CA1286840C - Process for the production of foams based on aromatic isocyanates using mg(oh) _and the foams produced thereby - Google Patents
Process for the production of foams based on aromatic isocyanates using mg(oh) _and the foams produced therebyInfo
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- CA1286840C CA1286840C CA000546616A CA546616A CA1286840C CA 1286840 C CA1286840 C CA 1286840C CA 000546616 A CA000546616 A CA 000546616A CA 546616 A CA546616 A CA 546616A CA 1286840 C CA1286840 C CA 1286840C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A PROCESS FOR THE PRODUCTION OF FOAMS
BASED ON AROMATIC ISOCYANATES USING
MG(OH)2AND THE FOAMS PRODUCED THEREBY
ABSTRACT OF THE DISCLOSURE
Combustion modified foams are produced by reacting an organic aromatic polyisocyanate with an isocyanate reactive compound in the presence of a blowing agent and Mg(OH)2. The Mg(OH)2 is generally used in a quantity of from 4-100 parts by weight based on the foam taken as 100 parts by weight. Mg(OH)2 having a particle size of from 0.5-50 m is preferably used.
The foams produced by the process are particularly useful in construction applications.
BASED ON AROMATIC ISOCYANATES USING
MG(OH)2AND THE FOAMS PRODUCED THEREBY
ABSTRACT OF THE DISCLOSURE
Combustion modified foams are produced by reacting an organic aromatic polyisocyanate with an isocyanate reactive compound in the presence of a blowing agent and Mg(OH)2. The Mg(OH)2 is generally used in a quantity of from 4-100 parts by weight based on the foam taken as 100 parts by weight. Mg(OH)2 having a particle size of from 0.5-50 m is preferably used.
The foams produced by the process are particularly useful in construction applications.
Description
t~
Mo2957 LeA 24,794 A PROCESS FOR THE PRODUCTION OF FOAMS
BASED ON AROMATIC ISOCYANATES USING
MG(OH)2 AND THE FOAMS PRODUCED THEREBY
BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of combustion-modified foams and to the foams produced by that process.
Foams based on aromatic isocyanates are known to be flammable if they have not been treated in some manner to increase their fire resistance~
Side effects of combustion such as the optical smoke density (hereinafter called simply smoke density) may be more of a hazard in the event of fire than the fire itself. The smoke density is therefore becoming increasingly important in the discussions about the risks during fires involving isocyanate-based foams.
Attempts to protect foams based on aromatic isocyanates against ignition by the addition of metal compounds (such as antimony trioxide) have been made. Heavy metal oxides such as antimony trioxide can reduce the smoke density but often give rise to the risk of an increased heavy metal load.
The use of Mg(OH)2 has already been proposed for various plastics materials, for example polyethylene and polypropylene (see, for example, Plastics Technology, July 1985, 25 page 70 et seq), and for polyurethanes based on hexamethylene diisocyanates (JA 58-225,116, Hitachi Cable), but not for foams based on aromatic isocyanates.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide 30 foams based on aromatic isocyanates which produce a low smoke density in a fire without increasing the heavy metal load. It is also an object of this invention to provide a process for the production of such foams.
s~, ~
These and other objects which will be apparent to those skilled in the art are accomplished by incorporating Mg(OH)2 into a foam forming mixture.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to the use of Mg(OH)2 in the production of foams based on aromatic isocyanates and to the product foams. The Mg(OH)2 does not have the disadvantage of the heavy metal load but has a smoke-suppressing effect in foams based on aromatic isocyanates. It is particularly surprising that this suppression also takes place in foams which contain combustion modifying agents containing phosphorus or nonionic halogen (that is, halogen in a Form other than ionic halide).
In the present invention, it is preferable to use Mg(OH)2 in a quantity of from 4 to 100 parts by weight, preferably in a quantity of from 4 to 50 parts by weight, more preferably in a quantity of from 4 to 10 parts by weight, based on the foam formed from an aromatic isocyanate taken as 100 parts by weight.
It is also preferred to use Mg(OH)2 having a particle size of from 0.5 to 50 ~m7 most preferably from 5 to 40 ~m.
Although it is more preferred to use Mg(OH)2 alone as the smoke-reducing agent, it is also preferred to include Mg(OH)2 during the production of aromatic isocyanate-based foams containing from 2 to 20 parts by weight, based on the foam taken as 100 parts by weight, of nonionic halogen and/or phosphorus compounds.
The production of foams based on isocyanates is known and is described, for example, in German Offenlegungsschriften NOS. 1,694,142, 1,694,215 and 1,720,768 and in Kunststoff-Handbuch, Volume VII, Polyurethane, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966 and in the new edition of this book, edited by G. Oertel, Carl Hanser Verlag, Munich, Vienna 1983. These are predominantly urethane and/or isocyanurate and/or allophanate and/or uretdione and/or urea and/or carbodiimide group-containing foams. In the present .t ,b lZb~tj8~0 invention, Mg(OH)2 is preferably used in the production of polyurethane and polyisocyanurate foams.
Suitable starting components for the production of the foams based on aromatic isocyanates include aromatic polyisocyanates of the type described, for example, by W.
Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, preferably those corresponding to the formula Q(NCO)n in which n represents 2-4 and Q represents an aromatic hydrocarbon radical containing from 6 to 15 (preferably from 6 to 13) carbon atoms, such as 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-diisocyanate and napthylene-1,5-diisocyanate. Triphenyl-methane-4,4',4"-triisocyanate and polyphenylpolymethylene polyisocyanates of the type obtained by aniline formaldehyde condensation and subsequent phosgenation (described, for example, in Ge 874,430 and 848,671) may also be used in the present invention. It is also possible to use the isocyanate-group-containing distillation residues produced dur;ng industrial isocyanate production, optionally dissolved in one or more of the above-mentioned polyisocyanates. It is also possible to use any mixtures of the above-mentioned polyisocyanates.
The commercially available aromatic polyisocyanates such as 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates of the type produced by aniline formaldehyde condensation and subsequent phosgenation ("crude MDI"), and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates") derived from 2,4- and/or Mo2957 ~ 34~
Mo2957 LeA 24,794 A PROCESS FOR THE PRODUCTION OF FOAMS
BASED ON AROMATIC ISOCYANATES USING
MG(OH)2 AND THE FOAMS PRODUCED THEREBY
BACKGROUND OF THE INVENTION
The present invention relates to a process for the production of combustion-modified foams and to the foams produced by that process.
Foams based on aromatic isocyanates are known to be flammable if they have not been treated in some manner to increase their fire resistance~
Side effects of combustion such as the optical smoke density (hereinafter called simply smoke density) may be more of a hazard in the event of fire than the fire itself. The smoke density is therefore becoming increasingly important in the discussions about the risks during fires involving isocyanate-based foams.
Attempts to protect foams based on aromatic isocyanates against ignition by the addition of metal compounds (such as antimony trioxide) have been made. Heavy metal oxides such as antimony trioxide can reduce the smoke density but often give rise to the risk of an increased heavy metal load.
The use of Mg(OH)2 has already been proposed for various plastics materials, for example polyethylene and polypropylene (see, for example, Plastics Technology, July 1985, 25 page 70 et seq), and for polyurethanes based on hexamethylene diisocyanates (JA 58-225,116, Hitachi Cable), but not for foams based on aromatic isocyanates.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide 30 foams based on aromatic isocyanates which produce a low smoke density in a fire without increasing the heavy metal load. It is also an object of this invention to provide a process for the production of such foams.
s~, ~
These and other objects which will be apparent to those skilled in the art are accomplished by incorporating Mg(OH)2 into a foam forming mixture.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to the use of Mg(OH)2 in the production of foams based on aromatic isocyanates and to the product foams. The Mg(OH)2 does not have the disadvantage of the heavy metal load but has a smoke-suppressing effect in foams based on aromatic isocyanates. It is particularly surprising that this suppression also takes place in foams which contain combustion modifying agents containing phosphorus or nonionic halogen (that is, halogen in a Form other than ionic halide).
In the present invention, it is preferable to use Mg(OH)2 in a quantity of from 4 to 100 parts by weight, preferably in a quantity of from 4 to 50 parts by weight, more preferably in a quantity of from 4 to 10 parts by weight, based on the foam formed from an aromatic isocyanate taken as 100 parts by weight.
It is also preferred to use Mg(OH)2 having a particle size of from 0.5 to 50 ~m7 most preferably from 5 to 40 ~m.
Although it is more preferred to use Mg(OH)2 alone as the smoke-reducing agent, it is also preferred to include Mg(OH)2 during the production of aromatic isocyanate-based foams containing from 2 to 20 parts by weight, based on the foam taken as 100 parts by weight, of nonionic halogen and/or phosphorus compounds.
The production of foams based on isocyanates is known and is described, for example, in German Offenlegungsschriften NOS. 1,694,142, 1,694,215 and 1,720,768 and in Kunststoff-Handbuch, Volume VII, Polyurethane, edited by Vieweg and Hochtlen, Carl Hanser Verlag, Munich 1966 and in the new edition of this book, edited by G. Oertel, Carl Hanser Verlag, Munich, Vienna 1983. These are predominantly urethane and/or isocyanurate and/or allophanate and/or uretdione and/or urea and/or carbodiimide group-containing foams. In the present .t ,b lZb~tj8~0 invention, Mg(OH)2 is preferably used in the production of polyurethane and polyisocyanurate foams.
Suitable starting components for the production of the foams based on aromatic isocyanates include aromatic polyisocyanates of the type described, for example, by W.
Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, preferably those corresponding to the formula Q(NCO)n in which n represents 2-4 and Q represents an aromatic hydrocarbon radical containing from 6 to 15 (preferably from 6 to 13) carbon atoms, such as 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and/or -4,4'-diisocyanate and napthylene-1,5-diisocyanate. Triphenyl-methane-4,4',4"-triisocyanate and polyphenylpolymethylene polyisocyanates of the type obtained by aniline formaldehyde condensation and subsequent phosgenation (described, for example, in Ge 874,430 and 848,671) may also be used in the present invention. It is also possible to use the isocyanate-group-containing distillation residues produced dur;ng industrial isocyanate production, optionally dissolved in one or more of the above-mentioned polyisocyanates. It is also possible to use any mixtures of the above-mentioned polyisocyanates.
The commercially available aromatic polyisocyanates such as 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates of the type produced by aniline formaldehyde condensation and subsequent phosgenation ("crude MDI"), and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates") derived from 2,4- and/or Mo2957 ~ 34~
2,6-tolylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl-methane diisocyanate are particularly preferred.
Starting materials which are reactive towards isocyanates that may be used to produce foams in accordance with 5 the present invention include compounds containing at least two hydrogen atoms and which generally have a molecular weight of from 400 to 10,000. These include amino-group-, thiol-group-, carboxyl-group-, and preferably hydroxyl-group-containing compounds, in particular compounds containing from 2 to 8 o hydroxyl groups, specifically those having a molecular weight of from 1000 to 5000, preferably from 800 to 3000. For example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides containing at least two, generally from 2 to 8, but preferably from 2 to 4, hydroxyl 15 groups of the type known to be useful in the production of homogeneous and cellular polyurethanes. Such hydroxyl-group-containing materials are described in detail, for example, in DE-OS 3,430,285, on pages 10 to 18. Mixtures of isocyanate reactive compounds may also be used.
Starting materials which may optionally be used to produce foams in accordance with the present invention include compounds containing at least two hydrogen atoms which are reactive towards isocyanates and have a molecular weight of from 32 to 399. These include compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups which serve as chain extenders or crosslinking agents.
These compounds generally contain from 2 to 8, preferably from 2 to 4, hydrogen atoms capable of reacting with isocyanates.
Mixtures of various compounds containing at least two hydrogen atoms capable of reacting towards isocyanates and having a molecular weight of from 32 to 399 can be used. Examples of such compounds are described in detail, for example, in DE-OS
Starting materials which are reactive towards isocyanates that may be used to produce foams in accordance with 5 the present invention include compounds containing at least two hydrogen atoms and which generally have a molecular weight of from 400 to 10,000. These include amino-group-, thiol-group-, carboxyl-group-, and preferably hydroxyl-group-containing compounds, in particular compounds containing from 2 to 8 o hydroxyl groups, specifically those having a molecular weight of from 1000 to 5000, preferably from 800 to 3000. For example, polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides containing at least two, generally from 2 to 8, but preferably from 2 to 4, hydroxyl 15 groups of the type known to be useful in the production of homogeneous and cellular polyurethanes. Such hydroxyl-group-containing materials are described in detail, for example, in DE-OS 3,430,285, on pages 10 to 18. Mixtures of isocyanate reactive compounds may also be used.
Starting materials which may optionally be used to produce foams in accordance with the present invention include compounds containing at least two hydrogen atoms which are reactive towards isocyanates and have a molecular weight of from 32 to 399. These include compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups which serve as chain extenders or crosslinking agents.
These compounds generally contain from 2 to 8, preferably from 2 to 4, hydrogen atoms capable of reacting with isocyanates.
Mixtures of various compounds containing at least two hydrogen atoms capable of reacting towards isocyanates and having a molecular weight of from 32 to 399 can be used. Examples of such compounds are described in detail, for example, in DE-OS
3,430,285, on pages 19 to 23.
Mo2957 :, 1 2~36 ~3 ~
Suitable blowing agents for producing foams in accordance with the present invent;on include water and/or readily volatile inorganic or organic substances. Appropriate organic blowing agents include acetone, ethylacetate, and halogen-substituted alkanes such as monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane. Suitable inorganic blowing agents include air, C02, and N20. A blowing action can also be achieved by addition of compounds which decompose at temperatures above room temperature with elimination of gases, such as nitrogen. Such compounds include, for example, azo compounds such as azodicarbonamide and azo;sobutyr;c acid nitrile. Further examples of blowing agents and details about the use of blowing agents are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 108 and 109, 453-455 and 507 to 510.
Substances which may optionally be used as auxiliaries and additives in the production of foams include catalysts, surface acti~e additives, reaction retarders, cell regulators, pigments, fillers, and other anxil;aries and additives known in the art.
Catalysts of the known type, for example, tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethyl-ethylene diamine, pentamethyl-diethylene triamine and higher homologs (DE-OS
2,624,527 and 2,624,528), 1,4-d;azabicyclo[2.2.2]octane, N-methyl-N'-dimethylaminoethylpiperazine, bis(dimethylam;no-alkyl)piperaz;nes, DE-OS 2,636,787), N,N-dimethylbenzylam;ne, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-2-phenylethylamine, 1,2-dimethyl;m;dazole, 2-methyl;midazole, monocyclic and bicyclic amidines (DE-OS 1,720,633), bis(dialkylamino)alkyl ether (US
Patent 3,330,782, DE-AS 030,558, DE-OS 17804,361 and 2,618,280) and amide group- (preferably formamide group-) containing Mo2957 r~, ~ 2~ 8 ~
tertiary amines according to DE-OS 2,~23,633 and 2,732,292) may be used. Known Mannich bases of secondary amines such as dimethylamine, aldehydes, preferably formaldehyde, ketones such as acetone, and phenols may also be used as catalysts. Tertiary amines containing hydrogen atoms which are active towards isocyanate groups as catalysts include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanol-amine, N,N-dimethylethanolamine, the reaction products thereof with alkylene oxides such as propylene oxide and/or ethylene ox;de, as well as secondary-tertiary amines disclosed in DE-OS
2,732,292.
Suitable catalysts also include silaamines with carbon-silicon bonds of the type described, for example, in DE-PS 1,229,290 (corresponding to US Patent 3,620,984).
2,2,4-Trimethyl-2-silamorpholine and 1,3-diethylaminoethyl-tetramethyl-disiloxane are specific examples.
Nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate, and alkali alcoholates such as sodium methylate may also be used as catalysts.
Hexahydrotriazines (DE-OS 1,769,043), as well as amide group-(preferably formamide group-) containing tertiary amines according to DE-OS 2,523,633 and 2,732,292 can also be used as catalysts.
Organic metal compounds, ;n part;cular organ;c t;n compounds may also be used in accordance with the present invent;on as catalysts. Examples of organ;c t;n compounds include sulfur-containing compounds such as d;-n-octyl-t;n mercapt;de (DE-AS 1,769,367; US Patent 3,645,927), preferably t;n(II) salts of carboxylic ac;ds, such as t;n(II) acetate, tin(II) octoate, tin(II) ethylhexoate and tin(II) laurate, and t;n(IV) compounds such as d;butyl t;n dilaurate.
Ali of the above-ment;oned catalysts may also be used as m;xtures.
Mo2957 .
.
lZ~;840 Further examples of catalysts and details about the mode of operation of the catalysts are disclosed in Kunststoff-Handbuch, Volume VII7 edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 96 to 102.
If a catalyst is used, it is generally used in a quantity of between about 0.001 and 10% by weight, based on the quantity of aromatic polyisocyanate.
Surface-active additives such as emulsifiers and foam stabilizers may also be included in foam forming mixtures.
o Suitable emulsifiers include the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine and stearic acid d;ethanolamine. Alkali or ammonium salts of sulfonic acids such as dodecylbenzol sulfonic acid, dinaphthylmethane disulfonic acid (e.g., ricinoleic acid) and polymeric fatty acids may also be used as surface-active additives.
Su;table foam stabilizers include polyether siloxanes, particularly water-soluble polyether siloxanes. These compounds are generally made up in such a way that a copolymer of ethylene oxide and propylene oxide is bound to a polydimethyl siloxane radical. Foam stabilizers of this type are described, for example, in U.S. Patents 2,834,748, 2,917,480 and 3,629,308.
Polysiloxane polyoxyalkylene copolymers which are branched via allophanate groups (disclosed in DE-OS 2,558,523) are of particular ;nterest in many cases.
Reaction retarders such as acid compounds (e.g.
hydrochloric acid and organic acid halides); known cell regulators such as paraffins, fatty alcohols and dimethyl-polysiloxanes; pigments; dyes; stabilizers against ageing and weathering effects; plasticizers; fungistatically and bacteriostatically acting substances; and fillers such as barium sulphate, diatomaceous earth, carbon black and whiting may also be included in the foam forming components used to produce foams in accordance with the present invention.
Mo2957 ''~.-68-~0 Further examples of surface-active additives, foam stabilizers, cell regulators, reaction retarders, plasticizers, dyes, fillers and fungistatically and bacteriostatically active substances which may optionally be used according to the invention as well as details about the method of use and mode of operation of these additives are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 103 to 113.
Any of various known combustion modifying agents containing phosphorus and/or halogen in a form other than ionic halide are useful in the process of this invention. Suitable combustion modifying agents of this type include trischloroethyl phosphate, dimethyl methanephosphonate, tricresyl phosphate, ammonium phosphate, and ammonium polyphosphate.
In the process of the present invention, the reaction components may be reacted by the known single stage process, the prepolymer process or the semi-prepolymer process. Generally the reactants are used in quantities such that the NC0 Index is from 50 to 300, preferably from 95 to 250. Examples of appropriate apparatus are described, for example, in U.S. Patent 2,764,565. Details about processing devices which may be used in the practice of the present invention are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 121 to 205.
Foam production may take place in closed molds. In this case, the reaction mixture is introduced into a mold.
Suitable mold materials include metals (for example, aluminum) and plastics (for example, epoxide resins). The reaction mixture foams in the mold and forms the shaped article. Foaming in the mold can be carried out in such a way that the molded product has a cellular structure on its surface. Foaming may also be carried out in such a way that the molded product has a dense skin and a cellular core. It is also possible to mold in such a way that sufficient reaction mixture is introduced into Mo2957 ~Z~;8 ~0 g the mold for the foam formed to just fill the mold. It is also possible to introduce more foamable reaction mixture into the mold than is required to fill the mold cavity with foam. In the latter case, "overcharging" takes place. Such a mode of operation is disclosed, for example, in U.S. Patents 3,178,490 and 3,182,104.
When carrying out foaming in a mold, known "external release agents" such as silicon oils are often used. However, so-called "internal release agents" may also be used, optionally o mixed with external release agents, of the type described for example, in DE-OS 2,121,670 and 2,307,587.
Foams can also be produced by block foaming or by the known laminator process.
The foams obtainable by the invention may be used as insulating boards such as roof insulation.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
The invention is described in more detail in the following Examples and Comparison Examples.
Examples B and F (according to the invention) have lower smoke densities than Comparison Examples A and E.
Comparison Example C shows that the use of phosphorus and nonionic halogen leads to an increase in the smoke density relative to Comparison Example A. However, the smoke density is also reduced relative to Comparison Example C by the use of Mg(OH)2, as shown by Example D (according to the invention).
As shown in Examples G and H in comparison with Example B, the average particle size of the Mg(OH)2 has a considerable influence on smoke suppression. Mg(OH)2 is most preferably used in particle sizes of from 25 to 40 ~m.
The smoke density is examined by the testing method described in ASTM-D-2843-70. The data show the "smoke density ratings" determined by this method.
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Mo2957 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such deta;l is solely for that purpose and that variations can be made therein by those skilled ;n the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
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Suitable blowing agents for producing foams in accordance with the present invent;on include water and/or readily volatile inorganic or organic substances. Appropriate organic blowing agents include acetone, ethylacetate, and halogen-substituted alkanes such as monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane. Suitable inorganic blowing agents include air, C02, and N20. A blowing action can also be achieved by addition of compounds which decompose at temperatures above room temperature with elimination of gases, such as nitrogen. Such compounds include, for example, azo compounds such as azodicarbonamide and azo;sobutyr;c acid nitrile. Further examples of blowing agents and details about the use of blowing agents are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 108 and 109, 453-455 and 507 to 510.
Substances which may optionally be used as auxiliaries and additives in the production of foams include catalysts, surface acti~e additives, reaction retarders, cell regulators, pigments, fillers, and other anxil;aries and additives known in the art.
Catalysts of the known type, for example, tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethyl-ethylene diamine, pentamethyl-diethylene triamine and higher homologs (DE-OS
2,624,527 and 2,624,528), 1,4-d;azabicyclo[2.2.2]octane, N-methyl-N'-dimethylaminoethylpiperazine, bis(dimethylam;no-alkyl)piperaz;nes, DE-OS 2,636,787), N,N-dimethylbenzylam;ne, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-2-phenylethylamine, 1,2-dimethyl;m;dazole, 2-methyl;midazole, monocyclic and bicyclic amidines (DE-OS 1,720,633), bis(dialkylamino)alkyl ether (US
Patent 3,330,782, DE-AS 030,558, DE-OS 17804,361 and 2,618,280) and amide group- (preferably formamide group-) containing Mo2957 r~, ~ 2~ 8 ~
tertiary amines according to DE-OS 2,~23,633 and 2,732,292) may be used. Known Mannich bases of secondary amines such as dimethylamine, aldehydes, preferably formaldehyde, ketones such as acetone, and phenols may also be used as catalysts. Tertiary amines containing hydrogen atoms which are active towards isocyanate groups as catalysts include triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanol-amine, N,N-dimethylethanolamine, the reaction products thereof with alkylene oxides such as propylene oxide and/or ethylene ox;de, as well as secondary-tertiary amines disclosed in DE-OS
2,732,292.
Suitable catalysts also include silaamines with carbon-silicon bonds of the type described, for example, in DE-PS 1,229,290 (corresponding to US Patent 3,620,984).
2,2,4-Trimethyl-2-silamorpholine and 1,3-diethylaminoethyl-tetramethyl-disiloxane are specific examples.
Nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate, and alkali alcoholates such as sodium methylate may also be used as catalysts.
Hexahydrotriazines (DE-OS 1,769,043), as well as amide group-(preferably formamide group-) containing tertiary amines according to DE-OS 2,523,633 and 2,732,292 can also be used as catalysts.
Organic metal compounds, ;n part;cular organ;c t;n compounds may also be used in accordance with the present invent;on as catalysts. Examples of organ;c t;n compounds include sulfur-containing compounds such as d;-n-octyl-t;n mercapt;de (DE-AS 1,769,367; US Patent 3,645,927), preferably t;n(II) salts of carboxylic ac;ds, such as t;n(II) acetate, tin(II) octoate, tin(II) ethylhexoate and tin(II) laurate, and t;n(IV) compounds such as d;butyl t;n dilaurate.
Ali of the above-ment;oned catalysts may also be used as m;xtures.
Mo2957 .
.
lZ~;840 Further examples of catalysts and details about the mode of operation of the catalysts are disclosed in Kunststoff-Handbuch, Volume VII7 edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 96 to 102.
If a catalyst is used, it is generally used in a quantity of between about 0.001 and 10% by weight, based on the quantity of aromatic polyisocyanate.
Surface-active additives such as emulsifiers and foam stabilizers may also be included in foam forming mixtures.
o Suitable emulsifiers include the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine and stearic acid d;ethanolamine. Alkali or ammonium salts of sulfonic acids such as dodecylbenzol sulfonic acid, dinaphthylmethane disulfonic acid (e.g., ricinoleic acid) and polymeric fatty acids may also be used as surface-active additives.
Su;table foam stabilizers include polyether siloxanes, particularly water-soluble polyether siloxanes. These compounds are generally made up in such a way that a copolymer of ethylene oxide and propylene oxide is bound to a polydimethyl siloxane radical. Foam stabilizers of this type are described, for example, in U.S. Patents 2,834,748, 2,917,480 and 3,629,308.
Polysiloxane polyoxyalkylene copolymers which are branched via allophanate groups (disclosed in DE-OS 2,558,523) are of particular ;nterest in many cases.
Reaction retarders such as acid compounds (e.g.
hydrochloric acid and organic acid halides); known cell regulators such as paraffins, fatty alcohols and dimethyl-polysiloxanes; pigments; dyes; stabilizers against ageing and weathering effects; plasticizers; fungistatically and bacteriostatically acting substances; and fillers such as barium sulphate, diatomaceous earth, carbon black and whiting may also be included in the foam forming components used to produce foams in accordance with the present invention.
Mo2957 ''~.-68-~0 Further examples of surface-active additives, foam stabilizers, cell regulators, reaction retarders, plasticizers, dyes, fillers and fungistatically and bacteriostatically active substances which may optionally be used according to the invention as well as details about the method of use and mode of operation of these additives are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 103 to 113.
Any of various known combustion modifying agents containing phosphorus and/or halogen in a form other than ionic halide are useful in the process of this invention. Suitable combustion modifying agents of this type include trischloroethyl phosphate, dimethyl methanephosphonate, tricresyl phosphate, ammonium phosphate, and ammonium polyphosphate.
In the process of the present invention, the reaction components may be reacted by the known single stage process, the prepolymer process or the semi-prepolymer process. Generally the reactants are used in quantities such that the NC0 Index is from 50 to 300, preferably from 95 to 250. Examples of appropriate apparatus are described, for example, in U.S. Patent 2,764,565. Details about processing devices which may be used in the practice of the present invention are disclosed in Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 121 to 205.
Foam production may take place in closed molds. In this case, the reaction mixture is introduced into a mold.
Suitable mold materials include metals (for example, aluminum) and plastics (for example, epoxide resins). The reaction mixture foams in the mold and forms the shaped article. Foaming in the mold can be carried out in such a way that the molded product has a cellular structure on its surface. Foaming may also be carried out in such a way that the molded product has a dense skin and a cellular core. It is also possible to mold in such a way that sufficient reaction mixture is introduced into Mo2957 ~Z~;8 ~0 g the mold for the foam formed to just fill the mold. It is also possible to introduce more foamable reaction mixture into the mold than is required to fill the mold cavity with foam. In the latter case, "overcharging" takes place. Such a mode of operation is disclosed, for example, in U.S. Patents 3,178,490 and 3,182,104.
When carrying out foaming in a mold, known "external release agents" such as silicon oils are often used. However, so-called "internal release agents" may also be used, optionally o mixed with external release agents, of the type described for example, in DE-OS 2,121,670 and 2,307,587.
Foams can also be produced by block foaming or by the known laminator process.
The foams obtainable by the invention may be used as insulating boards such as roof insulation.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
The invention is described in more detail in the following Examples and Comparison Examples.
Examples B and F (according to the invention) have lower smoke densities than Comparison Examples A and E.
Comparison Example C shows that the use of phosphorus and nonionic halogen leads to an increase in the smoke density relative to Comparison Example A. However, the smoke density is also reduced relative to Comparison Example C by the use of Mg(OH)2, as shown by Example D (according to the invention).
As shown in Examples G and H in comparison with Example B, the average particle size of the Mg(OH)2 has a considerable influence on smoke suppression. Mg(OH)2 is most preferably used in particle sizes of from 25 to 40 ~m.
The smoke density is examined by the testing method described in ASTM-D-2843-70. The data show the "smoke density ratings" determined by this method.
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Mo2957 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such deta;l is solely for that purpose and that variations can be made therein by those skilled ;n the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo2957
Claims (24)
1. A method for reducing smoke in a foam exposed to fire, wherein said foam is prepared by reacting a mixture of (a) an organic aromatic polyisocyanate and (b) an isocyanate-reactive compound in the presence of (c) a blowing agent, comprising adding to the reaction mixture a smoke-reducing agent consisting of Mg(OH)2 alone or in the presence of a combustion modifying agent containing phosphorus or nonionic halogen.
2. The method of Claim 1 wherein the smoke-reducing agent is Mg(OH)2 alone.
3. The method of Claim 2 wherein the Mg(OH)2 is included in a quantity of from 4 to 100 parts by weight based on the foam taken as 100 parts by weight.
4. The method of Claim 2 wherein the Mg(OH)2 is included in a quantity of from 4 to 50 parts by weight based on the foam taken as 100 parts by weight.
5. The method of Claim 2 wherein the Mg(OH)2 is included in a quantity of from 4 to 10 parts by weight based on the foam taken as 100 parts by weight.
6. The method of Claim 2 wherein the Mg(OH)2 has a particle size of from 0.5 to 50 µm.
7. The method of Claim 2 wherein the Mg(OH)2 has a particle size of from 5 to 40 µm.
8. The method of Claim 3 wherein the Mg(OH)2 has a particle size of from 0.5 to 50 µm.
9. The method of Claim 3 wherein the Mg(OH)2 has a particle size of from 5 to 40 µm.
10. The method of Claim 2 wherein the isocyanate reactive compound is a polyhydroxyl compound.
11. The method of Claim 2 for reducing smoke in a foam exposed to fire, wherein said foam is prepared by reacting a mixture of (a) an organic aromatic polyisocyanate and Mo2957 (b) a polyhydroxyl compound in the presence of (c) a blowing agent, comprising adding to the mixture a smoke-reducing agent consisting of Mg(OH)2 having a particle size of from 5 to 40 µm in a quantity of from 4 to 10 parts by weight based on the foam taken as 100 parts by weight.
12. The method of Claim 1 wherein the smoke-reducing agent is Mg(OH)2 in the presence of 2-20 parts by weight, based on the foam taken as 100 parts by weight, of a combustion modifying agent containing phosphorus or nonionic halogen.
13. The method of Claim 12 wherein the Mg(OH)2 is included in a quantity of from 4 to 100 parts by weight based on the foam taken as 100 parts by weight.
14. The method of Claim 12 wherein the Mg(OH)2 is included in a quantity of from 4 to 50 parts by weight based on the foam taken as 100 parts by weight.
15. The method of Claim 12 wherein the Mg(OH)2 is included in a quantity of from 4 to 10 parts by weight based on the foam taken as 100 parts by weight.
16. The method of Claim 12 wherein the Mg(OH)2 has a particle size of from 0.5 to 50 µm.
17. The method of Claim 12 wherein the Mg(OH)2 has a particle size of from 5 to 40 µm.
18. The method of Claim 13 wherein the Mg(OH)2 has a particle size of from 0.5 to 50 µm.
19. The method of Claim 13 wherein the Mg(OH)2 has a particle size of from 5 to 40 µm.
20. The method of Claim 12 wherein the isocyanate reactive compound is a polyhydroxyl compound.
21. The method of Claim 12 for reducing smoke gas in a foam exposed to fire, wherein said foam is prepared by reacting a mixture of (a) an organic aromatic polyisocyanate and (b) a polyhydroxyl compound in the presence of Mo2957 (c) a blowing agent, comprising adding to the mixture a smoke-reducing agent consisting of Mg(OH)2 having a particle size of from 5 to 40 µm in a quantity of from 4 to 100 parts by weight based on the foam taken as 100 parts by weight, in the presence of 2-20 parts by weight, based on the foam taken as 100 parts by weight, of a combustion modifying agent containing phosphorus or nonionic halogen.
22. A foam produced by the method of Claim 1.
23. A foam produced by the method of Claim 11.
24. A foam produced by the method of Claim 21.
Mo2957
Mo2957
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3632915.0 | 1986-09-27 | ||
| DE19863632915 DE3632915A1 (en) | 1986-09-27 | 1986-09-27 | USE OF MG (OH) (DOWN ARROW) 2 (DOWN ARROW) IN THE PRODUCTION OF FOAMS BASED ON AROMATIC ISOCYANATES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1286840C true CA1286840C (en) | 1991-07-23 |
Family
ID=6310515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000546616A Expired - Lifetime CA1286840C (en) | 1986-09-27 | 1987-09-10 | Process for the production of foams based on aromatic isocyanates using mg(oh) _and the foams produced thereby |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0265650A3 (en) |
| JP (1) | JPS63117029A (en) |
| CA (1) | CA1286840C (en) |
| DE (1) | DE3632915A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04283052A (en) * | 1990-09-25 | 1992-10-08 | Fmc Corp | Device for handling highly decomposable article |
| WO2023274699A1 (en) | 2021-07-01 | 2023-01-05 | Evonik Operations Gmbh | Production of hard polyurethane or polyisocyanurate foam |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1035927A (en) * | 1962-05-14 | 1966-07-13 | Avco Corp | Solid heat triggered foam compositions |
| US3730400A (en) * | 1972-03-02 | 1973-05-01 | Johnson & Son Inc S C | Pressure packages |
| GB1527668A (en) * | 1975-10-30 | 1978-10-04 | Burns & Russell Co | Smoke and fire resistant compositions |
| US4458036A (en) * | 1983-02-28 | 1984-07-03 | Stauffer Chemical Company | Flexible polyurethane foams containing glycoluril reaction products for a flame and ember drip retardance |
| EP0189098B1 (en) * | 1985-01-19 | 1992-05-06 | Asahi Glass Company Ltd. | Magnesium hydroxide, process for its production and resin composition containing it |
-
1986
- 1986-09-27 DE DE19863632915 patent/DE3632915A1/en not_active Withdrawn
-
1987
- 1987-09-10 CA CA000546616A patent/CA1286840C/en not_active Expired - Lifetime
- 1987-09-16 EP EP87113516A patent/EP0265650A3/en not_active Ceased
- 1987-09-25 JP JP62239139A patent/JPS63117029A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63117029A (en) | 1988-05-21 |
| DE3632915A1 (en) | 1988-03-31 |
| EP0265650A2 (en) | 1988-05-04 |
| EP0265650A3 (en) | 1988-11-30 |
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