CA2119479A1 - Mixtures of polyisocyanates with pentane and/or cyclopentane and process for the production of rigid foams containing urethane and optionally isocyanurate groups - Google Patents
Mixtures of polyisocyanates with pentane and/or cyclopentane and process for the production of rigid foams containing urethane and optionally isocyanurate groupsInfo
- Publication number
- CA2119479A1 CA2119479A1 CA002119479A CA2119479A CA2119479A1 CA 2119479 A1 CA2119479 A1 CA 2119479A1 CA 002119479 A CA002119479 A CA 002119479A CA 2119479 A CA2119479 A CA 2119479A CA 2119479 A1 CA2119479 A1 CA 2119479A1
- Authority
- CA
- Canada
- Prior art keywords
- pbw
- pentane
- mixtures
- cyclopentane
- mixture
- 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.)
- Abandoned
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
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2115/00—Oligomerisation
- C08G2115/02—Oligomerisation to isocyanurate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
MIXTURES OF POLYISOCYANATES WITH PENTANE
AND/OR CYCLOPENTANE AND PROCESS FOR THE
PRODUCTION OF RIGID FOAMS CONTAINING
URETHANE AND OPTIONALLY ISOCYANURATE GROUPS
ABSTRACT OF THE DISCLOSURE
Rigid foams containing urethane and optionally isocyanurate groups are prepared by reacting a mixture of a polyisocyanate and a hydrocarbon selected from the group consisting of pentane, cyclopentane, or mixtures thereof with one or more compounds containing at least two isocyanate-reactive hydrogen atoms.
AND/OR CYCLOPENTANE AND PROCESS FOR THE
PRODUCTION OF RIGID FOAMS CONTAINING
URETHANE AND OPTIONALLY ISOCYANURATE GROUPS
ABSTRACT OF THE DISCLOSURE
Rigid foams containing urethane and optionally isocyanurate groups are prepared by reacting a mixture of a polyisocyanate and a hydrocarbon selected from the group consisting of pentane, cyclopentane, or mixtures thereof with one or more compounds containing at least two isocyanate-reactive hydrogen atoms.
Description
~}~ 1 Ji `i '~ é ,13 Mo-4063 LeA 29 670-US
MIXTURES OF POLYISOCYANATES WITH PENTANE -:
AND/O~ CYCLOPENTANE AND PROCESS FOR THE ~ ~:
PRODUCTION OF RIGID FOAMS CONTAINING
URETHANE AND OPTIONALLY ISOCyANURATE GROUPS
BACKGROUND OF THE INVENT!ON
Pentane (n-pentane, i-pentane) and cyclopentane and mixtures thereof have recently acquired particular significance as blowing agents in the production of rigid polyurethane foams. The use of pentane as a blowing agent for the production of rigid polyurethane foams has been known for some time and is described, for example, in U.S. Patent 3,072,582, and in published European Applications 394 769 and 405 439.
In known processes, pentane is either incorporated as a blowing agent in the polyol component during production of the foam, in the same . .~.
way as chlorofluorocarbons ("CFCs"), or is directly introduced into the reaction mixture by means of a suitable mixing unit. One disadvantage of pentane is that it does not normally show sufficient solubility in the polyol component, so that the pentane concentration has to be kept low.
In order to obtain sufficiently low foam densities (which are necessary from an economics viewpoint), a rela!ively large quanti2y of water is added to the polyol component so that carbon dioxide gas ~ormed by reaction of waier with the isocyanate can act as an additional blowing agent. However, the high carbon dioxide content in the cell gas of the foam increases its thermal conductivity and thus reduces its heat insulat-ing effect. In order to limit the water content of the reaction mixture, pentane/polyol emulsions are often prepared with a quantity of pentane 1 which clearly exceeds its solubility in the polyol component. Unfortunate-`, Iy, these emulsions are only stable for a short time so that a considerable loss of pentane is observed during production of the foam.
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MIXTURES OF POLYISOCYANATES WITH PENTANE -:
AND/O~ CYCLOPENTANE AND PROCESS FOR THE ~ ~:
PRODUCTION OF RIGID FOAMS CONTAINING
URETHANE AND OPTIONALLY ISOCyANURATE GROUPS
BACKGROUND OF THE INVENT!ON
Pentane (n-pentane, i-pentane) and cyclopentane and mixtures thereof have recently acquired particular significance as blowing agents in the production of rigid polyurethane foams. The use of pentane as a blowing agent for the production of rigid polyurethane foams has been known for some time and is described, for example, in U.S. Patent 3,072,582, and in published European Applications 394 769 and 405 439.
In known processes, pentane is either incorporated as a blowing agent in the polyol component during production of the foam, in the same . .~.
way as chlorofluorocarbons ("CFCs"), or is directly introduced into the reaction mixture by means of a suitable mixing unit. One disadvantage of pentane is that it does not normally show sufficient solubility in the polyol component, so that the pentane concentration has to be kept low.
In order to obtain sufficiently low foam densities (which are necessary from an economics viewpoint), a rela!ively large quanti2y of water is added to the polyol component so that carbon dioxide gas ~ormed by reaction of waier with the isocyanate can act as an additional blowing agent. However, the high carbon dioxide content in the cell gas of the foam increases its thermal conductivity and thus reduces its heat insulat-ing effect. In order to limit the water content of the reaction mixture, pentane/polyol emulsions are often prepared with a quantity of pentane 1 which clearly exceeds its solubility in the polyol component. Unfortunate-`, Iy, these emulsions are only stable for a short time so that a considerable loss of pentane is observed during production of the foam.
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The problem addressed by the present invention was to provide . rigid polyurethane foams (optionally containing isocyanurate groups) which would show good heat insulation properties using pentane and/or cyclopentane as blowing agent. More particularly, the problem ad-6 dressed by the present invention was to enable pentane and/or cyclopen-tane to be added to the reaction cornponents in dissolved form and in 3 ~ high concentrations so that the concentration of water in the reaction mixture could be reduced for a given foam density and less carbon . dioxide would be used for foaming.
DESCRIPTION OF THE INVENTION
Surprisingly, the above noted problem has been solved by the discovery that up to 30% by weight of pentane and cyclopentane can be dissolved in polyisocyanates. The preferred polyisocyanates are , ~ polymethylene poiyphenyl polyisocyanates ("polymeric MDI") or in 15 urethane group containing polymeric MDI. As is known in the art, .~ polymerlc MDls are mixtures of methylene bis(phenyl isocyanates) and ~; higher functional polymethylene poly(phenyl isocyanates). By ;.$ incorporating pentane and/or cyclopentane in polymeric MDI or in urethane-modified polymeric MDI, little or no additional water is required 3 20 to form carbon dioxide as a co-blowing agent in the production of rigid low-density polyurethane foams because the polyisocyanate takes up a . sufficient quantity of pentane andlor cyclopentane which can be fully utilized to foam the reaction mixture.
i The present invention relates to mixtures of polyisocyanates and ~j~ 25 pentana and/orcyclopentane.
i The present invention also relates to a process for the production .~ of rigid foams containing urethane and optionally isocyanurate groups by ~j reaction of Mo4063 ``,' ' :.
. , , ~
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a) mixtures of polyisocyana~es and pentane and/or cyclopentane with ~ b) compounds containing at least ~wo isocyanate-reactive -!; hydrogen atoms and having molecular weights of 400 to ~: 5 10,000, and c) optionally, compounds containing at least two isocyanate-, . reactive hydrogen atoms and having molecular weights of .
32 to 399, optionally in the presence of d) other blowing agents and auxiliaries and additives known in , - 10 the polyurethane art.
In one preferred embodiment of the invention, the polyisocyanate . ~ used in component a) is a polymeric MDI having a diisocyanate contentj of from 25 to 70% by weight or a urethane-modified polymeric MDI with a diisocyanate content of from 35 to 70% by weight. The preferred component a) contains a hydrocarbon selected from the group consisting of n-pentane, i-pentane, cyclopentane, or mixtures thereof. The most preferred component a) contains from 1 to 30% by weight of the hydrocarbon with the balance being the polyisocyanate. The most preferred reaction mixtures also contain from 0.4 to 4% by weight (and preferably from 0.5 to 3.5% by weight) based upon the weight of component b) of water as co-blowing agent and foam stabilizers, `f ' tlameproofing agents and catalysts.
3 The rigid foam produced by the pr~cess of the invention have the following advantages over foams produced by known methods~
1) low thermal conductivity because the CO2 content in the ,~ cell gas is low, 2) a tough and elastic quality coupled with good adhesion to i ~j surface layermaterials.
Mo4063 .
.i .
DESCRIPTION OF THE INVENTION
Surprisingly, the above noted problem has been solved by the discovery that up to 30% by weight of pentane and cyclopentane can be dissolved in polyisocyanates. The preferred polyisocyanates are , ~ polymethylene poiyphenyl polyisocyanates ("polymeric MDI") or in 15 urethane group containing polymeric MDI. As is known in the art, .~ polymerlc MDls are mixtures of methylene bis(phenyl isocyanates) and ~; higher functional polymethylene poly(phenyl isocyanates). By ;.$ incorporating pentane and/or cyclopentane in polymeric MDI or in urethane-modified polymeric MDI, little or no additional water is required 3 20 to form carbon dioxide as a co-blowing agent in the production of rigid low-density polyurethane foams because the polyisocyanate takes up a . sufficient quantity of pentane andlor cyclopentane which can be fully utilized to foam the reaction mixture.
i The present invention relates to mixtures of polyisocyanates and ~j~ 25 pentana and/orcyclopentane.
i The present invention also relates to a process for the production .~ of rigid foams containing urethane and optionally isocyanurate groups by ~j reaction of Mo4063 ``,' ' :.
. , , ~
. - . ........................... . .
.
~r.,,~
.. .
"b, "~
`~3"`
a) mixtures of polyisocyana~es and pentane and/or cyclopentane with ~ b) compounds containing at least ~wo isocyanate-reactive -!; hydrogen atoms and having molecular weights of 400 to ~: 5 10,000, and c) optionally, compounds containing at least two isocyanate-, . reactive hydrogen atoms and having molecular weights of .
32 to 399, optionally in the presence of d) other blowing agents and auxiliaries and additives known in , - 10 the polyurethane art.
In one preferred embodiment of the invention, the polyisocyanate . ~ used in component a) is a polymeric MDI having a diisocyanate contentj of from 25 to 70% by weight or a urethane-modified polymeric MDI with a diisocyanate content of from 35 to 70% by weight. The preferred component a) contains a hydrocarbon selected from the group consisting of n-pentane, i-pentane, cyclopentane, or mixtures thereof. The most preferred component a) contains from 1 to 30% by weight of the hydrocarbon with the balance being the polyisocyanate. The most preferred reaction mixtures also contain from 0.4 to 4% by weight (and preferably from 0.5 to 3.5% by weight) based upon the weight of component b) of water as co-blowing agent and foam stabilizers, `f ' tlameproofing agents and catalysts.
3 The rigid foam produced by the pr~cess of the invention have the following advantages over foams produced by known methods~
1) low thermal conductivity because the CO2 content in the ,~ cell gas is low, 2) a tough and elastic quality coupled with good adhesion to i ~j surface layermaterials.
Mo4063 .
.i .
The production of foams containing urethane and optionally - isocyanurate groups is known and is described, for example, in German - Patent 1,112,285, in British Patent 1,104,394, in published German Applications 1,595,844 and 1,769,023 and in Kunststoff-Handbuch, Vol.
5 Vll, Polyurethane, edited by Vieweg und Hochtlen, Carl-Hanser-Verlag, Munchen 1966, and in the new edition of this book edited by G. Oertel.
Carl-Hanser-Verlag, MunchenNVien 1983.
Substantially any polyisocyanate can be used for the production of component a). Such isocyanates include aliphatic, cycloaliphatic, :......... 10 araliphatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chernie, 562, pa~es 75 to 136, for example those corresponding to the following formula:
, Q(NC)n .
~ 15 in which n = 2-4, preferably 2 and 3, and Q is an aliphatic hydrocarbon radical containing 2 to 18 (and preferably 6) carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15 (and preferably 5 to 10) carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 (and preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon radical containing 8 to 15 (and preferably 8 to 13) carbon atoms, for example the polyisocyanates desctibed in published German Application 2,832,253, pages 10-11. The aromatic isocyanates are - .:
, preferred. In general, it is particularly preferred to use the commercially available polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate ~';! 25 and mixtures of these isomers ("TDI"); polyphenyl polymethylene poly-i isocyanates obtained by phosgenation of aniline-formaldehyde condensates ("crude MDI"); and polyisocyanates containing carbodiimide ;j' Mo4063 ~,l i l .~ .
'~ : ' ., '~a groups, urethane groups, allophanate groups, isocyanurate groups, urea , groups or biuret groups (~modified polyisocyanates"), more particularly, modified polyisocyanates derived from 2,4- and/or 2,6-tolylene diisocyanate and from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
~ 5 As already mentioned, a polymeric MDI containing 25 to 70% by weight ~ of the diisocyanate or a urethane-modified polyrneric MDI containing 35 to 70% by weight of the diisocyanate are particularly preferred for the ~-; ' purposes of the present invention. As is known in the art, the urethane-~: modified potymeric MDls are produced by reacting an excess of c, 10 polymeric MDI with an isocyanate-reactive component (preferably a polyol).
Pentane (n- and/or i-pentane) and/or cyclopentane is added to and mixed with the polyisocyanates.
,~( Component b) consists of one or more from compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular . weights of from 400 to 10,000. In addition to aminofunctional, thiofunctional or carboxyfunctional compounds, the compounds in ~, question are preferably hydroxyfunctional compounds, more preferably , .j compounds containing 2 to 8 hydroxyl groups. More preferred are :; 20 hydroxyfunctional compoundswith molecularweights of 1,000to 6,000 ~,~ (most preferably 2,000 to 6,000). The preferred compounds include, for example polyethers and polyesters containing at least 2, generally 2 to 8 and preferably 2 to 6 hydroxyl groups, and also polycarbonates and ~` polyester amides of the type known in the art for the production of ` 25 homogeneous and cellular polyurethanes and described, for example, in published German Application 2,832,253, pages 11-18.
Optional component c) is selected from compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular weights in the range from 32 to 399. In this case, too, the compounds in Mo4063 ., ;;, ., :
.., ::.; ................................ .
'' ~, ' .' ' '' ' .t~ ~i /J ~ ~3 question are hydroxyfunctional and/or aminofunctional and/or thiofunctional and/or carboxyfunctional compounds. Preferred are ; hydroxyfunctional and/or aminofunctional compounds which are known in the art for use as chain-extending agents or crosslinking agents. These 5 compounds generally contain 2 to 8 and preferably 2 to 4 isocyanate-reactive hydrogen atoms. Examples of such compounds can be found in published German Application 2,832,253, pages 19 to 20.
Auxiliaries and additives are optionally used in the pro~uction of . the foams of the present invention. These include i) other readily volatile 10 organic substances and/or water as additional blowing agents, water preferably being used in a quantity of 0.5 to 3.5% by weight, based on comporlent b), ii) catalysts of the type known from polyurethane chemistry in quantities of up to 10% by weight, based on component b), iii) surface-active additives, such as emulsifiers and foam stabilizers, iv) 15 other additives such as flameproofing agents, for example phosphorus-' containing, halogen-free flameproofing agents, such as triethyl phosphate, diphenylcresyl phosphate, red phosphorus; reaction retarders, ; for example substances showing an acidic reaction, such as hydrochloric acid or organic acid halides; known cell regulators, such as paraffins or .
20 fatty alcohols or dimethyl polysiloxanes; pigments or dyes; stabilizers against the effects of ageing and weathering; plasticizers; fungistatic and I bacteriostatic agents; and fillers, such as barium sulfate, kieselguhr, carbon black or whiting.
These optional auxiliaries and additives are known and described, 25 for example, in published German Application 2,732,292, pages 21 to 24.
~; Further examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flameproofing agents, plasticizers, dyes, fungistatic and bacteriostatic agents which may option-ally be used in accordance with the invention and information on the use Mo4063 ~- , . '' : ': , .;,~,.~ ~ , ,~,,,:, , . . ,~
. .~.
Carl-Hanser-Verlag, MunchenNVien 1983.
Substantially any polyisocyanate can be used for the production of component a). Such isocyanates include aliphatic, cycloaliphatic, :......... 10 araliphatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chernie, 562, pa~es 75 to 136, for example those corresponding to the following formula:
, Q(NC)n .
~ 15 in which n = 2-4, preferably 2 and 3, and Q is an aliphatic hydrocarbon radical containing 2 to 18 (and preferably 6) carbon atoms, a cycloaliphatic hydrocarbon radical containing 4 to 15 (and preferably 5 to 10) carbon atoms, an aromatic hydrocarbon radical containing 6 to 15 (and preferably 6 to 13) carbon atoms or an araliphatic hydrocarbon radical containing 8 to 15 (and preferably 8 to 13) carbon atoms, for example the polyisocyanates desctibed in published German Application 2,832,253, pages 10-11. The aromatic isocyanates are - .:
, preferred. In general, it is particularly preferred to use the commercially available polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate ~';! 25 and mixtures of these isomers ("TDI"); polyphenyl polymethylene poly-i isocyanates obtained by phosgenation of aniline-formaldehyde condensates ("crude MDI"); and polyisocyanates containing carbodiimide ;j' Mo4063 ~,l i l .~ .
'~ : ' ., '~a groups, urethane groups, allophanate groups, isocyanurate groups, urea , groups or biuret groups (~modified polyisocyanates"), more particularly, modified polyisocyanates derived from 2,4- and/or 2,6-tolylene diisocyanate and from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
~ 5 As already mentioned, a polymeric MDI containing 25 to 70% by weight ~ of the diisocyanate or a urethane-modified polyrneric MDI containing 35 to 70% by weight of the diisocyanate are particularly preferred for the ~-; ' purposes of the present invention. As is known in the art, the urethane-~: modified potymeric MDls are produced by reacting an excess of c, 10 polymeric MDI with an isocyanate-reactive component (preferably a polyol).
Pentane (n- and/or i-pentane) and/or cyclopentane is added to and mixed with the polyisocyanates.
,~( Component b) consists of one or more from compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular . weights of from 400 to 10,000. In addition to aminofunctional, thiofunctional or carboxyfunctional compounds, the compounds in ~, question are preferably hydroxyfunctional compounds, more preferably , .j compounds containing 2 to 8 hydroxyl groups. More preferred are :; 20 hydroxyfunctional compoundswith molecularweights of 1,000to 6,000 ~,~ (most preferably 2,000 to 6,000). The preferred compounds include, for example polyethers and polyesters containing at least 2, generally 2 to 8 and preferably 2 to 6 hydroxyl groups, and also polycarbonates and ~` polyester amides of the type known in the art for the production of ` 25 homogeneous and cellular polyurethanes and described, for example, in published German Application 2,832,253, pages 11-18.
Optional component c) is selected from compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular weights in the range from 32 to 399. In this case, too, the compounds in Mo4063 ., ;;, ., :
.., ::.; ................................ .
'' ~, ' .' ' '' ' .t~ ~i /J ~ ~3 question are hydroxyfunctional and/or aminofunctional and/or thiofunctional and/or carboxyfunctional compounds. Preferred are ; hydroxyfunctional and/or aminofunctional compounds which are known in the art for use as chain-extending agents or crosslinking agents. These 5 compounds generally contain 2 to 8 and preferably 2 to 4 isocyanate-reactive hydrogen atoms. Examples of such compounds can be found in published German Application 2,832,253, pages 19 to 20.
Auxiliaries and additives are optionally used in the pro~uction of . the foams of the present invention. These include i) other readily volatile 10 organic substances and/or water as additional blowing agents, water preferably being used in a quantity of 0.5 to 3.5% by weight, based on comporlent b), ii) catalysts of the type known from polyurethane chemistry in quantities of up to 10% by weight, based on component b), iii) surface-active additives, such as emulsifiers and foam stabilizers, iv) 15 other additives such as flameproofing agents, for example phosphorus-' containing, halogen-free flameproofing agents, such as triethyl phosphate, diphenylcresyl phosphate, red phosphorus; reaction retarders, ; for example substances showing an acidic reaction, such as hydrochloric acid or organic acid halides; known cell regulators, such as paraffins or .
20 fatty alcohols or dimethyl polysiloxanes; pigments or dyes; stabilizers against the effects of ageing and weathering; plasticizers; fungistatic and I bacteriostatic agents; and fillers, such as barium sulfate, kieselguhr, carbon black or whiting.
These optional auxiliaries and additives are known and described, 25 for example, in published German Application 2,732,292, pages 21 to 24.
~; Further examples of surface-active additives and foam stabilizers, cell regulators, reaction retarders, stabilizers, flameproofing agents, plasticizers, dyes, fungistatic and bacteriostatic agents which may option-ally be used in accordance with the invention and information on the use Mo4063 ~- , . '' : ': , .;,~,.~ ~ , ,~,,,:, , . . ,~
. .~.
.
of ~hese addi~ives and their modes of action can be found in Kunststoff-Handbuch, Vol. Vll, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, , Munchen 1966, for example on pages 103 to 113.
' The production of the rigid foams of the present invention iscarried out using techniques known in the art. Thus, the reacticn components may be reacted by the one-shot process, by the prepolymer process or by the semiprepolymer process, often using machines, for example of the type described in U.S. Patent 2,764,566. Particulars of - procesising machines which may also be used in accordance with the present invention can be found in Kunststoff-Handbuch, Vol. Vll, edited by Vieweg and H~chtlen, Carl-Hanser-Verlag, Munchen 1966, for example on pages 121 to 205.
According to the invention, the foam production process is gener-` ally carried out at an index of 90 to 130 and often - for example in the production of foams containing urethane and isocyanurate groups - at an index above 130, for example in the range from 200 to 400.
The foams may be produced by slabstock foaming or by the laminator process. The products obtainable in accordance with the invention are preferably used as heat insulation materials, for example as insulation boards ~or roof insulation and in refrigerators and deep freezers.
The invention is further illustrated but is not intended to be limited ~-j by the following examples in which all parts and percentages are by weight unless othen~vise specified.
EXAMPLES
Example 1 LComparison) The A component was a polyol mixture having an OH number of 400. The A component was prepared by mixing:
Mo4063 : :
.
.1 ': ~ . : '. ; :
. -- 8 --47.85 pbw of a polyether (OH number of 450) prepared by f reaction of a mixture of sugar and glycerol with propylene oxide ~; 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol .
~ ~ and ethylene oxide ~, ., - 38.28 pbw of a polyether ~OH numbef of 380) prepared by !,'`, reaction of trimethyl propan0 with propylene oxide 1.91 pbw of water . 10 1.91 pbw of a commercial foam stabilizer (RS 201, a product of Union Carbide) 0.48 pbw of pentamethyl diethylenetriamine 2.3 pbw of N,N-dimethyl cyclohexylamine and 13.0 pbw of cyclopentane.
The B component was 148.0 pbw of polymerio MDI (Desmodur~
44V20, a product of Bayer AG, Leverkusen) (NCO group content 31.5%
by weight, diisocyanate content 42,5% by weight).
A mixture of A and B were intensively mixed at 20C by means of a stirrer (1,000 r.p.m.), the reaction mixture was introduced Into an open 20 box with intemal dimensions of 20 x 20 x 20 cm and left to foam therein.
A uniform rigid polyurethane foam having a density of 28 kg/m3 was obtained. A second foam (llOg) produced from the same mixtures was introduced in a closed mold (22 x 22 x 6 cm). The foam had a thermal conductivity of 22 to 23 mW/Km (mean temperature 24C) and a density of 38 kg/m3.
k` 1 25 Example 2 (accordina to the invention~
The A component was a polyol mixture having an OH number of ~¦ 400. The A component was prepared by mixing:
Mo4063 .u ~, . ~ .
J ~ f~
_ 9 47.85 pbw of a poiyether (OH number of 450) prepared by reaction of a mixture of sugar and glycerol with propylene oxide 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol ~:
and ethylene oxide 38.28 pbw of a polyether (OH number of 380) prepared by reaction of trimethyl propane with propylene oxide . 1.91 pbw of water 1.91 pbw of the commercial foam stabilizer used in Exarnple 1 0.48 pbw of pentamethyl diethylenetriamine and 2.3 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
148.0 pbw of the same polymeric MDI used in Example 1 and ; 15 13.00 pbw of cyclopentane.
~:i . ~ Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid polyurethane foam with a density of 26 kg/m3 was obtained . A moulded foam (as in Example 1) had a density of 35 to 36 kg/m3 and a thennal conductivity of 22 mW/Km (me~n temperature 24C).
:jl Examp e 3 (accordiny to the invention) The A component vvas a polyol mixture having an OH number of 400. The A component was prepared by mixing:
47.85 pbw of a polyether (OH number of 450) prepared by `:~ 25 reaction of a mixture of sugar and glycerol with .;~ propylene oxide ~`~ ' 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol ! and ethylene oxide Mo4063 ~!
~, .
I `'?.
,~
., 38.28 pbw of a polye~her (OH number of 380) prepared by reaction of trimethyl propane with propylene oxide 1.40 pbw of water ?~ 1.91 pbw of the commercial foam stabilizer used in Example 1 0.48 pbw of pentamethyl diethylenetriamine and 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
143.5 pbw of the same polymeric MDI used in Example 1 and 18.5 pbw of cyclopentane Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid polyurethane foam with a density of 24 kg/m3 was . obtained. A moulded foam (as in Example 1) had a thermal conductivity of 21 mW/Km '. (mean temperature 24C) and a density of 35 to 36 kg/m3.
ExamDle 4laccordinq to the invention) ~;
r J The A component was a poiyol mixture having an OH number of ~' 490. The A component was prepared by mixing:
44.25 pbw of a polyether ~OH numbsr of 460) prepared by reaction of a mixture of sugar and diethylene glycol `~, 20 with propylene oxid~
35.10 pbw of a polyether (OH number of 250) prepared by reaction of glycerol with propylene oxide 8.85 pbw of a polyether (OH number of 470) prepared by :
reaction of tolylenediamine with ethylene oxide and : :
propylene oxide 8.80 pbw of glycerol 1.0 pbw of water .0 pbw of a commercial foam stabllizer ~B 8407, a product of ~, GoldschmidtAG, Essen~ andd . Mo4063 ,1 ., .
:``1 .,.
~,-.~,: ~ . . , - .
,............................................ . .
; . .
. .
. ~ 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
147.0 pbw of the same polymeric MDI used in Example 1 and 22.0 pbw of cyclopentane.
Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid foam with a density of 23 kg/m3 was obtained. A moulded foarn (as in Example 1) had a thermal conductivity of 20 mW/Km (mean temperature24C) and a density of 35 to 36 kg/m3.
ExamPle 5 (accordina to the invention) ~ 10 The A component was a polyol mixture having an OH number of 550. The A component was prepared by mixing:
pbw of a polyether (OH number of 460) prepared by reaction of a mixture of sugar and diethylene glycol with propylene oxide , 15 25 pbw of a polyether (OH number of 250) prepared by . reaction of glycerol with propylene oxide .~, 10 pbw of a polyether (OH number of 470) prepared by . .l reaction of tolylenediamine with ethylene oxide and propylene oxide 15.0 pbw of a polye~er (OH number of 1,400) prepared by reaction of I mol of sorbitol with 2 mols of propylene oxide and addition of 3 mols of ethylene glycol 0.5 pbw of water ` 2.0 pbw of a commercial foam stabilizer (B 8407, a product of Goldschmidt AG, Essen) and .
:` 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
152.0 pbw of the same polymeric MDI used in Example 1 and 27.0 pbw of cyclopentane.
Mo4063 :`~
~ . .
.
.--"
. ~,,i . . ... . . :
¦ ~ Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid foam with a density of 23 kg/m3 was obtained. A mould~d foam (as in Example 1) had a the~mal conductivity of 19-20 mW/Km (mean temperature 24C) and a , ~ density of 35 t 36 kg/m3 .
Examples 6, 7, and 8 are directed to the production of foam~
' containing urethane and isocyanurate groups.
Example 6 (ComParison) ~,'i~ I
i l The A component was a mixture of , ., - ~ a) 100 pbw of a polyol mixture (OH number of 285, ~; 10 viscosity 2,000 mPa-s) consisting of:
32.8 pbw of a polyether (OH number of 380) prepared by reaction of a ~! mixture of sugar and water with , propylene oxide ' 15 5.~ pbw of a polyether (OH number of 180) prepared by reaction of ~- propylene glycol with ethylene H oxide ;:
-i 4.8 pbw of a polyether(OH numberof 640) prepared by reaction of : :~
.~ "
ethylenediamine with a mixture of ethylene oxide and propylene -, oxide ~ :~
,``. 19.2 pbw of an ester polyol (OH number of ~
210) prepared by reaction of .- ~ :
,~, adipic acid and phthalic acid with glycerol and propylene glycol '~
~ Mo4063 ~:-, ., ~, .......... ..
. ...
: ,. . ~ , -,' ,::
,, .
-'' , . ~.,,~
,J~ r -i; 28.8 pbw of tris-monochloroisopropyl phosphate as flameproofing agent 2.5 pbw of ethylene glycol 3.8 pbw of an ester product (OH number of 6~5) prepared by reaction of pththalic anhydride with di-; ethylene glycol and 1.9 pbw of a comrnercial polyether 3 ~ 10 polysiloxane foam stabilizer s (Tegostab~B 8~43, a produ~t of ~ ~ Goldschmidt AG, Essen i ~ b) 4.8 pbw of a 25% by weight potassium acetate solution , ~ in diethylene glycol c) 0.6 pbw of N,N-dimethyi cyclohexylamine ~- ~ d) 0.6 pbw of dimethyl ethanoiamine .
e) 2.2 pbw of water `; f) 10 pbw of n-pentane.
The B component was 250 pbw of polyisocyanate (Desmodur 20 44P7~, a product of Bayer AG, LeverkusenJ (NCO group content 28% by weight, diisocyanate content 38% by weight).
Mixtures A and B were intensively mixed at 2ûC by means of a sUrrer (1,000 r.p.m.3. The reaction mixture was introduced into an open box with internal dimensions of 20 x 20 x 20 cm and left to foam therein.
25 A uniform free-foamed rigid isocyanurate group-containing polyurethane foam having a density of 30 kg/m3 was obtained. A second reaction mixture with the same mixing ratios was introduced in a closed mold (20 x 20 x 6 cm). The moulded foam had a thermal conductivity of 24 mW/~m `~ ~mean temperature 24C) and a density of 45 kg/m3.
::`
`~` Mo4063 :
.
`:
, -, , - ~ . ~ , -.. ~.~,. . ~
.. -. , . . :
-,, .,- . .. . . .
~ ". . ..
: . i .: ~ - - ,., . i; .
-l Example 7 (accordina to the invention) - ~ ' The A component was a mixture of -~ a) 100 p~w of the same 285 OH number polyol mixture ; used in Example 6, b) 4.8 pbw of a 25% by weight potassium acetate solution in diethylene glycol c) 0.6 pbw of N,N-dimethyl cyclohexylamine ` d) 0.6 pbw of dimethyl ethanolamine and e) 2.2 pbw of water.
The B component was a mixture of `' 250 pbw of the same polyisocyanate used in Example 6 and 20 pbw of n-pentane.
Mixtures A and B were intensively mixed at 20C by means of a -15 stirrer (1,000 r.p.m.), and the reaction mixture was introduced into an ~ -open box with internal dimensions of 20 x 20 x 20 cm and left to foam therein. The mixtures thus prepared were reacted as described in Example 6. A free-foamed, uniform rigid foam having a density of 29 ~
kg/m3 was obtained. A moulded foam (as in Example 6) had a ~herrnal conductivity of 23 : . ~ ;-20 mWtKm (mean temperature 24C) and a den~ity of 45 kg/m3.
Example 8 (~cordina to the in\,ention) ~3 The A component was a mixture of a) 100 pbw of the same 285 OH number polyol mixture used in Example 6, ' b) 4.8 pbw of a 25% by weight potassium acetate solution in diethylene glycol c) 0.6 pbw of N,N-dimethyl cyclohexylamine d) 0.6 pbw of dimethyl ethanolamine and Mo4063 ,3 ~ .
.~
.i :
.1 ~:,:: , ....
e) 1 pbw of water.
The B component was a mixture of 250 pbw of the same polyisocyanate used in Example 6 and 29 pbw of cyclopentane.
Mixtures A and B were intensively mixed at 20C by means of a stirrer (1,000 r.p.m.), and the reaction mixture was introduced into an - open box with internal dimensions of 20 x 20 x 20 cm and left to foam ; therein. The mixtures thus prepared were reacted as described in ; - 10 Example 6. A free-foamed, uniform rigid foam having a density of 28 kg/m3 was obtained. A second reaction mixture was introduced in a closed mold (as in example 6). The moulded foam had a thelmal conductivity of 21 mW/Km tmean. temperature 24C) and a density of 45-46 kg/m3.
.. : 15 Although the invention has been described in detail in the ~ foregoing for the purpose of illustration, it is to be understood that such .~ detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
!
., ~ ' Mo4063 , ~. .. . .
.
~. :. . : . . . . .:
of ~hese addi~ives and their modes of action can be found in Kunststoff-Handbuch, Vol. Vll, edited by Vieweg and Hochtlen, Carl-Hanser-Verlag, , Munchen 1966, for example on pages 103 to 113.
' The production of the rigid foams of the present invention iscarried out using techniques known in the art. Thus, the reacticn components may be reacted by the one-shot process, by the prepolymer process or by the semiprepolymer process, often using machines, for example of the type described in U.S. Patent 2,764,566. Particulars of - procesising machines which may also be used in accordance with the present invention can be found in Kunststoff-Handbuch, Vol. Vll, edited by Vieweg and H~chtlen, Carl-Hanser-Verlag, Munchen 1966, for example on pages 121 to 205.
According to the invention, the foam production process is gener-` ally carried out at an index of 90 to 130 and often - for example in the production of foams containing urethane and isocyanurate groups - at an index above 130, for example in the range from 200 to 400.
The foams may be produced by slabstock foaming or by the laminator process. The products obtainable in accordance with the invention are preferably used as heat insulation materials, for example as insulation boards ~or roof insulation and in refrigerators and deep freezers.
The invention is further illustrated but is not intended to be limited ~-j by the following examples in which all parts and percentages are by weight unless othen~vise specified.
EXAMPLES
Example 1 LComparison) The A component was a polyol mixture having an OH number of 400. The A component was prepared by mixing:
Mo4063 : :
.
.1 ': ~ . : '. ; :
. -- 8 --47.85 pbw of a polyether (OH number of 450) prepared by f reaction of a mixture of sugar and glycerol with propylene oxide ~; 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol .
~ ~ and ethylene oxide ~, ., - 38.28 pbw of a polyether ~OH numbef of 380) prepared by !,'`, reaction of trimethyl propan0 with propylene oxide 1.91 pbw of water . 10 1.91 pbw of a commercial foam stabilizer (RS 201, a product of Union Carbide) 0.48 pbw of pentamethyl diethylenetriamine 2.3 pbw of N,N-dimethyl cyclohexylamine and 13.0 pbw of cyclopentane.
The B component was 148.0 pbw of polymerio MDI (Desmodur~
44V20, a product of Bayer AG, Leverkusen) (NCO group content 31.5%
by weight, diisocyanate content 42,5% by weight).
A mixture of A and B were intensively mixed at 20C by means of a stirrer (1,000 r.p.m.), the reaction mixture was introduced Into an open 20 box with intemal dimensions of 20 x 20 x 20 cm and left to foam therein.
A uniform rigid polyurethane foam having a density of 28 kg/m3 was obtained. A second foam (llOg) produced from the same mixtures was introduced in a closed mold (22 x 22 x 6 cm). The foam had a thermal conductivity of 22 to 23 mW/Km (mean temperature 24C) and a density of 38 kg/m3.
k` 1 25 Example 2 (accordina to the invention~
The A component was a polyol mixture having an OH number of ~¦ 400. The A component was prepared by mixing:
Mo4063 .u ~, . ~ .
J ~ f~
_ 9 47.85 pbw of a poiyether (OH number of 450) prepared by reaction of a mixture of sugar and glycerol with propylene oxide 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol ~:
and ethylene oxide 38.28 pbw of a polyether (OH number of 380) prepared by reaction of trimethyl propane with propylene oxide . 1.91 pbw of water 1.91 pbw of the commercial foam stabilizer used in Exarnple 1 0.48 pbw of pentamethyl diethylenetriamine and 2.3 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
148.0 pbw of the same polymeric MDI used in Example 1 and ; 15 13.00 pbw of cyclopentane.
~:i . ~ Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid polyurethane foam with a density of 26 kg/m3 was obtained . A moulded foam (as in Example 1) had a density of 35 to 36 kg/m3 and a thennal conductivity of 22 mW/Km (me~n temperature 24C).
:jl Examp e 3 (accordiny to the invention) The A component vvas a polyol mixture having an OH number of 400. The A component was prepared by mixing:
47.85 pbw of a polyether (OH number of 450) prepared by `:~ 25 reaction of a mixture of sugar and glycerol with .;~ propylene oxide ~`~ ' 9.57 pbw of an ester polyol (OH number of 290) prepared by reaction of phthalic anhydride with diethylene glycol ! and ethylene oxide Mo4063 ~!
~, .
I `'?.
,~
., 38.28 pbw of a polye~her (OH number of 380) prepared by reaction of trimethyl propane with propylene oxide 1.40 pbw of water ?~ 1.91 pbw of the commercial foam stabilizer used in Example 1 0.48 pbw of pentamethyl diethylenetriamine and 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
143.5 pbw of the same polymeric MDI used in Example 1 and 18.5 pbw of cyclopentane Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid polyurethane foam with a density of 24 kg/m3 was . obtained. A moulded foam (as in Example 1) had a thermal conductivity of 21 mW/Km '. (mean temperature 24C) and a density of 35 to 36 kg/m3.
ExamDle 4laccordinq to the invention) ~;
r J The A component was a poiyol mixture having an OH number of ~' 490. The A component was prepared by mixing:
44.25 pbw of a polyether ~OH numbsr of 460) prepared by reaction of a mixture of sugar and diethylene glycol `~, 20 with propylene oxid~
35.10 pbw of a polyether (OH number of 250) prepared by reaction of glycerol with propylene oxide 8.85 pbw of a polyether (OH number of 470) prepared by :
reaction of tolylenediamine with ethylene oxide and : :
propylene oxide 8.80 pbw of glycerol 1.0 pbw of water .0 pbw of a commercial foam stabllizer ~B 8407, a product of ~, GoldschmidtAG, Essen~ andd . Mo4063 ,1 ., .
:``1 .,.
~,-.~,: ~ . . , - .
,............................................ . .
; . .
. .
. ~ 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
147.0 pbw of the same polymeric MDI used in Example 1 and 22.0 pbw of cyclopentane.
Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid foam with a density of 23 kg/m3 was obtained. A moulded foarn (as in Example 1) had a thermal conductivity of 20 mW/Km (mean temperature24C) and a density of 35 to 36 kg/m3.
ExamPle 5 (accordina to the invention) ~ 10 The A component was a polyol mixture having an OH number of 550. The A component was prepared by mixing:
pbw of a polyether (OH number of 460) prepared by reaction of a mixture of sugar and diethylene glycol with propylene oxide , 15 25 pbw of a polyether (OH number of 250) prepared by . reaction of glycerol with propylene oxide .~, 10 pbw of a polyether (OH number of 470) prepared by . .l reaction of tolylenediamine with ethylene oxide and propylene oxide 15.0 pbw of a polye~er (OH number of 1,400) prepared by reaction of I mol of sorbitol with 2 mols of propylene oxide and addition of 3 mols of ethylene glycol 0.5 pbw of water ` 2.0 pbw of a commercial foam stabilizer (B 8407, a product of Goldschmidt AG, Essen) and .
:` 3.0 pbw of N,N-dimethyl cyclohexylamine.
The B component was a mixture of:
152.0 pbw of the same polymeric MDI used in Example 1 and 27.0 pbw of cyclopentane.
Mo4063 :`~
~ . .
.
.--"
. ~,,i . . ... . . :
¦ ~ Mixtures A and B were reacted as described in Example 1. A
free-foamed rigid foam with a density of 23 kg/m3 was obtained. A mould~d foam (as in Example 1) had a the~mal conductivity of 19-20 mW/Km (mean temperature 24C) and a , ~ density of 35 t 36 kg/m3 .
Examples 6, 7, and 8 are directed to the production of foam~
' containing urethane and isocyanurate groups.
Example 6 (ComParison) ~,'i~ I
i l The A component was a mixture of , ., - ~ a) 100 pbw of a polyol mixture (OH number of 285, ~; 10 viscosity 2,000 mPa-s) consisting of:
32.8 pbw of a polyether (OH number of 380) prepared by reaction of a ~! mixture of sugar and water with , propylene oxide ' 15 5.~ pbw of a polyether (OH number of 180) prepared by reaction of ~- propylene glycol with ethylene H oxide ;:
-i 4.8 pbw of a polyether(OH numberof 640) prepared by reaction of : :~
.~ "
ethylenediamine with a mixture of ethylene oxide and propylene -, oxide ~ :~
,``. 19.2 pbw of an ester polyol (OH number of ~
210) prepared by reaction of .- ~ :
,~, adipic acid and phthalic acid with glycerol and propylene glycol '~
~ Mo4063 ~:-, ., ~, .......... ..
. ...
: ,. . ~ , -,' ,::
,, .
-'' , . ~.,,~
,J~ r -i; 28.8 pbw of tris-monochloroisopropyl phosphate as flameproofing agent 2.5 pbw of ethylene glycol 3.8 pbw of an ester product (OH number of 6~5) prepared by reaction of pththalic anhydride with di-; ethylene glycol and 1.9 pbw of a comrnercial polyether 3 ~ 10 polysiloxane foam stabilizer s (Tegostab~B 8~43, a produ~t of ~ ~ Goldschmidt AG, Essen i ~ b) 4.8 pbw of a 25% by weight potassium acetate solution , ~ in diethylene glycol c) 0.6 pbw of N,N-dimethyi cyclohexylamine ~- ~ d) 0.6 pbw of dimethyl ethanoiamine .
e) 2.2 pbw of water `; f) 10 pbw of n-pentane.
The B component was 250 pbw of polyisocyanate (Desmodur 20 44P7~, a product of Bayer AG, LeverkusenJ (NCO group content 28% by weight, diisocyanate content 38% by weight).
Mixtures A and B were intensively mixed at 2ûC by means of a sUrrer (1,000 r.p.m.3. The reaction mixture was introduced into an open box with internal dimensions of 20 x 20 x 20 cm and left to foam therein.
25 A uniform free-foamed rigid isocyanurate group-containing polyurethane foam having a density of 30 kg/m3 was obtained. A second reaction mixture with the same mixing ratios was introduced in a closed mold (20 x 20 x 6 cm). The moulded foam had a thermal conductivity of 24 mW/~m `~ ~mean temperature 24C) and a density of 45 kg/m3.
::`
`~` Mo4063 :
.
`:
, -, , - ~ . ~ , -.. ~.~,. . ~
.. -. , . . :
-,, .,- . .. . . .
~ ". . ..
: . i .: ~ - - ,., . i; .
-l Example 7 (accordina to the invention) - ~ ' The A component was a mixture of -~ a) 100 p~w of the same 285 OH number polyol mixture ; used in Example 6, b) 4.8 pbw of a 25% by weight potassium acetate solution in diethylene glycol c) 0.6 pbw of N,N-dimethyl cyclohexylamine ` d) 0.6 pbw of dimethyl ethanolamine and e) 2.2 pbw of water.
The B component was a mixture of `' 250 pbw of the same polyisocyanate used in Example 6 and 20 pbw of n-pentane.
Mixtures A and B were intensively mixed at 20C by means of a -15 stirrer (1,000 r.p.m.), and the reaction mixture was introduced into an ~ -open box with internal dimensions of 20 x 20 x 20 cm and left to foam therein. The mixtures thus prepared were reacted as described in Example 6. A free-foamed, uniform rigid foam having a density of 29 ~
kg/m3 was obtained. A moulded foam (as in Example 6) had a ~herrnal conductivity of 23 : . ~ ;-20 mWtKm (mean temperature 24C) and a den~ity of 45 kg/m3.
Example 8 (~cordina to the in\,ention) ~3 The A component was a mixture of a) 100 pbw of the same 285 OH number polyol mixture used in Example 6, ' b) 4.8 pbw of a 25% by weight potassium acetate solution in diethylene glycol c) 0.6 pbw of N,N-dimethyl cyclohexylamine d) 0.6 pbw of dimethyl ethanolamine and Mo4063 ,3 ~ .
.~
.i :
.1 ~:,:: , ....
e) 1 pbw of water.
The B component was a mixture of 250 pbw of the same polyisocyanate used in Example 6 and 29 pbw of cyclopentane.
Mixtures A and B were intensively mixed at 20C by means of a stirrer (1,000 r.p.m.), and the reaction mixture was introduced into an - open box with internal dimensions of 20 x 20 x 20 cm and left to foam ; therein. The mixtures thus prepared were reacted as described in ; - 10 Example 6. A free-foamed, uniform rigid foam having a density of 28 kg/m3 was obtained. A second reaction mixture was introduced in a closed mold (as in example 6). The moulded foam had a thelmal conductivity of 21 mW/Km tmean. temperature 24C) and a density of 45-46 kg/m3.
.. : 15 Although the invention has been described in detail in the ~ foregoing for the purpose of illustration, it is to be understood that such .~ detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
!
., ~ ' Mo4063 , ~. .. . .
.
~. :. . : . . . . .:
Claims (9)
1. A mixture of a polyisocyanates and a hydrocarbon selected from the group consisting of pentane, cyclopentane, and mixtures thereof.
2. The mixture of Claim 1, wherein said hydrocarbon is selected from the group consisting of n-pentane, i-pentane, cyclopentane, and mixtures thereof.
3. The mixture of Claim 1 comprising from 1 to 30% by weight of said hydrocarbon and the balance being said polyisocyanate.
4. A process for the production of rigid foams containing urethane groups and optionally isocyanurate groups comprising reacting:
a) a mixture of a polyisocyanate and a hydrocarbon selected from the group consisting of pentane, cyclopentane, and mixtures thereof with b) one or more compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular weights of 400 to 10,000 and c) optionally compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32 to 399, d) optionally in the presence of other blowing agents, auxiliaries and/or additives.
a) a mixture of a polyisocyanate and a hydrocarbon selected from the group consisting of pentane, cyclopentane, and mixtures thereof with b) one or more compounds containing at least two isocyanate-reactive hydrogen atoms and having molecular weights of 400 to 10,000 and c) optionally compounds containing at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32 to 399, d) optionally in the presence of other blowing agents, auxiliaries and/or additives.
5. The process of Claim 4, wherein said polyisocyanate is a polymeric MDI with a diisocyanate content of from 25 to 70% by weight or a urethane-modified polymeric MDI with a diisocyanate content of from 35 to 70% by weight.
6. The process of Claim 5, wherein said hydrocarbon is selected from the group consisting of n-pentane, i-pentane, cyclopentane, or mixtures thereof.
7. The process of Claim 6, wherein component a) contains 1 to 30% by weight of said hydrocarbon with the balance being said polyisocyanate.
8. The process of Claim 4, wherein the reaction mixture contains from 0.4 to 4% by weight, based upon the amount of component b) of water as co-blowing agent.
9. A rigid foam produced by the process of Claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4309691A DE4309691A1 (en) | 1993-03-25 | 1993-03-25 | Process for the production of rigid foams containing urethane and optionally isocyanurate groups and their use as thermal insulation materials |
| DEP4309691.3 | 1993-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2119479A1 true CA2119479A1 (en) | 1994-09-26 |
Family
ID=6483817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002119479A Abandoned CA2119479A1 (en) | 1993-03-25 | 1994-03-21 | Mixtures of polyisocyanates with pentane and/or cyclopentane and process for the production of rigid foams containing urethane and optionally isocyanurate groups |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0617068A3 (en) |
| CA (1) | CA2119479A1 (en) |
| DE (1) | DE4309691A1 (en) |
| FI (1) | FI941344A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316513B1 (en) | 1996-06-10 | 2001-11-13 | Bayer Aktiengesellschaft | Process for the producing of hard polyurethane foams with low heat conductivity |
| US6339110B1 (en) | 1996-06-20 | 2002-01-15 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0184681B1 (en) * | 1995-01-24 | 1999-05-15 | 구보타 다다시 | Thermal insulating foamed material having carbon dioxide absorbent and method for manufacturing the same |
| CN102282190A (en) * | 2009-01-20 | 2011-12-14 | 巴斯夫欧洲公司 | Process for producing rigid polyurethane foams |
| EP3436494B1 (en) | 2016-03-29 | 2020-05-06 | Dow Global Technologies LLC | Semi-rigid polyurethane foam and process to make |
| KR102543009B1 (en) | 2017-01-23 | 2023-06-14 | 다우 글로벌 테크놀로지스 엘엘씨 | Flexible Polyurethane Foam and Manufacturing Method |
| CN111263781B (en) | 2017-11-10 | 2022-10-18 | 陶氏环球技术有限责任公司 | Polyurethane foam system |
| WO2019094157A1 (en) | 2017-11-10 | 2019-05-16 | Dow Global Technologies Llc | Polyurethane foam system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0160716A1 (en) * | 1984-05-04 | 1985-11-13 | Henkel Kommanditgesellschaft auf Aktien | Insulating foam |
| DE4109076A1 (en) * | 1991-03-20 | 1992-09-24 | Bayer Ag | METHOD FOR THE PRODUCTION OF URETHANE AND PRIMARY ISOCYANURATE GROUPS OF HARD FOAM MATERIALS AND THEIR USE AS DAEMING MATERIALS |
-
1993
- 1993-03-25 DE DE4309691A patent/DE4309691A1/en not_active Withdrawn
-
1994
- 1994-03-14 EP EP94103882A patent/EP0617068A3/en not_active Withdrawn
- 1994-03-21 CA CA002119479A patent/CA2119479A1/en not_active Abandoned
- 1994-03-23 FI FI941344A patent/FI941344A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316513B1 (en) | 1996-06-10 | 2001-11-13 | Bayer Aktiengesellschaft | Process for the producing of hard polyurethane foams with low heat conductivity |
| US6339110B1 (en) | 1996-06-20 | 2002-01-15 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
Also Published As
| Publication number | Publication date |
|---|---|
| FI941344A0 (en) | 1994-03-23 |
| FI941344A (en) | 1994-09-26 |
| DE4309691A1 (en) | 1994-09-29 |
| EP0617068A2 (en) | 1994-09-28 |
| EP0617068A3 (en) | 1995-03-01 |
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