible chain extenders are, particularly, difunc-tional compounds having molecular weights of 18 to less than 300. Preferably used are aliphatic diols with 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and hexamethylene glycol, and aromatic aliphatic diols such as bis-t2-hydroxyethyl) ether of hydroquinone.
Another feature of the process according to this invention is the use of water, which reacts with the isocyanate mixture and provides carbon dioxide, as biowing agent.
Preferably used are 2 to 8 percent by weight, in particular 2.5 to 5 percent by weight, of water based on the weight of the polyol. Instead of water alone, mixtures of water and chemically inert, low-boiling, possibly halogenated hydro-carbons can also be used as foaming agents. These include, for instance, possibly halogenated hydrocarbons having boiling points below 50C, preferably between -50C and 30C at atmospheric pressure. The following detailed listing is used as an example: halogenated hydrocarbons such as monochlorodi-fluoromethane, dichloromonofluoromethane, dichlorodifluoro-methane, and trichlorofluoromethane and their mixtures, and hydrocarbons such as propane, n-butane, and isobut~ne as well as dimethyl ether~ Suitable mixtures of water and possibly halogenated hydrocarbons generally consist of 5 to 70 percent ' by weight, preferably 10 to 50 percent by weight, of water and 30 to 95 percent by weight, preferably 50 to 90 percent by weight, of possibly halogenated hydrocarbons, with -the percent by weight being based on the total weight of -the glowing-agent mixture.
The required quantities of blowing agent mixture F
can be determined experimentally in a very simple manner as a function of the mixing ratio of water to possibly halogenated , ' ' .
l~Z~S9~
blowing agents as well as the desired density of the foam and amount to approximately 2 to 40, preferably 5 to 25, percent by weight based on the weight of the polyol.
Catalysts which accelerate the formation of poly-urethane, and possibly auxiliaries and additives which are normally used for the production of flexible polyurethane ~
foams can be added to -the foamable reaction mixture. These include, for example, surface-active materials, flame inhibitors, pore regulating materials, antioxidants, hydro-lysis prevention agents, dyes, fillers, and other additives.
Suitable catalysts for accelerating the reaction among the polyols, the water, optionally the chain extenders, and the polyisocyanate mixture according to this invention are, for instance, tertiary amines such as dimethylbenzyl-amine, N,N,N',N'-tetramethyldiaminoethyl ether, bis-(di-methylaminopropyl) urea, N-methyl- or N-ethylmorpholine, N,N'-dimethylpiperazine, 1,2-dimethyl imidazole, l-azabicyclo-(3,3,0)-octane, and preferably triethylenediamine, metal salts such as stannous octoate, lead octoate, and preferably tin-(II) salts and dibutyltin dilaurate, as well as especially mixtures of tertiary amines and organic tin sal-ts. Preferably, 0.5 to 5 percent by weight of catalys-t based on tertiary amines and/or 0.01 to 2.5 percent by weight of metal salts based on the polyol weight are used.
Further to be taken into consideration are, for instance, surface-active substances which serve to support the homogenization of the starting material and which are possibly also suited to regulate the cell s-tructure of the flexible polyurethane foams.
These include, for example, siloxane-oxyalkylene mixed polymerizates and other organo-polysiloxanes, oxy-ethylated alkyl phenols, oxyethylated fatty alcohols, paraffin ~z9~
oils, castor oil or ricinoleic ester, and turkey red oil, which are used in quantities of 0.2 to 6 parts per weight per 100 parts by weight of polyisocyanate mixture.
In order to improve the flame resistance, the flexible polyurethane foams produced according to this invention can contain flame inhitibors. These include, for instance, compounds containing phosphorus and/or halogen atoms, such as tricresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate, and tris-2,3-dibromo-propyl phosphate, inorganic flame inhibitors, such as antimony trioxide, arsenic oxide, ammonium phosphate, ammonium sulfate, among others, and preferably, derivatives of cyanic acid such r as cyanamide, dicyandiamide, guanidine, and particularly guanidine salts, biguanidine, and, in particular, melamine.
Derivatives of cyanic acid of this type are described, for instance, in German Patent Application P28 15 155.6 of BASF
Aktiengesellschaft. In general, it has proven advantageous to use 5 to 70 parts by weight of such flame inhibitors for 100 parts by weight of the mixtures consisting of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates with 55 to 85 percent by weight of two-nucleus isomers.
Further details concerning the above-mentioned other commonly used auxiliaries and additives are contained in the literature, for instance, in the monograph by J.H. Saunders and K.C. Frisch, "High Polymers", Volume XVI, Polyurethanes, - Part 1 and 2, Interscience Publishers, 1962 and 1964. r The flexible polyurethane foam can be manufactured according to the prepolymer process and preferably, according to the one-shot process.
~ If the flexible polyurethane foams are manufactured F-according to the one-shot process, usually a mixture of polyol, water, ca-talyst and possibly chain extenders, auxil-'~ ' .
~2~59~3 iaries and additives is brought to reaction with the poly-isocyanate mixture according to the invention at tempera-tures from 15 to 600C, preferably, 25 to 40C, in such quanti- -ties that the ratio of hydroxyl groups of the polyols and possibly chain extenders to NC0 groups of -the polylsocyanate mixtures is 0.1 to 0.4:1, preferably 0.15 to 0.3:1, and that the ratio of all Zerewitinoff active hydrogen atoms, bonded to polyol, possibly chain extenders and wa-ter, -to the NC0 groups of the polyisocyanate mixture is approximately 0.8 -to 1.3:1, preferably 0.95 to 1.1:1. When a mixing chamber with several input jets is used, the liquid raw materials can be fed into the mixing chamber individually or, i~ the components are solid, in form of solutions or suspensions, and then mixed intensively in the mixing chamber. However, it has proven to be particularly appropriate to work according to the two-component process and to combine the mixture of polyol, water, - catalyst, possibly chain extenders, auxiliaries and additives to form component A and to use the polyisocyanate mixture as component B.
For the manufacture of the prepolymer containing the NCO groups, the polyisocyanate mixture to be used according i to the invention is brought to reaction with the already re~erenced:polyols and/or chain extenders in such quantities ,~
that the ratio of NC0 groups to the total hydroxyl is 10:1 to 95:1, preferably 70:1 to 90:1.
The prepolymers containing the terminal NC0 groups are-subsequently mixed with water or mixtures of water and low-boiling, possibly halogenated hydrocarbons and possibly additional polyols and/or chain ex-tenders, and auxiliaries and additives, and are allowed to foam.
The f:Lexible polyurethane foams produced according to this invention have densities of approximateLy 10 to ~0 grams per liter. Due to thelr high load-bearing capacity and their large energy-absorption capacity upon impact, these ,;
materials are particularly well suited as energy absorbing materials for outfitting, particularly, the interiors of vehicles and as light impact-absorbing materials for the packaging sector, for foam backing of foils, textile coatings --etc.............................................................. r The parts referred to in the examples are relative to weight.
Examples l to 3 and Comparison Examples A to B
In order to manufacture a flexible polyure-thane foam, a mixture of a polyester polyol, water, possibly tri~
chlorofluoromethane, catalyst, and foam stabilizer is thoroughly mixed with a urethane-modified mixture of diphenyl-methane diisocyanates and polyphenylene polymethylene poly-isocyanates with a diphenylmethane diisocyanate content of 65 percent by weight at 25C, and is allowed to foam in an open mold. ~ :
The raw materials used and the quantities as well :~
as the mechanical propelti.es of the obtained flexible foams are surnmarized in the following tables: ;
The following materials are used in Table I: : ~1' Polyester Polyol A: Polyester polyol based on adipic acid, diethylene glycol, trimethylolpropane OH Number 60, Visc~ 75C l000 cps, ~.
Functionali-ty: 2.6 Polyester Polyol. B: Polyester polyol based on succinic, glu~aric, adipic acid, ethylerle glycol, trime-thylolpropane O~I Number 59, Visc. 75C l900 cps, r Functionality: 2.6 ~ - 12 -.
~295~3 Polyester Polyol C: Polyester polyol based on succinic, glutaric, adipic acid, ethylene glycol, diethylene glycol OH Number 56, Visc. 75C 600 cps, Functionality: 2.0 olyether Polyol: Polyether polyol based on glycerine-ethylene ox:ide-propylene oxide OH Number 42, Functionality: 3 ~Z959~3 TABLE I
Examples 1 2 3 Comparison Exam.ples A B
. . .
-Polyester Polyol A (Parts) 500 - - - 500 Polyester Polyol B (Parts) - 500 Polyester Polyol C (Parts) - - 500 - -Polyether Polyol (Parts) - - - 500 Water (Par-ts) 20 20 20 19.5 20 Trichlorofluoromethane (Parts) 50 50~ 50 - 50 Dimethylbenzylamine (Parts) 7.5 7.5 7.5 - 7.5 Triethylenediamine (Parts) 5.0 5.0 5.0 1.5 5.0 Dimethylethanolamine (Parts) - - - 1.5 Tin dioctoate (Parts) - - - 2.0 Foam stabilizers based on polysiloxane-polyoxyalkylene Trade produc-t of Goldschmitt AG, Essen:
Tegostab B 2888 (Parts) 15 15 15 _ 15 Tegostab~ BF 2370 (Parts) _ _ 3.5 Urethane-modified mixture consisting of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates:
~C0 content: 29.6 %
Viscosity: 150 cps Diphenylmethane diisocyanate content 65%
Content of three-nucleus isomers approximately 10 %
(Parts 550 550 550 Commercially a~ailable mixture from 2,4- and 2,6-toluene diisocyanates in a weight ratio of 80:20 (Parts) - - - 240.5 327.5 ~29598 TABLE II
Mechanical Properties of the Flexible Polyurethane Foams Produced Examples 1 2 3 Comparison Examples A B
Density (g/l) 24.8 23.9 25.025.0 21.0 Tensile Strength (N/mm ) 0.135 0.128 0.136 0.1 0.13 r Strength at 20% Compression, (N/mm2) O.580.41 - O.4~ 0.31 0.32 40% Compression, (N/mm2) 1.25 1.06 1.0 0.35 0.52 60% Compression, (N/mm2) 2.68 2.3 2.25 0.60 0.92 Sag Factor (60% - 20%) 4.6 5.6 5.1 1.9 2.8 Table II shows the surprisingly high load-bearing capacity of ~ :
the flexible foam produced by the process according to this invention (Examples 1 to 3).
- In order to determine the hydrolysis resistance, an aged foam sample produced in accordance with Example 1 and I :
another foam sample of the same age produced according to Comparison Example B were subjected to the following conditions:
A foam sample (20 grams) was stirred for one hour at 75C in 2 liters of a solution of 5 percent sodium hydroxide in alcohol/water (1:1).
While the foam produced in accordance with tbe invention did not show any decomposition as the result of the hydrolysis test, the foam produced accord.ing to Comparison Example B had completely dissolved after five minutes.
The energy absorption upon impact can be character-ized by the resiliency, that is, the distance in percent ofthe falling distance by which a steel ball bounces back after hitting a foam.sample (according to ASTM 15653O
- 15 - ~:
::
The greater the energy absorp-tion, the smaller the distance becomes over which the ball rebounds. Although values of 40 to 55 percent are measured with common ~lexible polyurethane foams and values of up to 80 percent are obtained with high-resiliency foams (literature: E.M. Maxey, Journal of Cellular Plastics, January/February, 1972, page 35 and following), values of 20 to 30 percent are obtained with flexible polyurethane foams produced according to the process of this invention.
!
: .
For some areas of application, it has proven to be advanta- r geous,to replace the pure polyester polyols with mixtures of polyester polyols and polyether polyols having a polyester r content of 60 to approximately lO0 percent by weight, preferably of 75 to 99.5 percent by weight.
Suitable polyester polyols may be produced, for instance, from dicarboxylic acids, preferably aliphatic dicarboxylic acids having 2 to 12, preferably ~ to 8, carbon atoms in the alkylene radical and polyvalent alcohols, prefer-ably diols. These acids include, for instance, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, pimelic acid, undecanedioic acid, dodecanedioic, acid and preferably adipic acid, cyclic dicarboxylic acids, such as 1,3- and l,~-cyclohexane dicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid. Examples of di- and multifunctional, particularly difunctional, alcohols are: propylene glycol, trimethylene _ 5 _ X - ,,~
"
. : ~ , ~Z9598 glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, l,10-decanediol, glycerine, trimethylolpropane, and preferably ethylene glycol and diethylene glycol. Alkanolamines such as triethanolamine and triisopropanoiamine can also be used as multifunctional alcohols. If trilfunctional compounds are used in the manufacture of the polyester polyols, their content must be chosen in such a manner that the functionality of the obtained polyester polyol is a maximum of 2.8,~ preferably 2 to 2.8.
Proven to have worked particular;y well and there-. fore preferably used are those polyester polyols which are produced by polycondensation of a dicarboxylic acid mixture r which, based on the total weight of the named dicarboxylic acids, contains: 20 to 35 percent by weight, preferably 28 to 33 percent by weight, succinic acid, 35 to 50 percent by weight, preferably 40 to 45 percent by weight, glutaric acid, and 20 to 32 percent by weight, preferably 24 to 28 percent by weight, adipic acid, and alcohol mixtures from ethylene glycol/diethylene glycol, ethylene glycol/trimethylolpropane, diethylene glycol/trimethylolpropane, ethylene glycol/trilso-propanolamine, and diethylene glycol/triisopropanolamine. In addition to the named dicarboxylic acids, the dicarboxylic acid mixture may contain up to 5 percent by weight, prefer-ably approximately 2 to 3 percent by weight, relative to the total weight, of impurities, which consist primarily of imides of the succinic and glutaric acids.
Dicarboxyli.c acid mixtures of the indicated type may, for instance, be obtained as by-products during the manufac.ture of adipic acid by oxidation of cyclohexanol or cyclohexanone with nitric acid. According to the inventioh, r the polyester polyols may be used as such or in the form of mixtures.
.: ; .
~ ;. ` - .. ' , . . ' 1~l%~598 As already stated, mixtures of polyester polyols and polyether polyols can also be used instead of the polyester polyols if the mixtures consist at least to 60 percent byweight of polyester polyols. Polyether polyols suitable for mixing have molecular weights of 400 to 7000, preferably 2000 to 5000, and functionalities of 2 to 3, preferably of 2 to 2.3, and particularly of approximately 2. t~
The preferably primarily linear polyether polyols are produced aeeording to known methods from one or more alkylene oxides with 2 to 4 earbon atoms in the alkylene radical and a starter molecule eontaining 2 to 3, preferably 2, bound ~
aetive hydrogen atoms. Suitable alkylene oxides are, for p instanee, 1,2- or 2,3- butylene oxide, styrene oxide, and preferably ethylene oxide and 1,2-propylene oxide. Comprable produets prepared from tetrahydrofuran and oxetane can also be employed. The above monomeric compounds may be used individually, alternatingly in sequence, or as mixtures.
Possible starter molecules include: water, dicarboxylic acids sueh as succinie aeid, adipie acid, phthalic acid, and terephthalie aeid, N,N'-dialkyl-substituted diamines with 1 to 4 ea~bon atoms in the alkyl radical, such as dialkyl-substituted ethylenediamine, 1,2- or 1j3-propanediamine, 1,4-butanediamine, hexamethylenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenyl methane, as well as N-alkyldiethanolamine, and preferably, multifunctional, particularly difunctional, alco- 5 hols sueh as ethylene glyeol, propylene glycol, trimethylene glyeol, diethylene glycol, dipropylene glycol, 1,4-butanediol, hexamethylene glyeol, and trifunctional alcohols such as glyeerine and trimethylolpropane.
It may, under eertain eireumstanees, be appropriate to also use, in addition to the polyester polyols or mixtures of polyester and polyether polyols chain extenders for the - . .: .
: . : :: . . :. .
: . - . - . ;,, .
13l29591~
manufacture of the flexible polyure-thane foams. Possible chain extenders are, particularly, difunc-tional compounds having molecular weights of 18 to less than 300. Preferably used are aliphatic diols with 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and hexamethylene glycol, and aromatic aliphatic diols such as bis-t2-hydroxyethyl) ether of hydroquinone.
Another feature of the process according to this invention is the use of water, which reacts with the isocyanate mixture and provides carbon dioxide, as biowing agent.
Preferably used are 2 to 8 percent by weight, in particular 2.5 to 5 percent by weight, of water based on the weight of the polyol. Instead of water alone, mixtures of water and chemically inert, low-boiling, possibly halogenated hydro-carbons can also be used as foaming agents. These include, for instance, possibly halogenated hydrocarbons having boiling points below 50C, preferably between -50C and 30C at atmospheric pressure. The following detailed listing is used as an example: halogenated hydrocarbons such as monochlorodi-fluoromethane, dichloromonofluoromethane, dichlorodifluoro-methane, and trichlorofluoromethane and their mixtures, and hydrocarbons such as propane, n-butane, and isobut~ne as well as dimethyl ether~ Suitable mixtures of water and possibly halogenated hydrocarbons generally consist of 5 to 70 percent ' by weight, preferably 10 to 50 percent by weight, of water and 30 to 95 percent by weight, preferably 50 to 90 percent by weight, of possibly halogenated hydrocarbons, with -the percent by weight being based on the total weight of -the glowing-agent mixture.
The required quantities of blowing agent mixture F
can be determined experimentally in a very simple manner as a function of the mixing ratio of water to possibly halogenated , ' ' .
l~Z~S9~
blowing agents as well as the desired density of the foam and amount to approximately 2 to 40, preferably 5 to 25, percent by weight based on the weight of the polyol.
Catalysts which accelerate the formation of poly-urethane, and possibly auxiliaries and additives which are normally used for the production of flexible polyurethane ~
foams can be added to -the foamable reaction mixture. These include, for example, surface-active materials, flame inhibitors, pore regulating materials, antioxidants, hydro-lysis prevention agents, dyes, fillers, and other additives.
Suitable catalysts for accelerating the reaction among the polyols, the water, optionally the chain extenders, and the polyisocyanate mixture according to this invention are, for instance, tertiary amines such as dimethylbenzyl-amine, N,N,N',N'-tetramethyldiaminoethyl ether, bis-(di-methylaminopropyl) urea, N-methyl- or N-ethylmorpholine, N,N'-dimethylpiperazine, 1,2-dimethyl imidazole, l-azabicyclo-(3,3,0)-octane, and preferably triethylenediamine, metal salts such as stannous octoate, lead octoate, and preferably tin-(II) salts and dibutyltin dilaurate, as well as especially mixtures of tertiary amines and organic tin sal-ts. Preferably, 0.5 to 5 percent by weight of catalys-t based on tertiary amines and/or 0.01 to 2.5 percent by weight of metal salts based on the polyol weight are used.
Further to be taken into consideration are, for instance, surface-active substances which serve to support the homogenization of the starting material and which are possibly also suited to regulate the cell s-tructure of the flexible polyurethane foams.
These include, for example, siloxane-oxyalkylene mixed polymerizates and other organo-polysiloxanes, oxy-ethylated alkyl phenols, oxyethylated fatty alcohols, paraffin ~z9~
oils, castor oil or ricinoleic ester, and turkey red oil, which are used in quantities of 0.2 to 6 parts per weight per 100 parts by weight of polyisocyanate mixture.
In order to improve the flame resistance, the flexible polyurethane foams produced according to this invention can contain flame inhitibors. These include, for instance, compounds containing phosphorus and/or halogen atoms, such as tricresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate, and tris-2,3-dibromo-propyl phosphate, inorganic flame inhibitors, such as antimony trioxide, arsenic oxide, ammonium phosphate, ammonium sulfate, among others, and preferably, derivatives of cyanic acid such r as cyanamide, dicyandiamide, guanidine, and particularly guanidine salts, biguanidine, and, in particular, melamine.
Derivatives of cyanic acid of this type are described, for instance, in German Patent Application P28 15 155.6 of BASF
Aktiengesellschaft. In general, it has proven advantageous to use 5 to 70 parts by weight of such flame inhibitors for 100 parts by weight of the mixtures consisting of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates with 55 to 85 percent by weight of two-nucleus isomers.
Further details concerning the above-mentioned other commonly used auxiliaries and additives are contained in the literature, for instance, in the monograph by J.H. Saunders and K.C. Frisch, "High Polymers", Volume XVI, Polyurethanes, - Part 1 and 2, Interscience Publishers, 1962 and 1964. r The flexible polyurethane foam can be manufactured according to the prepolymer process and preferably, according to the one-shot process.
~ If the flexible polyurethane foams are manufactured F-according to the one-shot process, usually a mixture of polyol, water, ca-talyst and possibly chain extenders, auxil-'~ ' .
~2~59~3 iaries and additives is brought to reaction with the poly-isocyanate mixture according to the invention at tempera-tures from 15 to 600C, preferably, 25 to 40C, in such quanti- -ties that the ratio of hydroxyl groups of the polyols and possibly chain extenders to NC0 groups of -the polylsocyanate mixtures is 0.1 to 0.4:1, preferably 0.15 to 0.3:1, and that the ratio of all Zerewitinoff active hydrogen atoms, bonded to polyol, possibly chain extenders and wa-ter, -to the NC0 groups of the polyisocyanate mixture is approximately 0.8 -to 1.3:1, preferably 0.95 to 1.1:1. When a mixing chamber with several input jets is used, the liquid raw materials can be fed into the mixing chamber individually or, i~ the components are solid, in form of solutions or suspensions, and then mixed intensively in the mixing chamber. However, it has proven to be particularly appropriate to work according to the two-component process and to combine the mixture of polyol, water, - catalyst, possibly chain extenders, auxiliaries and additives to form component A and to use the polyisocyanate mixture as component B.
For the manufacture of the prepolymer containing the NCO groups, the polyisocyanate mixture to be used according i to the invention is brought to reaction with the already re~erenced:polyols and/or chain extenders in such quantities ,~
that the ratio of NC0 groups to the total hydroxyl is 10:1 to 95:1, preferably 70:1 to 90:1.
The prepolymers containing the terminal NC0 groups are-subsequently mixed with water or mixtures of water and low-boiling, possibly halogenated hydrocarbons and possibly additional polyols and/or chain ex-tenders, and auxiliaries and additives, and are allowed to foam.
The f:Lexible polyurethane foams produced according to this invention have densities of approximateLy 10 to ~0 grams per liter. Due to thelr high load-bearing capacity and their large energy-absorption capacity upon impact, these ,;
materials are particularly well suited as energy absorbing materials for outfitting, particularly, the interiors of vehicles and as light impact-absorbing materials for the packaging sector, for foam backing of foils, textile coatings --etc.............................................................. r The parts referred to in the examples are relative to weight.
Examples l to 3 and Comparison Examples A to B
In order to manufacture a flexible polyure-thane foam, a mixture of a polyester polyol, water, possibly tri~
chlorofluoromethane, catalyst, and foam stabilizer is thoroughly mixed with a urethane-modified mixture of diphenyl-methane diisocyanates and polyphenylene polymethylene poly-isocyanates with a diphenylmethane diisocyanate content of 65 percent by weight at 25C, and is allowed to foam in an open mold. ~ :
The raw materials used and the quantities as well :~
as the mechanical propelti.es of the obtained flexible foams are surnmarized in the following tables: ;
The following materials are used in Table I: : ~1' Polyester Polyol A: Polyester polyol based on adipic acid, diethylene glycol, trimethylolpropane OH Number 60, Visc~ 75C l000 cps, ~.
Functionali-ty: 2.6 Polyester Polyol. B: Polyester polyol based on succinic, glu~aric, adipic acid, ethylerle glycol, trime-thylolpropane O~I Number 59, Visc. 75C l900 cps, r Functionality: 2.6 ~ - 12 -.
~295~3 Polyester Polyol C: Polyester polyol based on succinic, glutaric, adipic acid, ethylene glycol, diethylene glycol OH Number 56, Visc. 75C 600 cps, Functionality: 2.0 olyether Polyol: Polyether polyol based on glycerine-ethylene ox:ide-propylene oxide OH Number 42, Functionality: 3 ~Z959~3 TABLE I
Examples 1 2 3 Comparison Exam.ples A B
. . .
-Polyester Polyol A (Parts) 500 - - - 500 Polyester Polyol B (Parts) - 500 Polyester Polyol C (Parts) - - 500 - -Polyether Polyol (Parts) - - - 500 Water (Par-ts) 20 20 20 19.5 20 Trichlorofluoromethane (Parts) 50 50~ 50 - 50 Dimethylbenzylamine (Parts) 7.5 7.5 7.5 - 7.5 Triethylenediamine (Parts) 5.0 5.0 5.0 1.5 5.0 Dimethylethanolamine (Parts) - - - 1.5 Tin dioctoate (Parts) - - - 2.0 Foam stabilizers based on polysiloxane-polyoxyalkylene Trade produc-t of Goldschmitt AG, Essen:
Tegostab B 2888 (Parts) 15 15 15 _ 15 Tegostab~ BF 2370 (Parts) _ _ 3.5 Urethane-modified mixture consisting of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates:
~C0 content: 29.6 %
Viscosity: 150 cps Diphenylmethane diisocyanate content 65%
Content of three-nucleus isomers approximately 10 %
(Parts 550 550 550 Commercially a~ailable mixture from 2,4- and 2,6-toluene diisocyanates in a weight ratio of 80:20 (Parts) - - - 240.5 327.5 ~29598 TABLE II
Mechanical Properties of the Flexible Polyurethane Foams Produced Examples 1 2 3 Comparison Examples A B
Density (g/l) 24.8 23.9 25.025.0 21.0 Tensile Strength (N/mm ) 0.135 0.128 0.136 0.1 0.13 r Strength at 20% Compression, (N/mm2) O.580.41 - O.4~ 0.31 0.32 40% Compression, (N/mm2) 1.25 1.06 1.0 0.35 0.52 60% Compression, (N/mm2) 2.68 2.3 2.25 0.60 0.92 Sag Factor (60% - 20%) 4.6 5.6 5.1 1.9 2.8 Table II shows the surprisingly high load-bearing capacity of ~ :
the flexible foam produced by the process according to this invention (Examples 1 to 3).
- In order to determine the hydrolysis resistance, an aged foam sample produced in accordance with Example 1 and I :
another foam sample of the same age produced according to Comparison Example B were subjected to the following conditions:
A foam sample (20 grams) was stirred for one hour at 75C in 2 liters of a solution of 5 percent sodium hydroxide in alcohol/water (1:1).
While the foam produced in accordance with tbe invention did not show any decomposition as the result of the hydrolysis test, the foam produced accord.ing to Comparison Example B had completely dissolved after five minutes.
The energy absorption upon impact can be character-ized by the resiliency, that is, the distance in percent ofthe falling distance by which a steel ball bounces back after hitting a foam.sample (according to ASTM 15653O
- 15 - ~:
::
The greater the energy absorp-tion, the smaller the distance becomes over which the ball rebounds. Although values of 40 to 55 percent are measured with common ~lexible polyurethane foams and values of up to 80 percent are obtained with high-resiliency foams (literature: E.M. Maxey, Journal of Cellular Plastics, January/February, 1972, page 35 and following), values of 20 to 30 percent are obtained with flexible polyurethane foams produced according to the process of this invention.
!
: .
Claims (7)
1. Process for the manufacture of flexible poly-urethane foams from organic polyisocyanates, polyols, catalysts, blowing agents, and optionally chain extenders, auxiliaries and additives, wherein:
a mixture of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates having a diphenyl-methane diisocyanate content of 55 to 85 percent by weight based on the weight of the isocyanate mixture is used as organic polyisocyanates;
polyester polyols or mixtures of polyester polyols and polyether polyols with a polyester polyol content of 60 to approximately 100 percent by weight based on the total weight of said polyol mixture are used as polyols; and water or mixtures of water and low-boiling halogenated hydrocarbons are used as blowing agents.
a mixture of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates having a diphenyl-methane diisocyanate content of 55 to 85 percent by weight based on the weight of the isocyanate mixture is used as organic polyisocyanates;
polyester polyols or mixtures of polyester polyols and polyether polyols with a polyester polyol content of 60 to approximately 100 percent by weight based on the total weight of said polyol mixture are used as polyols; and water or mixtures of water and low-boiling halogenated hydrocarbons are used as blowing agents.
2. Process according to claim 1 wherein the isocyanate mixture used as organic polyisocyanates is produced by reacting diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates the so produced mixture being a urethane-modified mixture and having a diphenylmethane diisocyanate content of 55 to 85 percent by weight based on the weight of the isocyanate mixture and multivalent hydroxyl compounds, said urethane-modified mixture also having an NCO content of 20 to 34 percent by weight based on the total weight of said urethane-modified mixture.
3. Process according to claim 1 wherein the mixture of diphenylmethane diisocyanates and polyphenylene polymethylene polyisocyanates contains less than 10 percent by weight of 2,4'-diphenylmethane diisocyanate based on the weight of the diphenylmethane diisocyanate.
4. Process according to claim 2 wherein the mixture of diphenylmethane diisocyanates and polyphenylene poly-methylene polyisocyanates contains less than 10 percent by weight of 2,4'-diphenylmethane diisocyanate based on the weight of the diphenylmethane diisocyanate isomers.
5. Process according to claim 1 wherein polyester polyols having a molecular weight of 750 to 5000 and a functionality of 2 to 3.5 are used.
6. Process according to claim 5 wherein the poly-ester polyols are produced by polycondensation of a di-carboxylic acid mixture containing 20 to 35 percent by weight of succinic acid, 35 to 50 percent by weight glutaric acid, and 20 to 32 percent by weight of adipic acid with the per-centages by weight based on the total weight of the di-carboxylic acid mixture, and di- or tri-functional alcohols.
7. Process according to claim 1 wherein the poly-ester polyols are produced by polycondensation of a di-carboxylic acid mixture containing 20 to 35 percent by weight of succinic acid, 35 to 50 percent by weight glutaric adid, and 20 to 32 percent by weight of adipic acid with -the per-centages by weight based on the total weight of the di-carboxylic acid mixture, and di- or tri-functional alcohols.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19782815540 DE2815540A1 (en) | 1978-04-11 | 1978-04-11 | FLEXIBLE POLYURETHANE FOAM WITH HIGH WEARING AND SHOCK ABSORPTION CAPABILITY |
| DEP2815540.0 | 1978-04-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1129598A true CA1129598A (en) | 1982-08-10 |
Family
ID=6036670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA325,400A Expired CA1129598A (en) | 1978-04-11 | 1979-04-10 | Process for the manufacture of flexible polyurethane foams with high load-bearing and high energy-absorption capacity |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0004617B1 (en) |
| JP (1) | JPS54137099A (en) |
| CA (1) | CA1129598A (en) |
| DE (2) | DE2815540A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789719A (en) * | 1988-03-15 | 1988-12-06 | Neochem Polymers Inc. | Manufacture of block polyester polyols, and polyurethanes derived therefrom |
| US4975523A (en) * | 1988-03-28 | 1990-12-04 | Du Pont Neochem | Manufacture of block polyester polyols, and polyurethanes derived therefrom |
| US20150299373A1 (en) * | 2012-10-26 | 2015-10-22 | Bayer Materialscience Ag | Method for producing soft polyurethane foam based on polyester polyols |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3028501A1 (en) * | 1980-07-26 | 1982-03-04 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTICALLY PROCESSABLE POLYURETHANE ELASTOMERS WITH IMPROVED ABRASION RESISTANCE AND A METHOD FOR THE PRODUCTION THEREOF |
| BR8104219A (en) * | 1980-09-29 | 1982-08-31 | Texaco Development Corp | PROCESS FOR THE PREPARATION OF A MOLDED FLEXIBLE POLYURETHANE PRODUCT |
| DE3100523A1 (en) * | 1981-01-10 | 1982-08-12 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FLEXIBLE POLYURETHANE SOFT FOAMS WITH IMPROVED HYDROLYSIS RESISTANCE AND GOOD PUNCHABILITY |
| DE3100524A1 (en) * | 1981-01-10 | 1982-08-12 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FLEXIBLE POLYURETHANE SOFT FOAMS AND POLYESTER-POLYOL-POLYETHER-POLYOL BLENDS TO BE USED THEREFOR |
| JPS5869219A (en) * | 1981-10-22 | 1983-04-25 | Takeda Chem Ind Ltd | Production of polyurethane foam |
| GB2119393B (en) * | 1982-04-08 | 1985-12-11 | Caligen Foam Ltd | Polyurethane foam |
| CA1215719A (en) * | 1983-05-04 | 1986-12-23 | Georges N. Altounian | Polyols and process for preparing the same; polyurethanes derived therefrom |
| JPS59206428A (en) * | 1983-05-10 | 1984-11-22 | Dainippon Ink & Chem Inc | Cellular polyurethane elastomer for vibration damping material |
| GB8406050D0 (en) * | 1984-03-08 | 1984-04-11 | Ici Plc | Polyol compositions |
| JP2578163B2 (en) * | 1988-04-30 | 1997-02-05 | 日本発条株式会社 | Cushion body for seat |
| DE4001044C2 (en) * | 1990-01-16 | 2001-12-13 | Elastogran Gmbh | Process for the preparation of flexible viscoelastic polyurethane foams having an improved sound absorption capacity and polyether-polyol-polyester-polyol mixtures which can be used for this purpose |
| JPH0586163A (en) * | 1991-09-26 | 1993-04-06 | Mitsui Toatsu Chem Inc | Low-viscosity polymethylene polyphenylene polyisocyanate composition prevented from crystallization |
| JP4666278B2 (en) * | 2004-02-13 | 2011-04-06 | 日本ポリウレタン工業株式会社 | A method for producing highly breathable and low resilience polyurethane foam. |
| MX2020007599A (en) | 2018-01-19 | 2020-09-03 | Hexion Inc | Polyester-polyol compositions for polyurethane foam with improved hydrolytic stability. |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1352704A (en) * | 1970-09-10 | 1974-05-08 | Ici Ltd | Foamed polymers |
| JPS56446B2 (en) * | 1972-05-02 | 1981-01-08 | ||
| GB1478045A (en) * | 1973-12-03 | 1977-06-29 | Ici Ltd | Polyurethane foams |
| GB1475541A (en) * | 1974-01-29 | 1977-06-01 | Ici Ltd | Polyurethane foams |
| JPS5336879B2 (en) * | 1974-06-06 | 1978-10-05 | ||
| GB1501858A (en) * | 1974-07-12 | 1978-02-22 | Ici Ltd | Solid unfoamed urea copolymer compositions containing silica |
| GB1485986A (en) * | 1974-08-27 | 1977-09-14 | Ici Ltd | Cellular polyurethanes |
| GB1479096A (en) * | 1975-05-29 | 1977-07-06 | Ici Ltd | Polymeric materials |
| DE2623961A1 (en) * | 1976-05-28 | 1977-12-15 | Bayer Ag | PROCESS FOR THE PRODUCTION OF POLYURETHANES |
| DE2704196A1 (en) * | 1977-02-02 | 1978-08-10 | Basf Ag | PROCESS FOR THE MANUFACTURING OF RIGID POLYURETHANE FOAM |
-
1978
- 1978-04-11 DE DE19782815540 patent/DE2815540A1/en active Pending
-
1979
- 1979-03-24 DE DE7979100893T patent/DE2967231D1/en not_active Expired
- 1979-03-24 EP EP79100893A patent/EP0004617B1/en not_active Expired
- 1979-04-10 CA CA325,400A patent/CA1129598A/en not_active Expired
- 1979-04-10 JP JP4260179A patent/JPS54137099A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789719A (en) * | 1988-03-15 | 1988-12-06 | Neochem Polymers Inc. | Manufacture of block polyester polyols, and polyurethanes derived therefrom |
| US4975523A (en) * | 1988-03-28 | 1990-12-04 | Du Pont Neochem | Manufacture of block polyester polyols, and polyurethanes derived therefrom |
| US20150299373A1 (en) * | 2012-10-26 | 2015-10-22 | Bayer Materialscience Ag | Method for producing soft polyurethane foam based on polyester polyols |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0004617A1 (en) | 1979-10-17 |
| DE2815540A1 (en) | 1979-10-25 |
| DE2967231D1 (en) | 1984-10-31 |
| EP0004617B1 (en) | 1984-09-26 |
| JPS54137099A (en) | 1979-10-24 |
| JPS6338368B2 (en) | 1988-07-29 |
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