WO1990003997A1 - Effet de l'emploi de modifiants chimiques dans la polymerisation de mousse de polyurethane - Google Patents

Effet de l'emploi de modifiants chimiques dans la polymerisation de mousse de polyurethane Download PDF

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Publication number
WO1990003997A1
WO1990003997A1 PCT/AU1989/000426 AU8900426W WO9003997A1 WO 1990003997 A1 WO1990003997 A1 WO 1990003997A1 AU 8900426 W AU8900426 W AU 8900426W WO 9003997 A1 WO9003997 A1 WO 9003997A1
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WO
WIPO (PCT)
Prior art keywords
foam
mixture according
additive
properties
block
Prior art date
Application number
PCT/AU1989/000426
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English (en)
Inventor
Allen Wood
Michael David Joubert
Original Assignee
Pacific Dunlop Limited
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 Pacific Dunlop Limited filed Critical Pacific Dunlop Limited
Publication of WO1990003997A1 publication Critical patent/WO1990003997A1/fr

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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
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0014—Use of organic additives
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the present invention relates in general to polyurethane foams including both flexible foams and rigid foams and to methods for their manufacture-
  • the present invention relates to improvements in the foaming and/or curing step of the method used in the manufacture of foamed material.
  • the present invention finds application in the formulation of a foamable mixture for making foam material by including in the formulation an additive which undergoes a chemical and/or physical change to produce a gaseous and/or vaporous material so that foam material with more controllable, reproducible and/or uniform properties can be manufactured.
  • Another aspect of the present invention relates to the incorporation of additives that undergo an endothermic change during the foaming and/or curing step so that less heat may be produced during the exotherm.
  • polyurethane flexible or rigid foams are produced by reacting a suitable polyol or mixture of polyols with di- or polyisocyanates in the presence of stabilizers, eell control agents, blowing agents, catalysts and the like.
  • the reaction is of a polyaddition type and is strongly
  • the polyols used in flexible foam production are generally diols or triols having a molecular weight of about 1000 to 7000. It is to be noted that the present invention may be used in the manufacture of both polyether polyurethanes and polyester polyurethanes.
  • the isocyanates used in flexible foam production are mostly based on toluene-diisocyanates and/or on
  • raethyl-diphenyl-diisocyanates in their various monomeric or polymeric forms or may be based or other aliphatic or aromatic isocyanates.
  • the stabilizer/cell control agent/surfactant is the stabilizer/cell control agent/surfactant
  • the blowing agents are included so as to expand during the foaming and/or expansion stage of the reaction to fill the pores in the foam structure to make the product a cellular plastic.
  • Water which is one example of the blowing agent is generally present in formulations at a concentration of from about 0.06 to 4.0 parts by weight based upon 100 p.b.w. of the polyol or polyols. However, it is to be noted that higher amounts of water may be used.
  • the water/isocyanate reaction will liberate carbon dioxide gas in a strongly exothermic reaction. This reaction contributes to the exotherm produced during the manufacture of the flexible polyurethane.
  • monofluoro-trichloro methane and/or methylene chloride or other similar substances may act as auxiliary blowing agents.
  • Air may also be used as a nucleating agent and may be added by injecting it into the reaction mix to facilitate the formation of the cellular structure.
  • the reactant may also be used as a nucleating agent and may be added by injecting it into the reaction mix to facilitate the formation of the cellular structure.
  • reactants, catalysts, additives and the like are mixed in a pre-determined ratio.
  • the density of the foam produced in a given polyol/isocyanate system is typically from aoout 12 to 70 kg/m 3 or more - and is determined by the amount of blowing agent or agents present in the reaction mixture.
  • ingredients in a foam mix or system may include solid or liquid fillers, modifiers, cross linkers andother reactive or non-reactive components aimed at modifying the physical properties, combustion performance, weldability or other characteristics of the end product.
  • the final physical properties of the resulting cellular plastic are determined by the nature and amounts of reacting and non-reacting components present in the initial mixture.
  • the final physical properties are generally reached after full cure which may last 1 to 2 days after manufacture of the foam.
  • the density of the cellular plastic is determined by the ratio and concentration of the chemical and/or physical blowing agents present in the reaction mix as well as by the presence or absence of inert or reactive fillers, which may be present as either solids or liquids.
  • the final hardness of the resulting cellular plastic is determined by the nature of the polyols, the stoichioraetric ratio of the isocyanates to the polyol or polyols, the nature of the cross linking agent or agents if more than a single agent is present, whether other reactive components and water are present as well as whether liquid extenders or solid fillers are present in the reaction mix, including their quantity and in the case of solids their particle size distribution.
  • the first technique is
  • the liquid foam reaction mixture is injected into a suitably constructed enclosure - the mould - where the liquid is allowed to expand by foaming such that on expansion and solidification the polyurethane foam takes on the shape of the mould to form a solid block of foam of the desired shape.
  • the final curing process takes place either at room temperature or in temperature controllable ovens or tunnels at temperatures above ambient.
  • the present invention is more suitable in the process of slabstock production rather than in the process of producing shaped foamed articles by the
  • the present invention can be useful and also find, application in treating moulded pieces as well.
  • the post curing of slabstock foams takes place traditionally at the ambient temperature of the storage area.
  • the blocks are set apart from each other by a minimum
  • the blocks are stored spaced apart from each other so as to allow air to circulate between to provide more uniform cooling and to prevent heat build up and thus, reduce the danger of auto-ignition of the freshly produced foam.
  • the cure or post-cure of the freshly manufactured and cut blocks from the slabstock production line takes place in a fresh foam or "hot block storage" room, where the inner core or inner portion of each block reaches a temperature of about 100° to 175°C in from up to 200 seconds after formation, maintains this temperature for a further period of up to several hours and then gradually cools down to ambient temperature. This process is slow, taking about 10 to 36 hours, because the foam by its nature is an excellent insulator of heat.
  • the ambient temperature and humidity conditions within the fresh foam or hot block storage area at this stage of the curing process are not totally predictable or at least are not accurately controllable which leads to further variations in properties of the cured
  • the properties which are more controlled are hardness, density, tensile strength, elongation,
  • a method for the production of a foam material preferably a polyurethane foam material, comprising including in the foamable liquid reaction mixture an additive which is capable of undergoing an endothermic reaction or is capable of forming a vapour and/or decomposing into one or more gaseous materials at a known preselected temperature or over a known preselected range of temperatures said vapour or gaseous material beneficially influencing the properties of the foamed material when forming and/or when formed.
  • a foamable reaction mixture for forming a polyurethane flexible foam that is capable of expanding and polymerizing to form a shaped piece or block of foam wherein at least one additional additive which is capable of
  • the decomposition occurs endothermically.
  • the properties of the foamed material are beneficially influenced by reducing the maximum temperature reacted during the curing process.
  • the additive material that is additionally added typically includes materials which decompose or give up their water of crystallization or breakdown endothermically when heated. Examples of such additive materials typically decompose or give up their water of crystallization at temperatures between 10°C and 200°C preferably at a
  • Ammonium carbonate which decomposes to ammonia and carbon dioxide at a temperature of 58°C.
  • additive materials typically include the following: gas saturated adsorptive carbons, zeolites, molecular sieves, and the like, polypropylene, polyethylene, and other plastics, calcium stearate, and similar materials which are endothermic due to their melting properties in the required temperature range.
  • the additional material is included in the reaction mixture at the time of formulation of the liquid mixture in addition to the usual, typical or conventional materials that are incorporated in the reaction mixture.
  • the products of the decomposition of the additional material include a gas or mixture of gases or a vapour or mixture of vapours.
  • the gaseous decomposition products influence the curing step of the solid urethane polymeric structure.
  • the selective influence of the vapour or gases may be localised.
  • the inner core of a freshly produced block will stay for longer periods of time at higher exotherm temperatures, say at from 120° to 165°C. Peripheral areas of the same block will stay for shorter periods at the high exotherm level or will be at lower exotherm levels.
  • the block may be insulated all around so that the heat distribution is more uniform, and accordingly so is the cooling-down process which allows the decomposition products to develop as fully as possible, because variation in the cooling rate of different parts of the block will not oe as great and the rate overall will be slowed down compared to the situation where the block is uninsulated.
  • the additional material is a hydrated mineral salt, giving up its water of crystallisation at elevated temperatures.
  • the developing water vapour from the decomposition of, say for example, hydrated calcium sulphate CaSO 4 .2H 2 O, would occupy the cells of the freshly produced cellular polyurethane thereby providing a controlled humidity condition for curing.
  • endothermic chemical reaction i.e. the loss of water of crystallisation, will reduce the maximum exotherm temperature of the foaming
  • the additional material is a compound like the ammonium salts, such as for example ammonium carbonate or the ammonium acetates.
  • the additional material is any such compound which decomposes at about 60° to 180°C, typically 100° to 170°C, more typically 120° to 165°C, often giving up vapours or gases which can influence the secondary chemical reactions which take place during the curing period immediately following the foam formation.
  • the additional material can be organic or inorganic and may be a solid or liquid at ambient or room temperature. If the additional material is a solid, it may sublime at an elevated temperature to give off a gas.
  • the solid material may undergo a change from solid to liquid to gas. If the additional material is a liquid, it may undergo a change from liquid to vapour.
  • the final physical properties of the polyurethane foam polymer as well as the temperatures developed during the foaming and/or curing step, such as from the time the exotherm begins and thereafter, can be directly influenced by the presence of the vapour or gas from the additive material when inside the cells of the foamed blocks, or can be influenced by the endothermic nature of the change in phase, e.g. melting of the additive.
  • the foamed material may then cool down faster because there are no or very little free isocyanate groups left unreacted to enter into further
  • the amount of the additives included in the reaction mixture may vary widely depending on the particular additive chosen and the end result sought. Typical ranges are from .05 pph to 170 pph expressed as parts per hundred based on the total amount of polyol present in the reaction mixture. More typically, the amounts range from .2 to 100 pph, even more typically 2 to 30 pph.
  • Typical materials useful as additives in the present invention include mineral hydrates, organo metallic hydrates and dessicant materials also adsorptive carbons, molecular sieves, zeolites, polyethylene, polypropylene, calcium
  • gypsum G75 which is supplied by Commercial Minerals Limited of Camberwell, Victoria and which has the following
  • Another aspect of the present invention relates to the incorporation of additive materials which may either enter into endothermic reactions with other materials already present in the formulation or may undergo a change which is endothermic. Any material added to the foaming mixture which undergoes or enters into an endothermic reaction will reduce the amount of exotherm since heat will be taken away from the exotherm to drive the endothermic reaction.
  • Figure 1 is a schematic representation of a foam block showing the position of representative test samples taken from the block upon which performance tests were conducted;
  • Figure 2 is a plot of hardness as a function of vertical position of the selected test sample within the block;
  • Figure 3 is a plot of hardness as a function of horizontal position of the selected test sample within the block
  • Figure 4 is a plot of exotherm temperature as a function of time for various locations of the test samples within the block;
  • Figure 5 is a plot of the internal foam temperature developed within the block as a function of time for varying quantities of additives
  • Figure 6 is a plot of the internal foam temperature developed within the block as a function of time for different additives
  • Figure 7 is a plot of density as a function of vertical position of the test sample within the block.
  • Figure 8 is a plot of hardness as a function of vertical position of the test sample within the block.
  • Figure 1 there is shown schematically a block of foam generally denoted by A, from which representative test samples are taken generally denoted by b, and tested for various properties such as hardness, density and the like.
  • test samples are denoted by one of the reference numerals 1 to 9 in a horizontal plane or grid and by one of the reference numerals 1 to 14 in a vertical plane or column. It is to be noted that none of the samples tested are taken from the extreme edges of the block but rather the block is skinned by removing one or more layers from the block prior to subdividing the block into the test samples. The block is skinned to remove the extreme outer layers because the
  • each horizontal position is broadly divided into 3 main areas which are denoted as top, middle, or bottom of the block. Although each of the 9 horizontal positions is associated with 14 vertical positions, in practice each horizontal position is usually only associated with 3 vertical positions, making a choice of 27 different samples. By selectively taking the samples from the choice of 27 positions it is possible to gain an overall picture of the block. If more detailed information is provided.
  • EXP refers to an experimental batch of foam having the additive , in this case 4.0 pph of G75, whereas the
  • REF refers to a standard foam block formulation for producing a conventional foam block without additive.
  • the hardness of the EXP blocks being of the order of 85 to 105N whereas the hardness of the REF blocks is from 125 to 145N. Additionally, the EXP blocks exhibit more homogeneous properties with less variation than do the REF blocks.
  • the test samples at vertical positions 6 to 10 of the REF blocks, particularly the REF block at the centre exhibits a greater variation from about 130N to about 145N when compared to the more even hardness obtained in the EXP blocks of about 94 ⁇ 1 N.
  • the additive produces a foam with more uniform properties than is achieved without the inclusion of the additive and thus the final properties of the foam are more controllable. It also reduces the foam hardness relative to the REF block.
  • Figure 3 illustrates the difference in hardness obtained between the experimental foam, EXP, containing additive and the reference foam, REF, not containing the additive for each of the 9 horizontal positions at the same vertical level. From the top vertical position, a test sample was taken from each of the 9 horizontal positions which are number 1 through to 9 as per the positions illustrated in Figure 1. Similarly, 9 test samples were taken from the middle vertical level and tested. Also, 9 test samples were taken from the bottom vertical position and tested. The 27 test samples in all were tested for hardness and the results plotted in Figure 3 in groups of threes. The results from the EXP block were compared to the results from the REF block.
  • the variation of hardness within a single vertical level of 9 test samples was greater for the REF block than for the EXP block.
  • the variation of the REF block being generally of the order of between about 10 and 15N whereas the variation of the EXP block was about 5N.
  • the EXP block was. appreciably softer.
  • the variation between adjacent positions of the REF block, particularly between edge locations and centre locations was considerably greater than the variation between corresponding adjacent positions in the EXP block. This is particularly illustrated in the values of hardness obtained at positions 4, 5 and 6 of the block for the middle and bottom test samples of the REF block which vary by about 13N when compared to the values obtained at the
  • Figure 4 illustrates a temperature-time profile of the cooling of the foam block during post cure for two samples of each of the REF block and EXP block in which a first sample was taken at the edge of the block while the other sample was taken at the centre of the block.
  • the temperature-time profile clearly indicates that the inclusion of the additive results in a lower maximum temperature being attained during the exotherm, about 150°C for the REF block at the edge as compared to about 125°C for the EXP block at the edge, and faster rate of cooling as in the case of the centre test sample where both initial temperatures were about 150°C but the REF block took 600 minutes to cool to 120°C whereas the EXP block took about 400 minutes to cool to 120°C.
  • Figure 5 is a time-temperature profile for the exotherm during the manufacture of the foam block for
  • the additive was G75 and was added in amounts of 0 pph (corresponding to a conventional formulation) 5, 10, 20, 40, 60 pph. With the exception of the formulation containing 50 pph G75, the exotherm temperature in all other cases was less than the exotherm of the conventional formulation. This clearly indicates that once the additive has been added above a critical threshold the heat generated by the exotherm is somehow modified so as not to reach such a high level.
  • Figure 6 illustrates the modifying effect or the maximum temperature of exotherm of additives other than G75.
  • the other additives used are magnesium sulphate, sodium tetraborate and sodium orthophosphate as indicated. All three of these other additives reduce the maximum temperature of exotherm at 5.0 pph levels of addition. Clearly, the observed beneficial effect of the present invention is apparent with a range of additives.
  • Figure 7 illustrates the difference in density of each of the test samples at position 1 through to 14 of one column of test samples similar to that of Figure 2 in relation to hardness for a different overall formulation than that used in Figure 2.
  • the variation of density between the test samples of the EXP block is about the same as that of the REF block, the REF block is somewhat less dense and
  • Figure 8 illustrate a hardness profile for a
  • Gypsum G-75 0 30.00 T;D.I. 80:20 60.8 68.00 68.-00
  • Example 11 is shown a comparison of 3 batches of foam denoted as Batches 1, 2 and 3.
  • Batch 1 corresponds to a standard reference formulation which includes the auxiliary blowing agent but no additive.
  • the auxiliary agent is CFCll which is a chlorofluorohydrocarbon.
  • Batch 2 corresponds to a formulation falling within the scope of the present invention and has an additive material incorporated but no auxiliary blowing agent.
  • Batch 3 contains no additive and no auxiliary agent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé et un traitement améliorés de fabrication de matière alvéolaire, une matière en mousse de polyuréthane et de préférence une matière en mousse souple dans laquelle un additif supplémentaire est incorporé dans le mélange liquide transformable en mousse. L'additif est capable de subir ou d'entrer dans une réaction endothermique, ou est capable de se transformer ou de se décomposer en un ou plusieurs produits gazeux dans une plage présélectionnée de températures. La réaction ou décomposition endothermique ou la production de produit gazeux influe de manière bénéfique sur les propriétés de la matière moussée lors de la formation ou une fois qu'elle est formée. Les propriétés de la matière alvéolaire produite selon le procédé et le traitement améliorés sont plus uniformes, reproductibles et régulables que les propriétés correspondantes de mousses produites par des formulations classiques.
PCT/AU1989/000426 1988-10-07 1989-10-02 Effet de l'emploi de modifiants chimiques dans la polymerisation de mousse de polyurethane WO1990003997A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPJ084888 1988-10-07
AUPJ0848 1988-10-07

Publications (1)

Publication Number Publication Date
WO1990003997A1 true WO1990003997A1 (fr) 1990-04-19

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CA (1) CA2000208A1 (fr)
NZ (1) NZ230878A (fr)
WO (1) WO1990003997A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6777457B2 (en) 1998-12-11 2004-08-17 Woodbridge Foam Corporation Isocyanate-based polymer foam and process for production thereof
US7737192B2 (en) 2004-07-28 2010-06-15 Inoac Corporation Process for producing flexible polyurethane foam
WO2015065935A1 (fr) 2013-10-28 2015-05-07 Royal Adhesives And Sealants, Llc Utilisation de tamis moléculaires pour expanser des mousses à composant unique lors d'une exposition à l'humidité

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3132171A (en) * 1970-07-31 1973-01-18 Fisons Limited Foamable thermoplastic compositions
US3753933A (en) * 1972-04-24 1973-08-21 Dow Chemical Co Polyurethane foams from solid foaming agents
US4028289A (en) * 1976-10-05 1977-06-07 Vast Products Inc. Foamed polyester resin
AU1357176A (en) * 1975-06-04 1977-11-10 Bayer Ag Process for production of polyurethane foams
AU7103781A (en) * 1981-05-26 1981-12-03 Sekisui Kagaku Kogyo Kabushiki Kaisha Production of polyethylene foam
JPS572340A (en) * 1980-06-06 1982-01-07 Asahi Glass Co Ltd Semirigid polyurethane foam for absorbing energy
SU897789A1 (ru) * 1980-04-17 1982-01-15 Всесоюзный Научно-Исследовательский И Проектно-Конструкторский Институт Полимерных Строительных Материалов Порообразующа смесь
DE3704802A1 (de) * 1987-02-16 1987-10-08 Horst Ing Grad Kaiser Verfahren zur veraenderung der mechanischen eigenschaften von polyurethan-schaumstoffen
EP0319866A2 (fr) * 1987-12-11 1989-06-14 Bayer Ag Procédé pour la préparation de pièces moulées de mousse de polyuréthane

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3132171A (en) * 1970-07-31 1973-01-18 Fisons Limited Foamable thermoplastic compositions
US3753933A (en) * 1972-04-24 1973-08-21 Dow Chemical Co Polyurethane foams from solid foaming agents
AU1357176A (en) * 1975-06-04 1977-11-10 Bayer Ag Process for production of polyurethane foams
US4028289A (en) * 1976-10-05 1977-06-07 Vast Products Inc. Foamed polyester resin
SU897789A1 (ru) * 1980-04-17 1982-01-15 Всесоюзный Научно-Исследовательский И Проектно-Конструкторский Институт Полимерных Строительных Материалов Порообразующа смесь
JPS572340A (en) * 1980-06-06 1982-01-07 Asahi Glass Co Ltd Semirigid polyurethane foam for absorbing energy
AU7103781A (en) * 1981-05-26 1981-12-03 Sekisui Kagaku Kogyo Kabushiki Kaisha Production of polyethylene foam
DE3704802A1 (de) * 1987-02-16 1987-10-08 Horst Ing Grad Kaiser Verfahren zur veraenderung der mechanischen eigenschaften von polyurethan-schaumstoffen
EP0319866A2 (fr) * 1987-12-11 1989-06-14 Bayer Ag Procédé pour la préparation de pièces moulées de mousse de polyuréthane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT ACCESSION NO. 99150 E/46, Class A60 E12; & SU,A,897789 (POLYMER CONS MAT), 18 January 1982 (18.01.82). *
PATENT ABSTRACTS OF JAPAN, C98, page 151; & JP,A,57 002 340 (ASAHI GLASS K.K.), 7 January 1982 (07.01.82). *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6777457B2 (en) 1998-12-11 2004-08-17 Woodbridge Foam Corporation Isocyanate-based polymer foam and process for production thereof
US7737192B2 (en) 2004-07-28 2010-06-15 Inoac Corporation Process for producing flexible polyurethane foam
WO2015065935A1 (fr) 2013-10-28 2015-05-07 Royal Adhesives And Sealants, Llc Utilisation de tamis moléculaires pour expanser des mousses à composant unique lors d'une exposition à l'humidité

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Publication number Publication date
CA2000208A1 (fr) 1990-04-07
NZ230878A (en) 1991-08-27

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