CA2154045A1 - Method of manufacturing foam materials containing rigid urethane and optional isocyanurate groups - Google Patents
Method of manufacturing foam materials containing rigid urethane and optional isocyanurate groupsInfo
- Publication number
- CA2154045A1 CA2154045A1 CA 2154045 CA2154045A CA2154045A1 CA 2154045 A1 CA2154045 A1 CA 2154045A1 CA 2154045 CA2154045 CA 2154045 CA 2154045 A CA2154045 A CA 2154045A CA 2154045 A1 CA2154045 A1 CA 2154045A1
- Authority
- CA
- Canada
- Prior art keywords
- reacting
- rigid
- groups
- foam materials
- foam
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
Abstract
The present invention relates to a process for the production of foam materials containing rigid urethane and/or optionally isocyanurate groups, and the foam materials produced by this process. This process comprises reacting a) one or more polyisocyanates, with b) one or more compounds containing at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 400 to 10,000, in the presence of c) organic fillers, and d) water and/or foaming agents comprising light volatile organic substances, and, optionally, e) compounds containing at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 32 to 399 and/or f) known auxiliary substances and additives.
The organic fillers used according to the present invention consist essentially of a rigid foam polyurethane powder.
The organic fillers used according to the present invention consist essentially of a rigid foam polyurethane powder.
Description
Le A 30 526-US 215 40~
BAYER AKTIENGESELLSC~IAFT 51368 Leverkusen Konzernzentrale RP
Patente Konzern GM/m-SP
RIGID URET~ANE AND OPTIONAL ISOCYANURATE GROUPS
BACKGROUND OF THE INVENTION
The invention relates to use of pulverulent polyurethane (PUR) rigid foam waste occurring in the manufacture of PUR rigid foam materials in a proportion of 3 to10 25 wt.% depending on the application. There is a general problem of usefully disposing of this waste.
Re-use of ground PUR rigid foam production waste in PUR rigid foam materials is the nearest approach to recycling, along with the possibilities of combustion, compression of gr~n~ tes or solvolysis.
1 5 It is known to improve individual properties (e.g. hardness) of rigid foam by using finely-divided, insoluble, non-reactive fillers less than 0.25 mm in diameter and in proportions up to 40 wt.% as described in, for example, German Offenlegungs-schrift 2,024,810, or quartz sand of undefined particle size in about 30 to 80 wt.%
as described in, for example, German Offenlegungschrift 2,617,358. It is also 20 known to manufacture soft foam by using very fine-grain soft PUR foam meal which occurs as waste during the manufacturing process.
Finely-divided fillers of this kind, made from soft foam m~t~ri~, are, of course, of a suitable nature for being incorporated into the PUR matrix. The level of mechanical properties can be maint~ined simply by ch~n~in~ the formulation.
25 Other finely-divided solids (such as melamine or ammonium polyphosphate) havenot hitherto been used in practice in rigid PUR foam m~t~ri~ . Aside from bubbleformation, open cells and inferior mechanical properties, the main problem, is that the foam material is brittle (compare Table 1, Examples 1 and 2 in relation to Le A 30 526-US 21 S ~ n ~ s Table 2, Examples 3 to 11). Consequently, these filled PUR rigid foam m~teri~l~
have not been used in practice.
It has now unexpectedly been found that operating with a device such as that described in, for example, German Auslegeschrift 3,841,671 (believed to correspond to U.S. Patent 5,152,943) and/or European Patent Application 431,388,the disclosures of which are herein incorporated by reference, rigid PUR foam powder in surprisingly coarse grains can be used in a proportion up to 10 wt.% in the production of low-density rigid PUR foam m~t~ri~l~, without the afore-mentioned adverse effects such as brittleness.
Other solid fillers (Table 1) increase the gross density and brittleness of the foam material but have no advantageous influence on the mechanical properties such as, for example, bending strength when heated. By comparison, in the method according to the invention, polyol and isocyanate are replaced weight for weightby solid polyurethane powder, with the resulting properties at comparable gross density being the same as for non-filled foam material (Table 2). There is no increase in brittleness.
SIJMMARY OF THE INVENTION
The invention relates to a process for the production of foam materials cont~ining rigid urethane and/or optionally isocyanurate groups. This process comprises thesteps of reacting a) one or more polyisocyanates, with b) one or more compounds c-)nt~ining at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 400 to 10,000, in the presence of c) one or more organic fillers and d) water and/or one or more foaming agents wherein said foaming agents comprise light volatile organic substances, wherein the organic filler c) consists essentially of a polyurethane rigid foam powder.
Le A 30 526-US 2 1 S 4 0 ~ S
The reaction of polyisocyanates and compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weigh~ of 400 to 10,000 may additionally occur in the presence of e) compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of 32 to 399 and/or f~ known auxiliary substances and additives.
According to the invention, the particle size of the polyurethane rigid foam powder is advantageously in the range from 0.3 to 2.0 mm, and preferably 0.5 to 1.0 mm. Therefore, preference is given to filled, rigid PUR foam materials that contain rigid PUR foam powder having a particle size of between 0.5 and 1.0 mm in diameter.
According to the invention, it is also possible to use polyurethane rigid foam powders which contain impurities, such as, for example, paper or fibers. The presence of these impurities is due to the manuf~ctllring process of the poly-urethane rigid foam from which the powders are produced.
The foam materials cont~ining rigid urethane groups and/or, optionally, iso-cyanurate groups are produced from suitable materials such as those described hereinbelow.
Suitable isocyanates for the process of the present invention include, for example, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates, described e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75to 136, e.g. substances having the formula:
Q(NCO)n in which n equals 2-4, preferably 2-3, and Q denotes an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 carbon atoms; a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10 carbon atoms; an aromatic hydrocarbon radical having 6 Le A 30 526-US
to 15, preferably 6 to 13 carbon atoms; or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 carbon atoms.
Some examples of such polyisocyanates include those described in, for example, German Offenlegungschrift 2,832,253, pages 10-11, the disclosure of which is herein incorporated by reference. As a rule, particular preference is given to polyisocyanates which are easily and readily available in industry such as, for example, 2,4 and 2,6-toluylene diisocyanate, or any mixtures of these isomers ("TDI"); polyphenyl polymethylene polyisocyanates produced by conri~n~tion of aniline and formaldehyde and subsequent phosgenation ("crude MDI") and polyisocyanates ("modified polyisocyanates") cont~inin~ carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, particularly modified polyisocyanates derived from 2,4- and/or 2,6-toluylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
The process of the invention also requires, as starting cbmponents, compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of from about 400 to 10,000. These compounds include compounds cont~ining amino groups, thio groups, carboxyl groups, or, preferably,hydroxyl groups, and particularly compounds cont~ining from 2 to 8 hydroxyl groups, especially those compounds having a molecular weight of 1,000 to 6,000, and preferably of 2,000 to 6,000. Suitable examples include polyethers or polyesters containing at least two, preferably 2 to 8, and most preferably. 2 to 6 hydroxyl groups, or polycarbonates and polyester amides such as those known per se in the manufacture of homogeneous and cellular polyurethanes and are described in, for example, German Offenlegung-schrift 2,832,253, pages 11-18, the disclosure of which is herein incorporated by reference.
The organic fillers suitable for the present invention include, for example, those polyurethane hard foam powders previously described above.
Suitable compounds to be used as foaming agents include, for example, water and/or the light volatile organic substances known per se. In particular, the light volatile organic substances are preferably selected from the group consisting ofpentane, isopentane, cyclopentane, hexafluorobutane, pentafluoropropane, and mixtures thereof.
Le A 30 526-US 2154045 In addition, the starting components may also be compounds having at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 32 to 399. These low molecular weight active hydrogen cont~ining components may contain active hydrogen atoms in the form of, for 5 example, hydroxyl groups, amino groups, thiol groups, carboxyl groups, or mixtures thereof. It is preferred that these compounds contain hydroxyl groups and/or amino groups, and function as chain-lengthening agents or cross-linking agents. These compounds usually have 2 to 8, preferably 2 to 4 active hydrogen atoms which are capable of reacting with isocyanate groups. Suitable examples of1 0 such compounds are described in, for example, German Offenlegung-schrift 2,832,253, pages 19 - 20, the disclosure of which is herein incorporated by reference.
It is also within the scope of the present invention that the starting components may optionally include auxiliary substances and additives such as, for example, 1 5 catalysts of known kind in quantities of up to 10% by weight, based on the weight of component b); surface-active additives such as, for- example, emulsifiers andfoam stabilizers; and retarders such as, for example, acid-reacting substances such as hydrochloric acid or organic acid halides, or cell regulators of known kind such as paraffins or fatty alcohols or dimethyl polysiloxanes or pigments or dyestuffs 20 and flame retardants of known kind, e.g. tricresyl phosphate, or stabilizers against ageing and weather, plasticizers or fungistatic and bacteriostatic substances orother fillers such as barium sulphate, kieselguhr, carbon black or whiting.
These optional auxiliary substances and additives include materials such as those described in, for example, German Offenlegung-schrift 2,732,292, pages 21 - 24, 25 the disclosure of which is herein incorporated by reference.
Suitable examples of other optional additives which may be used according to theinvention include, for example, surface-active additives and foam stabilizers and cell regulators, retarders, stabilizers, flame-retarding substances, plasticizers, dyestuffs and other fillers and fungistatic and bacteriostatic substances. Specific 30 details about the use and operation of these additives, are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 - 113.
Le A 30 526-US 2154q45 A suitable method of producing rigid polyurethane foam materials is presented below.
The components may be reacted in the known single-stage process, the prepolymer process or the semi-prepolymer process, often using machinery such as that described in, for example, U.S. Patent 2,764,565, the disclosure of which is herein incorporated by reference. Details of processing equipment which can also be used according to the invention are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 121 to 205.
1 0 The foam materials can be made by, for example, slab production or by the known double conveyor-belt method.
The products obtainable according to the invention are suitable for use as, for example, insulating slabs for roofs.
The invention is further illustrated but is not intended to be limited by the 1 5 following examples in which all parts and percentages are by weight unless otherwise specified.
EXAl\IPLES
The polyurethane foam materials were produced by using polyol formulations A
and B described hereinbelow.
Formulation A
A polyol mixture having an OH number of 553 was prepared by mixing the following components:
1. 26.9 parts of a polyether polyol having an OH number of 380, and was prepared by the propoxylation of a mixture of saccharose, propylene glycol and water;
2. 22.0 parts of a polyether polyol having an OH number of 620, and was prepared by the propoxylation of ethylene diamine;
Le A 30 526-US
21540~5 3. 16.0 parts of a polyether polyol having an OH number of 445, and was prepared by the propoxylation of a saccharose and ethylene glycol rnixture;
BAYER AKTIENGESELLSC~IAFT 51368 Leverkusen Konzernzentrale RP
Patente Konzern GM/m-SP
RIGID URET~ANE AND OPTIONAL ISOCYANURATE GROUPS
BACKGROUND OF THE INVENTION
The invention relates to use of pulverulent polyurethane (PUR) rigid foam waste occurring in the manufacture of PUR rigid foam materials in a proportion of 3 to10 25 wt.% depending on the application. There is a general problem of usefully disposing of this waste.
Re-use of ground PUR rigid foam production waste in PUR rigid foam materials is the nearest approach to recycling, along with the possibilities of combustion, compression of gr~n~ tes or solvolysis.
1 5 It is known to improve individual properties (e.g. hardness) of rigid foam by using finely-divided, insoluble, non-reactive fillers less than 0.25 mm in diameter and in proportions up to 40 wt.% as described in, for example, German Offenlegungs-schrift 2,024,810, or quartz sand of undefined particle size in about 30 to 80 wt.%
as described in, for example, German Offenlegungschrift 2,617,358. It is also 20 known to manufacture soft foam by using very fine-grain soft PUR foam meal which occurs as waste during the manufacturing process.
Finely-divided fillers of this kind, made from soft foam m~t~ri~, are, of course, of a suitable nature for being incorporated into the PUR matrix. The level of mechanical properties can be maint~ined simply by ch~n~in~ the formulation.
25 Other finely-divided solids (such as melamine or ammonium polyphosphate) havenot hitherto been used in practice in rigid PUR foam m~t~ri~ . Aside from bubbleformation, open cells and inferior mechanical properties, the main problem, is that the foam material is brittle (compare Table 1, Examples 1 and 2 in relation to Le A 30 526-US 21 S ~ n ~ s Table 2, Examples 3 to 11). Consequently, these filled PUR rigid foam m~teri~l~
have not been used in practice.
It has now unexpectedly been found that operating with a device such as that described in, for example, German Auslegeschrift 3,841,671 (believed to correspond to U.S. Patent 5,152,943) and/or European Patent Application 431,388,the disclosures of which are herein incorporated by reference, rigid PUR foam powder in surprisingly coarse grains can be used in a proportion up to 10 wt.% in the production of low-density rigid PUR foam m~t~ri~l~, without the afore-mentioned adverse effects such as brittleness.
Other solid fillers (Table 1) increase the gross density and brittleness of the foam material but have no advantageous influence on the mechanical properties such as, for example, bending strength when heated. By comparison, in the method according to the invention, polyol and isocyanate are replaced weight for weightby solid polyurethane powder, with the resulting properties at comparable gross density being the same as for non-filled foam material (Table 2). There is no increase in brittleness.
SIJMMARY OF THE INVENTION
The invention relates to a process for the production of foam materials cont~ining rigid urethane and/or optionally isocyanurate groups. This process comprises thesteps of reacting a) one or more polyisocyanates, with b) one or more compounds c-)nt~ining at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 400 to 10,000, in the presence of c) one or more organic fillers and d) water and/or one or more foaming agents wherein said foaming agents comprise light volatile organic substances, wherein the organic filler c) consists essentially of a polyurethane rigid foam powder.
Le A 30 526-US 2 1 S 4 0 ~ S
The reaction of polyisocyanates and compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weigh~ of 400 to 10,000 may additionally occur in the presence of e) compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of 32 to 399 and/or f~ known auxiliary substances and additives.
According to the invention, the particle size of the polyurethane rigid foam powder is advantageously in the range from 0.3 to 2.0 mm, and preferably 0.5 to 1.0 mm. Therefore, preference is given to filled, rigid PUR foam materials that contain rigid PUR foam powder having a particle size of between 0.5 and 1.0 mm in diameter.
According to the invention, it is also possible to use polyurethane rigid foam powders which contain impurities, such as, for example, paper or fibers. The presence of these impurities is due to the manuf~ctllring process of the poly-urethane rigid foam from which the powders are produced.
The foam materials cont~ining rigid urethane groups and/or, optionally, iso-cyanurate groups are produced from suitable materials such as those described hereinbelow.
Suitable isocyanates for the process of the present invention include, for example, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates, described e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75to 136, e.g. substances having the formula:
Q(NCO)n in which n equals 2-4, preferably 2-3, and Q denotes an aliphatic hydrocarbon radical having 2 to 18, preferably 6 to 10 carbon atoms; a cycloaliphatic hydrocarbon radical having 4 to 15, preferably 5 to 10 carbon atoms; an aromatic hydrocarbon radical having 6 Le A 30 526-US
to 15, preferably 6 to 13 carbon atoms; or an araliphatic hydrocarbon radical having 8 to 15, preferably 8 to 13 carbon atoms.
Some examples of such polyisocyanates include those described in, for example, German Offenlegungschrift 2,832,253, pages 10-11, the disclosure of which is herein incorporated by reference. As a rule, particular preference is given to polyisocyanates which are easily and readily available in industry such as, for example, 2,4 and 2,6-toluylene diisocyanate, or any mixtures of these isomers ("TDI"); polyphenyl polymethylene polyisocyanates produced by conri~n~tion of aniline and formaldehyde and subsequent phosgenation ("crude MDI") and polyisocyanates ("modified polyisocyanates") cont~inin~ carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, particularly modified polyisocyanates derived from 2,4- and/or 2,6-toluylene diisocyanate or from 4,4'- and/or 2,4'-diphenyl methane diisocyanate.
The process of the invention also requires, as starting cbmponents, compounds cont~inin~ at least two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of from about 400 to 10,000. These compounds include compounds cont~ining amino groups, thio groups, carboxyl groups, or, preferably,hydroxyl groups, and particularly compounds cont~ining from 2 to 8 hydroxyl groups, especially those compounds having a molecular weight of 1,000 to 6,000, and preferably of 2,000 to 6,000. Suitable examples include polyethers or polyesters containing at least two, preferably 2 to 8, and most preferably. 2 to 6 hydroxyl groups, or polycarbonates and polyester amides such as those known per se in the manufacture of homogeneous and cellular polyurethanes and are described in, for example, German Offenlegung-schrift 2,832,253, pages 11-18, the disclosure of which is herein incorporated by reference.
The organic fillers suitable for the present invention include, for example, those polyurethane hard foam powders previously described above.
Suitable compounds to be used as foaming agents include, for example, water and/or the light volatile organic substances known per se. In particular, the light volatile organic substances are preferably selected from the group consisting ofpentane, isopentane, cyclopentane, hexafluorobutane, pentafluoropropane, and mixtures thereof.
Le A 30 526-US 2154045 In addition, the starting components may also be compounds having at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 32 to 399. These low molecular weight active hydrogen cont~ining components may contain active hydrogen atoms in the form of, for 5 example, hydroxyl groups, amino groups, thiol groups, carboxyl groups, or mixtures thereof. It is preferred that these compounds contain hydroxyl groups and/or amino groups, and function as chain-lengthening agents or cross-linking agents. These compounds usually have 2 to 8, preferably 2 to 4 active hydrogen atoms which are capable of reacting with isocyanate groups. Suitable examples of1 0 such compounds are described in, for example, German Offenlegung-schrift 2,832,253, pages 19 - 20, the disclosure of which is herein incorporated by reference.
It is also within the scope of the present invention that the starting components may optionally include auxiliary substances and additives such as, for example, 1 5 catalysts of known kind in quantities of up to 10% by weight, based on the weight of component b); surface-active additives such as, for- example, emulsifiers andfoam stabilizers; and retarders such as, for example, acid-reacting substances such as hydrochloric acid or organic acid halides, or cell regulators of known kind such as paraffins or fatty alcohols or dimethyl polysiloxanes or pigments or dyestuffs 20 and flame retardants of known kind, e.g. tricresyl phosphate, or stabilizers against ageing and weather, plasticizers or fungistatic and bacteriostatic substances orother fillers such as barium sulphate, kieselguhr, carbon black or whiting.
These optional auxiliary substances and additives include materials such as those described in, for example, German Offenlegung-schrift 2,732,292, pages 21 - 24, 25 the disclosure of which is herein incorporated by reference.
Suitable examples of other optional additives which may be used according to theinvention include, for example, surface-active additives and foam stabilizers and cell regulators, retarders, stabilizers, flame-retarding substances, plasticizers, dyestuffs and other fillers and fungistatic and bacteriostatic substances. Specific 30 details about the use and operation of these additives, are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 - 113.
Le A 30 526-US 2154q45 A suitable method of producing rigid polyurethane foam materials is presented below.
The components may be reacted in the known single-stage process, the prepolymer process or the semi-prepolymer process, often using machinery such as that described in, for example, U.S. Patent 2,764,565, the disclosure of which is herein incorporated by reference. Details of processing equipment which can also be used according to the invention are described in Kunststoff-Handbuch, Volume VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 121 to 205.
1 0 The foam materials can be made by, for example, slab production or by the known double conveyor-belt method.
The products obtainable according to the invention are suitable for use as, for example, insulating slabs for roofs.
The invention is further illustrated but is not intended to be limited by the 1 5 following examples in which all parts and percentages are by weight unless otherwise specified.
EXAl\IPLES
The polyurethane foam materials were produced by using polyol formulations A
and B described hereinbelow.
Formulation A
A polyol mixture having an OH number of 553 was prepared by mixing the following components:
1. 26.9 parts of a polyether polyol having an OH number of 380, and was prepared by the propoxylation of a mixture of saccharose, propylene glycol and water;
2. 22.0 parts of a polyether polyol having an OH number of 620, and was prepared by the propoxylation of ethylene diamine;
Le A 30 526-US
21540~5 3. 16.0 parts of a polyether polyol having an OH number of 445, and was prepared by the propoxylation of a saccharose and ethylene glycol rnixture;
4. 13.0 parts of a polyether polyol having an OH number of 460, and was prepared by the propoxylation and ethoxylation of ortho toluylene diamine;
5. 10.0 parts of glycerol as a cross-linking agent;
6. 1.6 parts of water as a co-foaming agent;
7. 9.0 parts of tris (~3-chloroisopropyl)phosphate (flame retardant); and 8 1.5 parts of a polyether polyol-modified polysiloxane foam stabilizer.
Formulation B
10 A polyol mixture having an OH number of 404 was prepared by mixing the following components 1. 34.0 parts of a polyether polyol having an OH number of 380, and was prepared by the propoxylation of a mixture of saccharose, propylene glycol and water;
2. 35.0 parts of a polyether polyol having an OH number of 550, and was prepared by the propoxylation of trimethylol propane;
3. 19.0 parts of a polyether polyol having an OH number of 435, and was prepared by the propoxylation of a mixture of phthalic acid, sorbitol and diethylene glycol;
4. 10.0 parts of tris (13-chloroisopropyl)phosphate flame retardant, 5. 0.7 parts of water as a co-foaming agent; and 6. 1.3 parts of a polyether polyol-modified polysiloxane foam stabilizer.
Le A 30 526-US
The polyol formulations A and B were reacted in known manner, in accordance with the formulations in Tables 1 and 2, to obtain rigid polyurethane foam m ~tP.ri ~
The following isocyanates were used in the production of rigid polyurethane foam5 materials:
Isocyanate A: commercially available as Desmodurg) VP PU 1584 from Bayer AG (a modified Isocyanate based on Polymeric MDI with a NCO-content of approx. 28.3%) Isocyanate B: commercially available as Desmodur~) VP PU 1194 from Bayer AG
(a Polymeric MDI with a NCO-content of approx. 30.5%) Le A 30 526-US 2 1 5 ~ 0 4 ~
Table 1: Rigid PUR foam materials cnnt~inin~ powdered fillers other than PUR powder:
Comparison Example Number 1 2 Formulation A 100 Formulation B - 100 Dibutyl tin dilauratel) - 0.012 Desmorapid~ PVl) - 0.25 Dimetlhjyl cyclohexyl 1 0 amine 1.3 Solkane S 141b, Messrs. Solvay 22 23 Isocyanate A: - 122 Isocyanate B 175 1 5 Melamine2) (particle size 0.04 mm) 5 Exolit 4223) (particle size 0.024 mm) - 5 Gross density (kg/m3) 32.9 33.7 Vibration test, 600 rotations (Loss of weight (%)) 11.8 10.7 heeated (gC) g 162 126 1) Catalyst 2) Melamine (grade 003, commercially available from DSM-Chemicals) 3) Exolit~ 422, (ammonium polyphosphate, commercially available from Messrs. Hoechst) Table 2: PUR rigid foam powder cont~ining PUR hard foam w Comp. Examples according to the invention Comp. Examples according to the ~
invenhon c Example number 3 4 5 6 7 8 9 10 11 u~
Formulation A 100 100 100 100 100 - -Formulation B - - - - - 100 100 100 100 Dibutyl tin dilaurate - - - - - 0.012 0.012 0.012 0.012 Desmorapid ~) PV - - - - - 0.25 0.25 0.25 0.25 o Dimethyl cyclohexylamine 1.3 1.3 1.3 1.3 1.3 Solkane S 141B, Messrs 22 22 22 22 22 23 23 23 23 Solvay Isocyanate A - - - - - 122 122 122 122 Isocyanate B 175 175 175 175 175 Pl~R Powder in foarn (wt%) - 3 5 10 5* - 3 3 5 Particle size (mm) - 0.5 0.5 0.5 0.5 0 5 1.6 0.5 * Inc. paper :~, Table 2: (Cont.) w Comp. Examples according to the invention Comp. Examples according to the ~' invention c Example number 3 4 5 6 7 8 9 10 11 Gross density (kg/m3) 31.1 31.0 32.0 32.5 31.3 31.9 32.1 31.6 31.5 Vibrationtest, 600 rotations 6.7 6.1 5.6 6.1 6.4 4.8 5.5 4.3 4.9 (%) Bending strength when 186 175 188 191 194 132 141 135 140 heated C
Shear strength (MPa) 0.15 0.16 0.17 0.17 0.17 1.18 0.18 0.16 0.17 Tensile strength (MPa) 0.26 -.34 0.33 0.32 0.32 0.41 0.41 0.41 0.43 Proportion of closed cells >91 >91 >92 >91 >92 92 96 95 94 (%) o Le A 30 526-US
2ls4n4s Following properties were identified from following methods: -Table 1 Gross density DIN 53420 Vibration Test ASTM C-421 Bending strength DIN 53424 when heated Table 2 Gross density DIN 53420 Vibration Test ASTM C-421 Bending strength DIN 53424 when heated Shear strength DIN 53427 Tensile strength DIN 53430 Proportion of closed cells ISO 4590 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.
Formulation B
10 A polyol mixture having an OH number of 404 was prepared by mixing the following components 1. 34.0 parts of a polyether polyol having an OH number of 380, and was prepared by the propoxylation of a mixture of saccharose, propylene glycol and water;
2. 35.0 parts of a polyether polyol having an OH number of 550, and was prepared by the propoxylation of trimethylol propane;
3. 19.0 parts of a polyether polyol having an OH number of 435, and was prepared by the propoxylation of a mixture of phthalic acid, sorbitol and diethylene glycol;
4. 10.0 parts of tris (13-chloroisopropyl)phosphate flame retardant, 5. 0.7 parts of water as a co-foaming agent; and 6. 1.3 parts of a polyether polyol-modified polysiloxane foam stabilizer.
Le A 30 526-US
The polyol formulations A and B were reacted in known manner, in accordance with the formulations in Tables 1 and 2, to obtain rigid polyurethane foam m ~tP.ri ~
The following isocyanates were used in the production of rigid polyurethane foam5 materials:
Isocyanate A: commercially available as Desmodurg) VP PU 1584 from Bayer AG (a modified Isocyanate based on Polymeric MDI with a NCO-content of approx. 28.3%) Isocyanate B: commercially available as Desmodur~) VP PU 1194 from Bayer AG
(a Polymeric MDI with a NCO-content of approx. 30.5%) Le A 30 526-US 2 1 5 ~ 0 4 ~
Table 1: Rigid PUR foam materials cnnt~inin~ powdered fillers other than PUR powder:
Comparison Example Number 1 2 Formulation A 100 Formulation B - 100 Dibutyl tin dilauratel) - 0.012 Desmorapid~ PVl) - 0.25 Dimetlhjyl cyclohexyl 1 0 amine 1.3 Solkane S 141b, Messrs. Solvay 22 23 Isocyanate A: - 122 Isocyanate B 175 1 5 Melamine2) (particle size 0.04 mm) 5 Exolit 4223) (particle size 0.024 mm) - 5 Gross density (kg/m3) 32.9 33.7 Vibration test, 600 rotations (Loss of weight (%)) 11.8 10.7 heeated (gC) g 162 126 1) Catalyst 2) Melamine (grade 003, commercially available from DSM-Chemicals) 3) Exolit~ 422, (ammonium polyphosphate, commercially available from Messrs. Hoechst) Table 2: PUR rigid foam powder cont~ining PUR hard foam w Comp. Examples according to the invention Comp. Examples according to the ~
invenhon c Example number 3 4 5 6 7 8 9 10 11 u~
Formulation A 100 100 100 100 100 - -Formulation B - - - - - 100 100 100 100 Dibutyl tin dilaurate - - - - - 0.012 0.012 0.012 0.012 Desmorapid ~) PV - - - - - 0.25 0.25 0.25 0.25 o Dimethyl cyclohexylamine 1.3 1.3 1.3 1.3 1.3 Solkane S 141B, Messrs 22 22 22 22 22 23 23 23 23 Solvay Isocyanate A - - - - - 122 122 122 122 Isocyanate B 175 175 175 175 175 Pl~R Powder in foarn (wt%) - 3 5 10 5* - 3 3 5 Particle size (mm) - 0.5 0.5 0.5 0.5 0 5 1.6 0.5 * Inc. paper :~, Table 2: (Cont.) w Comp. Examples according to the invention Comp. Examples according to the ~' invention c Example number 3 4 5 6 7 8 9 10 11 Gross density (kg/m3) 31.1 31.0 32.0 32.5 31.3 31.9 32.1 31.6 31.5 Vibrationtest, 600 rotations 6.7 6.1 5.6 6.1 6.4 4.8 5.5 4.3 4.9 (%) Bending strength when 186 175 188 191 194 132 141 135 140 heated C
Shear strength (MPa) 0.15 0.16 0.17 0.17 0.17 1.18 0.18 0.16 0.17 Tensile strength (MPa) 0.26 -.34 0.33 0.32 0.32 0.41 0.41 0.41 0.43 Proportion of closed cells >91 >91 >92 >91 >92 92 96 95 94 (%) o Le A 30 526-US
2ls4n4s Following properties were identified from following methods: -Table 1 Gross density DIN 53420 Vibration Test ASTM C-421 Bending strength DIN 53424 when heated Table 2 Gross density DIN 53420 Vibration Test ASTM C-421 Bending strength DIN 53424 when heated Shear strength DIN 53427 Tensile strength DIN 53430 Proportion of closed cells ISO 4590 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.
Claims (7)
1. In a process for the production of foam materials containing rigid urethane by reacting a) one or more polyisocyanates, with b) one or more compounds containing at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 400 to 10,000, in the presence of c) one or more organic fillers and d) water and/or one or more foaming agents wherein said foaming agents comprise light volatile organic substances, the improvement wherein said organic filler c) consists essentially of a rigid foam polyurethane powder.
2. The process of Claim 1, wherein said foam materials additionally contain isocyanurate groups.
3. The process of Claim 1, wherein said reaction additionally occurs in the presence of e) compounds containing at least two hydrogen atoms capable of reacting with isocyanate groups and having a molecular weight of 32 to 399.
4. The process of Claim 1, wherein said reaction additionally occurs in the presence of f) known auxiliary substances and additives.
5. The process of Claim 1, wherein said rigid foam polyurethane powder has a particle size of 0.3 to 2.0 mm.
6. The process of Claim 5, wherein said particle size of said rigid foam polyurethane powder is from 0.5 to 1.0 mm.
7. The process of Claim 1, wherein said rigid foam polyurethane powder c) is present in an amount of 0.1 to 10% by weight, based on 100% by weight of all components.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4425614.0 | 1994-07-20 | ||
| DE4425614 | 1994-07-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2154045A1 true CA2154045A1 (en) | 1996-01-21 |
Family
ID=6523634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2154045 Abandoned CA2154045A1 (en) | 1994-07-20 | 1995-07-17 | Method of manufacturing foam materials containing rigid urethane and optional isocyanurate groups |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0693526A1 (en) |
| JP (1) | JPH0867730A (en) |
| CA (1) | CA2154045A1 (en) |
| FI (1) | FI953475A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120196066A1 (en) * | 2011-01-27 | 2012-08-02 | Basf Se | Polyurethane having improved insulating properties |
| CN103459503A (en) * | 2011-01-27 | 2013-12-18 | 巴斯夫欧洲公司 | Polyurethane with improved insulating properties |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19528938C2 (en) * | 1995-08-07 | 1999-01-14 | Johann Ganz | Process for the production of a molding compound |
| DE19633891A1 (en) * | 1996-08-22 | 1998-02-26 | Basf Ag | Processes for the reuse of polyurethanes |
| US6258867B1 (en) * | 1999-07-23 | 2001-07-10 | Bayer Corporation | Method for making semi-rigid energy-absorbing foam with polyurethane fillers |
| CN100491432C (en) * | 2004-10-22 | 2009-05-27 | 四川大学 | Preparation of engineering plastics powder filled hard polyurethane foam |
| KR100838820B1 (en) * | 2006-05-15 | 2008-06-17 | 진양화학 주식회사 | Thermoplastic polyurethane composition |
| JP2019099631A (en) * | 2017-11-30 | 2019-06-24 | 株式会社イノアックコーポレーション | Chip dispersion soft polyurethane foam and its production method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2764656A (en) | 1952-07-26 | 1956-09-25 | Clare & Co C P | Relay |
| US3640920A (en) | 1969-05-21 | 1972-02-08 | Atlas Chem Ind | Rigid low-density filled cellular polyurethanes |
| ATA323175A (en) | 1975-04-28 | 1976-11-15 | Sempiran Patentverwert | METHOD FOR MANUFACTURING A POLYADDITIONAL PLASTIC |
| DE2732292A1 (en) | 1977-07-16 | 1979-02-01 | Bayer Ag | METHOD FOR MANUFACTURING POLYURETHANE PLASTICS |
| DE2832253A1 (en) | 1978-07-22 | 1980-01-31 | Bayer Ag | METHOD FOR PRODUCING MOLDED FOAMS |
| GB2053944A (en) * | 1979-07-13 | 1981-02-11 | Hairlok Ltd | Utilisation of expanded polymer scrap |
| DE3004004A1 (en) * | 1980-02-04 | 1981-08-13 | Recticel Deutschland Kunststoffe GmbH, 5342 Rheinbreitbach | Polyurethane foaming mix production - by mixing specific size screened particle polyurethane with one polyurethane polymerisation reagent |
| DE3033330A1 (en) * | 1980-09-04 | 1982-04-29 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF LIQUID MIXTURES OF COMPOUNDS CONTAINING ISOCYANATE GROUPS, AND THEIR USE AS A BUILDING COMPONENT IN THE PRODUCTION OF POLYURETHANE PLASTICS |
| DE3841671C1 (en) | 1988-12-10 | 1989-10-26 | Maschinenfabrik Hennecke Gmbh, 5090 Leverkusen, De | |
| DE3939954A1 (en) | 1989-12-02 | 1991-06-06 | Hennecke Gmbh Maschf | METHOD AND DEVICE FOR THE PRODUCTION OF PLASTICS, ESPECIALLY FOAM |
-
1995
- 1995-07-07 EP EP95110627A patent/EP0693526A1/en not_active Withdrawn
- 1995-07-17 CA CA 2154045 patent/CA2154045A1/en not_active Abandoned
- 1995-07-18 JP JP7202754A patent/JPH0867730A/en active Pending
- 1995-07-18 FI FI953475A patent/FI953475A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120196066A1 (en) * | 2011-01-27 | 2012-08-02 | Basf Se | Polyurethane having improved insulating properties |
| CN103459503A (en) * | 2011-01-27 | 2013-12-18 | 巴斯夫欧洲公司 | Polyurethane with improved insulating properties |
| US8986801B2 (en) * | 2011-01-27 | 2015-03-24 | Basf Se | Polyurethane having improved insulating properties |
| CN103459503B (en) * | 2011-01-27 | 2016-06-15 | 巴斯夫欧洲公司 | There is the polyurethane of the heat-proof quality of improvement |
Also Published As
| Publication number | Publication date |
|---|---|
| FI953475A0 (en) | 1995-07-18 |
| JPH0867730A (en) | 1996-03-12 |
| EP0693526A1 (en) | 1996-01-24 |
| FI953475A (en) | 1996-01-21 |
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