EP0517858A4 - Process for producing n=c=o foams and the controlled pre- and post-expansion thereof - Google Patents

Process for producing n=c=o foams and the controlled pre- and post-expansion thereof

Info

Publication number
EP0517858A4
EP0517858A4 EP19910907521 EP91907521A EP0517858A4 EP 0517858 A4 EP0517858 A4 EP 0517858A4 EP 19910907521 EP19910907521 EP 19910907521 EP 91907521 A EP91907521 A EP 91907521A EP 0517858 A4 EP0517858 A4 EP 0517858A4
Authority
EP
European Patent Office
Prior art keywords
blowing agent
foam
process according
expansion
mixing zone
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.)
Withdrawn
Application number
EP19910907521
Other languages
French (fr)
Other versions
EP0517858A1 (en
Inventor
Earl N. Doyle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DOYLE Earl N
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP0517858A1 publication Critical patent/EP0517858A1/en
Publication of EP0517858A4 publication Critical patent/EP0517858A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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

Definitions

  • Polyurethanes and other associated polymers based on diisocyanate chemistry are foamed for use in thermal insulation, floatation, and rigidizing applications.
  • these foam products can be employed in refrigeration systems, building materials, storage tanks, truck and railway tankers and cars which form the bulk of the thermal insulation industry.
  • these foams can be used in a flotation environment which encompasses, the filling of cavities in boats, barges, drilling platforms, etc., with low- density foams to prevent sinking of the vessel when accidents occur.
  • These foams have also been used to rigidize aircraft, helicopter blades, automobiles, and the like.
  • the reactants which are reacted with diisocyanates vary greatly depending on the desired end product.
  • the most widely used reactants are those compounds which terminate with an -OH group, -NH group or a -SH group.
  • the other reactant employed in the reaction is selected from diamines, water, dimethylol urea, and even dimethylol elamine, with the diamine being more preferred.
  • the "modified" phenolics are so called, since the reaction is not an acid cure, as in production of pure phenolics.
  • the isocyanates employed in such reactions range in functionality from about 2.0 to about 2.9.
  • the polymers can be prepared using prepolymers which have a functionality well above 3.0.
  • blowing agents In order to foam these polymers into low- density materials, blowing agents are used. In the past, the chlorofluorocarbons were the preferred blowing agents. However, due to the world-wide limitations on, and upcoming elimination of these products, alternative blowing agents must be found.
  • U.S. Patent 4,337,318 to Doyle is an example illustrating alternate blowing agents which have been used to replace the chlorofluorocarbons.
  • liquid carbon dioxide is used to achieve complete and immediate foaming of the polyurethane as it emerges from a mixing zone. This technique is known as "pre-expansion" of the foam. The process occurs in the absence of "post-expansion", i.e., the expansion of the foam which occurs over time after the foam leaves the mixing zone.
  • any desired percentage of pre-expansion and post-expansion may be obtained, where liquid C0 2 is preferably employed as the principal blowing agent, with the further use of co-blowing agents and other techniques such as altering the pressure to the mixing zone that allow for the controlled pre- and post-expansion of the foamed polymer.
  • the process of the present invention comprises:
  • the equipment employed in preforming the above process is essentially the same as the standard equipment employed with conventional processes.
  • either positive-displacement piston-type pumps, or variable-speed gear or vane type pumps may be employed.
  • the only requirement is that the equipment must be capable of producing pressures to the mixing zone on the order of about 300 to about 5000 psi.
  • each pump pumping a separate component to the mixing zone.
  • two or more of the components may be pre- blended and then pumped to the mixing zone a ⁇ a separate stream.
  • formulation ⁇ may be altered, modified, and changed almost instantaneously.
  • the blowing agent(s) may be introduced at any point prior to the mixing zone, e.g., into one or more of the reactant streams, or it may be introduced directly into the mixing zone.
  • the preferred principal blowing agent is liquid carbon dioxide / because of low cost, high gas production, and good stability associated with its use.
  • any liquid gas having a boiling point below approximately -100"F may be used, such as nitrogen, helium, argon, tetrafluoromethane, fluoroform, hexafluoroethane, chlorotrifluoromethane, or mixtures thereof.
  • One technique for controlling the amount of pre- and post-expansion of the foam involves the use of co- blowing agents.
  • Other co-blowing agents include higher- boiling solvents, such as methylene chloride, ethyl chloride, chloroform, methyl chloroform, and hydrochlorofluorocarbons, such as Freon 21, 22, 113, 114 and the like.
  • non-halogenated hydrocarbons such as hexane, heptane, butene-1, butane, and the like may be used.
  • the co-blowing agents may be introduced as a separate stream(s) to the mixing zone, or may be pre- blended into one or more of the other components prior to the mixing zone.
  • the co-blowing agent would compri ⁇ e a minor amount of the total blowing agent, in an amount ⁇ ufficient to provide the desirable amount of post-expansion.
  • water employed as the co-blowing agent
  • about 1 lb. of water provides the same amount of foaming as about 7 lbs. of the liquid carbon dioxide.
  • approximately 3 lbs. of Freon 22 would provide the same amount of foaming as about 2 lbs. of the liquid carbon dioxide.
  • controlled amounts of post expansion of the foam can be obtained by lowering the pressure at which the ingredients are subjected to at the mixing zone.
  • the use of pressures at the mixing zone of about 300-500 psi provides for considerable amounts of post- expansion.
  • the higher the pressure at the mixing zone the lesser the amount of post-expan ⁇ ion i ⁇ derived from the liquid carbon dioxide.
  • the degree of po ⁇ t-expansion is related to the percentage of C0 2 in the mixture. In particular, the higher the percentage of carbon dioxide in the total mix, the lesser the amount of post- expansion that may be obtained.

Abstract

A method for producing polymeric foams based upon the N=C=O technology, intended for thermal insulation, floatation, rigidization, and like comprises the use of a liquid gas blowing agent, such as a liquid CO2 in the production of the foam. In addition, the present invention relates to the control of the amount of pre-expansion and post-expansion of the foam. This control can be provided through both the use of a co-blowing agent as well as controlling the pressure at the mixing zone.

Description

PROCESS FOR PRODUCING N-C-O FOAMS AND THE CONTROLLED PRE- AND POST-EXPANSIONTHEREOF
Background of the Invention
The present invention relates to a process for utilizing liquid gases such as carbon dioxide as a sole, or co-blowing agent for polyurethanes, modified isocyanurates, isocyanurates, polyureas, carbodiimides, and modified phenolics, and all types of polymeric foams based on N=C=0 technology.
Polyurethanes and other associated polymers based on diisocyanate chemistry are foamed for use in thermal insulation, floatation, and rigidizing applications. For example, these foam products can be employed in refrigeration systems, building materials, storage tanks, truck and railway tankers and cars which form the bulk of the thermal insulation industry. Moreover, these foams, can be used in a flotation environment which encompasses, the filling of cavities in boats, barges, drilling platforms, etc., with low- density foams to prevent sinking of the vessel when accidents occur. These foams have also been used to rigidize aircraft, helicopter blades, automobiles, and the like.
Each of these polymers is based in principal on the N=C=0 backbone. The reactants which are reacted with diisocyanates vary greatly depending on the desired end product. For example, in making a polyurethane, the most widely used reactants are those compounds which terminate with an -OH group, -NH group or a -SH group. In making typical polyurethanes, a molar ratio of about 1 : 1 to about l.l : 1 for the, N=C=0 to the other reactant is employed. Modified Isocyanurates typically employ a molar ratio of 1.5 : 1, up to about 3 : 1 for the, N=C=0 to reactant while pure Isocyanurates employ molar ratios above about 3:1. Special catalysts which are known in the art, are utilized to trimerize the excesses of N=C=0.
Polyureas may be made using a variety of formulations which are also based on the N=C=0 technology. The other reactant employed in the reaction is selected from diamines, water, dimethylol urea, and even dimethylol elamine, with the diamine being more preferred. Carbodiimides may also be produced using a variety of formulations, with the most preferred being the reaction of the N=C=0 with polycarboxylic acids, again utilizing special catalysts for the reaction. The "modified" phenolics are so called, since the reaction is not an acid cure, as in production of pure phenolics. The modified phenolics are made by reacting the N=C=0 with hydroxyl-bearing phenols, nonyl phenols and diphenols such as resorcinol.
All these above-described polymers have the common N=C=0 backbone, while the remaining reactants are chosen in order to form the desired polymer having more or less the above nomenclatures. The isocyanates employed in such reactions range in functionality from about 2.0 to about 2.9. In addition, the polymers can be prepared using prepolymers which have a functionality well above 3.0.
In order to foam these polymers into low- density materials, blowing agents are used. In the past, the chlorofluorocarbons were the preferred blowing agents. However, due to the world-wide limitations on, and upcoming elimination of these products, alternative blowing agents must be found. U.S. Patent 4,337,318 to Doyle is an example illustrating alternate blowing agents which have been used to replace the chlorofluorocarbons. In this patent, liquid carbon dioxide is used to achieve complete and immediate foaming of the polyurethane as it emerges from a mixing zone. This technique is known as "pre-expansion" of the foam. The process occurs in the absence of "post-expansion", i.e., the expansion of the foam which occurs over time after the foam leaves the mixing zone.
Summary of the Invention
By the process of the present invention, any desired percentage of pre-expansion and post-expansion may be obtained, where liquid C02 is preferably employed as the principal blowing agent, with the further use of co-blowing agents and other techniques such as altering the pressure to the mixing zone that allow for the controlled pre- and post-expansion of the foamed polymer.
In particular, the process of the present invention comprises:
(a) mixing together in a mixing zone at ambient temperature (i) a first component comprising a diisocyanate having a functionality within the range of about 2.0 to about 2.9 or a prepoly er having a functionality greater than about 3.0; (ii) at leaεt one surfactant capable of producing a closed cell foam, (iii) at least one catalyst, (iv) a blend of one or more compounds within the group consisting of -OH terminated compounds, -C00H terminated compounds, -NH terminated compounds, -SH terminated compounds, hydroxyl-containing phenols, ureas, melamines and water? and (v) at least one blowing agent, said mixture being subjected in said mixing zone to a pressure sufficient to maintain said at least one blowing agent in the liquid state at ambient temperature, said pressure being from about 300 to about 5000 psi;
(b) ejecting said mixture from said mixing zone to atmospheric pressure, thereby completely and instantaneously vaporizing said blowing agent: and
(c) curing the resulting foam.
Description of the Invention The present invention relates to a process for making a polymer foam which comprises the reaction between an isocyanate with one or more compound which iε effective in providing a polymer having an N=C=0 backbone. The procesε of the preεent invention alεo relates to the use of at least one blowing agent such as liquid carbon dioxide in the production of polymers having an N=C=0 backbone.
The equipment employed in preforming the above process is essentially the same as the standard equipment employed with conventional processes. For example, either positive-displacement piston-type pumps, or variable-speed gear or vane type pumps may be employed. The only requirement is that the equipment must be capable of producing pressures to the mixing zone on the order of about 300 to about 5000 psi.
In the procesε of the preεent invention, ten separate pumps or more may be employed, with each pump pumping a separate component to the mixing zone. In many cases, two or more of the components may be pre- blended and then pumped to the mixing zone aε a separate stream. Through the use of thiε type of equipment, formulationε may be altered, modified, and changed almost instantaneously. The blowing agent(s) may be introduced at any point prior to the mixing zone, e.g., into one or more of the reactant streams, or it may be introduced directly into the mixing zone. The preferred principal blowing agent is liquid carbon dioxide/ because of low cost, high gas production, and good stability associated with its use. However, any liquid gas having a boiling point below approximately -100"F may be used, such as nitrogen, helium, argon, tetrafluoromethane, fluoroform, hexafluoroethane, chlorotrifluoromethane, or mixtures thereof.
One technique for controlling the amount of pre- and post-expansion of the foam involves the use of co- blowing agents.
Co-blowing agents which produce the desired degree of post-expansion include water, which when reacted stoichiometrically with the N=C=0, produces gaseous C02• Other co-blowing agents include higher- boiling solvents, such as methylene chloride, ethyl chloride, chloroform, methyl chloroform, and hydrochlorofluorocarbons, such as Freon 21, 22, 113, 114 and the like. In some cases, non-halogenated hydrocarbons such as hexane, heptane, butene-1, butane, and the like may be used.
The co-blowing agents may be introduced as a separate stream(s) to the mixing zone, or may be pre- blended into one or more of the other components prior to the mixing zone. In a majority of applications, the co-blowing agent would compriεe a minor amount of the total blowing agent, in an amount εufficient to provide the desirable amount of post-expansion. For example, where water is employed as the co-blowing agent, about 1 lb. of water provides the same amount of foaming as about 7 lbs. of the liquid carbon dioxide. As another example, approximately 3 lbs. of Freon 22 would provide the same amount of foaming as about 2 lbs. of the liquid carbon dioxide. In another aspect of the present invention, controlled amounts of post expansion of the foam can be obtained by lowering the pressure at which the ingredients are subjected to at the mixing zone. For example, where liquid carbon dioxide is the sole blowing agent, the use of pressures at the mixing zone of about 300-500 psi provides for considerable amounts of post- expansion. Furthermore, the higher the pressure at the mixing zone, the lesser the amount of post-expanεion iε derived from the liquid carbon dioxide. For example, at about 1000 psi to 5000 psi, little to no post-expanεion iε εeen when liquid carbon dioxide iε the εole blowing agent. In addition, the degree of poεt-expansion is related to the percentage of C02 in the mixture. In particular, the higher the percentage of carbon dioxide in the total mix, the lesser the amount of post- expansion that may be obtained.
The pre-expansion, on the other hand, occurε almost instantaneous when the mixture emerges from the mixing zone, at pressures above about 1000 psi. The principals, preferred embodiments, and modes of operation of the present invention have been described in the foregoing. The invention however, is not to be limited to the particular embodiments disclosed, since they are illustrative only in εcope. Variations and modifications may be made by those skilled in the art without departing from the spirit of the invention. Accordingly, it is intended that the scope of the preεent invention be limited εolely by the εcope of the following claim including equivalents thereof.

Claims

CLAIMS :
1. A process for the production of low density foam having a N=C-0 backbone comprising the steps of:
(a) mixing together in a mixing zone at ambient temperature (i) a first component comprising a diisoσyanate having a functionality within the range of about 2.0 to 2.9 or a prepolymer having a functionality greater than about 3.0; (ii) at least one surfactant capable of producing a closed cell foam, (iii) at least one catalyst, (iv) a blend of one or more compounds within the group consisting of -OH terminated compounds, -COOH terminated compounds, -NH terminated compounds, -SH terminated compounds, hydroxyl-containing phenols, ureas, melamines and water; and (v) at least one blowing agent, said mixture being subjected in said mixing zone to a preεεure sufficient to maintain said at least one blowing agent in the liquid εtate at ambient temperature, said pressure being from about 300 to about 5000 psi;
(b) ejecting said mixture from said mixing zone to atmospheric pressure, thereby completely and instantaneously vaporizing said blowing agent: and
(c) curing the resulting foam.
2. The process according to claim 1 wherein the at least one blowing agent compriseε a liquid gaε having a boiling point below about -100°F.
3. The process according to claim 1 wherein the at least one blowing agent comprises liquid carbon dioxide. 4. The process according to claim 2 or 3 wherein the blowing agent further comprises a co-blowing agent which comprises water, high-boiling point solvents and non-halogenated hydrocarbons.
5. The process according to claim 4 wherein the co-blowing agent comprises a higher-boiling point solvent which comprises methylene chloride, ethyl chloride, chloroform, methyl chloroform, or a hydrochlorofluorocarbon.
6. The method according to claim 4 wherein the co-blowing agent compriseε a non-halogenated hydrocarbon which compriseε hexane, heptane, butene-1, butane or mixtures thereof.
7. The process according to claim 4 wherein the co-blowing agent comprises water.
8. The process according to claim 1 wherein the foam has a density of about 0.5 to about 6 lbs./cu. ft.
9. The procesε according to claim 1 wherein the foam comprises a polymer having a N=C=0 backbone.
10. The process according to claim 1 wherein the foam comprises a polyurethane, a modified isocyanurate, an isocyanurate, a polyurea, a carbodiimide or a modified phenolic.
11. The process according to claim 2 or 3 wherein a majority of the expansion of the foam occurs when the mixture exits the mixing zone. 12. The process according to claim 4 wherein the expansion of the foam includes both pre-expanεion and poεt-expansion.
13. The method according to claim 12 wherein the amount of co-blowing agent is selected so as to provide a predetermined amount of post-expansion of the foam.
14. The method according to claim 7 wherein the amount of water is selected so as to provide a predetermined amount of post-expansion of the foam.
15. The process according to claim 1 wherein the pressure at the mixing zone is selected εo aε to provide a predetermined amount of post-expansion of the foam.
16. The process according to claim 1 wherein at least two components are preblended prior to being introduced into the mixing zone.
17. The process according to claim 1 wherein at least one blowing agent is preblended with at lest one other component prior to being introduced into the mixing zone.
18. The process according to claim 4 wherein the co-blowing agent is preblended with at least one other component prior to being introduced into the mixing zone.
EP19910907521 1990-02-13 1991-02-12 Process for producing n=c=o foams and the controlled pre- and post-expansion thereof Withdrawn EP0517858A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47924690A 1990-02-13 1990-02-13
US479246 1990-02-13

Publications (2)

Publication Number Publication Date
EP0517858A1 EP0517858A1 (en) 1992-12-16
EP0517858A4 true EP0517858A4 (en) 1993-07-28

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EP (1) EP0517858A4 (en)
CA (1) CA2075975A1 (en)
WO (1) WO1991012287A1 (en)

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Publication number Priority date Publication date Assignee Title
TW261577B (en) * 1993-07-14 1995-11-01 Krypton Internat Sa
IT1270979B (en) * 1993-09-30 1997-05-26 Afros Spa Process and equipment for the continuous production of polyurethane foam in blocks
US5665287A (en) * 1993-07-14 1997-09-09 Foaming Technologies Cardio Bv Froth process for continous manufacture of polyurethane foam slab-stocks
US5831004A (en) * 1994-10-27 1998-11-03 Affymax Technologies N.V. Inhibitors of metalloproteases, pharmaceutical compositions comprising same and methods of their use
US5840698A (en) * 1994-10-27 1998-11-24 Affymax Technologies N.V. Inhibitors of collagenase-1 and stormelysin-I metalloproteases, pharmaceutical compositions comprising same and methods of their use
DK766713T4 (en) * 1994-11-02 2003-11-17 Solvay Fluor & Derivate Propellants containing liquid carbon dioxide
DE19502708C2 (en) * 1995-01-28 2003-10-23 Solvay Fluor & Derivate Process for the production of single or multi-component polyurethane foams
DE4442256C1 (en) * 1994-11-28 1996-07-25 Hennecke Gmbh Maschf Process for dissolving carbon dioxide in a liquid polymer

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US3184419A (en) * 1958-02-06 1965-05-18 Dunlop Rubber Co Method for the production of polyurethane foamed material
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
EP0089796A1 (en) * 1982-03-19 1983-09-28 Imperial Chemical Industries Plc Method of manufacturing polyurethane foams
EP0145250A1 (en) * 1983-11-05 1985-06-19 Flexible Foam Research Limited Improvements in polyurethanes
DE3916873A1 (en) * 1988-05-27 1989-12-14 Elastogran Polyurethane Gmbh Process for the preparation of cellular plastics by the polyisocyanate polyaddition process, and a catalyst combination therefor
EP0353061A2 (en) * 1988-07-29 1990-01-31 Pmc, Inc. Blowing agents for polyurethane foam

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Publication number Priority date Publication date Assignee Title
US3184419A (en) * 1958-02-06 1965-05-18 Dunlop Rubber Co Method for the production of polyurethane foamed material
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
EP0089796A1 (en) * 1982-03-19 1983-09-28 Imperial Chemical Industries Plc Method of manufacturing polyurethane foams
EP0145250A1 (en) * 1983-11-05 1985-06-19 Flexible Foam Research Limited Improvements in polyurethanes
DE3916873A1 (en) * 1988-05-27 1989-12-14 Elastogran Polyurethane Gmbh Process for the preparation of cellular plastics by the polyisocyanate polyaddition process, and a catalyst combination therefor
EP0353061A2 (en) * 1988-07-29 1990-01-31 Pmc, Inc. Blowing agents for polyurethane foam

Non-Patent Citations (1)

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Title
See also references of WO9112287A1 *

Also Published As

Publication number Publication date
EP0517858A1 (en) 1992-12-16
CA2075975A1 (en) 1991-08-14
WO1991012287A1 (en) 1991-08-22

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