CA2201586A1 - A process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent - Google Patents
A process for preparing polyurethane foam in the presence of a hydrocarbon blowing agentInfo
- Publication number
- CA2201586A1 CA2201586A1 CA002201586A CA2201586A CA2201586A1 CA 2201586 A1 CA2201586 A1 CA 2201586A1 CA 002201586 A CA002201586 A CA 002201586A CA 2201586 A CA2201586 A CA 2201586A CA 2201586 A1 CA2201586 A1 CA 2201586A1
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- Canada
- Prior art keywords
- parts
- compatibilizing agent
- polyol
- fatty
- compatibilizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C08G2110/0025—Foam properties rigid
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Disclosed is a process for preparing a rigid, hydrocarbon-blown, polyurethane foam by reacting a polyisocyanate with a polyurethane precursor composition comprising a polyol and a compatibilizing agent containing a compatibilizing radical of the formula: -(CnH2n+1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, and further wherein the compatibilizing agent is a fat, oil, monoglyceride, diglyceride, fatty acid, fatty alcohol, fatty amide, fatty amine, fatty acid ester, alkoxylated adduct of any of the foregoing, alkyl phenol or propoxylated adduct thereof, alkyl phenol or adduct thereof with ethylene oxide and propylene oxide, alkyl phenol or adduct thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol or a mixture thereof. A preferred compatibilizing agent is castor oil. The compatibilizing agent enhances the miscibility of the hydrocarbon blowing agent. Advantageously, the polyurethane precursor compositions exhibit improved storage stability.
Description
~20~586 WO 96/12759 PCT/US9~/13313 A PROCESS FOR PREPARING POLYURETHANE FOAM IN THE PRESENCE OFA HYDROCARBON
BLOWING AGENT
t This invention relates to a process for preparing a rigid, hydrocarbon blown, polyurethane foam by reacting a polyisocyanate with a polyol composition comprising a material which compatibilizes the hydrocarbon in the polyurethane formulation.
A recent trend in the manufacture of polyurethane foam, especially rigid polyurethane foam, is the use of hydrocarbon blowing agents as substitute or replacement for the traditionally employed blowing agents including trichlorofluoromethane. Such trend has 10 been motivated by the desire to eliminate the use of certain fully halogenated alkanes in an effort to protect the environment including the ozone content of the atmosphere. The general use of hydrocarbons as a blowing agent for polyurethane foam is widely reported in the literature. For example, U.S. Patent 5,096,933 discloses the use of cyclopentane, cyclohexane or mixtures thereof. U.S. Patent 5,182,309 discloses the use of pentane. U.S. Patent 5,001,164 15 discloses the use of pentane in combination with trichloroethane. U.S. Patent 5,286,759 discloses combinations of hydrocarbons containing at least 4 carbon atoms with perfluoroalkanes as a blowing agent for polyurethane foam manufacture. U.S. Patent 4,263,412 discloses the preparation of polyurethane foam in the presence of butane. Of the mentioned hydrocarbons, use of cyclopentane and pentane is presently favored due to 20 availability and general benefit to the physical properties of the foam.
However, to prepare polyurethane foam which exhibits attractive physical properties, advantageously all reactants should be readily miscible with one another and/or high efficiency mixing procedures be employed to ensure even distribution of all starting materials. In the presence of poor miscibility or poor mixing, the resulting foam may exhibit 25 inferior, unattractive, physical properties. Hydrocarbon blowing agents, especially when used in significant amounts as might be required to produce a low density foam, are generally not noted for having attractive miscibility with the majority of polyesl:er or polyether polyols commonly used to prepare polyurethane foam. Frequently separation results leading to poor mixing and/or poor foam quality.
In the art when problems of miscibility are encountered, using the traditional type of blowing agents, frequently they can be resolved by varying the amount of cell stabilizing agent or surfactant present in the foaming process. In many instances, the problem has been resolved by use of a surfactant in an amount of from 0.1 to 2 parts per 100 parts of polyol. Use of greater amounts of surfactants, normally a mineral oil of the polysiloxane type, 35 can lead to a significant decline in the physical properties of the resulting foam. For closed-cell rigid polyurethane foam, this can be a reduction of compressive strength, a loss of thermal insulation potential as a consequence of an acquired open-cell content, or poor mold filling (flow) characteristics. When preparing low density polyurethane foam in the presence of a ~ ~ 2 0 ~ 5 8 6 WO 9~/12759 PCT/US95/13313 hydrocarbon blowing agent with elevated loadings of the conventional surfactants, the poor miscibility problem is not satisfactorily resolved. Accordingly it would be desirable to provide for an alternative foaming process permitting the manufacture of polyurethane foam, especially low density foam, in the presence of a hydrocarbon blowing agent which does not t sufferfrom the above-mentioned deficiencies.
For this purpose, the use of compatibilizing agents has been investigated.
In a first aspect, this invention relates to a process for preparing a closed-celled polyurethane foam which includes reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition wherein the polyol composition comprises:
10 i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 5 to 25 parts, per 100 parts by total weight of the polyol composition, o~ a compatibilizing agent containing a compatibilizing radical of the formula ~(CnH2n+ 1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, and further wherein the compatibilizing agent is a fat, oil, monoglyceride, diglyceride, fatty acid, fatty alcohol, fatty amide, fatty amine, fatty acid ester, alkoxylated adduct of any of the foregoing, alkyl phenol or propoxylated adduct thereof, alkyl phenol or adduct thereof with ethylene oxide or propylene oxide, alkyl phenol or adduct thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol, or a mixture thereof.
In a second aspect, this invention is a process for preparing a closed-celled 25 polyurethane foam which comprises reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition, wherein the polyol composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and includes:
ii) from 5 to 25 parts, per 100 parts bytotal weight of the polyol composition, of a compatibilizing agent comprising a fat or oil having a hydroxyl number of from 100 to 550.
In a third aspect, this invention relates to a closed-celled polyurethane foam obtained according to an above-mentioned process.
In a fourth aspect, this invention relates to a blend, suitable for use in the inventive process as a polyurethane precursor composition, which comprises the above-mentioned polyol composition containing a compatibilizing agent as defined herein and further a blowing agentwhich is present in an amount of from 1 to 20 parts per 100 parts by 2 ~ 0 1 5 8 6 total weight of the composition and which is a C1 g hydrocarbon, and preferably butane, n-pentane, i-pentane, hexane, cydopentane, methylcyclopentane, cyclohexane, methylcyclohexane, isomer thereof, or a mixture of two or more thereof.
Surprisingly, it has been found that use of a compatibilizing agent as defined 5 enhances the miscibility of the hydrocarbon blowing agent and rninimizes the susceptibility to i separation of the formulation. The presence of the compatibilizing agent allows for an increased loading of the hydrocarbon blowing agent, thereby permitting the manufacture of foam having a lower density while retaining overall attractive physical properties.
The present invention relates to a process for preparing a rigid, closed-celled 10 polyurethane foam by reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition comprising a certain compatibilizing agent.
Advantageously, the resulting foam is of a low free rise density of from 10 to 50, preferably from 15 to 40, and more preferably from 15 to 35 kglm3.
The polyurethane precursor composition comprises: (a) an isocyanate-reactive 15 component, usually a polyether or polyester polyol, having a hydroxyl number value of from 100 to 1200, preferably from 100 to 800, more preferably from 200 to 800, and yet more preferably from 200 to 600 and preferably being a polyester or polyether polyol; and (b) a compatibilizing agent. The compatibilizing agent allows for attractive miscibility of the hydrocarbon blowing agent with the polyol and is present in an amount of from 5 to 25, 20 preferably from 6, more preferably from 7, and preferably up to 18, more preferably up to 15 parts by total weight of the polyol composition including polyol and compatibilizing agent.
The compatibilizing agent is defined herein as containing a compatibilizing radical of the formula ~(CnH2n+ 1) 25 wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, wherein the compatibilizing agent is a fat, oil, monoglyceride, diglyceride, fatty acid, fatty alcohol, fatty amide, fatty amine, fatty acid ester, alkoxylated adduct of any of the foregoing, alkyl phenol, or propoxylated adductthereof, alkyl phenol, or adductthereof 30 with ethylene oxide or propylene oxide, alkyl phenol, or adduct thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol or a mixture thereof.
In preferred embodiments each molecule contains only one active hydrogen atom.
The active hydrogen atoms contained in these compatibilizing agents are such as associated with hydroxyl, thiol, amine and carboxylic acid functionality. The presence of the 35 isocyanate reactive hydrogen atom is desired to permit reaction with the polyisocyanate, thereby incorporating, to the advantage of the polymer physical properties, the compatibilizing agent into the polyurethane polymer.
r 2 2 1) 1 5 8 6 Advantageously, the compatibilizing agent is a fat, oil, or alkoxylated adduct thereof, with hydroxyl functionality and having a hydroxyl numbervalue of from 100, preferablyfrom 130, more preferablyfrom 140, and up to 550, more preferably up to 300, still more preferably up to 200, and yet more preferably up to 180.
When fats or oils are selected, they prer~rdbly comprise a hydroxyl-substituted fattyacid constituent. Detailed descriptions of these materials and theirfatty acid constituents are well known. See, for example, the entry "Fats and Fatty Oils" in Ullmann's Encyclopedia of Indus~rial Chemistry, ISBN 0-89573-160-6, or alternatively Kirk-Othmer Encyclopedia of Chemical Technology, ISBN 0-471-02062-1. For the present inven1:ion, suitable compatibilizing 10 agents contain, as a fatty acid constituent, for example, ricinoleic acid, dihydroxystearic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, eicosanoic acid, or mixtures of two or more thereof. Preferred in one embodiment of the present invention is ricinoleic acid, which exhibits excellent miscibility with polar substances, such as alcohols including polyols, and limited miscibility with nonpolar substances such as hydrocarbons. A convenient and readily available 15 natural fatty oil source comprising a hydroxyl-substituted fatty acid constituent is castor oil which is understood to comprise on average 90 weight percent of a glyceride of ricinoleic acid, 4 weight percent of a glyceride of linoleic acid, with the balance to 100 percent of glycerides of dihydroxystearic acid, palmitic acid, stearic acid, oleic acid, linolenic acid and eicosanoic acid.
Castor oil, essentially independent of source, has a hydroxyl number of from 160 to 168.
Suitable polyols include polyester or polyether polyols such as are conventionally used in the preparation of rigid polyurethane foam and having a hydroxyl number value within the above-mentioned range. Additionally, such polyols will generally contain from 2 to 8, preferably from 3 to 8, and more preferably from 3 to 6 hydroxyl groups per molecule.
Examples of suitable, and preferred, polyols are polyether polyols as described more fully in U.S. Patent 4,394,491. Exemplary of such polyether polyols include those commercially available under the trademark VORANOL, which include VORANOL 202, VORANOL 360, VORANOL 370, VORANOL 446, VORANOL 490, VORANOL 575, VORANOL 640, VORANOL 800, VORANOL CP1000, VORANOL CP260, VORANOL CP450, and VORANOL RN482, all available from The Dow Chemical Company. Other preferred polyols include alkylene oxide derivatives of Mannich condensate as taught in, for example, U.S. Patents 3,297,597; 4,137,265 and 4,383,102; and amino-alkylpiperazine-initiated polyether polyols as described in U.S. Patents 4,704,410 and 4,704,411.
As mentioned, the polyurethane foaming process of this invention requires the presence of a hydrocarbon blowing agent which advantageously comprises a C1 8 aliphatic or 35 cycloaliphatic hydrocarbon, preferably C4 8, which is an alkane, alkene or alkyne. Such hydrocarbons are selected as the blowing agent because they have a boiling point lower than the reaction exotherm, generally more than 120C, and usually of from 150C to 200C, encountered when preparing a polyurethane foam. Suitable hydrocarbons include those -2 2 0 9 5 8 ~
~ WO 96/12759 PCT/US95/13313 - having a boiling point of less than 120C, preferably less than 100C, and more preferably less than 50C such as, for example, butane, n-pentane, i-pentane, cyclopentane, methyl-cyclopentane, hexane, cyc1Ohexane, methylcyclohexane, isomers thereof, or mixtures of two or more thereof. Preferred hydrocarbons, due to their ability to confer attractive thermal 5 insulation properties to the polyurethane foam, are n-pentane, i pentane and cyclopentane.
Especially p~er~rled is a mixture of isomers n-pentane and i-pentane wherein the ratio of n-pentaneto i-pentane isfrom 5:95 to 50:50, preferablyfrom 10:90to35:65. Thisfraction of i-pentane is found to be advantageous for optimum flow properl ies when preparing a polyurethane foam and for confe" ing attractive thermal insulation properties to the resulting 10 foam Typically the hydrocarbon will be present in an amount of from 1 to 20, preferably from 5 to 20, and more preferably from 7 to 18 parts per 100 parts by total weight of the composition comprising polyol and compatibilizing agent.
In addition to the hydrocarbon blowing agent, optionally a supplemental blowing means can be provided by the presence of water. Water reacts with polyisocyanate 15 leading to the production of carbon dioxide which is able to confer a réduced density to the polyurethane polymer. When present, the amount of water advantageously is from 0.5 to 10, preferably from 1.5 to 3, and more preferably from 2 to 6 parts per 100 parts by weight of the polyol composition including the fatty oil. In a highly prefer, ed embodiment of the invention, polyurethane foam is prepared in the presence of water and hydrocarbon blowing agent zo wherein, per 100 parts by weight of the polyol composition including the compatibilizing agent, the water is present in an amount of from 2 to 6 parts, and the hydrocarbon blowing agent being n-pentane, i-pentane, cyclopentane, or mixtures of at least two thereof is present in an amount of from 1 to 20 parts. In a lesser preferred embodiment, it is also possible to use conventional fluorocarbons or hydrogen-containing chlorofluorocarbons, as supplemental 25 physical blowing agent, including difluorochloromethane, difluoroethane, difluorochloroethane, tetrafluoroethane dichlorotrifluoroethane and others such as those taught, for example, in U.S. Patent4,945,119.
Suitable polyisocyanates include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. A crude polyisocyanate may also be used in the 30 practice of this invention, such as the crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. Preferred are aromatic polyisocyanates comprising a methylene diphenylisocyanate, polymethylene polyphenylisocyanate, or mixtures thereof. Suitable mixtures include those containing, based on total weight of polyisocyanate, 35 from 10 to 50 weight percent of methylene diphenylisocyanate; and from 90 to 50 weight percent of polymethylene polyphenylisocyanate. For the purpose of providing cross-linkages in the end polymer, advantageously such an aromatic polyisocyanate has an average isocyanate 220 ~86 functionality of at least 2.3, preferably from 2.5 to 3.5, and more preferably from 2.7 to 3.1.
Exemplary of commercially available aromatic polyisocyanates suitable for use in this invention include crude methylene diphenylisocyanate mixtures supplied by The Dow Chemical Company under the trademark VORANATE and designated as M220, M229, M269, M595 and M580.
The amount of polyisoyanate present when preparing the polyurethane foam is such to provide for an isocyanate reaction index of typically from 60 to 550, preferably from 70, more pl er~rdbly from 80, and preferably up to 300, more preferably up to 200, still more preferably up to 160, and yet more preferdbly up to 140. An isocyanate reaction index of 100 corresponds to one isocyanate group per isocyanate reactive hydrogen atom present including 10 those from the polyol composition containing compatibilizing agent and, if present, any water.
Optionally other ingredients may be present when preparing the polyurethane foam. Among these other ingredients are catalysts, surfactants, colorants, antioxidants, reinforcing agents, fillers, anli~ldlic agents and flame retardants. Suitable flame retardants include phosphorus containing substances such as tris(chloroalkyl)phosphate and 15 trisalkylphosphates, for example triethylphosphate; and nitrogen-containing substances such as melamine.
One or more catalysts for the reaction of the active hydrogen-containing compound with the polyisocyanate are advantageously present. Suitable catalysts include tertiary amine compounds and organometallic compounds. Exemplary tertiary amine catalysts 20 include triethylenediamine, pentamethyldiethylenetriamine, N-ethylmorpholine,N-cocomorpholine, N-methylmorpholine, tetramethylethylenediamine, dimethylbenzylamine, 1 -methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, diethylethanolamine,N,N-dimethyl-N',N'-dimethylisopropylpropylenediamine and N,N--diethyl-3-diethylaminopropylamine. Exemplary organometallic catalysts include organo-25 mercury, organolead, organoferric and organotin catalysts, with organotin catalysts beingprefer, ed among these. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin di-2-ethyl hexanoate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. A catalyst for the trimerization of polyisocyanates and formation of polyisocyanurate polymers, such as an alkali metal alkoxide, alkali metal 30 carboxylate, or quaternary amine compound, may also optionally be employed herein. When employed, the quantity of catalyst used is sufficient to increase the rate of polymerization reaction. Precise quantities must be determined experimentally, but generally will range from 0.01 to 3.0 parts by weight per 100 parts polyol depending on the type and activity of the catalyst.
It is generally highly preferred to employ a minor amount of a surfactant to stabilize the foaming reaction mixture until it cures. Such surfactants, distinguished from the compatibilizing agent, are generally manufactured mineral oils including liquid or solid organosilicone surfactants. Other, less preferred surfactants, include amine salts of long chain -WO 96/12759 2 2 ~ ~ 5 8 ~ PCT/US95/13313 alkyl acid sulfate esters, and alkyl sulfonate esters and alkyl arylsulfonic acids. Such surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and the formation of large, uneven cells. Typically, from 0.1 to 3 parts of the surfactant per 100 parts by weight polyol are sufficient for this purpose.
In making a polyurethane foam, the polyol(s), polyisocyanate and other components are contacted, thoroughly mixed and permitted to expand and cure into a cellular polymer. The particular mixing apparatus is not critical, and various types of mixing head and spray apparatus are conveniently used. It is often convenient, but not necessary, to preblend some of the raw materials prior to reacting the polyisocyanate and active hydrogen-containing 10 components. For example, it is often useful to blend the polyol(s), blowing agent, surfactants, catalysts and other components except for polyisocyanates, and then contact this mixture with the polyisocyanate. Alternatively, all components can be introduced individually to the mixing zone where the polyisocyanate and polyol(s) are contacted. It is also possible to prereact all or a portion of the polyol(s) with the polyisocyanate to form a prepolymer, although such is not 15 preferred. For optimum processing, it is found convenient to prepare the polyurethane by mixing at an ambient temperature the reactants which themselves have a temperature of from 1 0C to 35C, and preferably from 1 5C to 25C.
The polyurethane foam obtained in accordance with this invention is of value forthe appliance and construction industry where its attractive compressive strength, dimensional 20 stability and thermal insulation is highly desirable. The invention may also be used to provide polyurethane foam for semirigid applications such as for example sealant foam applications.
The invention is illustrated by way of the examples given hereinbelow. Unless otherwise indicated all amounts given are parts by weight.
Example 1 The storage stability of various hydrocarbon/-polyol mixtures optionally containing castor oil is reported in Table 1. The substances and relative amounts making up the hydrocarbon and polyol mixtures are also given in Table 1. The storage stability is determined in accordance with the following general procedure in which the hydrocarbon is blended into a polyol mixture, replesenldlive of a formulation typically used forthe manufacture of rigid 30 polyurethane foam, and the resulting blend allowed to stand at room temperature for 7 days.
After this period, the stability of the resulting blend is visually rated according to the following scheme:
"Separates" - blend separates into multiple layers.
"Turbid" - the turbid blend does not separate into multiple layers and does not become clear on agitation.
"Limit" - the turbid blend does not separate into multiple layers and on agitation becomes clear.
2 2 0 ~ 5 8 6 "Separates" - blend separates into multiple layers.
"Turbid" - the turbid blend does not separate into multiple layers and does not become clear on agitation.
" Limit" - the turbid blend does not separate into multiple layers and on agitation becomes clear.
''ClearU - the blend is clear and not separated into multiple layers.
Blends 1, 2 and 5 which separate are undesirable for the purposes of preparing a polyurethane foam; Blends 3 and 4 are observed to have a "clear or "limit" sta1:us and are preferred as they are more readily manipulated in a consistent manner to the benefit of the foaming process.
Table i partsbyweight Blend1* Blend2* Blend3 Blend4 Blend5*
CastorOil 0 3 7 10 28.5 Polyol 1 51 51 51 52.3 51 Polyol 2 14.3 14.3 14.3 12 14.3 15Polyol 3 28.5 25.5 21.5 20 Surfactant 1 2 2 2 1.5 2 Catalyst 2.2 2.2 2.2 2.2 2.2 Water 2 2 2 2 2 i-pentane 10 10 10 10 10 20n-pentane 3 3 3 3 3 Blend Stability after 7 days at:
i) 20C / Turbid Limit ClearSeparates ii) 5C Separates Separates Turbid Limit Separates * Not an example of this invention.
Polyol 1: a sorbitol-initiated oxypropylene poiyether polyol having a hydroxyl number of 480.
Polyol 2: an ethylenediamine-initiated oxypropylene polyether polyol having hydroxyl number of 640.
Polyol 3: a glycerine-initiated oxypropylene polyether polyol having a hydroxyl numberof 160.
Surfactant 1: TEGOSTAB B8462 a silicon-based surfactant from Th Goldschmidt AGCatalyst: a blend of urethane promoting catalysts containing 1.2 pbw dimethylcyclohexylamine, 0.4 pbw pentamethyldiethylenetriamine;
and 0.6 pbw of CURITHANE 206 a proprietary urethane promoting catalyst available from The Dow Chemical Company.
22~ ~58~ -- Example 2 Rigid polyurethane foam is machine-prepared in the presence of a hydrocarbon blowing agent and castor oil using the formulation as given in Table ll. High pressure mixing conditions with reactants being introd uced to the mixer head at a temperature of about 20C
5 are used. The results indicate that an improved blend stability is obtained while still maintaining an acceptable overall foam physical performance.
Table ll parts by weight Foam 1 * Foam ZFoam 3 Castor Oil 0 5 10 Polyol 1 O 50 48 50.5 Polyol 2 (~) 15 14 14 Polyol 3 ~3 28.5 27 18.5 Surfactant 1 (~) 2 1.5 1.5 Catalyst O Z.2 2.2 2.2 Water 2.3 2.3 2.3 i-pentane 9.5 10 10 n-pentane 3 3 3 Isocyanate (~) Index 115 115 115 Blend Stability after 7 days at 5Cseparates limit clear 20Free Rise Density (kg/m3) 22.6 21.7 22.4 Molded Foam properties, 34 3 32.6 32.9 Density (kg/m3) CompressiveStrength(kPa) 154.9 119.6 137 (ASTM C-518) 23.1 23.5 23.2 25Demold post expansion at 3 9 5 4 3 4 minutes (mm) Not an example of this invention.
(~) As given for Example 1.
(~) VORATEC SD100, a polymeric methylene diphenylisocyanate with an NCO functionality of 2.7, available from The Dow Chemical Company.
30 Example 3 The storage stability of various hydrocarbon/polyol mixtures containing compatibilizing agents other than castor oil i5 reported in Table ]Il. The alternative compatibilizing agents and relative amounts making up the hydrocarbon and polyol mixtures is also given in Table lll. The storage stability as reported is determined in accordance with the 35 general procedure described for Example 1.
220~586 Table lll partsbyweight Blend6* Blend7 Blend8 Blend9 Blend 10 Polyol 4 100 90 90 75 80 Cyclopentane 20 20 20 25 25 Compatibilizing 0 10 0 0 0 Agent2 10 o o Compatibilizing 0 0 0 25 0 Castor oil 0 0 0 0 20 Blend Stabilityat turbid clear clear clear clear * Not an example of this invention.
15 Polyol 4: a sucrose/glycerine oxypropylene polyol having a hydroxyl number of 490.
Compatibilizing Agent 1: C1zHz5-(OCH2CH2)4-OH
Compatibilizing Agent 2: p(CgH19)-C6H4-(OCH2CH2)2-OH
Compatibilizing Agent 3: monoglyceride adduct of oleic acid
BLOWING AGENT
t This invention relates to a process for preparing a rigid, hydrocarbon blown, polyurethane foam by reacting a polyisocyanate with a polyol composition comprising a material which compatibilizes the hydrocarbon in the polyurethane formulation.
A recent trend in the manufacture of polyurethane foam, especially rigid polyurethane foam, is the use of hydrocarbon blowing agents as substitute or replacement for the traditionally employed blowing agents including trichlorofluoromethane. Such trend has 10 been motivated by the desire to eliminate the use of certain fully halogenated alkanes in an effort to protect the environment including the ozone content of the atmosphere. The general use of hydrocarbons as a blowing agent for polyurethane foam is widely reported in the literature. For example, U.S. Patent 5,096,933 discloses the use of cyclopentane, cyclohexane or mixtures thereof. U.S. Patent 5,182,309 discloses the use of pentane. U.S. Patent 5,001,164 15 discloses the use of pentane in combination with trichloroethane. U.S. Patent 5,286,759 discloses combinations of hydrocarbons containing at least 4 carbon atoms with perfluoroalkanes as a blowing agent for polyurethane foam manufacture. U.S. Patent 4,263,412 discloses the preparation of polyurethane foam in the presence of butane. Of the mentioned hydrocarbons, use of cyclopentane and pentane is presently favored due to 20 availability and general benefit to the physical properties of the foam.
However, to prepare polyurethane foam which exhibits attractive physical properties, advantageously all reactants should be readily miscible with one another and/or high efficiency mixing procedures be employed to ensure even distribution of all starting materials. In the presence of poor miscibility or poor mixing, the resulting foam may exhibit 25 inferior, unattractive, physical properties. Hydrocarbon blowing agents, especially when used in significant amounts as might be required to produce a low density foam, are generally not noted for having attractive miscibility with the majority of polyesl:er or polyether polyols commonly used to prepare polyurethane foam. Frequently separation results leading to poor mixing and/or poor foam quality.
In the art when problems of miscibility are encountered, using the traditional type of blowing agents, frequently they can be resolved by varying the amount of cell stabilizing agent or surfactant present in the foaming process. In many instances, the problem has been resolved by use of a surfactant in an amount of from 0.1 to 2 parts per 100 parts of polyol. Use of greater amounts of surfactants, normally a mineral oil of the polysiloxane type, 35 can lead to a significant decline in the physical properties of the resulting foam. For closed-cell rigid polyurethane foam, this can be a reduction of compressive strength, a loss of thermal insulation potential as a consequence of an acquired open-cell content, or poor mold filling (flow) characteristics. When preparing low density polyurethane foam in the presence of a ~ ~ 2 0 ~ 5 8 6 WO 9~/12759 PCT/US95/13313 hydrocarbon blowing agent with elevated loadings of the conventional surfactants, the poor miscibility problem is not satisfactorily resolved. Accordingly it would be desirable to provide for an alternative foaming process permitting the manufacture of polyurethane foam, especially low density foam, in the presence of a hydrocarbon blowing agent which does not t sufferfrom the above-mentioned deficiencies.
For this purpose, the use of compatibilizing agents has been investigated.
In a first aspect, this invention relates to a process for preparing a closed-celled polyurethane foam which includes reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition wherein the polyol composition comprises:
10 i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 5 to 25 parts, per 100 parts by total weight of the polyol composition, o~ a compatibilizing agent containing a compatibilizing radical of the formula ~(CnH2n+ 1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, and further wherein the compatibilizing agent is a fat, oil, monoglyceride, diglyceride, fatty acid, fatty alcohol, fatty amide, fatty amine, fatty acid ester, alkoxylated adduct of any of the foregoing, alkyl phenol or propoxylated adduct thereof, alkyl phenol or adduct thereof with ethylene oxide or propylene oxide, alkyl phenol or adduct thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol, or a mixture thereof.
In a second aspect, this invention is a process for preparing a closed-celled 25 polyurethane foam which comprises reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition, wherein the polyol composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and includes:
ii) from 5 to 25 parts, per 100 parts bytotal weight of the polyol composition, of a compatibilizing agent comprising a fat or oil having a hydroxyl number of from 100 to 550.
In a third aspect, this invention relates to a closed-celled polyurethane foam obtained according to an above-mentioned process.
In a fourth aspect, this invention relates to a blend, suitable for use in the inventive process as a polyurethane precursor composition, which comprises the above-mentioned polyol composition containing a compatibilizing agent as defined herein and further a blowing agentwhich is present in an amount of from 1 to 20 parts per 100 parts by 2 ~ 0 1 5 8 6 total weight of the composition and which is a C1 g hydrocarbon, and preferably butane, n-pentane, i-pentane, hexane, cydopentane, methylcyclopentane, cyclohexane, methylcyclohexane, isomer thereof, or a mixture of two or more thereof.
Surprisingly, it has been found that use of a compatibilizing agent as defined 5 enhances the miscibility of the hydrocarbon blowing agent and rninimizes the susceptibility to i separation of the formulation. The presence of the compatibilizing agent allows for an increased loading of the hydrocarbon blowing agent, thereby permitting the manufacture of foam having a lower density while retaining overall attractive physical properties.
The present invention relates to a process for preparing a rigid, closed-celled 10 polyurethane foam by reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition comprising a certain compatibilizing agent.
Advantageously, the resulting foam is of a low free rise density of from 10 to 50, preferably from 15 to 40, and more preferably from 15 to 35 kglm3.
The polyurethane precursor composition comprises: (a) an isocyanate-reactive 15 component, usually a polyether or polyester polyol, having a hydroxyl number value of from 100 to 1200, preferably from 100 to 800, more preferably from 200 to 800, and yet more preferably from 200 to 600 and preferably being a polyester or polyether polyol; and (b) a compatibilizing agent. The compatibilizing agent allows for attractive miscibility of the hydrocarbon blowing agent with the polyol and is present in an amount of from 5 to 25, 20 preferably from 6, more preferably from 7, and preferably up to 18, more preferably up to 15 parts by total weight of the polyol composition including polyol and compatibilizing agent.
The compatibilizing agent is defined herein as containing a compatibilizing radical of the formula ~(CnH2n+ 1) 25 wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, wherein the compatibilizing agent is a fat, oil, monoglyceride, diglyceride, fatty acid, fatty alcohol, fatty amide, fatty amine, fatty acid ester, alkoxylated adduct of any of the foregoing, alkyl phenol, or propoxylated adductthereof, alkyl phenol, or adductthereof 30 with ethylene oxide or propylene oxide, alkyl phenol, or adduct thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol or a mixture thereof.
In preferred embodiments each molecule contains only one active hydrogen atom.
The active hydrogen atoms contained in these compatibilizing agents are such as associated with hydroxyl, thiol, amine and carboxylic acid functionality. The presence of the 35 isocyanate reactive hydrogen atom is desired to permit reaction with the polyisocyanate, thereby incorporating, to the advantage of the polymer physical properties, the compatibilizing agent into the polyurethane polymer.
r 2 2 1) 1 5 8 6 Advantageously, the compatibilizing agent is a fat, oil, or alkoxylated adduct thereof, with hydroxyl functionality and having a hydroxyl numbervalue of from 100, preferablyfrom 130, more preferablyfrom 140, and up to 550, more preferably up to 300, still more preferably up to 200, and yet more preferably up to 180.
When fats or oils are selected, they prer~rdbly comprise a hydroxyl-substituted fattyacid constituent. Detailed descriptions of these materials and theirfatty acid constituents are well known. See, for example, the entry "Fats and Fatty Oils" in Ullmann's Encyclopedia of Indus~rial Chemistry, ISBN 0-89573-160-6, or alternatively Kirk-Othmer Encyclopedia of Chemical Technology, ISBN 0-471-02062-1. For the present inven1:ion, suitable compatibilizing 10 agents contain, as a fatty acid constituent, for example, ricinoleic acid, dihydroxystearic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, eicosanoic acid, or mixtures of two or more thereof. Preferred in one embodiment of the present invention is ricinoleic acid, which exhibits excellent miscibility with polar substances, such as alcohols including polyols, and limited miscibility with nonpolar substances such as hydrocarbons. A convenient and readily available 15 natural fatty oil source comprising a hydroxyl-substituted fatty acid constituent is castor oil which is understood to comprise on average 90 weight percent of a glyceride of ricinoleic acid, 4 weight percent of a glyceride of linoleic acid, with the balance to 100 percent of glycerides of dihydroxystearic acid, palmitic acid, stearic acid, oleic acid, linolenic acid and eicosanoic acid.
Castor oil, essentially independent of source, has a hydroxyl number of from 160 to 168.
Suitable polyols include polyester or polyether polyols such as are conventionally used in the preparation of rigid polyurethane foam and having a hydroxyl number value within the above-mentioned range. Additionally, such polyols will generally contain from 2 to 8, preferably from 3 to 8, and more preferably from 3 to 6 hydroxyl groups per molecule.
Examples of suitable, and preferred, polyols are polyether polyols as described more fully in U.S. Patent 4,394,491. Exemplary of such polyether polyols include those commercially available under the trademark VORANOL, which include VORANOL 202, VORANOL 360, VORANOL 370, VORANOL 446, VORANOL 490, VORANOL 575, VORANOL 640, VORANOL 800, VORANOL CP1000, VORANOL CP260, VORANOL CP450, and VORANOL RN482, all available from The Dow Chemical Company. Other preferred polyols include alkylene oxide derivatives of Mannich condensate as taught in, for example, U.S. Patents 3,297,597; 4,137,265 and 4,383,102; and amino-alkylpiperazine-initiated polyether polyols as described in U.S. Patents 4,704,410 and 4,704,411.
As mentioned, the polyurethane foaming process of this invention requires the presence of a hydrocarbon blowing agent which advantageously comprises a C1 8 aliphatic or 35 cycloaliphatic hydrocarbon, preferably C4 8, which is an alkane, alkene or alkyne. Such hydrocarbons are selected as the blowing agent because they have a boiling point lower than the reaction exotherm, generally more than 120C, and usually of from 150C to 200C, encountered when preparing a polyurethane foam. Suitable hydrocarbons include those -2 2 0 9 5 8 ~
~ WO 96/12759 PCT/US95/13313 - having a boiling point of less than 120C, preferably less than 100C, and more preferably less than 50C such as, for example, butane, n-pentane, i-pentane, cyclopentane, methyl-cyclopentane, hexane, cyc1Ohexane, methylcyclohexane, isomers thereof, or mixtures of two or more thereof. Preferred hydrocarbons, due to their ability to confer attractive thermal 5 insulation properties to the polyurethane foam, are n-pentane, i pentane and cyclopentane.
Especially p~er~rled is a mixture of isomers n-pentane and i-pentane wherein the ratio of n-pentaneto i-pentane isfrom 5:95 to 50:50, preferablyfrom 10:90to35:65. Thisfraction of i-pentane is found to be advantageous for optimum flow properl ies when preparing a polyurethane foam and for confe" ing attractive thermal insulation properties to the resulting 10 foam Typically the hydrocarbon will be present in an amount of from 1 to 20, preferably from 5 to 20, and more preferably from 7 to 18 parts per 100 parts by total weight of the composition comprising polyol and compatibilizing agent.
In addition to the hydrocarbon blowing agent, optionally a supplemental blowing means can be provided by the presence of water. Water reacts with polyisocyanate 15 leading to the production of carbon dioxide which is able to confer a réduced density to the polyurethane polymer. When present, the amount of water advantageously is from 0.5 to 10, preferably from 1.5 to 3, and more preferably from 2 to 6 parts per 100 parts by weight of the polyol composition including the fatty oil. In a highly prefer, ed embodiment of the invention, polyurethane foam is prepared in the presence of water and hydrocarbon blowing agent zo wherein, per 100 parts by weight of the polyol composition including the compatibilizing agent, the water is present in an amount of from 2 to 6 parts, and the hydrocarbon blowing agent being n-pentane, i-pentane, cyclopentane, or mixtures of at least two thereof is present in an amount of from 1 to 20 parts. In a lesser preferred embodiment, it is also possible to use conventional fluorocarbons or hydrogen-containing chlorofluorocarbons, as supplemental 25 physical blowing agent, including difluorochloromethane, difluoroethane, difluorochloroethane, tetrafluoroethane dichlorotrifluoroethane and others such as those taught, for example, in U.S. Patent4,945,119.
Suitable polyisocyanates include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. A crude polyisocyanate may also be used in the 30 practice of this invention, such as the crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. Preferred are aromatic polyisocyanates comprising a methylene diphenylisocyanate, polymethylene polyphenylisocyanate, or mixtures thereof. Suitable mixtures include those containing, based on total weight of polyisocyanate, 35 from 10 to 50 weight percent of methylene diphenylisocyanate; and from 90 to 50 weight percent of polymethylene polyphenylisocyanate. For the purpose of providing cross-linkages in the end polymer, advantageously such an aromatic polyisocyanate has an average isocyanate 220 ~86 functionality of at least 2.3, preferably from 2.5 to 3.5, and more preferably from 2.7 to 3.1.
Exemplary of commercially available aromatic polyisocyanates suitable for use in this invention include crude methylene diphenylisocyanate mixtures supplied by The Dow Chemical Company under the trademark VORANATE and designated as M220, M229, M269, M595 and M580.
The amount of polyisoyanate present when preparing the polyurethane foam is such to provide for an isocyanate reaction index of typically from 60 to 550, preferably from 70, more pl er~rdbly from 80, and preferably up to 300, more preferably up to 200, still more preferably up to 160, and yet more preferdbly up to 140. An isocyanate reaction index of 100 corresponds to one isocyanate group per isocyanate reactive hydrogen atom present including 10 those from the polyol composition containing compatibilizing agent and, if present, any water.
Optionally other ingredients may be present when preparing the polyurethane foam. Among these other ingredients are catalysts, surfactants, colorants, antioxidants, reinforcing agents, fillers, anli~ldlic agents and flame retardants. Suitable flame retardants include phosphorus containing substances such as tris(chloroalkyl)phosphate and 15 trisalkylphosphates, for example triethylphosphate; and nitrogen-containing substances such as melamine.
One or more catalysts for the reaction of the active hydrogen-containing compound with the polyisocyanate are advantageously present. Suitable catalysts include tertiary amine compounds and organometallic compounds. Exemplary tertiary amine catalysts 20 include triethylenediamine, pentamethyldiethylenetriamine, N-ethylmorpholine,N-cocomorpholine, N-methylmorpholine, tetramethylethylenediamine, dimethylbenzylamine, 1 -methyl-4-dimethylaminoethylpiperazine,3-methoxy-N-dimethylpropylamine, diethylethanolamine,N,N-dimethyl-N',N'-dimethylisopropylpropylenediamine and N,N--diethyl-3-diethylaminopropylamine. Exemplary organometallic catalysts include organo-25 mercury, organolead, organoferric and organotin catalysts, with organotin catalysts beingprefer, ed among these. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin di-2-ethyl hexanoate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. A catalyst for the trimerization of polyisocyanates and formation of polyisocyanurate polymers, such as an alkali metal alkoxide, alkali metal 30 carboxylate, or quaternary amine compound, may also optionally be employed herein. When employed, the quantity of catalyst used is sufficient to increase the rate of polymerization reaction. Precise quantities must be determined experimentally, but generally will range from 0.01 to 3.0 parts by weight per 100 parts polyol depending on the type and activity of the catalyst.
It is generally highly preferred to employ a minor amount of a surfactant to stabilize the foaming reaction mixture until it cures. Such surfactants, distinguished from the compatibilizing agent, are generally manufactured mineral oils including liquid or solid organosilicone surfactants. Other, less preferred surfactants, include amine salts of long chain -WO 96/12759 2 2 ~ ~ 5 8 ~ PCT/US95/13313 alkyl acid sulfate esters, and alkyl sulfonate esters and alkyl arylsulfonic acids. Such surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and the formation of large, uneven cells. Typically, from 0.1 to 3 parts of the surfactant per 100 parts by weight polyol are sufficient for this purpose.
In making a polyurethane foam, the polyol(s), polyisocyanate and other components are contacted, thoroughly mixed and permitted to expand and cure into a cellular polymer. The particular mixing apparatus is not critical, and various types of mixing head and spray apparatus are conveniently used. It is often convenient, but not necessary, to preblend some of the raw materials prior to reacting the polyisocyanate and active hydrogen-containing 10 components. For example, it is often useful to blend the polyol(s), blowing agent, surfactants, catalysts and other components except for polyisocyanates, and then contact this mixture with the polyisocyanate. Alternatively, all components can be introduced individually to the mixing zone where the polyisocyanate and polyol(s) are contacted. It is also possible to prereact all or a portion of the polyol(s) with the polyisocyanate to form a prepolymer, although such is not 15 preferred. For optimum processing, it is found convenient to prepare the polyurethane by mixing at an ambient temperature the reactants which themselves have a temperature of from 1 0C to 35C, and preferably from 1 5C to 25C.
The polyurethane foam obtained in accordance with this invention is of value forthe appliance and construction industry where its attractive compressive strength, dimensional 20 stability and thermal insulation is highly desirable. The invention may also be used to provide polyurethane foam for semirigid applications such as for example sealant foam applications.
The invention is illustrated by way of the examples given hereinbelow. Unless otherwise indicated all amounts given are parts by weight.
Example 1 The storage stability of various hydrocarbon/-polyol mixtures optionally containing castor oil is reported in Table 1. The substances and relative amounts making up the hydrocarbon and polyol mixtures are also given in Table 1. The storage stability is determined in accordance with the following general procedure in which the hydrocarbon is blended into a polyol mixture, replesenldlive of a formulation typically used forthe manufacture of rigid 30 polyurethane foam, and the resulting blend allowed to stand at room temperature for 7 days.
After this period, the stability of the resulting blend is visually rated according to the following scheme:
"Separates" - blend separates into multiple layers.
"Turbid" - the turbid blend does not separate into multiple layers and does not become clear on agitation.
"Limit" - the turbid blend does not separate into multiple layers and on agitation becomes clear.
2 2 0 ~ 5 8 6 "Separates" - blend separates into multiple layers.
"Turbid" - the turbid blend does not separate into multiple layers and does not become clear on agitation.
" Limit" - the turbid blend does not separate into multiple layers and on agitation becomes clear.
''ClearU - the blend is clear and not separated into multiple layers.
Blends 1, 2 and 5 which separate are undesirable for the purposes of preparing a polyurethane foam; Blends 3 and 4 are observed to have a "clear or "limit" sta1:us and are preferred as they are more readily manipulated in a consistent manner to the benefit of the foaming process.
Table i partsbyweight Blend1* Blend2* Blend3 Blend4 Blend5*
CastorOil 0 3 7 10 28.5 Polyol 1 51 51 51 52.3 51 Polyol 2 14.3 14.3 14.3 12 14.3 15Polyol 3 28.5 25.5 21.5 20 Surfactant 1 2 2 2 1.5 2 Catalyst 2.2 2.2 2.2 2.2 2.2 Water 2 2 2 2 2 i-pentane 10 10 10 10 10 20n-pentane 3 3 3 3 3 Blend Stability after 7 days at:
i) 20C / Turbid Limit ClearSeparates ii) 5C Separates Separates Turbid Limit Separates * Not an example of this invention.
Polyol 1: a sorbitol-initiated oxypropylene poiyether polyol having a hydroxyl number of 480.
Polyol 2: an ethylenediamine-initiated oxypropylene polyether polyol having hydroxyl number of 640.
Polyol 3: a glycerine-initiated oxypropylene polyether polyol having a hydroxyl numberof 160.
Surfactant 1: TEGOSTAB B8462 a silicon-based surfactant from Th Goldschmidt AGCatalyst: a blend of urethane promoting catalysts containing 1.2 pbw dimethylcyclohexylamine, 0.4 pbw pentamethyldiethylenetriamine;
and 0.6 pbw of CURITHANE 206 a proprietary urethane promoting catalyst available from The Dow Chemical Company.
22~ ~58~ -- Example 2 Rigid polyurethane foam is machine-prepared in the presence of a hydrocarbon blowing agent and castor oil using the formulation as given in Table ll. High pressure mixing conditions with reactants being introd uced to the mixer head at a temperature of about 20C
5 are used. The results indicate that an improved blend stability is obtained while still maintaining an acceptable overall foam physical performance.
Table ll parts by weight Foam 1 * Foam ZFoam 3 Castor Oil 0 5 10 Polyol 1 O 50 48 50.5 Polyol 2 (~) 15 14 14 Polyol 3 ~3 28.5 27 18.5 Surfactant 1 (~) 2 1.5 1.5 Catalyst O Z.2 2.2 2.2 Water 2.3 2.3 2.3 i-pentane 9.5 10 10 n-pentane 3 3 3 Isocyanate (~) Index 115 115 115 Blend Stability after 7 days at 5Cseparates limit clear 20Free Rise Density (kg/m3) 22.6 21.7 22.4 Molded Foam properties, 34 3 32.6 32.9 Density (kg/m3) CompressiveStrength(kPa) 154.9 119.6 137 (ASTM C-518) 23.1 23.5 23.2 25Demold post expansion at 3 9 5 4 3 4 minutes (mm) Not an example of this invention.
(~) As given for Example 1.
(~) VORATEC SD100, a polymeric methylene diphenylisocyanate with an NCO functionality of 2.7, available from The Dow Chemical Company.
30 Example 3 The storage stability of various hydrocarbon/polyol mixtures containing compatibilizing agents other than castor oil i5 reported in Table ]Il. The alternative compatibilizing agents and relative amounts making up the hydrocarbon and polyol mixtures is also given in Table lll. The storage stability as reported is determined in accordance with the 35 general procedure described for Example 1.
220~586 Table lll partsbyweight Blend6* Blend7 Blend8 Blend9 Blend 10 Polyol 4 100 90 90 75 80 Cyclopentane 20 20 20 25 25 Compatibilizing 0 10 0 0 0 Agent2 10 o o Compatibilizing 0 0 0 25 0 Castor oil 0 0 0 0 20 Blend Stabilityat turbid clear clear clear clear * Not an example of this invention.
15 Polyol 4: a sucrose/glycerine oxypropylene polyol having a hydroxyl number of 490.
Compatibilizing Agent 1: C1zHz5-(OCH2CH2)4-OH
Compatibilizing Agent 2: p(CgH19)-C6H4-(OCH2CH2)2-OH
Compatibilizing Agent 3: monoglyceride adduct of oleic acid
Claims (13)
1. A process for preparing a closed-celled polyurethane foam which comprises reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition wherein the polyol composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the polyol composition, of a compatibilizing agent containing a compatibilizing radical of the formula (CnH2n+1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, and further wherein the compatibilizing agent is selected from: fats and oils; monoglycerides and diglycerides; fatty acids; fatty alcohols; fatty amides; fatty amines;
fatty acid esters; alkoxylated adducts of any of the foregoing; alkyl phenols and propoxylated adducts thereof; alkyl phenols and adducts thereof with ethylene oxide and propylene oxide;
alkyl phenols and adducts thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol and mixtures thereof.
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the polyol composition, of a compatibilizing agent containing a compatibilizing radical of the formula (CnH2n+1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, and further wherein the compatibilizing agent is selected from: fats and oils; monoglycerides and diglycerides; fatty acids; fatty alcohols; fatty amides; fatty amines;
fatty acid esters; alkoxylated adducts of any of the foregoing; alkyl phenols and propoxylated adducts thereof; alkyl phenols and adducts thereof with ethylene oxide and propylene oxide;
alkyl phenols and adducts thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol and mixtures thereof.
2. A process for preparing a closed-celled polyurethane foam which comprises reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition wherein the polyol composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the polyol composition, of a compatibilizing agent selected from a fat or oil or alkoxylated adduct thereof, having a hydroxyl number of from 100 to 550.
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the polyol composition, of a compatibilizing agent selected from a fat or oil or alkoxylated adduct thereof, having a hydroxyl number of from 100 to 550.
3. A process as claimed in Claims 1 or 2 wherein the hydrocarbon blowing agent comprises a C1-8 aliphatic or cycloaliphatic hydrocarbon which is an alkane, alkene or alkyne.
4. A process as claimed in Claim 2 wherein the compatibilizing agent has a hydroxyl number of from 130 to 180.
5. A process as claimed in Claims 1 or 2 wherein the compatibilizing agent is a fat or oil comprising a fatty acid constituent.
6. A process as claimed in Claim 5 wherein the fatty acid constituent is ricinoleic acid, dihydroxystearic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, eicosanoic acid, or a mixture of two or more thereof.
7. A process as claimed in Claim 6 wherein the fatty acid constituent is ricinoleic acid.
8. A process as claimed in Claims 1 or 2 wherein the compatibilizing agent is castor oil.
9. A process according to any one of Claims 1 to 8 which further comprises water in an amount of from 0.5 to 10 parts per 100 parts by total weight of the polyol composition.
10. A process for preparing a closed-celled polyurethane foam having a density of from 10 to 50 kg/m3 by reacting, in the presence of a hydrocarbon blowing agent, a polyisocyanate with a polyol composition wherein the polyol composition comprises:
i) a polyol composition containing a polyether polyol having a hydroxyl number value of from 100 to 1200, and including from 7 to 15 parts, per 100 parts by total weight of the polyol composition, of castor oil as a compatibilizing agent;
in the presence of ii) from 2 to 6 parts of water per 100 parts by weight of polyol composition; and iii) a hydrocarbon blowing agent being n-pentane, i-pentane, hexane, cyclopentane, methyl-cyclopentane, cyclohexane, methyicyclohexane or mixtures thereof, and wherein the polyisocyanate is present in an amount to provide for an isocyanate reaction index of from 60 to 550.
i) a polyol composition containing a polyether polyol having a hydroxyl number value of from 100 to 1200, and including from 7 to 15 parts, per 100 parts by total weight of the polyol composition, of castor oil as a compatibilizing agent;
in the presence of ii) from 2 to 6 parts of water per 100 parts by weight of polyol composition; and iii) a hydrocarbon blowing agent being n-pentane, i-pentane, hexane, cyclopentane, methyl-cyclopentane, cyclohexane, methyicyclohexane or mixtures thereof, and wherein the polyisocyanate is present in an amount to provide for an isocyanate reaction index of from 60 to 550.
11. A blend, suitable as a polyurethane precursor, which contains a hydrocarbon and a polyol composition, wherein the composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the composition, of a compatibilizing agent selected from fats, oils and alkoxylated adducts thereof, having a hydroxyl number of from 100 to 500, and wherein in the hydrocarbon, present in an amount of from 1 to 20 parts per 100 parts by total weight of said composition is selected from the group consisting of butane, n-pentane, i-pentane, hexane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, isomers thereof, or mixtures of two or more thereof.
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the composition, of a compatibilizing agent selected from fats, oils and alkoxylated adducts thereof, having a hydroxyl number of from 100 to 500, and wherein in the hydrocarbon, present in an amount of from 1 to 20 parts per 100 parts by total weight of said composition is selected from the group consisting of butane, n-pentane, i-pentane, hexane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, isomers thereof, or mixtures of two or more thereof.
12. A blend, suitable as a polyurethane precursor. which contains a hydrocarbon and a polyol composition, wherein the composition comprises:
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the composition, of a compatibilizing agent compatibilizing agent containing a compatibilizing radical of the formula -(CnH2n+1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, wherein the compatibilizing agent is selected from fats and oils; monoglycerides and diglycerides; fatty acids; fatty alcohols; fatty amides; fatty amines; fatty acid esters; alkoxylated adducts of any of the foregoing; alkyl phenols and propoxylated adducts thereof; alkyl phenols and adducts thereof with ethylene oxide and propylene oxide; alkyl phenols and adducts thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol:
and mixtures thereof.
i) a polyether or polyester polyol having a hydroxyl number value of from 100 to 1200; and ii) from 6 to 25 parts, per 100 parts by total weight of the composition, of a compatibilizing agent compatibilizing agent containing a compatibilizing radical of the formula -(CnH2n+1) wherein n is a number greater than or equal to 5, and wherein the compatibilizing agent contains at least one active hydrogen atom, provided that there is no more than one aromatic group per molecule, wherein the compatibilizing agent is selected from fats and oils; monoglycerides and diglycerides; fatty acids; fatty alcohols; fatty amides; fatty amines; fatty acid esters; alkoxylated adducts of any of the foregoing; alkyl phenols and propoxylated adducts thereof; alkyl phenols and adducts thereof with ethylene oxide and propylene oxide; alkyl phenols and adducts thereof with less than an average of four molecules of ethylene oxide per molecule of alkyl phenol:
and mixtures thereof.
13. A polyurethane foam obtained according to a process as claimed in Claims 1 to 10.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/326,430 US5451615A (en) | 1994-10-20 | 1994-10-20 | Process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent |
| US08/326,430 | 1994-10-20 | ||
| US52980095A | 1995-09-18 | 1995-09-18 | |
| US08/529,800 | 1995-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2201586A1 true CA2201586A1 (en) | 1996-05-02 |
Family
ID=26985402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002201586A Abandoned CA2201586A1 (en) | 1994-10-20 | 1995-10-19 | A process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0787165A2 (en) |
| JP (1) | JPH11500467A (en) |
| CN (1) | CN1068016C (en) |
| AU (1) | AU3833795A (en) |
| BR (1) | BR9509500A (en) |
| CA (1) | CA2201586A1 (en) |
| CZ (1) | CZ119297A3 (en) |
| HU (1) | HUT77801A (en) |
| PL (1) | PL319832A1 (en) |
| WO (1) | WO1996012759A2 (en) |
Families Citing this family (55)
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|---|---|---|---|---|
| DE19502969A1 (en) † | 1995-01-31 | 1996-08-01 | Elastogran Gmbh | Process for the production of rigid polyurethane foams |
| US5470501A (en) * | 1995-05-08 | 1995-11-28 | Basf Corporation | Processability of hydrocarbon blown, polyisocyanate based foams through use of a compatibilizing agent |
| IT1280096B1 (en) * | 1995-10-06 | 1997-12-29 | Ediltec S R L | POLYURETHANE FOAM |
| JP3105793B2 (en) * | 1996-08-13 | 2000-11-06 | 住友バイエルウレタン株式会社 | Method for producing rigid polyurethane foam and composition for rigid polyurethane foam |
| EP0938517B1 (en) | 1996-09-19 | 2005-07-20 | Dap Products Inc. | Stable, foamed caulk and sealant compounds and methods of use thereof |
| US6284077B1 (en) | 1997-08-29 | 2001-09-04 | Dap Products Inc. | Stable, foamed caulk and sealant compounds and methods of use thereof |
| US5910515A (en) * | 1997-03-24 | 1999-06-08 | Ediltec S.R.L. | Polyurethane foam |
| US6359022B1 (en) | 1997-10-10 | 2002-03-19 | Stepan Company | Pentane compatible polyester polyols |
| US5922779A (en) * | 1997-10-10 | 1999-07-13 | Stepan Company | Polyol blends for producing hydrocarbon-blown polyurethane and polyisocyanurate foams |
| GB2337266A (en) * | 1998-02-09 | 1999-11-17 | Basf Corp | Isocyanate-based rigid foam and process for making isocyanate-based rigid foam also stable polyester polyol compositions. |
| US6664363B1 (en) | 1998-02-23 | 2003-12-16 | Stepan Company | Low viscosity polyester polyols and methods for preparing same |
| US6258866B1 (en) * | 1999-02-03 | 2001-07-10 | Huntsman Petrochemical Corporation | Blowing agent compatabilization |
| US6420443B1 (en) | 1999-09-09 | 2002-07-16 | Crompton Corporation | Additives for enhanced hydrocarbon compatibility in rigid polyurethane foam systems |
| DE10060815A1 (en) * | 2000-12-07 | 2002-06-20 | Henkel Kgaa | Stone composite panels |
| DE10060817A1 (en) * | 2000-12-07 | 2002-06-20 | Henkel Kgaa | Stone composite panels for insulation |
| ATE537953T1 (en) * | 2002-12-27 | 2012-01-15 | Kahei Co Ltd | POLYURETHANE FOAM INSERT AND PRODUCTION METHOD FOR LAYER INSERT THEREFROM |
| MX2008016436A (en) | 2006-07-04 | 2009-03-02 | Huntsman Int Llc | Process for making visco-elastic foams. |
| WO2009032894A1 (en) * | 2007-09-07 | 2009-03-12 | Dow Global Technologies Inc. | Use of natural oil based compounds of low functionality to enhance foams |
| US20090082482A1 (en) * | 2007-09-21 | 2009-03-26 | Bayer Materialscience Llc | Storage stable polyol blends containing n-pentane |
| DE102008000243A1 (en) | 2008-02-06 | 2009-08-13 | Evonik Goldschmidt Gmbh | Novel compatibilizers to improve the shelf life of polyol blends |
| DE102008000255A1 (en) | 2008-02-08 | 2009-08-20 | Evonik Goldschmidt Gmbh | siloxane |
| DE102009001595A1 (en) | 2009-03-17 | 2010-09-23 | Evonik Goldschmidt Gmbh | Compatibilizer for improving the storage stability of polyol blends |
| PT2408835E (en) * | 2009-03-18 | 2014-03-06 | Basf Se | Method for producing rigid polyurethane foams |
| JP5528043B2 (en) * | 2009-09-24 | 2014-06-25 | 三井化学株式会社 | Polyurethane foam and method for producing the same |
| DE102010063241A1 (en) | 2010-12-16 | 2012-06-21 | Evonik Goldschmidt Gmbh | Silicone stabilizers for rigid polyurethane or polyisocyanurate foams |
| DE102011007479A1 (en) | 2011-04-15 | 2012-10-18 | Evonik Goldschmidt Gmbh | Composition containing specific amides and organomodified siloxanes, suitable for the production of polyurethane foams |
| DE102011007468A1 (en) | 2011-04-15 | 2012-10-18 | Evonik Goldschmidt Gmbh | Composition containing specific carbamate-type compounds suitable for the preparation of polyurethane foams |
| DE102011109541A1 (en) | 2011-08-03 | 2013-02-07 | Evonik Goldschmidt Gmbh | Use of polysiloxanes containing branched polyether radicals for the production of polyurethane foams |
| CN102558480A (en) * | 2011-12-21 | 2012-07-11 | 山东东大一诺威新材料有限公司 | Isopentane and n-pentane co-foaming polyurethane rigid foam combined polyether and preparation method thereof |
| DE102013201829A1 (en) | 2013-02-05 | 2014-08-07 | Evonik Industries Ag | Amines suitable for use in the production of polyurethanes |
| DE102013217395A1 (en) | 2013-09-02 | 2015-03-05 | Evonik Industries Ag | Use of mixtures of organofunctionally modified polysiloxanes with amides in the production of flexible polyurethane foams |
| EP2886591A1 (en) | 2013-12-19 | 2015-06-24 | Evonik Industries AG | Composition, suitable for the production of polyurethane foams, containing at least one nucleating agent |
| DE102013226575B4 (en) | 2013-12-19 | 2021-06-24 | Evonik Operations Gmbh | Composition suitable for the production of polyurethane foams, containing at least one unsaturated fluorocarbon or unsaturated fluorocarbon as blowing agent, polyurethane foams, processes for their production and their use |
| DE102014215387B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
| DE102014215384A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
| DE102014215380B4 (en) | 2014-08-05 | 2022-04-28 | Evonik Operations Gmbh | Nitrogen-containing compounds suitable for use in the manufacture of polyurethanes |
| DE102014215381B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
| DE102014215383B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
| DE102014215382A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
| DE102014215388A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
| EP3078696A1 (en) | 2015-04-08 | 2016-10-12 | Evonik Degussa GmbH | Production of low-emission polyurethanes |
| EP3176206A1 (en) | 2015-12-01 | 2017-06-07 | Evonik Degussa GmbH | Method for the preparation of fine cell foams using a cell aging inhibitor |
| EP3205678A1 (en) | 2016-02-10 | 2017-08-16 | Evonik Degussa GmbH | Aging-resistant and low-emission mattresses and/or cushions |
| EP3744745A1 (en) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Production of pu foams |
| US20210015269A1 (en) | 2019-07-19 | 2021-01-21 | Evonik Operations Gmbh | Shaped pu foam articles |
| EP3819323A1 (en) | 2019-11-07 | 2021-05-12 | Evonik Operations GmbH | Compression set |
| EP3865527A1 (en) | 2020-02-14 | 2021-08-18 | Evonik Operations GmbH | Production of pu foams |
| US20220106432A1 (en) | 2020-10-07 | 2022-04-07 | Evonik Operations Gmbh | Shaped flexible pu foam articles |
| CA3224261A1 (en) | 2021-07-02 | 2023-01-05 | Annegret Terheiden | Production of pu foams |
| WO2023161253A1 (en) | 2022-02-22 | 2023-08-31 | Evonik Operations Gmbh | Use of recycled polyol from amine-based hydrolysis process to produce pu foam |
| EP4257327A1 (en) | 2022-04-08 | 2023-10-11 | Evonik Operations GmbH | Optical determination of a control signal for slabstock polyurethane foam production |
| EP4257323A1 (en) | 2022-04-08 | 2023-10-11 | Evonik Operations GmbH | System and method for determining parameters for foam production |
| EP4257326A1 (en) | 2022-04-08 | 2023-10-11 | Evonik Operations GmbH | Optical determination of a control signal in response to detection of macroscopic polyurethane foam defects |
| EP4257324A1 (en) | 2022-04-08 | 2023-10-11 | Evonik Operations GmbH | System and method for automatically setting parameters for foam production |
| EP4257325A1 (en) | 2022-04-08 | 2023-10-11 | Evonik Operations GmbH | Optical prediction of polyurethane foam parameters |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3933335C2 (en) * | 1989-10-06 | 1998-08-06 | Basf Ag | Process for the production of rigid polyurethane foams with low thermal conductivity and their use |
| EP0445614A3 (en) * | 1990-03-09 | 1992-02-26 | Mobay Corporation | Process for the production of molded products using internal mold release agents |
| DE4121161A1 (en) * | 1991-06-27 | 1993-01-07 | Basf Ag | METHOD FOR PRODUCING HARD FOAM MATERIALS CONTAINING URETHANE OR URETHANE AND ISOCYANURATE GROUPS, AND EMULSIONS CONTAINING BLOWERS THEREOF |
-
1995
- 1995-10-19 PL PL95319832A patent/PL319832A1/en unknown
- 1995-10-19 BR BR9509500A patent/BR9509500A/en not_active Application Discontinuation
- 1995-10-19 AU AU38337/95A patent/AU3833795A/en not_active Abandoned
- 1995-10-19 CA CA002201586A patent/CA2201586A1/en not_active Abandoned
- 1995-10-19 WO PCT/US1995/013313 patent/WO1996012759A2/en active IP Right Grant
- 1995-10-19 CN CN95195788A patent/CN1068016C/en not_active Expired - Fee Related
- 1995-10-19 CZ CZ971192A patent/CZ119297A3/en unknown
- 1995-10-19 JP JP8514032A patent/JPH11500467A/en not_active Ceased
- 1995-10-19 HU HU9800905A patent/HUT77801A/en unknown
- 1995-10-19 EP EP95936350A patent/EP0787165A2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO1996012759A3 (en) | 1996-07-04 |
| CN1068016C (en) | 2001-07-04 |
| HUT77801A (en) | 1998-08-28 |
| CZ119297A3 (en) | 1997-08-13 |
| AU3833795A (en) | 1996-05-15 |
| JPH11500467A (en) | 1999-01-12 |
| PL319832A1 (en) | 1997-09-01 |
| MX9702869A (en) | 1997-07-31 |
| BR9509500A (en) | 1997-10-14 |
| EP0787165A2 (en) | 1997-08-06 |
| WO1996012759A2 (en) | 1996-05-02 |
| CN1161705A (en) | 1997-10-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |