CA1164149A - Process for the preparation of flexible polyurethane foams involving the use of aromatic monoamines - Google Patents
Process for the preparation of flexible polyurethane foams involving the use of aromatic monoaminesInfo
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- CA1164149A CA1164149A CA000379129A CA379129A CA1164149A CA 1164149 A CA1164149 A CA 1164149A CA 000379129 A CA000379129 A CA 000379129A CA 379129 A CA379129 A CA 379129A CA 1164149 A CA1164149 A CA 1164149A
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- polyol
- foams
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- polyurethane foams
- weight
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/2885—Compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- 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
- C08G2110/0016—Foam properties semi-rigid
-
- 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
-
- 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
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
PROCESS FOR THE PREPARTIAON OF FLEXIBLE POLYURETHANE
FOAMS INVOLVING THE USE OF AROMATIC MONOAMINES
Abstract of the Disclosure The invention relates a process for the prepara-tion of a polyurethane foam by reacting an organic polyiso-cyanate, polyol, and primary or secondary aromatic monoamine in the presence of a blowing agent and catalyst. The amines are used in quantities of 0.1 part to 4 parts by weight per 100 parts per weight of polyol.
The highly elastic polyurethane flexible foams are suited for the manufacture of upholstered furniture, matresses, automobile seats and head supports, as well as particularly for molded foams. The semi-rigid polyurethane foams are used as foam backing of dashboards in automobiles, thermal and sound insulation in buildings and vehicles, and for impact absorption in packaging materials.
FOAMS INVOLVING THE USE OF AROMATIC MONOAMINES
Abstract of the Disclosure The invention relates a process for the prepara-tion of a polyurethane foam by reacting an organic polyiso-cyanate, polyol, and primary or secondary aromatic monoamine in the presence of a blowing agent and catalyst. The amines are used in quantities of 0.1 part to 4 parts by weight per 100 parts per weight of polyol.
The highly elastic polyurethane flexible foams are suited for the manufacture of upholstered furniture, matresses, automobile seats and head supports, as well as particularly for molded foams. The semi-rigid polyurethane foams are used as foam backing of dashboards in automobiles, thermal and sound insulation in buildings and vehicles, and for impact absorption in packaging materials.
Description
~ 1~41~
PROCESS FOR THE PREPARATION OF FLEXIBLE POLYURETHANE
FOAMS INVOLVING THE USE OF_AROMATIC MONOAMINES
Background of the_Invention 1. Field of the Invention The invention relates to a process for the preparation of a polyurethane foam by reacting an organic polyisocyanate, a polyol, and a primary or secondary aromatic monoamine in the presence of a blowing agent and catalyst. The aromatic monoamines are used in quantities of 0.1 part to 4 parts by weight per 100 parts per weight of polyol.
PROCESS FOR THE PREPARATION OF FLEXIBLE POLYURETHANE
FOAMS INVOLVING THE USE OF_AROMATIC MONOAMINES
Background of the_Invention 1. Field of the Invention The invention relates to a process for the preparation of a polyurethane foam by reacting an organic polyisocyanate, a polyol, and a primary or secondary aromatic monoamine in the presence of a blowing agent and catalyst. The aromatic monoamines are used in quantities of 0.1 part to 4 parts by weight per 100 parts per weight of polyol.
2. Description of the Prior Art The preparation of polyurethane foams from organic polyisocyanates, polyols, blowing agents, catalysts, chain ex~tenders or cross-linking agents, auxiliaries and additives is known in the art, and has been described in numerous patents and other publications. See, for instance, the monograph by J.H. Saunders and K.C. Frisch, High Polymers, Volume XVI "Polyurethanes", Parts I and II (Interscience Publishers, New York) and the publication by R. Vieweg and A. Hoechtlen, Plastics Handbook, Volume VII, "Polyurethanes"
(Carl Hanser Publishers, Munich). In order to meet the requirements of all areas of application, the polyurethanes must have good mechanical properties with as low a density as possible. The mechanical properties should be manifested in high breaking elongation, tensile strength, graves tear strength, and compression strength. Therefore, there has been no lack of effort to produce flexible polyurethane foams with improved mechanical properties.
1 ~6~14~
One method of preparing polyurethane foams with good mechanical properties involves the use of reinforcing agents. Possible reinforcing agents for molded and slab foams of polyurethanes include, for instance, the so-called graft polyols or high molecular weight organic fillers.
Graft polyols are understood to be polyols which have polymers based on styrene, acrylonitrile and other vinyl monomers grafted by free radical polymerization to the polyether chain. High molecular weight organic fillers are understood to be similar polymers which, however, are not grafted to the polyether polyol but which are suspended in the polyether polyol. Other known fillers are polyureas based on 2,4-toluene diisocyanate and hydrazine.
The referenced reinforcing agents assist in improving many of the foam properties. The compression strength and the load-bearing capacity of the foams can be increased along with an increased open-celled content which causes a reduction of the after shrinking of flexible foams. Less important improvements are a slight increase in the tensile strength and a reduction in the breaking elongation of the foam. A problem with this approach, however, is that the required graft polymers and polymeric fillers must be produced in separate operations and are difficult to process using normal foaming equipment due to their high viscosity.
It is also kown that the mechanical properties of polyurethane foams can be improved by using polyether ~ 1 6 ~
polyols containing dispersions of copolymers. See, for example, German Patents 1,222,669, 1,152,536, and 1,152,537. If the vinyl monomers are directly copolymerized in the polyols, the resultant particles are generally so small that there is no tendency towards sedimentation.
However, a problem with using such dispersions is that they must be free of monomers in order to result in foams that are as odorless as possible because only such products can be used in the typical areas of application. This, however, means that the monomers must be separated from the disper-sions, for instance, with the aid of thin-film evaporators.
It is also known that polyurethane foam properties can be improved by incorporating inert fillers of an inorganic or organic nature directly into the reactants or directly into the foaming mixture, for instance, in the mixing chamber of the foaming machine. These processes also have serious drawbacks. Using conventional fillers, it is extremely difficult to produce dispersions having such a fine grain distribution that storage-stable mixtures are obtained. There is always a very pronounced danger of sediment formation. The result is that such dispersions must be stirred more or less intensively in order to avoid difficult redispersing processes.
For specific purposes of sound and thermal insulation, polyurethane foams filled with heavy spar are being used. However, the raw materials for this product must be processed on specially constructed machinery, ~ .lL64~
particularly, those workiny according to the principle of low-pressure technology and equipped with agitator mixing devices. The drawbacks encountered with the use of this type of processing machinery are so serious that filled polyurethane foams have not been produced on a large scale basis to date.
The mechanical properties of polyurethane foams may be also improved by the additional use of aromatic diamines, for instance, 3,3'-dichloro-4,4'-diaminodiphenyl-methane or 3,3'-dialkyl-substituted 4,4-diaminodiphenyl~
methanes (German Patent 1,240,654 equivalent to U.S.
(Carl Hanser Publishers, Munich). In order to meet the requirements of all areas of application, the polyurethanes must have good mechanical properties with as low a density as possible. The mechanical properties should be manifested in high breaking elongation, tensile strength, graves tear strength, and compression strength. Therefore, there has been no lack of effort to produce flexible polyurethane foams with improved mechanical properties.
1 ~6~14~
One method of preparing polyurethane foams with good mechanical properties involves the use of reinforcing agents. Possible reinforcing agents for molded and slab foams of polyurethanes include, for instance, the so-called graft polyols or high molecular weight organic fillers.
Graft polyols are understood to be polyols which have polymers based on styrene, acrylonitrile and other vinyl monomers grafted by free radical polymerization to the polyether chain. High molecular weight organic fillers are understood to be similar polymers which, however, are not grafted to the polyether polyol but which are suspended in the polyether polyol. Other known fillers are polyureas based on 2,4-toluene diisocyanate and hydrazine.
The referenced reinforcing agents assist in improving many of the foam properties. The compression strength and the load-bearing capacity of the foams can be increased along with an increased open-celled content which causes a reduction of the after shrinking of flexible foams. Less important improvements are a slight increase in the tensile strength and a reduction in the breaking elongation of the foam. A problem with this approach, however, is that the required graft polymers and polymeric fillers must be produced in separate operations and are difficult to process using normal foaming equipment due to their high viscosity.
It is also kown that the mechanical properties of polyurethane foams can be improved by using polyether ~ 1 6 ~
polyols containing dispersions of copolymers. See, for example, German Patents 1,222,669, 1,152,536, and 1,152,537. If the vinyl monomers are directly copolymerized in the polyols, the resultant particles are generally so small that there is no tendency towards sedimentation.
However, a problem with using such dispersions is that they must be free of monomers in order to result in foams that are as odorless as possible because only such products can be used in the typical areas of application. This, however, means that the monomers must be separated from the disper-sions, for instance, with the aid of thin-film evaporators.
It is also known that polyurethane foam properties can be improved by incorporating inert fillers of an inorganic or organic nature directly into the reactants or directly into the foaming mixture, for instance, in the mixing chamber of the foaming machine. These processes also have serious drawbacks. Using conventional fillers, it is extremely difficult to produce dispersions having such a fine grain distribution that storage-stable mixtures are obtained. There is always a very pronounced danger of sediment formation. The result is that such dispersions must be stirred more or less intensively in order to avoid difficult redispersing processes.
For specific purposes of sound and thermal insulation, polyurethane foams filled with heavy spar are being used. However, the raw materials for this product must be processed on specially constructed machinery, ~ .lL64~
particularly, those workiny according to the principle of low-pressure technology and equipped with agitator mixing devices. The drawbacks encountered with the use of this type of processing machinery are so serious that filled polyurethane foams have not been produced on a large scale basis to date.
The mechanical properties of polyurethane foams may be also improved by the additional use of aromatic diamines, for instance, 3,3'-dichloro-4,4'-diaminodiphenyl-methane or 3,3'-dialkyl-substituted 4,4-diaminodiphenyl~
methanes (German Patent 1,240,654 equivalent to U.S.
3,428,610) as cross-linking agents. The drawback of this process variation is that the cross-linking agents can be used in small quantities only for the preparation of low density foams and that some compounds of the referenced group are believed to be toxic.
U.S. patent 3,826,763 discloses that the mechanical properties of polyurethane foams can be improved by the use of aromatic monoamines. However, it has been found that the compression strength of the foam is adversely affected if more than about 4 parts by weight of aromatic monoamine is used per 100 parts of polyol.
Summary of the Invention The present invention generally relates to a process for the preparation of a polyurethane foam which comprises reac-ting an organic polyisocyanate, polyol, and a primary or secondary aromatic monoamine in the presence of a blowing agent, and catalsyt, ~ ~641~3 wherein the amount of said aromatic amine is.from 0.1 part to 4 parts by weight per 100 parts by weight of polyol .
In particular , the present invention provides a process for prepariny a polyurethane foam comprising A. reacting an oryanic polyisocyanate with a polyol and a primary or secondary aromatic amine to form an siocyanate terminated prepolymer ; and B. reacting the produc-t of (A) with a polyol in the presence of a blow.ing agent and catalys-t , wherein the amount of said aromatic amine is from 0.1 part to
U.S. patent 3,826,763 discloses that the mechanical properties of polyurethane foams can be improved by the use of aromatic monoamines. However, it has been found that the compression strength of the foam is adversely affected if more than about 4 parts by weight of aromatic monoamine is used per 100 parts of polyol.
Summary of the Invention The present invention generally relates to a process for the preparation of a polyurethane foam which comprises reac-ting an organic polyisocyanate, polyol, and a primary or secondary aromatic monoamine in the presence of a blowing agent, and catalsyt, ~ ~641~3 wherein the amount of said aromatic amine is.from 0.1 part to 4 parts by weight per 100 parts by weight of polyol .
In particular , the present invention provides a process for prepariny a polyurethane foam comprising A. reacting an oryanic polyisocyanate with a polyol and a primary or secondary aromatic amine to form an siocyanate terminated prepolymer ; and B. reacting the produc-t of (A) with a polyol in the presence of a blow.ing agent and catalys-t , wherein the amount of said aromatic amine is from 0.1 part to
4 parts per 100 parts by weigh-t of total polyol .
The polyurethane foams produced in accordance with this process excel because of their higher tensile strength , elast.icity , graves tear strength , and compression strength , as well as their increased number of open cells . This was surpri.sing particularly since it is known that polyurethane foams produced in the presence o:E monofunctional compounds such as stabilizers , antistatic agents , or flame retardants , which can be incorporated in the polyurethane structure , have poorer mechanical properties because the monofuncti.onal com-ponents terminate the polyaddition reac-tion thereby reducing the cross-linking density .
Preferably , flexible and semi-rigid polyurethane foams are produced according to the process of this invention .
The highly elastic polyurethane flexible foams are suited for the manufacture of upholstered furniture , ma-tresses , automobile seats and head supports , as well as particularly for molded foams . The semi-rigid polyurethane foams are used as -the foarn backi~g o dashboards in automobiles , thermal and sound insu-la.tion. in buildings and vehicles , and for impact absorption in packaging materials .
Desc~iption of the P~e~erred E~bodiment The ingredients for making the polyurethane foams of the subject invention will first be described . Then the specific processing conditions will be described in detail .
The polyurethane foams produced in accordance with this process excel because of their higher tensile strength , elast.icity , graves tear strength , and compression strength , as well as their increased number of open cells . This was surpri.sing particularly since it is known that polyurethane foams produced in the presence o:E monofunctional compounds such as stabilizers , antistatic agents , or flame retardants , which can be incorporated in the polyurethane structure , have poorer mechanical properties because the monofuncti.onal com-ponents terminate the polyaddition reac-tion thereby reducing the cross-linking density .
Preferably , flexible and semi-rigid polyurethane foams are produced according to the process of this invention .
The highly elastic polyurethane flexible foams are suited for the manufacture of upholstered furniture , ma-tresses , automobile seats and head supports , as well as particularly for molded foams . The semi-rigid polyurethane foams are used as -the foarn backi~g o dashboards in automobiles , thermal and sound insu-la.tion. in buildings and vehicles , and for impact absorption in packaging materials .
Desc~iption of the P~e~erred E~bodiment The ingredients for making the polyurethane foams of the subject invention will first be described . Then the specific processing conditions will be described in detail .
- 5 ~ -~ ~6~14~
Organic polyisocyanates which can be used to prepare the polyurethane foams include aliphatic, cyclo-aliphatic, arylaliphatic, heterocyclic and preferably aromatic multi~unctional isocyanates. Representative examples include: aliphatic diisocyanates such as ethylene-, 1,4~tetramethylene-, 1,6-hexamethylene- and 1,12-dodecanediisocyanate; cycloalphatic diisocyanates such as cyclohexane-1,3- and l,4-diisoc~anate as well as any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanate as well as any desired mixtures of these isomers, 4,4'- and 2,4'-diisocyanato-dicyclohexylmethane;
aromatic diisocyanates.such as 1,3- and 1,4-phenylene dii.socyanate, 2,4- and 2,6-toluene diisocyanate as well as any desired mixtures of these isomers, 2,2'-, 2,4'- and ~,4'-diphenylmethane diisocyanate and naphthalene-1,5-diisocyanate; aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate, 2,4,6-triisocyanatobenzene and polyphenyl polymethylene polyisocyanates. Also suitable are modified polyisocyanates, for instance, those descri~ed in ~.S. Patent 3,492,330, carbodiimide-group-containing polyisocyanates (see German Patent 1,092,007), allophanate-group-containing polyisocyanates (see British Patent 994,890 and ~elgian Patent 761,626), isocyanurate-group-containing polyisocyanates (see German Patents 1,022,789, 1,222,067, 1,027,394, and Canadian Patents Nos . 886,052 and 936,650 ) , urethane-group containing polyisocyanates tsee '~3 ~ 1~41~
Belgian Patent 752,261 and U.S. Patent 3,394,164), biuret-group-containing polyisocyanates (see German Patent 1,101,394 and British Patent 889,050) and ester-group-containing polyisocyanates (see British Patents 965,474, 1,072,956, U.S. Patent 3,567,7~3, and German Patent 1,231,688).
Preferably used are the commercially available aromatic di- and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate, as well as any desired mixtures of these isomers, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate, as well as any desired mixtures of these isomers, mixtures of 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (Crude MDI) and mixtures of toluene diisocyanates and crude MDI. The referenced di- and polyisocyanates may be used individually or in the form of mixtures.
Polyols which are preferably used to prepare the polyurethane foams of this invention are polyester polyols and polyether polyols having molecular weights of 200 to 8000, preferably 800 to 5000, and particularly 1800 to 3500. However, other hydroxyl group-containing polymers with the above-referenced molecular weights may also be used. These include polyester amides, polyacetals and poly carbonates, particularly those produced from diphenyl-carbonate and 1,6-hexanediol by transesterification.
The polyester polyols may be produced, for instance, from dicarboxylic acids, preferably aliphatic i I 6~ :1 49 dicarboxylic acids having 2 to 12, preferably 4 to 8, carbon atoms in the alkylene radical and multifunctional alcohols, preferably diols. Examples of dicarboxylic acids which can be used to prepare the polyether polyols include aliphatic dicarboxylic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dioic acid, dodecane dioic acid and preferably succinic and adipic acid and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid. Examples of bi- and multifunctional, particularly bi- and trifunctional alcohols which can be used to prepare the polyester polyols are ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, 1,10-decanediol, glycerine, trimethylol-propane, and preferably 1,4-butanediol and 1,6-hexanediol.
If multifunctional, particularly trif~lnctional alcohols are used for the preparation of the polyester polyols, the functionality of the resultant polyester polyols is a maximum of 6, preferably 2 to 4.
The polyester polyols have molecular weights of 500 to 2800, preferably of 1000 to 2000, and hydroxyl numbers from 40 to 280, preferably from 50 to 120.
Preferably used as polyols to prepare the poly-urethane foams, however, are polyether polyols which are produced according to familiar methods by reacting one or more cyclic ethers and an initiator molecule containing 2 to 4, preferably 2 to 3 active hydrogen atoms.
~ 1641~9 Examples of suitable cyclic ethers include 1,3-propane oxide, 1,2- and/or 2,3-butylene oxide, styrene oxide, tetrahydrofuran, and preferably alkylene oxides having 2 to 4 carbon atoms in the alkylene radical such as ethylene oxide and propylene oxide. The cyclic ethers may be used individually, alternatingly in sequence, or as mixtures.
Possible initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, and terephthalic acids, aliphatic and aromatic diamines (which may be N-mono-, N,N- and N,N'-dialkyl-substituted) having 1 to 4 carbon atoms in the alkyl radical such as unsubstituted and mono- and dialkyl-substituted alkylene diamines, diethylene triamine, tri-ethylene tetramine, l,3-propane diamine, 1,3- and/or 1,4-butane diamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylene diamine, phenylene diamine, 2,4- and 2,6-toluene diamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane; monoamines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, the toluidines and naphthylamines. Of particular interest among the compounds of the referenced groups are N,N,N',N'-tetrakis(2-hydroxyethyl~ethylene-diamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N''IN''-pentakis(2-hydroxypropyl)ethylenetriamine, phenyldiisopropanolamine, and higher alkylene oxide adducts of aniline.
~ 16~ l~9 Other possible initiator molecules include alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-diethanolamine, N-methyl- and N-ethyl-dipropanolamine and triethanolamine, hydrazine and hydrazides. Preferably used are multifunctional, particularly bi- and/or trifunctional, alcohols such as ethylene glycol, propylene glycol and trimethylene glycol, diethylene glycol, dipropyl glycol, l,4-butane glycol, 1,Ç-hexamethylene glycol, glycerine, trimethylolpropane and pentaerythritol.
Polyester amides which may be used as the polyol include, for instance, the primarily linear condensate obtained from multifunctional saturated or unsaturated carboxylic acids or their anhydrides and multifunctional saturated or unsaturated amino alcohols or mixtures of multifunctional alcohols and amino alcohols or polyamines.
Polyacetals which may be used as the polyol include the compounds which are produced from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
Polyacetals suitable for use in the process of this invention may also be produced by polymerizing cyclic acetals.
Polycarbonates, including those with hydroxyl groups, which may be used as the polyol, are those which are basically known and which can be produced, for instance, by reacting diols such as (1,3)-propanediol, (1,4)-butanediol and/or (1,6)-hexanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol with diaryl carbonates, for instance, diphenylcarbonate, or with phosgene.
The polyols may be used individually or in the form of mixtures. Mixtures of polyester and polyether polyols, for instance, have proven to work well. Depending upon the application of the polyurethane foam produced, the ratio of the components can be varied within wide limits, for instance, in a weight ratio of polyester polyol to polyether polyol of 20:80 to 80:20.
The aromatic monoamines which are used to prepare the polyurethane foams are primary and secondary aromatic monoamines. The aromatic monoamines may not be su~stituted with any groups which react with isocyanates. Representa-tive examples include primary and secondary aromatic monoamines with 6 to 18, preferably 6 to 12 carbon atoms.
Examples of substituents on the amines which do not react with isocyantes include alkyl radicals having 1 to 8, preferably 1 to 4 carbon atoms such as the methyl-, ethyl-, n-propyl-, iso-propyl-, n-butyl- and n-hexyl radical; alkoxy radicals having 1 to 7, preferably 1 to 3 carbon atoms such as the methoxy-, ethoxy-, n-propoxy- and iso-propoxy radical, aryl radicals such as the phenyl group and halogen atoms such as fluorine, chlorine and bromine.
Examples of arGmatic monoamines which have proven to work well include aniline, diphenylamine, 4-fluoro-aniline, N-methylaniline and 4-methoxyaniline, preferably aniline.
The aromatic monoamines may be used individually or as mixtures. They are used in quantities of 0.1 part to 4 parts by weight per 100 parts by weight of polyol.
Under certain circumstances, it may be advan-tageous to use chain extenders or cross-linking agents in addition to the aromatic monoamines for the preparation of the polyurethane foams. Representative examples of such materials include polyfunctional, particularly di- and trifunctional compounds having molecular weights of 17 to 600, preferably 60 to 300. The following are specific examples of such compounds: di- and trialkanolamines such as diethanolamine and triethanolamine, aliphatic and aromatic diamines such as ethylenediamine, 1,4-butane-diamine, 1,6-hexamethylenediamine, 4,4'-diaminodiphenyl-methane, 3,3'-dialkyl-substituted 4,4'-diaminodiphenyl-methane, 2,4- and 2,6-toluenediamine, and preferably the aliphatic diols and triols having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, glycerine and trimethylolpropane.
If chain extenders or cross-linking agents are used, they are in quantities of 1 part to 60 parts, prefer-ably of 10 to 30 parts by weight per 100 parts by weight of polyol.
The preferred blowing agent which is used in accordance with the process of this invention is water which reacts with isocyanate groups to form carbon dioxide. The amount of water which may be used advantageously is 0.1 part i 164~
to 8 parts by weight, preferably 1.5 parts to 5 parts by weight relative to 100 parts by weight of polyol.
Physically acting blowing agents may also be used as mixtures with water. Suited for this purpose are liquids which are inert with respect to the organic polyisocyanates and which have boiling points below 100C, preferably below 50C and particularly between -50C and 30C under atmospheric pressure so that they evaporate under the influence of the exothermal polyaddition reaction.
Representative examples include hydrocarbons such as pentane, n- and iso-butane and propane, ethers such as dimethylether and diethylether, ketones such as acetone and methylethylketone, and ethylacetate, and preferably halogenated hydrocarbons such as methylene chloride, trichlorofluoromethane, dichlorofluoromethane, dichloromono-fluoromethane, dichlorotetrafluoroethane and l,1,2-tri-chloro-1,2,2-trifluoroethane. Mixtures of these low boiling liquids with each other and/or with other substituted or nonsubstituted hydrocarbons may also be used.
The amount of physically acting blowing agents used in addition to water depends upon the foam density desired and is approximately 0 to 50 parts by weight, preferably 0 to 20 parts by weight per 100 parts by weight of polyol. Under certain conditions, it may be advantageous to mix the organic polyisocyanate with the physically acting blowing agent thereby reducing the viscosity.
~ 164~1~9 In order to accelerate the reaction between the polyols, water, chain extenders or cross-linking agents, and organic polyisocyantes, commonly used polyurethane catalysts are incorporated in the reaction mlxture~ Preferably used are conventional polyurethane catalysts such as tertiary amines, for instance, dimethylbenzylamine, dicyclhexyl-methylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyl-diamino-ethylether, bis(dimethylaminopropyl)urea, N-methyl-and/or N-ethylmorpholine, dimethylpiperazine, pyridine, 1,2-dimethylimidizole, 1-azobicyclo(3,3,0)octane, dimethylamino-ethanol, N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazine, for instance, N,N',N"-tris(dimethylaminopropyl)-s-hexa-hydrotriazine, and particularly triethylene diamine.
However, other suitable catalysts include metal salts such as iron-(II)-chloride, zinc chloride, lead octoate, and preferably tin salts such as tin dioctoate, tin diethyl-hexoate, and dibutyltin dilaurate, as well as particularly mixtures of tertiary amines and organic tin salts. Advan-tageously, 0.1 to 10 percent by weight, preferably 0.5 to 5 percent by weight of catalyst based on tertiary amines and/or 0.01 to 0.5 percent by weight, preferably 0.05 to 0.25 percent by weight of metal salts are used relative to the polyol weight.
Auxiliaries and additives may also be added to the reaction mixture. Examples include stabilizers, hydrolysis protection agents, pore regulators, fungistatically or bacteriostatically deterring substances, colors, pigments, ~ ~64 ~9 fillers, surface-active materials, plasticizers and flame retardants.
Exa~ples of surface-active substances include those which serve to support the homogenization of the raw materials and which may also be suited to regulate the cell structure of the foams. These include by way of example, siloxane-oxyalkylene-mixed polymerizates and other organo polysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil and/or resinoleic ester and turkish red oil which may be used in quantities of 0.2 to 8, preferably 0.5 to 5 parts by weight per 100 parts by weight of polyol.
It may also be advantageous to include a plasticizer in the reaction mixture in order to reduce brittleness of the foams. Commonly known plasticizers may be used. It is particularly advantageous to use those materials which contain phosphorus and/or halogen atoms and which, therefore, additionally increase the flame resistance of the polyurethane plsstics. These mateirals include tricresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate, and tris-2,3-dibromopropyl phosphate.
In addition to the already mentioned halogen-substituted phsophates, inorganic flame retardants may also be used to render the polyurethane foams flame resistant.
Examples of these include antimony trioxide, arsenic oxide, ammonium phosphate and calcium sulfate and melamine.
~ 16~ 9 It generally has proven to be advanatageous to use 5 to 50 parts by weight, preferably 5 to 25 parts by weight, of the referenced flame retardants per 100 parts by weight of polyol.
In order to prepare polyurethane foams according to the process of this invention, the ingredients are reacted at temperatures between 0C and 70~C, preferably 15C to 50C, in such quantities that 0.5 to 2, preferably 0.8 to 1.3, and particularly approximately one reactive hydrogen atom in the reactants is present per isocyanate group and such that the ratio of equivalents water to equivalents isocyanate groups is 0.5 to 5:1, preferably 0.7 to 0.9:1, and particularly 0.7S to 0.85:1.
The polyurethane foams may be produced according to the prepolymer or preferably according to the one-shot process. If the prepolymer process is used, it is advan-tageous to react the aromatic monoamine, optionally together with small quantities of polyol and the organic polyiso-cyanate in a prior reaction stage to form a urea and possibly urethane grcup containing polyisocyanate.
According to the one-shot process, the starting components, auxiliaries and additives are introduced individually via several feed nozzles when one mixing chamber is used and are intensively mixed in the mixing chamber. However, it has proven to be particularly advantageous to work according to the two-component process and to combine the polyols, primary and/or secondary aromatic monoamines, catalysts, i 16~1~9 blowing agents and possibly the chain extenders or cross-linking agents, auxiliaries and additives in the so-called A component and to use the organic polyisocyanates, possibly as a mixture with physical blowing agents, auxiliaries and additives as the B component. This method is now pre-dominantly used. An advantage of this process is the fact that the A and B components can be transported in a space-saving manner, can be stored for a limited amount of time, and only require intensive mixing prior to the manufacture of the polyurethane foams.
The polyurethane foams produced in accordance with the method of this invention have densities of 15 to 200 kilograms per cubic meter, preferably 30 to 60 kilograms per cubic meter and are characterized by their increased tensile strength, breaking elongation, graves tear strength and improved compression stength and/or compression factor.
The following examples will serve to illustrate in more detail the practice of this invention. The parts referred to in the examples are by weight and the tempera-tures are in degrees Centigrade unless otherwise specified.
~ 1~41~!~
Examples 1 to 6 and Comparison Example A
In order to prepare flexible polyurethane foams, A
and B components, which are at room temperature, are intensively mixed at room temperature and 800 grams of the mixture are filled into a closed mold (40 centimeters by 40 centimeters by 10 centimeters) preheated to 40C, and are allowed to foam.
The quantities of the starting components used as well as the densities and mechanical properties measured in the resultant polyurethane foams are ~ummarized in Table 1.
The isocyanate index for the examples and the comparison example was 100.
~ 164149 uc~ ~ l .~ ~ ~ I
o o o o OD O O
o ._ I
In ~ 1 0~ 0 0 o ~ ~
~1,, .~, I ~ o o OD O O
oo o o I CO o o I ~ ~ I I , I , I ~ o ~ ~
o .C
o o ~ C o ~, o ~ r 3 T ~ u ~
o a o g o ` 1 ~ ,~r~ o ~
~r In ~ ~ Ln O
~ ~ ~ o ~
.,, I. ~ oU~
o o ~ U~
U~ ~ ~ o a~ o ~ ~D
n ~ ~ o I O O r ~ O
a~ O ~ ~_ ~ o ~ In ~ ~ o ~
a~ ~ o ~D O
~ 1-- .
~ Ln ~ ~ o U~
a~
r_ ~ C ~ ~
a --oo~ ~
c x o ~y ,-, O ~ ~o t_ "~ ~ In ~ ~ ' H
~ td,~cO U a ~ Z
-- I~ ~ o a c ~
~ I " ~ o o V
~ aJ o V
~ ~ ! a ~ ~ o~3 ~ ~ ,X~-, C ~
Organic polyisocyanates which can be used to prepare the polyurethane foams include aliphatic, cyclo-aliphatic, arylaliphatic, heterocyclic and preferably aromatic multi~unctional isocyanates. Representative examples include: aliphatic diisocyanates such as ethylene-, 1,4~tetramethylene-, 1,6-hexamethylene- and 1,12-dodecanediisocyanate; cycloalphatic diisocyanates such as cyclohexane-1,3- and l,4-diisoc~anate as well as any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanate as well as any desired mixtures of these isomers, 4,4'- and 2,4'-diisocyanato-dicyclohexylmethane;
aromatic diisocyanates.such as 1,3- and 1,4-phenylene dii.socyanate, 2,4- and 2,6-toluene diisocyanate as well as any desired mixtures of these isomers, 2,2'-, 2,4'- and ~,4'-diphenylmethane diisocyanate and naphthalene-1,5-diisocyanate; aromatic polyisocyanates such as 4,4',4"-triphenylmethane triisocyanate, 2,4,6-triisocyanatobenzene and polyphenyl polymethylene polyisocyanates. Also suitable are modified polyisocyanates, for instance, those descri~ed in ~.S. Patent 3,492,330, carbodiimide-group-containing polyisocyanates (see German Patent 1,092,007), allophanate-group-containing polyisocyanates (see British Patent 994,890 and ~elgian Patent 761,626), isocyanurate-group-containing polyisocyanates (see German Patents 1,022,789, 1,222,067, 1,027,394, and Canadian Patents Nos . 886,052 and 936,650 ) , urethane-group containing polyisocyanates tsee '~3 ~ 1~41~
Belgian Patent 752,261 and U.S. Patent 3,394,164), biuret-group-containing polyisocyanates (see German Patent 1,101,394 and British Patent 889,050) and ester-group-containing polyisocyanates (see British Patents 965,474, 1,072,956, U.S. Patent 3,567,7~3, and German Patent 1,231,688).
Preferably used are the commercially available aromatic di- and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate, as well as any desired mixtures of these isomers, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate, as well as any desired mixtures of these isomers, mixtures of 2,2'-, 2,4'-, 4,4'-diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates (Crude MDI) and mixtures of toluene diisocyanates and crude MDI. The referenced di- and polyisocyanates may be used individually or in the form of mixtures.
Polyols which are preferably used to prepare the polyurethane foams of this invention are polyester polyols and polyether polyols having molecular weights of 200 to 8000, preferably 800 to 5000, and particularly 1800 to 3500. However, other hydroxyl group-containing polymers with the above-referenced molecular weights may also be used. These include polyester amides, polyacetals and poly carbonates, particularly those produced from diphenyl-carbonate and 1,6-hexanediol by transesterification.
The polyester polyols may be produced, for instance, from dicarboxylic acids, preferably aliphatic i I 6~ :1 49 dicarboxylic acids having 2 to 12, preferably 4 to 8, carbon atoms in the alkylene radical and multifunctional alcohols, preferably diols. Examples of dicarboxylic acids which can be used to prepare the polyether polyols include aliphatic dicarboxylic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dioic acid, dodecane dioic acid and preferably succinic and adipic acid and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid. Examples of bi- and multifunctional, particularly bi- and trifunctional alcohols which can be used to prepare the polyester polyols are ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, 1,10-decanediol, glycerine, trimethylol-propane, and preferably 1,4-butanediol and 1,6-hexanediol.
If multifunctional, particularly trif~lnctional alcohols are used for the preparation of the polyester polyols, the functionality of the resultant polyester polyols is a maximum of 6, preferably 2 to 4.
The polyester polyols have molecular weights of 500 to 2800, preferably of 1000 to 2000, and hydroxyl numbers from 40 to 280, preferably from 50 to 120.
Preferably used as polyols to prepare the poly-urethane foams, however, are polyether polyols which are produced according to familiar methods by reacting one or more cyclic ethers and an initiator molecule containing 2 to 4, preferably 2 to 3 active hydrogen atoms.
~ 1641~9 Examples of suitable cyclic ethers include 1,3-propane oxide, 1,2- and/or 2,3-butylene oxide, styrene oxide, tetrahydrofuran, and preferably alkylene oxides having 2 to 4 carbon atoms in the alkylene radical such as ethylene oxide and propylene oxide. The cyclic ethers may be used individually, alternatingly in sequence, or as mixtures.
Possible initiator molecules include water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid, and terephthalic acids, aliphatic and aromatic diamines (which may be N-mono-, N,N- and N,N'-dialkyl-substituted) having 1 to 4 carbon atoms in the alkyl radical such as unsubstituted and mono- and dialkyl-substituted alkylene diamines, diethylene triamine, tri-ethylene tetramine, l,3-propane diamine, 1,3- and/or 1,4-butane diamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylene diamine, phenylene diamine, 2,4- and 2,6-toluene diamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane; monoamines such as methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, the toluidines and naphthylamines. Of particular interest among the compounds of the referenced groups are N,N,N',N'-tetrakis(2-hydroxyethyl~ethylene-diamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N''IN''-pentakis(2-hydroxypropyl)ethylenetriamine, phenyldiisopropanolamine, and higher alkylene oxide adducts of aniline.
~ 16~ l~9 Other possible initiator molecules include alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-diethanolamine, N-methyl- and N-ethyl-dipropanolamine and triethanolamine, hydrazine and hydrazides. Preferably used are multifunctional, particularly bi- and/or trifunctional, alcohols such as ethylene glycol, propylene glycol and trimethylene glycol, diethylene glycol, dipropyl glycol, l,4-butane glycol, 1,Ç-hexamethylene glycol, glycerine, trimethylolpropane and pentaerythritol.
Polyester amides which may be used as the polyol include, for instance, the primarily linear condensate obtained from multifunctional saturated or unsaturated carboxylic acids or their anhydrides and multifunctional saturated or unsaturated amino alcohols or mixtures of multifunctional alcohols and amino alcohols or polyamines.
Polyacetals which may be used as the polyol include the compounds which are produced from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldimethylmethane, hexanediol and formaldehyde.
Polyacetals suitable for use in the process of this invention may also be produced by polymerizing cyclic acetals.
Polycarbonates, including those with hydroxyl groups, which may be used as the polyol, are those which are basically known and which can be produced, for instance, by reacting diols such as (1,3)-propanediol, (1,4)-butanediol and/or (1,6)-hexanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol with diaryl carbonates, for instance, diphenylcarbonate, or with phosgene.
The polyols may be used individually or in the form of mixtures. Mixtures of polyester and polyether polyols, for instance, have proven to work well. Depending upon the application of the polyurethane foam produced, the ratio of the components can be varied within wide limits, for instance, in a weight ratio of polyester polyol to polyether polyol of 20:80 to 80:20.
The aromatic monoamines which are used to prepare the polyurethane foams are primary and secondary aromatic monoamines. The aromatic monoamines may not be su~stituted with any groups which react with isocyanates. Representa-tive examples include primary and secondary aromatic monoamines with 6 to 18, preferably 6 to 12 carbon atoms.
Examples of substituents on the amines which do not react with isocyantes include alkyl radicals having 1 to 8, preferably 1 to 4 carbon atoms such as the methyl-, ethyl-, n-propyl-, iso-propyl-, n-butyl- and n-hexyl radical; alkoxy radicals having 1 to 7, preferably 1 to 3 carbon atoms such as the methoxy-, ethoxy-, n-propoxy- and iso-propoxy radical, aryl radicals such as the phenyl group and halogen atoms such as fluorine, chlorine and bromine.
Examples of arGmatic monoamines which have proven to work well include aniline, diphenylamine, 4-fluoro-aniline, N-methylaniline and 4-methoxyaniline, preferably aniline.
The aromatic monoamines may be used individually or as mixtures. They are used in quantities of 0.1 part to 4 parts by weight per 100 parts by weight of polyol.
Under certain circumstances, it may be advan-tageous to use chain extenders or cross-linking agents in addition to the aromatic monoamines for the preparation of the polyurethane foams. Representative examples of such materials include polyfunctional, particularly di- and trifunctional compounds having molecular weights of 17 to 600, preferably 60 to 300. The following are specific examples of such compounds: di- and trialkanolamines such as diethanolamine and triethanolamine, aliphatic and aromatic diamines such as ethylenediamine, 1,4-butane-diamine, 1,6-hexamethylenediamine, 4,4'-diaminodiphenyl-methane, 3,3'-dialkyl-substituted 4,4'-diaminodiphenyl-methane, 2,4- and 2,6-toluenediamine, and preferably the aliphatic diols and triols having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, glycerine and trimethylolpropane.
If chain extenders or cross-linking agents are used, they are in quantities of 1 part to 60 parts, prefer-ably of 10 to 30 parts by weight per 100 parts by weight of polyol.
The preferred blowing agent which is used in accordance with the process of this invention is water which reacts with isocyanate groups to form carbon dioxide. The amount of water which may be used advantageously is 0.1 part i 164~
to 8 parts by weight, preferably 1.5 parts to 5 parts by weight relative to 100 parts by weight of polyol.
Physically acting blowing agents may also be used as mixtures with water. Suited for this purpose are liquids which are inert with respect to the organic polyisocyanates and which have boiling points below 100C, preferably below 50C and particularly between -50C and 30C under atmospheric pressure so that they evaporate under the influence of the exothermal polyaddition reaction.
Representative examples include hydrocarbons such as pentane, n- and iso-butane and propane, ethers such as dimethylether and diethylether, ketones such as acetone and methylethylketone, and ethylacetate, and preferably halogenated hydrocarbons such as methylene chloride, trichlorofluoromethane, dichlorofluoromethane, dichloromono-fluoromethane, dichlorotetrafluoroethane and l,1,2-tri-chloro-1,2,2-trifluoroethane. Mixtures of these low boiling liquids with each other and/or with other substituted or nonsubstituted hydrocarbons may also be used.
The amount of physically acting blowing agents used in addition to water depends upon the foam density desired and is approximately 0 to 50 parts by weight, preferably 0 to 20 parts by weight per 100 parts by weight of polyol. Under certain conditions, it may be advantageous to mix the organic polyisocyanate with the physically acting blowing agent thereby reducing the viscosity.
~ 164~1~9 In order to accelerate the reaction between the polyols, water, chain extenders or cross-linking agents, and organic polyisocyantes, commonly used polyurethane catalysts are incorporated in the reaction mlxture~ Preferably used are conventional polyurethane catalysts such as tertiary amines, for instance, dimethylbenzylamine, dicyclhexyl-methylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyl-diamino-ethylether, bis(dimethylaminopropyl)urea, N-methyl-and/or N-ethylmorpholine, dimethylpiperazine, pyridine, 1,2-dimethylimidizole, 1-azobicyclo(3,3,0)octane, dimethylamino-ethanol, N,N',N"-tris(dialkylaminoalkyl)hexahydrotriazine, for instance, N,N',N"-tris(dimethylaminopropyl)-s-hexa-hydrotriazine, and particularly triethylene diamine.
However, other suitable catalysts include metal salts such as iron-(II)-chloride, zinc chloride, lead octoate, and preferably tin salts such as tin dioctoate, tin diethyl-hexoate, and dibutyltin dilaurate, as well as particularly mixtures of tertiary amines and organic tin salts. Advan-tageously, 0.1 to 10 percent by weight, preferably 0.5 to 5 percent by weight of catalyst based on tertiary amines and/or 0.01 to 0.5 percent by weight, preferably 0.05 to 0.25 percent by weight of metal salts are used relative to the polyol weight.
Auxiliaries and additives may also be added to the reaction mixture. Examples include stabilizers, hydrolysis protection agents, pore regulators, fungistatically or bacteriostatically deterring substances, colors, pigments, ~ ~64 ~9 fillers, surface-active materials, plasticizers and flame retardants.
Exa~ples of surface-active substances include those which serve to support the homogenization of the raw materials and which may also be suited to regulate the cell structure of the foams. These include by way of example, siloxane-oxyalkylene-mixed polymerizates and other organo polysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil and/or resinoleic ester and turkish red oil which may be used in quantities of 0.2 to 8, preferably 0.5 to 5 parts by weight per 100 parts by weight of polyol.
It may also be advantageous to include a plasticizer in the reaction mixture in order to reduce brittleness of the foams. Commonly known plasticizers may be used. It is particularly advantageous to use those materials which contain phosphorus and/or halogen atoms and which, therefore, additionally increase the flame resistance of the polyurethane plsstics. These mateirals include tricresyl phosphate, tris-2-chloroethyl phosphate, tris-chloropropyl phosphate, and tris-2,3-dibromopropyl phosphate.
In addition to the already mentioned halogen-substituted phsophates, inorganic flame retardants may also be used to render the polyurethane foams flame resistant.
Examples of these include antimony trioxide, arsenic oxide, ammonium phosphate and calcium sulfate and melamine.
~ 16~ 9 It generally has proven to be advanatageous to use 5 to 50 parts by weight, preferably 5 to 25 parts by weight, of the referenced flame retardants per 100 parts by weight of polyol.
In order to prepare polyurethane foams according to the process of this invention, the ingredients are reacted at temperatures between 0C and 70~C, preferably 15C to 50C, in such quantities that 0.5 to 2, preferably 0.8 to 1.3, and particularly approximately one reactive hydrogen atom in the reactants is present per isocyanate group and such that the ratio of equivalents water to equivalents isocyanate groups is 0.5 to 5:1, preferably 0.7 to 0.9:1, and particularly 0.7S to 0.85:1.
The polyurethane foams may be produced according to the prepolymer or preferably according to the one-shot process. If the prepolymer process is used, it is advan-tageous to react the aromatic monoamine, optionally together with small quantities of polyol and the organic polyiso-cyanate in a prior reaction stage to form a urea and possibly urethane grcup containing polyisocyanate.
According to the one-shot process, the starting components, auxiliaries and additives are introduced individually via several feed nozzles when one mixing chamber is used and are intensively mixed in the mixing chamber. However, it has proven to be particularly advantageous to work according to the two-component process and to combine the polyols, primary and/or secondary aromatic monoamines, catalysts, i 16~1~9 blowing agents and possibly the chain extenders or cross-linking agents, auxiliaries and additives in the so-called A component and to use the organic polyisocyanates, possibly as a mixture with physical blowing agents, auxiliaries and additives as the B component. This method is now pre-dominantly used. An advantage of this process is the fact that the A and B components can be transported in a space-saving manner, can be stored for a limited amount of time, and only require intensive mixing prior to the manufacture of the polyurethane foams.
The polyurethane foams produced in accordance with the method of this invention have densities of 15 to 200 kilograms per cubic meter, preferably 30 to 60 kilograms per cubic meter and are characterized by their increased tensile strength, breaking elongation, graves tear strength and improved compression stength and/or compression factor.
The following examples will serve to illustrate in more detail the practice of this invention. The parts referred to in the examples are by weight and the tempera-tures are in degrees Centigrade unless otherwise specified.
~ 1~41~!~
Examples 1 to 6 and Comparison Example A
In order to prepare flexible polyurethane foams, A
and B components, which are at room temperature, are intensively mixed at room temperature and 800 grams of the mixture are filled into a closed mold (40 centimeters by 40 centimeters by 10 centimeters) preheated to 40C, and are allowed to foam.
The quantities of the starting components used as well as the densities and mechanical properties measured in the resultant polyurethane foams are ~ummarized in Table 1.
The isocyanate index for the examples and the comparison example was 100.
~ 164149 uc~ ~ l .~ ~ ~ I
o o o o OD O O
o ._ I
In ~ 1 0~ 0 0 o ~ ~
~1,, .~, I ~ o o OD O O
oo o o I CO o o I ~ ~ I I , I , I ~ o ~ ~
o .C
o o ~ C o ~, o ~ r 3 T ~ u ~
o a o g o ` 1 ~ ,~r~ o ~
~r In ~ ~ Ln O
~ ~ ~ o ~
.,, I. ~ oU~
o o ~ U~
U~ ~ ~ o a~ o ~ ~D
n ~ ~ o I O O r ~ O
a~ O ~ ~_ ~ o ~ In ~ ~ o ~
a~ ~ o ~D O
~ 1-- .
~ Ln ~ ~ o U~
a~
r_ ~ C ~ ~
a --oo~ ~
c x o ~y ,-, O ~ ~o t_ "~ ~ In ~ ~ ' H
~ td,~cO U a ~ Z
-- I~ ~ o a c ~
~ I " ~ o o V
~ aJ o V
~ ~ ! a ~ ~ o~3 ~ ~ ,X~-, C ~
Claims (10)
1. A process for preparing a polyurethane foam comprising A. reacting an organic polyisocyanate with a polyol and a primary or secondary aromatic amine to form an isocyanate terminated prepolymer ; and B. reacting the product of (A) with a polyol in the presence of a blowing agent and catalyst, wherein the amount of said aromatic amine is from 0.1 part to 4 parts per 100 parts by weight of total polyol .
2. The process of claim 1 wherein the organic polyisocyanate is reacted with a chain extcnder or crosslinker in addition to a polyol and primary or secondary monoamine .
3. The process of claim 1 wherein the ratio of isocyanate groups to active hydrogen atoms in the compounds containing active hydrogen atoms is from 0.8:1 to 1.3:1 .
4. The process of claim 1 wherein water is used as a blowing agent .
5. The process of claim 1 wherein the polyol is a polyether polyol having a molecular weight of 1000 to 2000 .
6. The process of claim 1 wherein the organic polyisocyanate is selected from the group consisting of toluene diisocyanates , diphenylmethane diisocyanates , polyphenyl-polymethylene diisocyanates , and mixtures thereof .
7. The process of claim 1 , wherein a surface-active substance is added to the reaction mixture to support the homogenation of the reactants or to regulate the cell struc-ture of the foams .
8. The process of claim 3 wherein the amount of water used is such that the ratio of equivalent water to equivalent isocyanate groups is 0.7:1 to 0.9:1 .
9. The process of claim 1 wherein the aromatic monoamine is aniline .
10. A polyurethane foam prepared in accordance with claim 1 .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803021293 DE3021293A1 (en) | 1980-06-06 | 1980-06-06 | METHOD FOR PRODUCING ELASTIC POLYURETHANE FOAMS |
| DEP3021293.2 | 1980-06-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164149A true CA1164149A (en) | 1984-03-20 |
Family
ID=6103989
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000379138A Expired CA1161996A (en) | 1980-06-06 | 1981-06-05 | Process for the preparation of flexible polyurethane foams involving the use of aliphatic monoamines |
| CA000379129A Expired CA1164149A (en) | 1980-06-06 | 1981-06-05 | Process for the preparation of flexible polyurethane foams involving the use of aromatic monoamines |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000379138A Expired CA1161996A (en) | 1980-06-06 | 1981-06-05 | Process for the preparation of flexible polyurethane foams involving the use of aliphatic monoamines |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0041618A3 (en) |
| CA (2) | CA1161996A (en) |
| DE (1) | DE3021293A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0268906A3 (en) * | 1986-11-26 | 1988-12-07 | The Dow Chemical Company | Compatibilized blends of alpha, omega-alkylene glycols and polyether polyols and process for preparing the same |
| US4719247A (en) * | 1987-02-10 | 1988-01-12 | Ici Americas Inc. | Deformable polyurethane having improved cure time |
| AU631523B2 (en) * | 1987-05-21 | 1992-12-03 | Foamex L.P. | Flame retardant internally cured polyurethane foam having improved properties |
| GB9404127D0 (en) * | 1994-03-03 | 1994-04-20 | Polyol Int Bv | Process for producing a soft, flexible, hot molded poyurethane foam |
| AUPM479994A0 (en) * | 1994-03-30 | 1994-04-28 | Bostik Australia Pty. Limited | Improvements relating to automotive interior liner and/or moisture shield |
| CA2640381A1 (en) | 2006-03-14 | 2007-09-20 | Huntsman International Llc | Composition made from a diisocyanate and a monoamine and process for preparing it |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1795662C3 (en) * | 1963-10-12 | 1975-01-30 | Bayer Ag, 5090 Leverkusen | Process for the production of water-soluble or water-swellable surface-active addition products |
| GB1091604A (en) * | 1964-03-12 | 1967-11-22 | Lankro Chem Ltd | Improvements in or relating to polyurethane foams |
| GB1120441A (en) * | 1965-01-26 | 1968-07-17 | Ici Ltd | Manufacture of polyurethanes |
| GB1250401A (en) * | 1968-01-08 | 1971-10-20 | ||
| US3513491A (en) * | 1968-03-13 | 1970-05-26 | Donald W Gordon | Athlete's landing pit with foam-block cushion units |
-
1980
- 1980-06-06 DE DE19803021293 patent/DE3021293A1/en not_active Withdrawn
-
1981
- 1981-05-11 EP EP81103572A patent/EP0041618A3/en not_active Withdrawn
- 1981-06-05 CA CA000379138A patent/CA1161996A/en not_active Expired
- 1981-06-05 CA CA000379129A patent/CA1164149A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0041618A3 (en) | 1982-10-27 |
| EP0041618A2 (en) | 1981-12-16 |
| CA1161996A (en) | 1984-02-07 |
| DE3021293A1 (en) | 1981-12-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |