CA2221015A1 - Pressurized, isocyanate-terminated prepolymers containing oxazolidone and urethane groups for one-component foams - Google Patents
Pressurized, isocyanate-terminated prepolymers containing oxazolidone and urethane groups for one-component foams Download PDFInfo
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- CA2221015A1 CA2221015A1 CA 2221015 CA2221015A CA2221015A1 CA 2221015 A1 CA2221015 A1 CA 2221015A1 CA 2221015 CA2221015 CA 2221015 CA 2221015 A CA2221015 A CA 2221015A CA 2221015 A1 CA2221015 A1 CA 2221015A1
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- isocyanate
- terminated prepolymer
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G2190/00—Compositions for sealing or packing joints
Abstract
A pressurized, blowing agent-containing, isocyanate-terminated prepolymer containing oxazolidone and urethane groups can be prepared by reacting an isocyanate component with a polyol component, wherein the isocyanate component (A) used is a reaction product containing terminal isocyanate groups and obtained by reacting at least one isocyanate containing at least two isocyanate groups in the molecule with a mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and a polyester polyol and the polyol component (B) used comprises at least one polyether terminated by primary hydroxyl groups and having a functionality of ~2.
Description
CA 0222101~ 1997-12-22 ' 0050/47638 Pressurized, isocyanate-terminated prepolymers containing oxazolidone and urethane groups for one-component foams The present invention relates to pressurized, isocyanate-terminated prepolymers containing oxazolidone and urethane groups which can be processed into one-component polyurethane foams.
One-component polyurethane foams, also known as in-situ foams, are frequently-used construction materials which are employed mainly in the building industry, for example for the installation of doors and windows in buildings or as filler material for 15 hollow spaces resulting from the method of construction or for openings in walls for pipe installations.
The in-situ foams are formed by isocyanate-terminated prepolymers present in pressure containers being discharged by means of 20 blowing agents, foamed by frothing action and cured by means of atmospheric moisture.
To prepare the pressurized prepolymers, two principal methods are known;
1. The isocyanate component and the polyol component are introduced into the pressure container in the desired ratio, the container is closed and the blowing agent is injected.
The prepolymer which forms and the blowing agent are intensively mixed with one another in a shaking or tumbling apparatus.
One-component polyurethane foams, also known as in-situ foams, are frequently-used construction materials which are employed mainly in the building industry, for example for the installation of doors and windows in buildings or as filler material for 15 hollow spaces resulting from the method of construction or for openings in walls for pipe installations.
The in-situ foams are formed by isocyanate-terminated prepolymers present in pressure containers being discharged by means of 20 blowing agents, foamed by frothing action and cured by means of atmospheric moisture.
To prepare the pressurized prepolymers, two principal methods are known;
1. The isocyanate component and the polyol component are introduced into the pressure container in the desired ratio, the container is closed and the blowing agent is injected.
The prepolymer which forms and the blowing agent are intensively mixed with one another in a shaking or tumbling apparatus.
2. The prepolymer is formed from the isocyanate and polyol components in a reactor and then introduced into the pressure container, the container is closed and the blowing agent is injected. The prepolymer is intensively mixed with the blowing agent in shaking or tumbling apparatus.
40 In order to achieve an optimum distribution of the foam in the joints and hollow spaces to be filled with foam, a low prepolymer viscosity is desirable. In the past, the chlorofluorocarbons customary as blowing agents contributed to lowering the viscosity. ~ince continued use of such compounds is not possible 45 for environmental reasons, plasticizers or solvents have fre~uently been added to the prepolymers, as described, for example, in DE-A-4 025 843 or EP-A-480 342. However, the use of 0050/47638 CA 0222l0l~ l997-l2-22 .
such compounds leads, since they are not built into the foam, to considerable shrinkage of the foams. DE-A-33 17 193, DE-A-39 11 784 and DE-A-38 29 104 also describe the addition of compounds which are said to lower the viscosity of the 5 prepolymers. However, here too, considerable shrinkage and embrittlement of the foams result.
In addition, in the case of the foams of the prior art, the different property requirements for the foam, particularly the 10 ratio of open to closed cells, had to be taken into account for the two possible ways of discharging the in-situ foam from the aerosol can, viz. discharge via a foaming gun and discharge via a foaming tube, customarily designated as elbow discharge.
Thus, a conventional, largely closed-celled foam permits only gun processing, while in the case of elbow processing it would have additional and thus excessive shrinkage. On the other hand, a largely open-celled foam can only be satisfactorily processed by 20 elbow discharge, while the bubbles in it would be too large if discharged by means of a gun.
For this reason, specific foam formulations have hitherto been prepared for the two methods of discharge.
It is an object of the present invention to provide a prepolymer for one-component polyurethane foams which, owing to its low viscosity, is readily processible and can be processed into foams having low shrinkage, an optimum ratio of open to closed cells 30 and improved mechanical properties and which permits discharge both via a gun and via an elbow.
We have found that this object is achieved by an isocyanate-35 terminated prepolymer containing oxazolidone and urethane groups which can be prepared by reacting an isocyanate component with a polyol component, wherein the isocyanate component (A) used is a reaction product containing terminal isocyanate groups and obtained by reacting at least one isocyanate containing at least 40 two isocyanate groups in the molecule with a mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and at least one polyester polyol and the polyol component (B) used comprises at least one polyether terminated by 45 primary hydroxyl groups and having a functionality of >2.
- CA 0222l0l~ l997-l2-22 The present invention accordingly provides isocyanate-terminated prepolymers containing oxazolidone and urethane groups as described above.
5 The present invention further provides a process for preparing the isocyanate-terminated prepolymers, provides for their use for producing one-component polyurethane foams and also provides the one-component polyurethane foams.
As regards the isocyanate components (A) used according to the present invention and their formative components, the following may be said:
15 As isocyanates containing at least two isocyanate groups in the molecule, it is possible to use the customary and known diisocyanates and polyisocyanates, for example aliphatic isocyanates such as hexamethylene l,6-diisocyanate (HDI), isophorone diisocyanate, aromatic isocyanates such as tolylene 20 diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polyphenylene-polymethylene polyisocyanates (raw MDI). The isocyanates can also be modified by incorporation of, for example, uretdione, isocyanurate and allophanate groups.
For one-component polyurethane foam, preference is given to using raw MDI.
The polyester polyols used according to the present invention are 30 prepared in a known manner by polycondensation of polybasic carboxylic acids with polyhydric alcohols. Such products are described, for example, in the Kunststoff-Handbuch, Volume 7, "Polyurethane", edited by Gunter Oertel, Carl-Hauser-Verlag Munich, 3rd edition 1993, pages 67 to 74.
Polyester polyols derived from dibasic carboxylic acids, in particular aliphatic dicarboxylic acids, and diols are particularly advantageous for preparing the prepolymers of the 40 present invention. Polyesterols based on adipic acid and diethylene glycol have been found to be particularly useful. The molecular weight of these polyesterols should be from 100 to 2000 g/mol (weight average). If the molecular weights are too high, the viscosity of the polyesterols increases excessively.
CA 0222101~ 1997-12-22 0050/47~38 As compounds containlng at least two groups which react with isocyanate and at least one epoxide group in the molecule, it is possible to use polyols obtained by epoxidation of natural materials, for example epoxidized soyabean oil but in particular 5 epoxidized polybutadienediols. The molecular weight should be from 600 to 4000 g/mol (weight average) since in this weight range they can, despite their incompatibility with the polyesterpolyol, be built into the urethane/oxazolidone-modified isocyanate to form oxazolidone structures.
The polyester polyol and the epoxidized compound are preferably used in a weight ratio of from 100:1 to 1:100, in particualr from 50:1 to 1:5. Furthermore, it has been found to be useful to use the mixture of polyester polyol and epoxidized compound in an 15 amount of from 0.1 to 20 % by weight, preferably from 2 to 10 %
by weight, based on the isocyanate used.
The polyisocyanate modified as described with oxazolidone and 20 urethane groups is reacted with the polyol component (B) to give the prepolymer of the present invention. According to the present invention, the polyol component comprises at least one high molecular weight polyether terminated by primary hydroxyl groups and having a functionality of >2 and a molecular weight of 25 >1500 g/mol, preferably from 3000 to 20,000 g/mol. These polyether polyols provided with primary OH groups and having a high molecular weight are particularly advantageous since as reactive polyols they form high molecular weight reaction products and thus effect, in the cured one-component foam, not 30 only good elasticity behavior but also optimum low-temperature curing without embrittlement.
Among the pure polyether polyols having the abovementioned characteristics, polyethylene glycols are particularly useful.
35 These are used in combination with customary polyhydroxyl compounds and additives in such a way that, despite their melting point above 20~C, they give a polyol component which is liquid at room temperature. Apart from the advantages mentioned, the use of these polyether polyols gives additional advantages via their 40 physically cell-opening high molecular weight reaction products with the isocyanate in the aerosol can. The pure polyether polyols having a high molecular weight and primary OH groups also include the polyethers derived from more than one alkylene oxide.
Here, suitable polyols are those in whose preparation ethylene 45 oxide as final addition generates primary OH groups.
CA 0222101~ 1997-12-22 Other particularly useful polyether polyols are those which have the abovementioned characteristics and which are prepared using a polyesterpolyol, in particular a fatty acid ester having OH functionality, as initiator.
Ethoxylated castor oil which can also be partially propoxylated is particularly useful. The mean molecular weight (weight average) is preferably >1500 g/mol, in particular from 1500 to 8000 g/mol. Higher molecular weights lead to increased prepolymer 10 viscosities-Apart from the ethoxylated fatty acid esters, the polyolcomponent comprises the hydroxy-functional compounds customary 15 for the production of rigid polyurethane foams, usually polyether polyols and/or polyester polyols as are described, for example, in Kunststoff-Handbuch, loc sit., and also, if desired, short-chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol as chain extenders, short-chain at least trihydric alcohols such as glycerol or trimethylolpropane as crosslinkers and also catalysts and, if desired, stabilizers, colorants and/or monools as molecular weight regulators.
Catalysts used are preferably strongly basic amines or organic 25 metal compounds, in particular tin compounds or synergistically acting mixtures of strongly basic amines and organic metal compounds. Examples of strongly basic amines are: amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, 30 tris(dialkylaminoalkyl)-s-hexahydrotriazines such as tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine, but preferably tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, bis(morpholinoethyl) ether, 35 N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, bis(di-methylaminopropyl)urea, dimethylpiperazine, 40 1,2-dimethylimidazole, bis(4-N,N-dimethylaminocyclohexyl)methane, 1-aza-bicyclo(3.3.0)octane and 1,4-diazabicyclo(2.2.2)octane.
Suitable organic tin compounds are, for example: tin(II) salts of organic carboxylic acids, eg. tin(II) diacetate, tinn(II) 45 dioctoate, tin(II) diethylhexoate and tin(II) dilaurate, and also dialkyl tin(IV) salts of carboxylic acids, eg. dibutyltin CA 0222101~ 1997-12-22 diacetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin dimercaptide and dioctyltin diacetate.
Particularly suitable stabilizers are siloxane-oxyalkylene 5 copolymers.
The prepolymer of the present invention is present in a pressure container and is dissolved in a liquefied gas or liquefied gas 10 mixture which functions as blowing agent. Suitable blowing agents are customary liquefied gases and also other substances having a boiling point of <50~C. Examples which may be mentioned are:
Dimethyl ether, propane, n- or iso-butane, pentane, methyl 15 isobutyl ether and also halogenated hydrocarbons such as dichlorofluoromethane, monofluorotrichloromethane, trifluorotrichloroethane, trifluoromethane, 1,1-dichloro-l,fluoroethane, monochlororifluoroethane, monochlorodifluoroethane, difluoroethane, 20 dichlorotrifluoroethane, monochlorotetrafluoroethane, pentafluoroethane, tetrafluoroethane, dichloromonofluoroethane.
Particularly suitable blowing agents are alkanes and also mixtures of alkanes, fluorinated alkanes and dimethyl ether.
The preparation of the prepolymers of the present invention is preferably carried out in two stages: firstly, the urethane-/oxazolidone-modified polyisocyanate is prepared. For this purpose, the necessary amounts of isocyanate are initially 30 charged and the mixture of polyesterol and epoxidized polyol is metered in. Since the two compounds are not miscible with one other, they are preferably added in the form of an emulsion. The reaction is carried out at from 60 to 110~C, preferably from 80 to 90~C, while stirring. After a reaction time of from about 2 to 35 6 hours, the modification is complete and the reaction mixture is cooled to room temperature.
The reaction of the isocyanate component thus prepared with the 40 polyol component can be carried out in two possible ways:
1. The polyol component is metered into aerosol cans. The isocyanate component is then metered in, the aerosol can is closed by means of a valve and the blowing agent is metered in. The mixture constituents in the aerosol can are then intensively mixed and homogenized in a subsequent shaking or tumbling apparatus. The subsequent reaction forms the CA 0222l0l~ lss7-l2-22 prepolymer in the aerosol cans. After warm storage at about 50~C for about 24 hours or storage at room temperature for about 3 days, the foam is ready to use.
5 2. The isocyanate component is reacted with the polyol component in a reactor, the reaction mixture is introduced into an aerosol can, the latter is closed by means of a valve and the blowing agent is introduced. The subsequent procedure is as described above.
The weight ratio of polyol component to isocyanate component is about 100:~140 or an index of >400.
15 Compared with the prior art, the prepolymer of the present invention has the following advantages:
The built-in oxazolidone groups have a cell-opening action in the foam and thus reduce the shrinkage. On the other hand, the 20 solubility of the reaction product in excess isocyanate is improved. This is particularly surprising when epoxidized polybutadienediol is used, since this compound is extremely hydrophobic and normally does not mix with the other constituents of the reaction mixture. The resulting foams cure readily, have 25 very good mechanical properties, in particular display no embrittlement, and have an excellent low-temperature behavior.
The foams can be discharged from the pressure container either via a gun or via an elbow.
The invention is illustrated by the following examples.
Examples Example 1 1.1 Preparation of the urethane-/oxazolidone-modified isocyanate A stirred reactor provided with a heating and cooling facility and a temperature measurement device was charged with 95 kg of a raw diphenylmethane diisocyanate. In a separate mixing vessel, 6 kg of an adipic acid/diethylene glycol polyester alcohol having a molecular weight of 450 g/mol (OH number = 250 mg KOH/g) were mixed with 0.67 kg of an epoxidized polybutadienediol having an OH number of 180 mg KOH/g. The mixture gave a stable emulsion of the CA 0222l0l~ l997-l2-22 otherwise immiscible liquids. With the stirrer running, 5 kg of this emulsion were added to the raw diphenylmethane diisocyanate and thoroughly mixed. The contents of the reactor were then slowly heated to about 80~C while continuing the stirring. After reaching 80~C, this temperature was held for about 2 hours and the reaction product was then slowly cooled to room temperature. The urethane-/oxazolidone-modified isocyanate obtained had the following properties:
Isocyanate content: 28.7 % of NCO
Viscosity (25~C): 350 mPa s 15 1.2 Preparation of the polyol component 1750 g of a polyester alcohol based on a dicarboxylic acid mixture (glutaric acid, succinic acid, adipic acid) and ethylene glycol and having an OH number of 56 mg KOH/g, 300 g of a polyether alcohol based on sucrose/pentaerythritol/propylene oxide and having an OH
number of 410 mg KOH/g, 350 g of a polyether based on glycerol/propylene oxide/ethylene oxide and having an OH
number of 35 mg KOH/g, 400 g of a polyethylene glycol having a molecular weight of 600 g/mol, 325 g of an ethoxylated castor oil having a molecular weight of 4200 g/mol (OH number of 40 mg KOH/g), 125 g of a siloxane-oxyalkylene copolymer as foam stabilizer, 40 g of bis(morpholinoethyl) ether, 10 g of 4-methyl-4-hydroxypentan-2-one, 50 g of 1,4-butanediol and 1650 g of trichloropropyl phosphate were weighed one after the other into a mixing vessel and were homogenized by subsequent thorough mixing to give a polyol component.
1.3 Preparation of the prepolymers in aerosol cans having universal valves 280 g of the above-described polyol component were introduced into a 1 1 aerosol can. After addition of 434 g of the urethane-/oxazolidone-modified raw diphenylmethane diisocyanate as described in 1.1, the aerosol can was closed with a universal valve. Immediately after closing the can, 40 g of dimethyl ether, 72 g of tetrafluoroethane and 24 g of a gas mixture consisting of 80 % of butane and 20 % of propane were introduced one after the other through the valve into the aerosol can by means of a gas-metering apparatus.
After metering in each individual gas or the gas mixture, the contents of the aerosol can were homogenized by intensive CA 0222l0l~ l997-l2-22 shaking. After warm storage at 50~C for 24 hours, the prepolymer reaction was sufficiently complete for the aerosol can to be ready for producing the one-component foam.
5 1.4 Production of the one-component foams The prepolymers were discharged from the above-described aerosol cans both by means of a gun and by means of an elbow.
This was achieved by mounting the aerosol can on the respective dlscharge apparatus. The discharged prepolymers displayed very good frothing action and cured in the presence of atmospheric moisture or moisture from the substrate to give a foam having a very well structured surface, thin foam skin and very fine foam cells ln each case. The cured one-component foam displayed very good mechanical properties, as shown in the table below.
Foams as described in Example 1 Gun dischargeElbow discharge Density in kg/m3 14 16 Tensile strength in 11.5 12 N/cm2 Elongation at break 34 34 in %
Shear strength in N/ 6 7 cm2 Compressive stress at 5.8 6,7 10 % deformation in 30 N/cm2 In addition, the shrinkage of the foam after storage under controlled conditions (40~C/90 % relative humidity) was very low.
Shrinkage of the foam as described in Example 1 Gun discharge Elbow discharge - 1.46 % - 1.75 %
The foams as described in Example 1 were also cold-stable, ie. they displayed no embrittlement at all at processing temperatures of about 5~C.
CA 0222101~ 1997-12-22 The foam was classlfied in the burning class B2 as specified in DIN 4102.
Example 2 2.1 Preparation of the urethane-/oxazolidone-modified isocyanate A stirred reactor provided with a heating and cooling facility and a temperature measurement device was charged with 94.8 kg of a raw diphenylmethane diisocyanate. In a separate mixing vessel, 6 kg of an adipic acid/diethylene glycol polyester alcohol having a molecular weight of 450 g/mol (OH number = 250 mg KOH/g) and 0.93 kg of an epoxidized polybutadienediol having an OH number of 120 mg KOH/g were mixed. The mixture gave a stable emulsion of the otherwise immiscible liquids. With the stirrer running, 5.2 kg of this emulsion were added to the raw diphenylmethane diisocyanate and thoroughly mixed. The contents of the reactor were then slowly warmed to about 80~C while continuing the stirring. After reaching 80~C, this temperature was held for about 2 hours and the reaction product was then slowly cooled to room temperature. The urethane-/oxazolidone-modified isocyanate obtained had the following properties:
Isocyanate content: 28.5 % of NCO
Viscositity (25~C): 370 mPa s 30 2.2 Preparation of the polyol component 3400 g of a reaction product of a dicarboxylic acid mixture (glutaric acid, succinic acid, adipic acid) and a polypropylene glycol polyether having a molecular weight of 450 g/mol and an OH number of 50 mg KOH/g, 300 g of a polyether alcohol based on sucrose/pentaerythritol/propylene oxide and having an OH number of 410 mg KOH/g, 350 g of a polyether alcohol based on glycerol/propylene oxide/ethylene oxide and having an OH number of 35 mg KOH/g, 400 g of a polyethylene glycol having a molecular weight of 600 g/mol, 325 g of an ethoxylated castor oil having a molecular weight of 4200 g/mol (OH number = 40 mg KOH/g), 125 g of a siloxane-oxyalkylene copolymer as foam stabilizer, 40 g of bis(morpholinoethyl) ether and 60 g of 1,4-butanediol were weighed one after the other into a mixing vessel and CA 0222101~ 1997-12-22 homogenized by subsequent thorough mixing to give a polyol component.
2.3 Preparation of the prepolymer in aerosol cans having universal valves 245 g of the above-described polyol component were introduced into a 1 l aerosol can. After additlon of 380 g of the urethane-/oxazolidone-modified raw diphenylmethane diisocyanate as described in 2.1, the aerosol can was closed with a universal valve. Immediately after closing the can, 44 g of dimethyl ether, 36 g of tetrafluoroethane and 66 g of a gas mixture consisting of 80 % of butane and 20 % of propane were introduced one after the other through the valve into the aerosol can by means of a gas-metering apparatus.
After metering in each individual gas or the gas mixture, the contents of the aerosol can were homogenized by intensive shaking. After warm storage at 50~C for 24 hours, the prepolymer reaction was sufficiently complete for the prepolymer to be ready for production of the one-component polyurethane foam.
2.4 Production of the one-component polyurethane foams The prepolymers were discharged from the above-described aerosol cans both by means of a gun and by means of an elbow.
This was achieved by mounting the aerosol can on the respective discharge apparatus. The discharged prepolymers displayed very good frothing action and cured in the presence of atmospheric moisture or moisture from the substrate to give in each case a foam having a very well structured surface, thin foam skin and very fine foam cells. The cured one-component foam displayed good mechanical properties, as shown in the table below.
CA 0222101~ 1997-12-22 Foams as described in Example 2 Gun discharge Elbow discharge Density in kg/m3 15 16 5 Tensile strength in 9.5 11 N/cm2 Elongation at break 32 28 in %
Shear strength in N/ 6 7 cm2 Compressive stress at 5.6 6.2 10 % deformation in N/cm2 In addition, the shrinkage of the foam after storage under controlled conditions (40~C/90 % relative humidity) was very low.
Shrinkage of the foam as described in Example 2 Gun discharge Elbow discharge - 1.15 % - 1.28 %
The foams as described in Example 2 were also cold-stable, ie. they displayed no embrittlement at all at processing temperatures of about 5~C.
40 In order to achieve an optimum distribution of the foam in the joints and hollow spaces to be filled with foam, a low prepolymer viscosity is desirable. In the past, the chlorofluorocarbons customary as blowing agents contributed to lowering the viscosity. ~ince continued use of such compounds is not possible 45 for environmental reasons, plasticizers or solvents have fre~uently been added to the prepolymers, as described, for example, in DE-A-4 025 843 or EP-A-480 342. However, the use of 0050/47638 CA 0222l0l~ l997-l2-22 .
such compounds leads, since they are not built into the foam, to considerable shrinkage of the foams. DE-A-33 17 193, DE-A-39 11 784 and DE-A-38 29 104 also describe the addition of compounds which are said to lower the viscosity of the 5 prepolymers. However, here too, considerable shrinkage and embrittlement of the foams result.
In addition, in the case of the foams of the prior art, the different property requirements for the foam, particularly the 10 ratio of open to closed cells, had to be taken into account for the two possible ways of discharging the in-situ foam from the aerosol can, viz. discharge via a foaming gun and discharge via a foaming tube, customarily designated as elbow discharge.
Thus, a conventional, largely closed-celled foam permits only gun processing, while in the case of elbow processing it would have additional and thus excessive shrinkage. On the other hand, a largely open-celled foam can only be satisfactorily processed by 20 elbow discharge, while the bubbles in it would be too large if discharged by means of a gun.
For this reason, specific foam formulations have hitherto been prepared for the two methods of discharge.
It is an object of the present invention to provide a prepolymer for one-component polyurethane foams which, owing to its low viscosity, is readily processible and can be processed into foams having low shrinkage, an optimum ratio of open to closed cells 30 and improved mechanical properties and which permits discharge both via a gun and via an elbow.
We have found that this object is achieved by an isocyanate-35 terminated prepolymer containing oxazolidone and urethane groups which can be prepared by reacting an isocyanate component with a polyol component, wherein the isocyanate component (A) used is a reaction product containing terminal isocyanate groups and obtained by reacting at least one isocyanate containing at least 40 two isocyanate groups in the molecule with a mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and at least one polyester polyol and the polyol component (B) used comprises at least one polyether terminated by 45 primary hydroxyl groups and having a functionality of >2.
- CA 0222l0l~ l997-l2-22 The present invention accordingly provides isocyanate-terminated prepolymers containing oxazolidone and urethane groups as described above.
5 The present invention further provides a process for preparing the isocyanate-terminated prepolymers, provides for their use for producing one-component polyurethane foams and also provides the one-component polyurethane foams.
As regards the isocyanate components (A) used according to the present invention and their formative components, the following may be said:
15 As isocyanates containing at least two isocyanate groups in the molecule, it is possible to use the customary and known diisocyanates and polyisocyanates, for example aliphatic isocyanates such as hexamethylene l,6-diisocyanate (HDI), isophorone diisocyanate, aromatic isocyanates such as tolylene 20 diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and mixtures of diphenylmethane diisocyanate and polyphenylene-polymethylene polyisocyanates (raw MDI). The isocyanates can also be modified by incorporation of, for example, uretdione, isocyanurate and allophanate groups.
For one-component polyurethane foam, preference is given to using raw MDI.
The polyester polyols used according to the present invention are 30 prepared in a known manner by polycondensation of polybasic carboxylic acids with polyhydric alcohols. Such products are described, for example, in the Kunststoff-Handbuch, Volume 7, "Polyurethane", edited by Gunter Oertel, Carl-Hauser-Verlag Munich, 3rd edition 1993, pages 67 to 74.
Polyester polyols derived from dibasic carboxylic acids, in particular aliphatic dicarboxylic acids, and diols are particularly advantageous for preparing the prepolymers of the 40 present invention. Polyesterols based on adipic acid and diethylene glycol have been found to be particularly useful. The molecular weight of these polyesterols should be from 100 to 2000 g/mol (weight average). If the molecular weights are too high, the viscosity of the polyesterols increases excessively.
CA 0222101~ 1997-12-22 0050/47~38 As compounds containlng at least two groups which react with isocyanate and at least one epoxide group in the molecule, it is possible to use polyols obtained by epoxidation of natural materials, for example epoxidized soyabean oil but in particular 5 epoxidized polybutadienediols. The molecular weight should be from 600 to 4000 g/mol (weight average) since in this weight range they can, despite their incompatibility with the polyesterpolyol, be built into the urethane/oxazolidone-modified isocyanate to form oxazolidone structures.
The polyester polyol and the epoxidized compound are preferably used in a weight ratio of from 100:1 to 1:100, in particualr from 50:1 to 1:5. Furthermore, it has been found to be useful to use the mixture of polyester polyol and epoxidized compound in an 15 amount of from 0.1 to 20 % by weight, preferably from 2 to 10 %
by weight, based on the isocyanate used.
The polyisocyanate modified as described with oxazolidone and 20 urethane groups is reacted with the polyol component (B) to give the prepolymer of the present invention. According to the present invention, the polyol component comprises at least one high molecular weight polyether terminated by primary hydroxyl groups and having a functionality of >2 and a molecular weight of 25 >1500 g/mol, preferably from 3000 to 20,000 g/mol. These polyether polyols provided with primary OH groups and having a high molecular weight are particularly advantageous since as reactive polyols they form high molecular weight reaction products and thus effect, in the cured one-component foam, not 30 only good elasticity behavior but also optimum low-temperature curing without embrittlement.
Among the pure polyether polyols having the abovementioned characteristics, polyethylene glycols are particularly useful.
35 These are used in combination with customary polyhydroxyl compounds and additives in such a way that, despite their melting point above 20~C, they give a polyol component which is liquid at room temperature. Apart from the advantages mentioned, the use of these polyether polyols gives additional advantages via their 40 physically cell-opening high molecular weight reaction products with the isocyanate in the aerosol can. The pure polyether polyols having a high molecular weight and primary OH groups also include the polyethers derived from more than one alkylene oxide.
Here, suitable polyols are those in whose preparation ethylene 45 oxide as final addition generates primary OH groups.
CA 0222101~ 1997-12-22 Other particularly useful polyether polyols are those which have the abovementioned characteristics and which are prepared using a polyesterpolyol, in particular a fatty acid ester having OH functionality, as initiator.
Ethoxylated castor oil which can also be partially propoxylated is particularly useful. The mean molecular weight (weight average) is preferably >1500 g/mol, in particular from 1500 to 8000 g/mol. Higher molecular weights lead to increased prepolymer 10 viscosities-Apart from the ethoxylated fatty acid esters, the polyolcomponent comprises the hydroxy-functional compounds customary 15 for the production of rigid polyurethane foams, usually polyether polyols and/or polyester polyols as are described, for example, in Kunststoff-Handbuch, loc sit., and also, if desired, short-chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol as chain extenders, short-chain at least trihydric alcohols such as glycerol or trimethylolpropane as crosslinkers and also catalysts and, if desired, stabilizers, colorants and/or monools as molecular weight regulators.
Catalysts used are preferably strongly basic amines or organic 25 metal compounds, in particular tin compounds or synergistically acting mixtures of strongly basic amines and organic metal compounds. Examples of strongly basic amines are: amidines such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, 30 tris(dialkylaminoalkyl)-s-hexahydrotriazines such as tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine, but preferably tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, bis(morpholinoethyl) ether, 35 N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, bis(di-methylaminopropyl)urea, dimethylpiperazine, 40 1,2-dimethylimidazole, bis(4-N,N-dimethylaminocyclohexyl)methane, 1-aza-bicyclo(3.3.0)octane and 1,4-diazabicyclo(2.2.2)octane.
Suitable organic tin compounds are, for example: tin(II) salts of organic carboxylic acids, eg. tin(II) diacetate, tinn(II) 45 dioctoate, tin(II) diethylhexoate and tin(II) dilaurate, and also dialkyl tin(IV) salts of carboxylic acids, eg. dibutyltin CA 0222101~ 1997-12-22 diacetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin dimercaptide and dioctyltin diacetate.
Particularly suitable stabilizers are siloxane-oxyalkylene 5 copolymers.
The prepolymer of the present invention is present in a pressure container and is dissolved in a liquefied gas or liquefied gas 10 mixture which functions as blowing agent. Suitable blowing agents are customary liquefied gases and also other substances having a boiling point of <50~C. Examples which may be mentioned are:
Dimethyl ether, propane, n- or iso-butane, pentane, methyl 15 isobutyl ether and also halogenated hydrocarbons such as dichlorofluoromethane, monofluorotrichloromethane, trifluorotrichloroethane, trifluoromethane, 1,1-dichloro-l,fluoroethane, monochlororifluoroethane, monochlorodifluoroethane, difluoroethane, 20 dichlorotrifluoroethane, monochlorotetrafluoroethane, pentafluoroethane, tetrafluoroethane, dichloromonofluoroethane.
Particularly suitable blowing agents are alkanes and also mixtures of alkanes, fluorinated alkanes and dimethyl ether.
The preparation of the prepolymers of the present invention is preferably carried out in two stages: firstly, the urethane-/oxazolidone-modified polyisocyanate is prepared. For this purpose, the necessary amounts of isocyanate are initially 30 charged and the mixture of polyesterol and epoxidized polyol is metered in. Since the two compounds are not miscible with one other, they are preferably added in the form of an emulsion. The reaction is carried out at from 60 to 110~C, preferably from 80 to 90~C, while stirring. After a reaction time of from about 2 to 35 6 hours, the modification is complete and the reaction mixture is cooled to room temperature.
The reaction of the isocyanate component thus prepared with the 40 polyol component can be carried out in two possible ways:
1. The polyol component is metered into aerosol cans. The isocyanate component is then metered in, the aerosol can is closed by means of a valve and the blowing agent is metered in. The mixture constituents in the aerosol can are then intensively mixed and homogenized in a subsequent shaking or tumbling apparatus. The subsequent reaction forms the CA 0222l0l~ lss7-l2-22 prepolymer in the aerosol cans. After warm storage at about 50~C for about 24 hours or storage at room temperature for about 3 days, the foam is ready to use.
5 2. The isocyanate component is reacted with the polyol component in a reactor, the reaction mixture is introduced into an aerosol can, the latter is closed by means of a valve and the blowing agent is introduced. The subsequent procedure is as described above.
The weight ratio of polyol component to isocyanate component is about 100:~140 or an index of >400.
15 Compared with the prior art, the prepolymer of the present invention has the following advantages:
The built-in oxazolidone groups have a cell-opening action in the foam and thus reduce the shrinkage. On the other hand, the 20 solubility of the reaction product in excess isocyanate is improved. This is particularly surprising when epoxidized polybutadienediol is used, since this compound is extremely hydrophobic and normally does not mix with the other constituents of the reaction mixture. The resulting foams cure readily, have 25 very good mechanical properties, in particular display no embrittlement, and have an excellent low-temperature behavior.
The foams can be discharged from the pressure container either via a gun or via an elbow.
The invention is illustrated by the following examples.
Examples Example 1 1.1 Preparation of the urethane-/oxazolidone-modified isocyanate A stirred reactor provided with a heating and cooling facility and a temperature measurement device was charged with 95 kg of a raw diphenylmethane diisocyanate. In a separate mixing vessel, 6 kg of an adipic acid/diethylene glycol polyester alcohol having a molecular weight of 450 g/mol (OH number = 250 mg KOH/g) were mixed with 0.67 kg of an epoxidized polybutadienediol having an OH number of 180 mg KOH/g. The mixture gave a stable emulsion of the CA 0222l0l~ l997-l2-22 otherwise immiscible liquids. With the stirrer running, 5 kg of this emulsion were added to the raw diphenylmethane diisocyanate and thoroughly mixed. The contents of the reactor were then slowly heated to about 80~C while continuing the stirring. After reaching 80~C, this temperature was held for about 2 hours and the reaction product was then slowly cooled to room temperature. The urethane-/oxazolidone-modified isocyanate obtained had the following properties:
Isocyanate content: 28.7 % of NCO
Viscosity (25~C): 350 mPa s 15 1.2 Preparation of the polyol component 1750 g of a polyester alcohol based on a dicarboxylic acid mixture (glutaric acid, succinic acid, adipic acid) and ethylene glycol and having an OH number of 56 mg KOH/g, 300 g of a polyether alcohol based on sucrose/pentaerythritol/propylene oxide and having an OH
number of 410 mg KOH/g, 350 g of a polyether based on glycerol/propylene oxide/ethylene oxide and having an OH
number of 35 mg KOH/g, 400 g of a polyethylene glycol having a molecular weight of 600 g/mol, 325 g of an ethoxylated castor oil having a molecular weight of 4200 g/mol (OH number of 40 mg KOH/g), 125 g of a siloxane-oxyalkylene copolymer as foam stabilizer, 40 g of bis(morpholinoethyl) ether, 10 g of 4-methyl-4-hydroxypentan-2-one, 50 g of 1,4-butanediol and 1650 g of trichloropropyl phosphate were weighed one after the other into a mixing vessel and were homogenized by subsequent thorough mixing to give a polyol component.
1.3 Preparation of the prepolymers in aerosol cans having universal valves 280 g of the above-described polyol component were introduced into a 1 1 aerosol can. After addition of 434 g of the urethane-/oxazolidone-modified raw diphenylmethane diisocyanate as described in 1.1, the aerosol can was closed with a universal valve. Immediately after closing the can, 40 g of dimethyl ether, 72 g of tetrafluoroethane and 24 g of a gas mixture consisting of 80 % of butane and 20 % of propane were introduced one after the other through the valve into the aerosol can by means of a gas-metering apparatus.
After metering in each individual gas or the gas mixture, the contents of the aerosol can were homogenized by intensive CA 0222l0l~ l997-l2-22 shaking. After warm storage at 50~C for 24 hours, the prepolymer reaction was sufficiently complete for the aerosol can to be ready for producing the one-component foam.
5 1.4 Production of the one-component foams The prepolymers were discharged from the above-described aerosol cans both by means of a gun and by means of an elbow.
This was achieved by mounting the aerosol can on the respective dlscharge apparatus. The discharged prepolymers displayed very good frothing action and cured in the presence of atmospheric moisture or moisture from the substrate to give a foam having a very well structured surface, thin foam skin and very fine foam cells ln each case. The cured one-component foam displayed very good mechanical properties, as shown in the table below.
Foams as described in Example 1 Gun dischargeElbow discharge Density in kg/m3 14 16 Tensile strength in 11.5 12 N/cm2 Elongation at break 34 34 in %
Shear strength in N/ 6 7 cm2 Compressive stress at 5.8 6,7 10 % deformation in 30 N/cm2 In addition, the shrinkage of the foam after storage under controlled conditions (40~C/90 % relative humidity) was very low.
Shrinkage of the foam as described in Example 1 Gun discharge Elbow discharge - 1.46 % - 1.75 %
The foams as described in Example 1 were also cold-stable, ie. they displayed no embrittlement at all at processing temperatures of about 5~C.
CA 0222101~ 1997-12-22 The foam was classlfied in the burning class B2 as specified in DIN 4102.
Example 2 2.1 Preparation of the urethane-/oxazolidone-modified isocyanate A stirred reactor provided with a heating and cooling facility and a temperature measurement device was charged with 94.8 kg of a raw diphenylmethane diisocyanate. In a separate mixing vessel, 6 kg of an adipic acid/diethylene glycol polyester alcohol having a molecular weight of 450 g/mol (OH number = 250 mg KOH/g) and 0.93 kg of an epoxidized polybutadienediol having an OH number of 120 mg KOH/g were mixed. The mixture gave a stable emulsion of the otherwise immiscible liquids. With the stirrer running, 5.2 kg of this emulsion were added to the raw diphenylmethane diisocyanate and thoroughly mixed. The contents of the reactor were then slowly warmed to about 80~C while continuing the stirring. After reaching 80~C, this temperature was held for about 2 hours and the reaction product was then slowly cooled to room temperature. The urethane-/oxazolidone-modified isocyanate obtained had the following properties:
Isocyanate content: 28.5 % of NCO
Viscositity (25~C): 370 mPa s 30 2.2 Preparation of the polyol component 3400 g of a reaction product of a dicarboxylic acid mixture (glutaric acid, succinic acid, adipic acid) and a polypropylene glycol polyether having a molecular weight of 450 g/mol and an OH number of 50 mg KOH/g, 300 g of a polyether alcohol based on sucrose/pentaerythritol/propylene oxide and having an OH number of 410 mg KOH/g, 350 g of a polyether alcohol based on glycerol/propylene oxide/ethylene oxide and having an OH number of 35 mg KOH/g, 400 g of a polyethylene glycol having a molecular weight of 600 g/mol, 325 g of an ethoxylated castor oil having a molecular weight of 4200 g/mol (OH number = 40 mg KOH/g), 125 g of a siloxane-oxyalkylene copolymer as foam stabilizer, 40 g of bis(morpholinoethyl) ether and 60 g of 1,4-butanediol were weighed one after the other into a mixing vessel and CA 0222101~ 1997-12-22 homogenized by subsequent thorough mixing to give a polyol component.
2.3 Preparation of the prepolymer in aerosol cans having universal valves 245 g of the above-described polyol component were introduced into a 1 l aerosol can. After additlon of 380 g of the urethane-/oxazolidone-modified raw diphenylmethane diisocyanate as described in 2.1, the aerosol can was closed with a universal valve. Immediately after closing the can, 44 g of dimethyl ether, 36 g of tetrafluoroethane and 66 g of a gas mixture consisting of 80 % of butane and 20 % of propane were introduced one after the other through the valve into the aerosol can by means of a gas-metering apparatus.
After metering in each individual gas or the gas mixture, the contents of the aerosol can were homogenized by intensive shaking. After warm storage at 50~C for 24 hours, the prepolymer reaction was sufficiently complete for the prepolymer to be ready for production of the one-component polyurethane foam.
2.4 Production of the one-component polyurethane foams The prepolymers were discharged from the above-described aerosol cans both by means of a gun and by means of an elbow.
This was achieved by mounting the aerosol can on the respective discharge apparatus. The discharged prepolymers displayed very good frothing action and cured in the presence of atmospheric moisture or moisture from the substrate to give in each case a foam having a very well structured surface, thin foam skin and very fine foam cells. The cured one-component foam displayed good mechanical properties, as shown in the table below.
CA 0222101~ 1997-12-22 Foams as described in Example 2 Gun discharge Elbow discharge Density in kg/m3 15 16 5 Tensile strength in 9.5 11 N/cm2 Elongation at break 32 28 in %
Shear strength in N/ 6 7 cm2 Compressive stress at 5.6 6.2 10 % deformation in N/cm2 In addition, the shrinkage of the foam after storage under controlled conditions (40~C/90 % relative humidity) was very low.
Shrinkage of the foam as described in Example 2 Gun discharge Elbow discharge - 1.15 % - 1.28 %
The foams as described in Example 2 were also cold-stable, ie. they displayed no embrittlement at all at processing temperatures of about 5~C.
Claims (27)
1. A pressurized, blowing agent-containing, isocyanate-terminated prepolymer containing oxazolidone and urethane groups which can be prepared by reacting an isocyanate component (A) with a polyol component (B), wherein the isocyanate component (A) used is a reaction product containing terminal isocyanate groups and obtained by reacting at least one isocyanate containing at least two isocyanate groups in the molecule with a mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and a polyester polyol and the polyol component (B) used comprises at least one polyether terminated by primary hydroxyl groups and having a functionality of ~2.
2. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule is a polyol containing epoxide groups.
3. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyol containing epoxide groups is an epoxidized polybutadienediol.
4. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the epoxidized polybutadienediol has a molecular weight (weight average) of from 600 to 4000 g/mol.
5. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyester polyol is a reaction product of a diol and a dicarboxylic acid.
6. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyester polyol is a reaction product of diethylene glycol and adipic acid.
7. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyester polyol has a molecular weight (weight average) of from 100 to 2000 g/mol.
8. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the weight ratio of the polyol containing epoxide groups to the polyester polyol is from 100:1 to 1:100.
9. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the weight ratio of the polyol containing epoxide groups to the polyester polyol is from 50:1 to 1:5.
10. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the isocyanate used is a mixture of diphenylmethane diisocyanate and polyphenylene-polymethylene polyisocyanates.
11. An isocyanate-terminated prepolymer as claimed in claim 1, wherein for the preparation of the isocyanate component (A) the mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule is used in an amount of from 0.1 to 20 % by weight, based on the isocyanate containing at least two isocyanate groups in the molecule.
12. An isocyanate-terminated prepolymer as claimed in claim 1, wherein for the preparation of the isocyanate component (A) the mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule is used in an amount of from 2 to 10 % by weight, based on the isocyanate containing at least two isocyanate groups in the molecule.
13. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyether terminated by primary hydroxyl groups and having a functionality of ~2 which is used is a polyethylene glycol.
14. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyethylene glycol has a molecular weight (weight average) of <1000 g/mol.
15. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyethylene glycol has a molecular weight of from 3000 to 20,000 g/mol.
16. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the polyether terminated by primary hydroxyl groups which is used is an alkoxylated fatty acid ester.
17. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the alkoxylated fatty acid ester used is alkoxylated castor oil.
18. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the alkoxylated fatty acid ester used is ethoxylated castor oil.
19. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the ethoxylated castor oil has a molecular weight (weight average) of >1500 g/mol.
20. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the weight ratio of polyol components to isocyanate components is 100:>140.
21. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the blowing agents have a boiling point of <50°C.
22. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the blowing agents used are alkanes.
23. An isocyanate-terminated prepolymer as claimed in claim 1, wherein the blowing agents used are mixtures of alkanes, fluorinated alkanes and dimethyl ether.
24. A process for preparing a pressurized, blowing agent-containing, isocyanate-terminated prepolymer containing oxazolidine and urethane groups as claimed in claim 1, which comprises reacting an isocyanate containing at least two isocyanate groups in the molecule with a mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and a polyester polyol and reacting this reaction product with at least one polyether B terminated by primary hydroxyl groups.
25. A process as claimed in claim 19, wherein the reaction of the isocyanate with the mixture of at least one compound containing at least two functional groups which react with isocyanate and at least one epoxide group in the molecule and a polyester polyol to give the component A is carried out at from 60°C to 110°C.
26. A process for producing a one-component polyurethane foam, wherein a pressurized, blowing agent-containing, isocyanate-terminated prepolymer containing oxazolidone and urethane groups as claimed in claim 1 is depressurized, foamed by frothing action and cured in the presence of atmospheric moisture.
27. A one-component polyurethane foam which can be produced as claimed in claim 26.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996154149 DE19654149A1 (en) | 1996-12-23 | 1996-12-23 | Pressurized isocyanate-terminated prepolymers for one-component foams containing oxazolidone and urethane groups |
| DE19654149.2 | 1996-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2221015A1 true CA2221015A1 (en) | 1998-06-23 |
Family
ID=7816105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2221015 Abandoned CA2221015A1 (en) | 1996-12-23 | 1997-12-22 | Pressurized, isocyanate-terminated prepolymers containing oxazolidone and urethane groups for one-component foams |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0850964A1 (en) |
| CA (1) | CA2221015A1 (en) |
| DE (1) | DE19654149A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6894083B2 (en) | 2000-08-08 | 2005-05-17 | Dow Global Technologies Inc. | Polyurethane foam composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046761B (en) * | 2016-06-24 | 2019-02-19 | 上海华峰材料科技研究院（有限合伙） | High adhesiveness two-component epoxy-polyurethane intermingling material and preparation method thereof |
| WO2018138048A1 (en) * | 2017-01-25 | 2018-08-02 | Basf Se | Cold flexible polyurethane formulation |
| CN111440435A (en) * | 2020-04-27 | 2020-07-24 | 北京茂华聚氨酯建材有限公司 | High-flame-retardance polyurethane insulation board and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424316A (en) * | 1981-10-08 | 1984-01-03 | Stauffer Chemical Company | Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom |
| US4766158A (en) * | 1987-08-03 | 1988-08-23 | Olin Corporation | Urethane-containing oxazolidone-modified isocyanurate foams and a composition and method for their production |
| DE4130329A1 (en) * | 1991-09-12 | 1993-03-18 | Bayer Ag | HEAT-CURABLE REACTION RESIN MIXTURES, A METHOD FOR THE PRODUCTION THEREOF AND THE USE FOR THE PRODUCTION OF PRESSING MATERIALS AND MOLDED BODIES |
-
1996
- 1996-12-23 DE DE1996154149 patent/DE19654149A1/en not_active Withdrawn
-
1997
- 1997-12-17 EP EP97122261A patent/EP0850964A1/en not_active Withdrawn
- 1997-12-22 CA CA 2221015 patent/CA2221015A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6894083B2 (en) | 2000-08-08 | 2005-05-17 | Dow Global Technologies Inc. | Polyurethane foam composition |
| USRE43432E1 (en) | 2000-08-08 | 2012-05-29 | Dow Global Technologies Llc | Polyurethane foam composition |
| US9150764B2 (en) | 2000-08-08 | 2015-10-06 | Dow Global Technologies Llc | Polyurethane foam composition |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9710275A (en) | 1998-10-31 |
| DE19654149A1 (en) | 1998-06-25 |
| EP0850964A1 (en) | 1998-07-01 |
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