USRE30676E - Flame resistant polyurethane foam and process for producing the same - Google Patents
Flame resistant polyurethane foam and process for producing the same Download PDFInfo
- Publication number
- USRE30676E USRE30676E US06/110,501 US11050180A USRE30676E US RE30676 E USRE30676 E US RE30676E US 11050180 A US11050180 A US 11050180A US RE30676 E USRE30676 E US RE30676E
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- US
- United States
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- hydrogen atom
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- divalent
- Prior art date
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- Expired - Lifetime
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- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 52
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 27
- -1 amine compound Chemical class 0.000 claims abstract description 70
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 70
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 20
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000962 organic group Chemical group 0.000 claims description 89
- 150000001875 compounds Chemical class 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 23
- 125000002723 alicyclic group Chemical group 0.000 claims description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 125000002947 alkylene group Chemical group 0.000 claims description 17
- 229920006395 saturated elastomer Polymers 0.000 claims description 17
- 229920002545 silicone oil Polymers 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000004604 Blowing Agent Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 33
- 239000007788 liquid Substances 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- 229910052698 phosphorus Inorganic materials 0.000 description 19
- 239000011574 phosphorus Substances 0.000 description 19
- 239000006260 foam Substances 0.000 description 17
- 238000005187 foaming Methods 0.000 description 16
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000007706 flame test Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
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- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000012972 dimethylethanolamine Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 2
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- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
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- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
Definitions
- the present invention relates to a process of producing a rigid polyurethane foam having flame resistance and more particularly, it relates to a process for producing a rigid polyurethane foam having a high flame resistance and unaccompanied by a reduction in the properties of the polyurethane foam or by the formation of scorching.
- the invention further relates to a flame resistant rigid polyurethane produced by such a process.
- the term "rigid polyurethane foam” used herein refers to a foam which loses its original rigidity when the foam is compressed to a compression ratio more than 50% due to the rupture of cells.
- the rigidity of a given foam is generally indicated by a rigidity at a 10% compression ratio.
- Polyurethane foams have hitherto been used in a large number of fields due to their specific properties but have a serious disadvantage in that polyurethane foams are easily flammable.
- Japanese Pat. Publn Nos. 1750/'63; 9197/'70; etc. disclose the use of phosphorus-containing compounds or halogen-containing compounds as flame retarders for polyurethane foams but, in such known techniques the phosphorus-containing compound must be added to such an extent that the content of phosphorus in the foam is higher than 1% or the flame retarder must be blended so that the content thereof is 5 to 30% by weight of the polyurethane foam.
- the properties of the polyurethane foam are degraded, for example, the hardness is reduced, the strength is reduced, etc.
- the extent of the reduction of the amount of retarder depends upon the extent of flame resistance required in the polyurethane foam and the properties of the flame retarder used, but it is preferred that the amount be as small as possible and further it is most preferred that a flame retarder not be used at all.
- rigid polyurethane foam having excellent flame resistance with less reduction in the desired properties thereof can be produced using a greatly reduced amount of a flame retarder or without using any flame retarder by blending the raw materials for producing the polyurethane with a specific amine compound.
- a process of producing a flame resistant rigid polyurethane foam comprises reacting a mixture of a polyetherpolyol and/or a polyesterpolyol having an active hydrogen atom, a polyisocyanate, water and/or a volatile foaming agent as a foaming agent, and an emulsifying agent and containing in the reaction system at least one amine compound represented by any one of the following general formulae (I), (II), (III), (IV), (V), (VI), and (VII): ##STR1## wherein A 1 , A 2 , A 3 , A 4 , and A 5 each represents a hydrogen atom or a monovalent organic group, wherein at least one of A 1 to A 5 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R 1 is a divalent organic group, a trivalent organic group or a tetravalent organic group; R 2 represents a divalent organic group; m
- a flame resistant rigid polyurethane foam produced by the aforesaid process is provided.
- the process of this invention it becomes possible to produce a rigid polyurethane foam having high flame-resisting properties unaccompanied by the occurrence of scorching due to decreasing the amount of flame retarder to such an extent that has been considered to be impossible to provide flame resisting properties using conventional techniques.
- a feature common to the amine compounds represented by aforesaid general formulae (I)-(VII) is that they contain a hydrogen atom active to an isocyanate group.
- a feature of the present invention lies in the discovery that by adding the aforesaid amine compound to the reaction system used in the production of polyurethane foam, the amine compound is introduced in the molecular structure of the polyurethane foam and in this case by properly controlling the reaction of the active hydrogen atom in the amine compound with the isocyanate group, the polymer chain of the foam has excellent flame-resisting properties.
- control of the reaction between such an active hydrogen atom and an isocyanate group in this invention can be attained by permitting nitrogen atoms to exist in the same molecule relative to the active hydrogen atom. That is, it is believed that the reaction is controlled favorably by a catalytic activity of the lone electron pair (the electron pair which does not contribute to the covalent bond) of the nitrogen atom present in the same molecule.
- Examples of monovalent groups represented by A 1 to A 5 include saturated or unsaturated alkyl groups, aryl groups, alicyclic groups and substituted alkyl, aryl and alicyclic groups.
- the number of carbon atoms of the alkyl group can range from 1 to 22 and the number of carbon atoms forming the ring of the alicyclic group can range from about 3 to 6.
- suitable substituents are an amino group, a hydroxyl group, a cyano group, a halogen atom, a mercapto group and the like.
- organic groups represented by A 1 to A 5 are organic groups including ##STR8## groupings in their structure. Suitable such groups are, for example, ##STR9## wherein R represents a saturated or unsaturated lower alkyl group or an aryl group and R' represents a saturated or unsaturated lower alkylene group having, preferably, 1 to 22 carbon atoms.
- Suitable examples of the organic groups of A 1 to A 5 are ##STR10## and the like.
- Examples of the divalent organic group represented by R 1 and R 2 in the general formula (I) are a saturated or unsaturated alkylene group, an arylene group, a divalent alicyclic group, and substituted groups of these groups, the alkylene group having about 1 to 22 carbon atoms and the number of carbon atoms forming the ring of the alicyclic group being about 3 to 6.
- Specific examples of suitable divalent organic groups are as follows: ##STR11## wherein R 9 and R 10 each represents a hydrogen atom or a lower alkyl group having, preferably, 1 to 8 carbon atoms, and R 11 represents an alkylene group having, preferably, 1 to 22 carbon atoms.
- the above illustrated groups may also be partially or fully hydrogenated.
- Suitable examples of R 9 and R 10 are a hydrogen atom and a methyl group, and suitable examples of R 11 are --CH 2 -- or --C 4 H 8 --.
- specific examples of the divalent organic groups are organic groups having at least one of --O--, ##STR12## and --S-- in the groups. For example, there are ##STR13##
- Examples of the trivalent and tetravelent organic groups represented by R 1 in general formula (I) are a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group and a heterocyclic group.
- examples of the divalent organic groups represented by R 3 , R 4 and R 5 are a saturated or unsaturated alkylene group, an arylene group, or a divalent alicyclic group.
- the alkylene group has about 1 to 22 carbon atoms and the number of carbons forming the ring of the alicyclic group is about 3 to 6.
- specific examples of these organic group are divalent organic groups containing ##STR75## groupings in the groups.
- Examples of monovalent organic groups represented by A 6 , A 7 , and A 8 are the same as the monovalent organic group represented by A 1 to A 5 and described for the general formula (I).
- the monovalent organic groups represented by A 9 , A 10 , A 11 and A 12 are the same as the monovalent organic groups represented by A 1 to A 5 and described for general formula (I).
- the monovalent organic groups represented by A 13 and A 14 are the same as the monovalent organic groups represented by A 1 to A 5 and described for the general formula (I).
- Examples of the divalent organic groups represented by R 6 and R 7 in the general formula (IV) are a saturated or unsaturated alkylene group, an arylene group, or a divalent alicyclic group.
- the alkylene group has about 1 to 22 carbon atoms and the number of carbons forming the ring of the alicyclic group is about 3 to 6.
- specific examples of these organic groups are divalent organic groups containing ##STR78## groupings in the groups.
- Examples of monovalent organic groups represented by A 20 to A 22 in the general formula (VI) are the same as the monovalent organic groups represented by A 1 to A 5 and described for the formula (I).
- Examples of monovalent organic groups represented by A 23 and A 24 in the general formula (VII) are the same as the monovalent organic groups represented by A 1 to A 5 and described for the formula (I).
- Examples of organic groups represented by R 8 in the general formula (VII) are a monovalent, divalent, or trivalent saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic group, hydroxyl-substituted groups of these aliphatic, aromatic and alicyclic groups, and the aforesaid groups each substituted by a saturated or unsaturated alkyl group having about 1 to 10 carbon atoms or an aryl group.
- the number of carbon atoms of the aliphatic hydrocarbon group ranges from about 1 to 22 and the number of carbons forming the ring of the alicyclic group ranges from about 3 to 6.
- R 8 are ##STR82## wherein A 29 , A 30 , A 31 , A 32 , and A 33 each represents the same monovalent organic groups, represented by A 1 to A 5 and described for the formula (I) or a hydrogen atom.
- R 8 , A 23 , and A 24 be a hydrogen atom or a group having a hydrogen atom active to an isocyanate group and examples of groups having an active hydrogen atom are a hydroxy-substituted alkyl group and an alkyl group substituted with an --SH group.
- amine compound represented by general formula (I), (II), (III), (IV), (V), (VI) or (VII), individually in the production of polyurethane foam it is possible to render the polyurethane foam flame resistant, but more excellent flame-resisting effects can be obtained by using a combination of two kinds of any amine compounds.
- a combination of an amine compound wherein at least one member of the monovalent groups A 1 to A 24 is a hydrogen atom and an amine compound wherein all the monovalent organic groups A 1 to A 24 are hydroxyl-containing groups or those having hydroxyl-containing groups and organic groups having no active hydrogen atom is especially preferred.
- the polyurethane foam obtained using the aforesaid amine compounds without using a flame retarder is self-extinguishing with a burning distance of 14 to 22 mm as tested in accordance with ASTM D 1692-68.
- the polyurethane foams thus prepared show self-extinguishing properties with a burning distance of 0 to 4 mm using the ASTM D 1692-68 test.
- a flame retarder can be used in combination with the aforesaid amine compound or compounds although as is apparent from the above set forth results, the flame-resisting effects can be obtained without using such flame retarder.
- Suitable flame retarders which can be used in this invention in such a case are phosphorus-containing compounds. Examples of these phosphorus-containing compounds are those compounds containing phosphorus only and which do not contain any halogen such as, for example, triphenyl phosphate, tricresyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate.
- Vercol 82 (trade name, the structure of which is believed to be ##STR84## produced by Mobil Oil Co.), ammonium polyphosphate, bis(dipropylene glycol)dipropylene glycol phosphonate, tri(dipropylene glycol)phosphite, heptaquisdipropylene glycol triphosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate and trioctyl phosphate.
- Compounds containing phosphorus and halogen can be also used as the flame retarder where desired and examples of such compounds are tri-2,3-dibromopropyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate.
- Phosgard 2XC-20 (trade name of Monsanto Chemical Co., for a product having the formula ##STR85## and monodichloropropylbis(dibromopropyl)phosphate.
- Compounds containing phosphorus and halogen provide superior flame-resisting effects to the effects obtained with a compound containing phosphorus only and this is believed to be based on the synergistic effect of the phosphorus and halogen.
- the above-described compounds can be used individually or in combination.
- the aforesaid phosphorus-containing compound can be used together with an organo halogen compound such as tetrabromophthalic anhydride, tetrabromobisphenol A, tetrabromobutane, hexabromobenzene, dichloropropanol, and dibromopropanol.
- the amount of the phosphorus-containing compound used in this invention can be much smaller than the amount employed using conventional technique and can be less than about 0.5% by weight to the weight of polyurethane foam.
- the polyetherpolyol or the polyesterpolyol used in this invention can be free by selected to achieve the desired polyurethane foam. That is, as the polyetherpolyol or polyesterpolyol for rigid polyurethane foam, polyols having a hydroxyl value of about 150 to 900 mg KOH/g can be used individually or as a mixture thereof.
- the polyetherpolyol used in this invention can be prepared by the addition polymerization reaction of an organic compound having at least two active hydrogen atoms and an alkylene oxide.
- organic compounds having at least two hydrogen atoms which can be used as the raw material for producing the polyetherpolyol suitable for this invention are an alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-diol, butane-1,3-diol, hexane-2,5-diol, octadecanediol, octadecenediol, cyclohexane-1,4-dimethanol, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol, mannitol, sorbitol, and sucrose.
- alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-dio
- alkylene oxides which can be used for the addition polymerization reaction are ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and the like.
- polyetherpolyol prepared by addition polymerizing the alkylene oxide and a mixture of two or more of the abovedescribed raw materials having at least two active hydrogen atoms and further it is also possible to use the polyetherpolyol prepared by random- or block-copolymerizing two or more alkylene oxides.
- the polyesterpolyol used in this invention can be prepared by the polymerization reaction of a polyol having at least two active hydroxyl groups and a polybasic acid.
- polyols examples are, as in the case of polyetherpolyols, an alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-diol, butane-1,3-diol, hexane-2,5-diol, octadecanediol, octadecenediol, cyclohexane-1,4-dimethanol, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol, mannitol, sorbitol, sucrose, etc.
- alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-diol, butane-1,3-di
- Suitable polybasic acids are adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, 1,2,4-benzenetricarboxylic acid, thiodiglycolic acid, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, trimellitic acid, a dimerized or trimerized fatty acid, tartaric acid, etc.
- the polyisocyanate used in the present invention is a material conventionally used for producing polyurethane foams in the art and can be appropriately represented by the general formula
- R 26 represents an aliphatic group, an aromatic group, a substituted aliphatic group, or a substituted aromatic group and n 3 has a mean value of 1.5 to 3.0.
- R 26 represents an aliphatic group, an aromatic group, a substituted aliphatic group, or a substituted aromatic group and n 3 has a mean value of 1.5 to 3.0. Examples of the group R 26 are ##STR86##
- Typical examples of the above-described polyisocyanate are ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1,4-naphthylene diisocyanate, xylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene di
- polyisocyanates Of the above-described polyisocyanates, the most widely used polyisocyanates are tolylene diisocyanate, crude polymethylenepolyphenylene isocyanate, crude tolylene diisocyanate, etc., and mixtures thereof.
- the above isocyanate or a mixture of isocyanates can be used in an amount of from 0.5 to 3 equivalents, preferably from 1.0 to 2.0 equivalents, per 1 equivalent of the polyetherpolyol and/or polyesterpolyol.
- catalysts can be used in this invention.
- examples of catalysts are amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, dimethylethanolamine, and the like and metal carboxylates as stannous octoate, dibutyltin dilaurate, lead octylate, and the like. That is, any catalysts which have been used conventionally for the production of polyurethane foams can be used in this invention.
- a suitable amount of the catalyst is less than about 5% by weight, preferably 2 to 3% by weight, of the polyetherpolyol and/or polyesterpolyol. The lesser the amount of the catalyst, the better the results can be obtained.
- foaming agents conventionally employed as the foaming agents for polyurethane foams can be used in this invention.
- foaming agents are well-known and a few specific examples of these agents are monofluorotrichloromethane, methylene chloride, water, etc.
- the amount of the foaming agent is suitably less than about 5% by weight, preferably less than 2% by weight, based on the total weight of the starting materials when water is employed as the foaming agent, and is less than about 70% by weight, preferably 10 to 60% by weight, when a volatile foaming agent is employed.
- a silicone oil such as F-220, F-230, F-260, F-305 and F-307 (trademark of silicone oil, made by Shinetsu Chemical Industry Co.); L-520, L-5340 and L-5420 (trademark of silicone oil, made by Union Carbide Corp.); DC-190, DC-192, DC-193 and DC-195 (trademark of silicone oil, made by Dow Corning Co.); etc.
- Such an emulsifying agent can be used in an amount less than about 2%, preferably less than 1.2% by weight based on the total weight of the starting materials for the polyurethane foams.
- polyurethane foam can be prepared according to any of the above-described methods of can be prepared using other methods to achieve the objects of this invention.
- the polyetherpolyols for rigid polyurethane foams as shown in Table 1 were prepared by addition-polymerizing propylene oxide to the starting materials shown in the same table.
- the polyesterpolyol for rigid polyurethane foams as shown in Table 1 was prepared by condensation reaction of glycerine, adipic acid and ethylene glycol.
- Rigid polyurethane foams were prepared using the amine compounds, the flame retarders, and the polyetherpolyols prepared as previously described.
- the compositions for forming polyurethane foams, the foaming techniques, and the method of testing the flame resistance employed in this example were as follows:
- the polyisocyanate the temperature of which had been adjusted to 20° C. was poured into the mixture and then the mixture was mixed for 10 seconds using a mixer at 4000 r.p.m.
- the product thus obtained was poured into a plasticlined steel box.
- foaming was completed in 150 seconds.
- the foamed product was allowed to stand for 24 hours at room temperature (about 20° C. to 30° C.) and cut into pieces for measuring the various properties thereof. The results showed that all foams prepared had good appearance and were enclosed cellular type elastic foams.
- the flame test was conducted according to the methods of American Standard of Testing Method D1692-68 (ASTM D1692-68) and the result was evaluated by the burning distance (mm) in each case.
- the distance between the first marked line and the second marked line of the sample piece was 100 mm.
- Rigid polyurethane foams were prepared using the amine compounds, the polyetherpolyols, and silicone oils previously described.
- the compositions of the foaming materials, the foaming procedure, and the flame test employed in this example were as follows:
- test results obtained are shown in TAble 4.
- the amine compounds of this invention make it possible to provide a good flame-resisting property to the polyurethane foam without causing any deterioration of physical properties of the foam.
- Rigid polyurethane foams were prepared using the combination of two kinds of the amine compounds and the polyetherpolyols previously described.
- the composition of the foaming mixtures, the foaming procedures, and the flame resistance test employed in this example were as follows:
- Rigid polyurethane foams were prepared using the polyetherpolyols, the silicone oils, and the combination of two kinds of the amine compounds, and the phosphorus-containing compounds as previously described.
- the compositions of the foaming mixtures, the foaming procedure, and the flame test results were as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A process for producing a flame resistant rigid polyurethane foam by reacting a reaction mixture comprising a polyetherpolyol and/or a polyesterpolyol having an active hydrogen atom, a polyisocyanate, water and/or a volatile foaming agent and an emulsifying agent, in which a specific amine compound shown by the general formula as defined hereinafter in the specification is added to the reaction system, the weight ratio of amine compound to polyetherpolyol and/or polyesterpolyol being from 70:30 to 30:70, and also the flame resistant rigid polyurethane foam produced by the process.
Description
This is a continuation of application Ser. No. 483,339 filed June 26, 1974, and now abandoned.
1. Field of the Invention
The present invention relates to a process of producing a rigid polyurethane foam having flame resistance and more particularly, it relates to a process for producing a rigid polyurethane foam having a high flame resistance and unaccompanied by a reduction in the properties of the polyurethane foam or by the formation of scorching. The invention further relates to a flame resistant rigid polyurethane produced by such a process. The term "rigid polyurethane foam" used herein refers to a foam which loses its original rigidity when the foam is compressed to a compression ratio more than 50% due to the rupture of cells. The rigidity of a given foam is generally indicated by a rigidity at a 10% compression ratio.
2. Description of the Prior Art
Polyurethane foams have hitherto been used in a large number of fields due to their specific properties but have a serious disadvantage in that polyurethane foams are easily flammable.
Recently, however, regulations on the extent for rendering polyurethane materials flame retardant or flame resistant have become more and more severe, and this property is particularly important in the application thereof in the fields of automobiles, railway vehicles, aircraft, etc.
The rendering of flame-retarding properties or flame resistance to polyurethane foams is an important problem as described above, but it has not yet been solved by conventional techniques. The methods which have been industrially employed at present still have a large number of difficulties.
Some techniques for rendering polyurethane foams flame retardant are described in the specifications of, e.g., Japanese Pat. Publication Nos. 1750/'63; 9197/'70, 349/'64; 4846/'64; 8696/'64; 26335/'71; 21358/'69; 13037/'66; 2269/'71; Belgian Pat. No. 723,246; U.S. Pat. Nos. 3,262,894; 3,309,342; 3,385,900; 3,402,132; 3,407,150; 3,455,850; 3,530,205; and 3,535,406; British Pat. Nos. 918,636; 954,712; 999,588; and 1,043,832; etc., but these techniques are insufficient for satisfying the necessary requirements.
For example, Japanese Pat. Publn Nos. 1750/'63; 9197/'70; etc., disclose the use of phosphorus-containing compounds or halogen-containing compounds as flame retarders for polyurethane foams but, in such known techniques the phosphorus-containing compound must be added to such an extent that the content of phosphorus in the foam is higher than 1% or the flame retarder must be blended so that the content thereof is 5 to 30% by weight of the polyurethane foam. As a result of using such a large amount of flame retarder, the properties of the polyurethane foam are degraded, for example, the hardness is reduced, the strength is reduced, etc. Furthermore, when the polyurethane material is foamed excessively, the so-called scorching phenomenon occurs which lowers the commercial value of the article. Moreover, since in such cases the concentration of the flame retarder is high, the flame retarder tends to volatilize away due to the action of heat or with the passage of time, which results in a reduction in the flame-proofing or flame-resisting effects. In order to prevent the formation of such scorching, the content of the flame retarder must be reduced to as small an amount as possible. Therefore, the development of a foaming technique which can render polyurethane foams flame retardant using as little an amount of flame retarder as is possible or without using any flame retarder has been highly desired.
As described above, an important problem has been to improve the flame resistance of the polyurethane foam by blending a halogen-containing or phosphorus-containing compound in an amount as small as possible.
The extent of the reduction of the amount of retarder depends upon the extent of flame resistance required in the polyurethane foam and the properties of the flame retarder used, but it is preferred that the amount be as small as possible and further it is most preferred that a flame retarder not be used at all.
With such in mind, the inventors have investigated and as the result of their investigations have discovered that rigid polyurethane foam having excellent flame resistance with less reduction in the desired properties thereof can be produced using a greatly reduced amount of a flame retarder or without using any flame retarder by blending the raw materials for producing the polyurethane with a specific amine compound.
Thus, according to the present invention a process of producing a flame resistant rigid polyurethane foam is provided which comprises reacting a mixture of a polyetherpolyol and/or a polyesterpolyol having an active hydrogen atom, a polyisocyanate, water and/or a volatile foaming agent as a foaming agent, and an emulsifying agent and containing in the reaction system at least one amine compound represented by any one of the following general formulae (I), (II), (III), (IV), (V), (VI), and (VII): ##STR1## wherein A1, A2, A3, A4, and A5 each represents a hydrogen atom or a monovalent organic group, wherein at least one of A1 to A5 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R1 is a divalent organic group, a trivalent organic group or a tetravalent organic group; R2 represents a divalent organic group; m1 represents 0 or a positive integer smaller than 8; and n1 represents 1, 2 or 3; ##STR2## wherein A6, A7, and A8 each represents a hydrogen atom or a monovalent organic group, with at least one of A6 to A8 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R3, R4 and R5 each represents a divalent organic group; ##STR3## wherein A9, A10, A11, and A12 each represents a hydrogen atom or a monovalent organic group, with at least one of A9 to A12 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; ##STR4## wherein A13 and A14 each represents a hydrogen atom or a monovalent organic group, with at least one of A13 and A14 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group and R6 and R7 each represents a divalent organic group; ##STR5## wherein A15, A16, A17, A18, and A19 each represents a hydrogen atom or a monovalent organic group, with at least one of A15 to A19 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; ##STR6## wherein A20, A21 and A22 each represents a hydrogen atom or a monovalent organic group, with at least one of A20 to A22 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; ##STR7## wherein R6 represents a hydrogen atom, a monovalent organic group, a divalent organic group, or a trivalent organic group; A23 and A24 each represents a hydrogen atom or a monovalent organic group, at least one of the R8, A23, and A24 being a hydrogen atom or a group having a hydrogen atom active to an isocyanate group; Z represents an oxygen atom or a sulfur atom; and n2 is an integer of 1 to 3.
Furthermore, according to this invention, a flame resistant rigid polyurethane foam produced by the aforesaid process is provided. By the process of this invention, it becomes possible to produce a rigid polyurethane foam having high flame-resisting properties unaccompanied by the occurrence of scorching due to decreasing the amount of flame retarder to such an extent that has been considered to be impossible to provide flame resisting properties using conventional techniques.
A feature common to the amine compounds represented by aforesaid general formulae (I)-(VII) is that they contain a hydrogen atom active to an isocyanate group. A feature of the present invention lies in the discovery that by adding the aforesaid amine compound to the reaction system used in the production of polyurethane foam, the amine compound is introduced in the molecular structure of the polyurethane foam and in this case by properly controlling the reaction of the active hydrogen atom in the amine compound with the isocyanate group, the polymer chain of the foam has excellent flame-resisting properties. The control of the reaction between such an active hydrogen atom and an isocyanate group in this invention can be attained by permitting nitrogen atoms to exist in the same molecule relative to the active hydrogen atom. That is, it is believed that the reaction is controlled favorably by a catalytic activity of the lone electron pair (the electron pair which does not contribute to the covalent bond) of the nitrogen atom present in the same molecule.
Examples of monovalent groups represented by A1 to A5 include saturated or unsaturated alkyl groups, aryl groups, alicyclic groups and substituted alkyl, aryl and alicyclic groups. In this case, the number of carbon atoms of the alkyl group can range from 1 to 22 and the number of carbon atoms forming the ring of the alicyclic group can range from about 3 to 6. Examples of suitable substituents are an amino group, a hydroxyl group, a cyano group, a halogen atom, a mercapto group and the like.
Furthermore, specific examples of the organic groups represented by A1 to A5 are organic groups including ##STR8## groupings in their structure. Suitable such groups are, for example, ##STR9## wherein R represents a saturated or unsaturated lower alkyl group or an aryl group and R' represents a saturated or unsaturated lower alkylene group having, preferably, 1 to 22 carbon atoms.
Suitable examples of the organic groups of A1 to A5 are ##STR10## and the like.
Examples of the divalent organic group represented by R1 and R2 in the general formula (I) are a saturated or unsaturated alkylene group, an arylene group, a divalent alicyclic group, and substituted groups of these groups, the alkylene group having about 1 to 22 carbon atoms and the number of carbon atoms forming the ring of the alicyclic group being about 3 to 6. Specific examples of suitable divalent organic groups are as follows: ##STR11## wherein R9 and R10 each represents a hydrogen atom or a lower alkyl group having, preferably, 1 to 8 carbon atoms, and R11 represents an alkylene group having, preferably, 1 to 22 carbon atoms. The above illustrated groups may also be partially or fully hydrogenated. Suitable examples of R9 and R10 are a hydrogen atom and a methyl group, and suitable examples of R11 are --CH2 -- or --C4 H8 --. Furthermore, specific examples of the divalent organic groups are organic groups having at least one of --O--, ##STR12## and --S-- in the groups. For example, there are ##STR13##
Also, Examples of substituents of these divalent organic groups are --CH3, CH3 CH2 --, ##STR14##
Examples of the trivalent and tetravelent organic groups represented by R1 in general formula (I) are a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group and a heterocyclic group.
Also, specific examples of the trivalent organic groups and tetravalent organic groups represented by R1 are as follows: ##STR15##
Typical examples of amine compounds represented by the general formula (I) are shown below:
__________________________________________________________________________
Description
__________________________________________________________________________
##STR16## (Compound Designation) Light Yellow
Solid (I-1)
##STR17## (Compound Designation) Black-Brown
Solid (I-2)
##STR18## Black-Brown Solid (I-3)
##STR19## Light-Yellow Solid (I-4)
##STR20## Light-Yellow Solid (I-5)
##STR21## Light-Yellow Solid (I-6)
##STR22## Yellow Liquid (I-7)
##STR23## Yellow Solid (I-8)
##STR24## Yellow Liquid (I-9)
##STR25## Colorless Transparent Liquid (I-10)
##STR26## Yellow Liquid (I-11)
##STR27## Yellow Liquid (I-12)
##STR28## Light-Yellow Liquid (I-13)
##STR29## Light-Yellow Solid (I-14)
##STR30## (Compound Designation) Brown Liquid
(I-15)
##STR31## Brown Liquid (I-16)
##STR32## Yellow Liquid (I-17)
##STR33## Yellow Liquid (I-18)
##STR34## Yellow Liquid (I-19)
##STR35## Yellow Liquid (I-20)
##STR36## White Solid (I-21)
##STR37## Light-Yellow Solid (I-22)
##STR38## Black Brown Solid (I-23)
##STR39## Light-Yellow Solid (I-24)
##STR40## Light-Yellow Solid (I-25)
##STR41## Light-Yellow Solid (I-26)
##STR42## (Compound Designation) Transparent
Liquid (I-27)
##STR43## White Solid (I-28)
##STR44## White Solid (I-29)
##STR45## White Solid (I-30)
##STR46## Light-Yellow Liquid (I-31)
##STR47## Brown Solid (I-32)
##STR48## Light-Yellow Liquid (I-33)
##STR49## Brown Liquid (I-34)
##STR50## Colorless Transpar- ent Liquid
(I-35)
##STR51## Light-Yellow Solid (I-36)
##STR52## Brown Solid (I-37)
##STR53## Light-Yellow Solid (I-38)
##STR54## Colorless Transpar- ent Liquid
(I-39)
##STR55## (Compound Designation) Yellow Brown
Liquid (I-40)
##STR56## Colorless Transpar- ent Liquid
(I-41)
##STR57## Colorless Transpar- ent Liquid
(I-42)
##STR58## Colorless Transpar- ent Liquid
(I-43)
##STR59## Colorless Transpar- ent Highly
Viscous Liquid (I-41-A)
##STR60## Colorless Transpar- ent Liquid
(I-44)
##STR61## White Solid (I-45)
##STR62## Yellow Solid (I-46)
##STR63## Yellow Solid (I-47)
##STR64## Yellow Solid (I-48)
##STR65## (Compound Designation) Yellow Solid
(I-49)
##STR66## Yellow Solid (I-50)
##STR67## Yellow Solid (I-51)
##STR68## Yellow Liquid (I-52)
##STR69## Yellow Solid (I-53)
##STR70## Yellow Solid (I-54)
##STR71## Yellow Solid (I-55)
##STR72## Yellow Solid (I-56)
##STR73## Light Yellow Solid (I-57)
##STR74## Light Yellow Liquid (I-58)
__________________________________________________________________________
In the amine compounds represented by the general formula (II), examples of the divalent organic groups represented by R3, R4 and R5 are a saturated or unsaturated alkylene group, an arylene group, or a divalent alicyclic group. In this case, the alkylene group has about 1 to 22 carbon atoms and the number of carbons forming the ring of the alicyclic group is about 3 to 6. Furthermore, specific examples of these organic group are divalent organic groups containing ##STR75## groupings in the groups. Examples of monovalent organic groups represented by A6, A7, and A8 are the same as the monovalent organic group represented by A1 to A5 and described for the general formula (I).
Typical examples of amine compounds represented by the general formula (II) are shown below: ##STR76##
In the amine compounds represented by general formula (III), the monovalent organic groups represented by A9, A10, A11 and A12 are the same as the monovalent organic groups represented by A1 to A5 and described for general formula (I).
Typical examples of compounds represented by general formula (III) are shown below: ##STR77##
In the amine compounds represented by the general formula (IV), the monovalent organic groups represented by A13 and A14 are the same as the monovalent organic groups represented by A1 to A5 and described for the general formula (I).
Examples of the divalent organic groups represented by R6 and R7 in the general formula (IV) are a saturated or unsaturated alkylene group, an arylene group, or a divalent alicyclic group. In this case, the alkylene group has about 1 to 22 carbon atoms and the number of carbons forming the ring of the alicyclic group is about 3 to 6. Furthermore, specific examples of these organic groups are divalent organic groups containing ##STR78## groupings in the groups.
Typical examples of compounds represented by general formula (IV) are shown below: ##STR79##
In the amine compounds represented by general formula (V), the monovalent organic groups shown by A15 to A19 are the same as the monovalent organic groups represented by A1 to A5 and described for general formula (I). Typical examples of compounds represented by general formula (V) are shown below: ##STR80##
Examples of monovalent organic groups represented by A20 to A22 in the general formula (VI) are the same as the monovalent organic groups represented by A1 to A5 and described for the formula (I).
Typical examples of amine compounds represented by the general formula (VI) are shown below: ##STR81##
Examples of monovalent organic groups represented by A23 and A24 in the general formula (VII) are the same as the monovalent organic groups represented by A1 to A5 and described for the formula (I). Examples of organic groups represented by R8 in the general formula (VII) are a monovalent, divalent, or trivalent saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic group, hydroxyl-substituted groups of these aliphatic, aromatic and alicyclic groups, and the aforesaid groups each substituted by a saturated or unsaturated alkyl group having about 1 to 10 carbon atoms or an aryl group. The number of carbon atoms of the aliphatic hydrocarbon group ranges from about 1 to 22 and the number of carbons forming the ring of the alicyclic group ranges from about 3 to 6. Other examples of R8 are ##STR82## wherein A29, A30, A31, A32, and A33 each represents the same monovalent organic groups, represented by A1 to A5 and described for the formula (I) or a hydrogen atom. In the amine compounds of the general formula (VII), it is essential at least one of R8, A23, and A24 be a hydrogen atom or a group having a hydrogen atom active to an isocyanate group and examples of groups having an active hydrogen atom are a hydroxy-substituted alkyl group and an alkyl group substituted with an --SH group.
Typical examples of compounds represented by general formula (VII) are shown below: ##STR83##
Even in the case of using the above-described amine compound individually, quite excellent flame-resisting effects can be obtained without the necessity of using a phosphorus-containing compound when a polyetherpolyol having a polyoxyethylene chain or polyester-polyol prepared by using a polyglycol-containing ethylene glycol is used as the foaming material together with the amine compound.
As described above, by blending the amine compound represented by general formula (I), (II), (III), (IV), (V), (VI) or (VII), individually in the production of polyurethane foam, it is possible to render the polyurethane foam flame resistant, but more excellent flame-resisting effects can be obtained by using a combination of two kinds of any amine compounds. A combination of an amine compound wherein at least one member of the monovalent groups A1 to A24 is a hydrogen atom and an amine compound wherein all the monovalent organic groups A1 to A24 are hydroxyl-containing groups or those having hydroxyl-containing groups and organic groups having no active hydrogen atom is especially preferred.
The polyurethane foam obtained using the aforesaid amine compounds without using a flame retarder is self-extinguishing with a burning distance of 14 to 22 mm as tested in accordance with ASTM D 1692-68. When two kinds of amine compounds selected from the two groups described above were used without adding a flame retarder, the polyurethane foams thus prepared show self-extinguishing properties with a burning distance of 0 to 4 mm using the ASTM D 1692-68 test.
In the present invention, a flame retarder can be used in combination with the aforesaid amine compound or compounds although as is apparent from the above set forth results, the flame-resisting effects can be obtained without using such flame retarder. Suitable flame retarders which can be used in this invention in such a case are phosphorus-containing compounds. Examples of these phosphorus-containing compounds are those compounds containing phosphorus only and which do not contain any halogen such as, for example, triphenyl phosphate, tricresyl phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethyl phosphonate. Vercol 82 (trade name, the structure of which is believed to be ##STR84## produced by Mobil Oil Co.), ammonium polyphosphate, bis(dipropylene glycol)dipropylene glycol phosphonate, tri(dipropylene glycol)phosphite, heptaquisdipropylene glycol triphosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate and trioctyl phosphate.
Compounds containing phosphorus and halogen can be also used as the flame retarder where desired and examples of such compounds are tri-2,3-dibromopropyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate. Phosgard 2XC-20 (trade name of Monsanto Chemical Co., for a product having the formula ##STR85## and monodichloropropylbis(dibromopropyl)phosphate.
Compounds containing phosphorus and halogen provide superior flame-resisting effects to the effects obtained with a compound containing phosphorus only and this is believed to be based on the synergistic effect of the phosphorus and halogen. The above-described compounds can be used individually or in combination. Furthermore, if desired, the aforesaid phosphorus-containing compound can be used together with an organo halogen compound such as tetrabromophthalic anhydride, tetrabromobisphenol A, tetrabromobutane, hexabromobenzene, dichloropropanol, and dibromopropanol.
The amount of the phosphorus-containing compound used in this invention can be much smaller than the amount employed using conventional technique and can be less than about 0.5% by weight to the weight of polyurethane foam.
The polyetherpolyol or the polyesterpolyol used in this invention can be free by selected to achieve the desired polyurethane foam. That is, as the polyetherpolyol or polyesterpolyol for rigid polyurethane foam, polyols having a hydroxyl value of about 150 to 900 mg KOH/g can be used individually or as a mixture thereof.
The polyetherpolyol used in this invention can be prepared by the addition polymerization reaction of an organic compound having at least two active hydrogen atoms and an alkylene oxide.
Examples of organic compounds having at least two hydrogen atoms which can be used as the raw material for producing the polyetherpolyol suitable for this invention are an alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-diol, butane-1,3-diol, hexane-2,5-diol, octadecanediol, octadecenediol, cyclohexane-1,4-dimethanol, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol, mannitol, sorbitol, and sucrose.
Also, suitable examples of alkylene oxides which can be used for the addition polymerization reaction are ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, and the like.
It is possible in this invention to use the polyetherpolyol prepared by addition polymerizing the alkylene oxide and a mixture of two or more of the abovedescribed raw materials having at least two active hydrogen atoms and further it is also possible to use the polyetherpolyol prepared by random- or block-copolymerizing two or more alkylene oxides.
Moreover, the polyesterpolyol used in this invention can be prepared by the polymerization reaction of a polyol having at least two active hydroxyl groups and a polybasic acid.
Examples of the polyols are, as in the case of polyetherpolyols, an alkylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butane-2,3-diol, butane-1,3-diol, hexane-2,5-diol, octadecanediol, octadecenediol, cyclohexane-1,4-dimethanol, glycerine, trimethylolethane, trimethylolpropane, pentaerythritol, mannitol, sorbitol, sucrose, etc.
Examples of suitable polybasic acids are adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, 1,2,4-benzenetricarboxylic acid, thiodiglycolic acid, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, trimellitic acid, a dimerized or trimerized fatty acid, tartaric acid, etc.
Depending on the kind of polyurethane foam to be produced, higher flame-resisting effects can be obtained as the case may be when the polyetherpolyol or the polyesterpolyol contains oxyethylene groups. In this case, such a purpose can be easily attained by using ethylene oxide or ethylene glycol as a part of the raw material for the production of the polyetherpolyol or the polyesterpolyol.
The polyisocyanate used in the present invention is a material conventionally used for producing polyurethane foams in the art and can be appropriately represented by the general formula
R.sup.26 (NCO).sub.n3
wherein R26 represents an aliphatic group, an aromatic group, a substituted aliphatic group, or a substituted aromatic group and n3 has a mean value of 1.5 to 3.0. Examples of the group R26 are ##STR86##
Typical examples of the above-described polyisocyanate are ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1,4-naphthylene diisocyanate, xylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, furfurylidene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, triisopropenylbenzene diisocyanate, p-isocyanatophenylthiophosphoric acid triester, p-isocyanatophenylphosphoric acid triester, 1-(isocyanatophenyl)ethylisocyanate, 4,4',4"-triisocyanatotriphenylmethane, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotriene, 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, and the like. They may be used individually or as a mixture thereof.
Of the above-described polyisocyanates, the most widely used polyisocyanates are tolylene diisocyanate, crude polymethylenepolyphenylene isocyanate, crude tolylene diisocyanate, etc., and mixtures thereof.
The above isocyanate or a mixture of isocyanates can be used in an amount of from 0.5 to 3 equivalents, preferably from 1.0 to 2.0 equivalents, per 1 equivalent of the polyetherpolyol and/or polyesterpolyol.
If necessary, catalysts can be used in this invention. Examples of catalysts are amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, dimethylethanolamine, and the like and metal carboxylates as stannous octoate, dibutyltin dilaurate, lead octylate, and the like. That is, any catalysts which have been used conventionally for the production of polyurethane foams can be used in this invention.
A suitable amount of the catalyst is less than about 5% by weight, preferably 2 to 3% by weight, of the polyetherpolyol and/or polyesterpolyol. The lesser the amount of the catalyst, the better the results can be obtained.
Any foaming agents conventionally employed as the foaming agents for polyurethane foams can be used in this invention. These foaming agents are well-known and a few specific examples of these agents are monofluorotrichloromethane, methylene chloride, water, etc. The amount of the foaming agent is suitably less than about 5% by weight, preferably less than 2% by weight, based on the total weight of the starting materials when water is employed as the foaming agent, and is less than about 70% by weight, preferably 10 to 60% by weight, when a volatile foaming agent is employed.
As an emulsifying agent, a silicone oil such as F-220, F-230, F-260, F-305 and F-307 (trademark of silicone oil, made by Shinetsu Chemical Industry Co.); L-520, L-5340 and L-5420 (trademark of silicone oil, made by Union Carbide Corp.); DC-190, DC-192, DC-193 and DC-195 (trademark of silicone oil, made by Dow Corning Co.); etc., can be used. Such an emulsifying agent can be used in an amount less than about 2%, preferably less than 1.2% by weight based on the total weight of the starting materials for the polyurethane foams.
Various methods of preparing polyurethane foams are described in Japanese Patent Pub. Nos. 7541/'56; 4241/'56; 5742/'57; 7094/'58; 9275/'59; 17498/'60; 8195/'61; 7895/'62; 6000/'63; 2097/'64; 12639/'66; 10630/'67; 19039/'68; 21318/'68; 40075/'70; etc., and according to the most practical method of those known methods, a polyetherpolyol (and/or a polyesterpolyol), polyisocyanate, a forming agent, an amine compound, and other additives, for example, dyes, pigments, fillers, antioxidants, plasticizers and the like are uniformly blended in a short period of time followed by foaming and molding and then the foamed product is heated externally or is allowed to stand to complete the curing of the product. Also, a similar method to that above in which, however, the polyetherpolyol and the polyisocyanate have been partially or completely reacted with each other prior to the blending is useful and has been widely employed. The polyurethane foam can be prepared according to any of the above-described methods of can be prepared using other methods to achieve the objects of this invention.
Now, the invention will be described further by reference to following examples. Unless otherwise indicated, all parts, percents, ratios and the like are by weight.
To confirm the effects and advanages of this invention, Compounds I-1 to VII-5, described hereinbefore were prepared and furthermore for the purpose of comparison the compounds shown by the following formulae were also prepared. ##STR87##
It will readily be understood that the above-described compounds prepared for the purposes of comparison are different from and outside the scope of the amine compounds of this invention since each of Compounds Y-1, Y-2, Y-3, Y-4, Y-5, Y-6, and Y-7 has none of hydrogen atom or organic group having a hydrogen atom active to an isocyanate group directly connected to the nitrogen atom although these compound may be considered similar to compounds of general formulae (I) to (VII) in this invention.
The polyetherpolyols for rigid polyurethane foams as shown in Table 1 were prepared by addition-polymerizing propylene oxide to the starting materials shown in the same table. The polyesterpolyol for rigid polyurethane foams as shown in Table 1 was prepared by condensation reaction of glycerine, adipic acid and ethylene glycol.
TABLE 1
______________________________________
Starting Hydroxyl
Polyol
Material Value Viscosity
Type
______________________________________
(mgKOH/g) (CPS/25° C.
K-1 Sucrose 450 7000 Polyetherpolyol
K-2 Sorbitol 450 12000 "
K-3 Sucrose 500 33000 "
K-4 Pentacry-
500 3500 "
thritol
K-5 Glycer- 500 152000 Polyesterpolyol
ine
______________________________________
Also, the phosphorus-containing compounds as shown in Table 2 were prepared as flame retarders.
TABLE 2
______________________________________
Phosphorus- Phosphorus Content
Containing
Chemical Name in the Compound
Compound No.
or Trade Name (%)
______________________________________
P-1 Trischloroethyl 10.8
Phosphate
P-2 tris-2,3-Dibromo-
4.4
propyl phosphate
P-3 Fyrol &* 12.9
______________________________________
*Trade name for diethylN,N-bis(2-hydroxyethyl)aminomethyl phosphate,
produced by Staufer Chemicals Co.
After preparing the raw materials as described above, rigid polyurethane foams were prepared as shown in the following examples.
Rigid polyurethane foams were prepared using the amine compounds, the flame retarders, and the polyetherpolyols prepared as previously described. The compositions for forming polyurethane foams, the foaming techniques, and the method of testing the flame resistance employed in this example were as follows:
______________________________________
Composition parts by weight
______________________________________
Polyetherpolyol.sup.(1) variable
Water 1.0
Freon 11.sup.(2) 35
Silicone Oil DC-193.sup.(3)
10
Phosphorus-Containing Compound.sup.(1)
variable
Amine Compound.sup.(1) variable
Millionate MP.sup.(4) 110 (index).sup.(5)
______________________________________
Note
.sup.(1) As shown in Table 3.
.sup.(2) Trade name of monofluorotrichloromethane, produced by Darkin
Industry Co.
.sup.(3) Trademark of silicone oil, produced by Dow Corning Co.
.sup.(4) Crude polymethylene polyphenylene isocyanate produced by Nippon
Polyurethane Co.
.sup.(5) The term "110 (index)" means that the amount of the isocyanate i
larger than the equivalent amount of the hydroxyl group to be reacted wit
the isocyanate by 10%.
In a two liter polyethylene beaker was placed 1 kg of the polyetherpolyol and then all of the remaining components except for the polyisocyanate were added to the polyetherpolol followed by mixing. Then, the temperature of the mixture was adjusted to 20° C.
Thereafter, the polyisocyanate, the temperature of which had been adjusted to 20° C. was poured into the mixture and then the mixture was mixed for 10 seconds using a mixer at 4000 r.p.m. The product thus obtained was poured into a plasticlined steel box. When the system was allowed to foam freely, foaming was completed in 150 seconds. Thereafter, the foamed product was allowed to stand for 24 hours at room temperature (about 20° C. to 30° C.) and cut into pieces for measuring the various properties thereof. The results showed that all foams prepared had good appearance and were enclosed cellular type elastic foams.
The flame test was conducted according to the methods of American Standard of Testing Method D1692-68 (ASTM D1692-68) and the result was evaluated by the burning distance (mm) in each case. The distance between the first marked line and the second marked line of the sample piece was 100 mm.
The relation between the amine compounds and the flame resistance of the foams prepared is shown in Table 3, in which all of the numeral values shown by parts are based 100 parts by weight of the polyetherpolyol or polyesterpolyol.
TABLE 3
__________________________________________________________________________
Burning
Compression Strength
Phosphorus-
Dimethyl- Distance
(kg/cm.sup.2)
Amine Containing
ethanol
Rise
Foam (mm) Parallel
Perpendicular
Polyol Compound
Compound
Amine Time
Density
ASTM D
to Rise
to Rise
No.
(part)
No. (part)
No.
(part)
(part)
(sec)
(kg/cm.sup.3)
1692-68
Direction
Direction
__________________________________________________________________________
K-1
100 -- -- P-1
15 3.0 102
33.4 75 1.4 0.4
K-1
60 I-56
40 -- -- 0.5 92 31.6 45 2.4 1.1
K-1
60 I-35
40 -- -- 0.5 95 32.0 40 2.5 1.3
K-1
60 I-36
40 -- -- 0.5 89 32.2 38 2.4 1.3
K-1
60 I-37
40 -- -- 0.5 93 31.8 42 2.6 1.2
K-1
60 I-38
40 -- -- 0.5 96 31.7 36 2.5 1.4
K-1
60 I-57
40 -- -- 0.5 94 32.0 38 2.4 1.2
K-1
60 I-42
40 -- -- 0.5 90 33.1 51 2.4 1.0
K-1
60 I-41-A
40 -- -- 0.5 91 32.6 27 2.6 1.4
K-1
60 I-40
40 -- -- 0.5 95 34.0 33 2.7 1.3
K-1
60 III-3
40 -- -- 0.5 94 31.5 43 2.5 1.2
K-1
80 I-56
20 -- -- 0.5 150
34.0 100 2.2 0.9
K-1
90 I-56
10 -- -- 0.5 260
34.5 100 2.1 0.8
K-1
20 I-56
80 -- -- 0.5 40 34.1 100 2.2 0.8
K-3
80 I-35
20 -- -- 2.0 96 33.4 100 2.0 0.7
K-3
70 I-35
30 -- -- 1.0 93 32.1 68 2.4 1.2
K-3
50 I-35
50 -- -- 0.3 88 31.5 30 2.7 1.3
K-3
40 I-35
60 -- -- 0 87 32.0 38 2.9 1.2
K-3
30 I-35
70 -- -- 0 65 33.0 70 2.7 1.2
K-2
50 I-37
50 P-3
5 0.5 91 31.0 0 2.4 1.3
K-1
50 I-37
50 P-3
5 0.5 95 30.5 0 2.4 1.1
K-4
50 I-37
50 -- -- 0.3 93 31.3 40 2.3 1.0
K-3
50 I-35
50 P-1
5 0.5 94 32.0 0 2.2 1.0
K-3
50 I-35
50 P-2
5 0.5 90 31.8 0 2.3 1.1
K-1
60 Y-1 40 -- -- 1.0 92 33.3 100 1.8 0.9
K-1
60 Y-2 40 -- -- 1.0 92 33.2 100 1.6 0.8
K-1
60 Y-3 40 -- -- 1.0 95 31.6 100 1.2 0.6
K-1
60 Y-4 40 -- -- 1.0 78 32.5 100 1.5 0.7
K-1
60 Y-5 40 -- -- 1.0 78 33.4 100 1.4 0.7
K-1
60 Y-6 40 -- -- 0.5 85 33.2 100 1.7 0.8
K-1
60 Y-7 40 -- -- 0.5 82 32.2 100 1.0 0.5
K-5
10 I-56
90 -- -- 0.5 75 33.2 100 1.8 0.9
K-5
20 I-56
80 -- -- 0.5 76 34.0 100 1.6 0.8
K-5
40 I-56
60 -- -- 0.5 80 32.5 45 2.5 1.2
K-5
60 I-56
40 -- -- -- 85 33.6 36 2.8 1.5
K-5
65 I-56
35 -- -- 0.5 90 32.4 35 2.6 1.4
K-5
80 I-56
20 -- -- 1.5 90 30.8 100 1.4 0.7
K-1
60 II-1
40 -- -- 0.5 95 31.4 44 2.4 1.2
K-1
60 II-2
40 -- -- 0.5 91 32.3 38 2.2 1.1
K-1
60 III-1
40 -- -- 0.5 86 30.1 26 2.8 1.4
K-1
60 III-2
40 -- -- 0.5 92 32.5 35 2.4 1.4
K-1
60 III-4
40 -- -- 0.5 87 33.0 24 2.5 1.2
K-1
50 III-5
40 -- -- 0.5 87 30.8 20 2.4 1.2
K-1
50 IV-1
50 -- -- 0.5 78 31.6 25 2.2 1.1
K-3
40 IV-2
60 -- -- -- 90 31.9 24 26 1.3
K-3
40 V-1 60 -- -- -- 92 33.0 18 2.4 1.4
K-3
40 V-2 60 -- -- -- 90 32.5 21 2.3 1.2
K-3
40 V-3 60 -- -- -- 88 32.4 28 2.1 1.1
K-3
40 VI-1
60 -- -- -- 88 31.8 34 2.1 0.9
K-3
40 VI-2
60 -- -- -- 95 31.7 38 2.6 1.2
K-3
40 VI-3
60 -- -- -- 80 31.5 45 2.5 1.3
K-1
40 VI-4
60 -- -- -- 85 32.4 44 2.3 1.2
K-1
40 VI-5
60 -- -- 0.5 95 32.6 42 2.4 1.2
K-1
40 VI-6
60 -- -- 0.5 96 32.1 46 2.3 1.2
K-3
60 VII-1
40 -- -- 0.5 87 32.0 43 2.5 1.4
K-3
60 VII-2
40 -- -- 0.5 94 30.9 42 2.2 1.2
K-3
60 VII-3
40 -- -- 0.5 90 32.1 38 2.3 1.3
K-3
60 VII-4
40 -- -- 0.5 92 32.0 39 2.3 1.2
__________________________________________________________________________
As is apparent from the results shown in Table 3, good flame-resisting effects can be obtained in the cases where the amine compounds of this invention are used, as compared with those obtained by using Reference Compounds (Y-1 to Y-7). In addition, it is apparent that the properties of the resulting foams such as an increase of density, a lowering of compression strength almost do not deteriorate when the amine compounds of this invention are used. Further, the above results suggest that excellent results can be attained when the amine compounds are used in a proportion of 70 to 30 parts by weight relative to 30 to 70 parts by weight of the polyetherpolyols or polyesterpolyols.
Rigid polyurethane foams were prepared using the amine compounds, the polyetherpolyols, and silicone oils previously described. The compositions of the foaming materials, the foaming procedure, and the flame test employed in this example were as follows:
______________________________________
Composition Parts by Weight
______________________________________
Polyetherpolyol.sup.(1)
variable
Freon 11 variable
Silicone Oil L-5420.sup.(2)
1.5
Dabco 33 LV.sup.(3) variable
Phosphorus-Containing Compound.sup.(1)
variable
Amine Compound.sup.(1)
variable
PAP.sup.(4) (index)
______________________________________
Note:
.sup.(1) As shown in Table 4.
.sup.(2) Trademark of silicone oil, produced by Union Carbide Co.
.sup.(3) Trademark of triethylenediamine, produced by Houdry Process &
Chemicals Co.
.sup.(4) Trademark of polyisocyanate, produced by the Upjohn Co.
TABLE 4
__________________________________________________________________________
Burning
Compression Strength
Phosphorus- Distance
(kg/cm.sup.2)
Amine Containing
Dabco
Freon
Rise
Foam (mm) Parallel
Perpendicular
Polyol Compound
Compound
33LV
11 Time
Density
ASTM D
to Rise
to Rise
No.
(part)
No. (part)
No.
(part)
(part)
(part)
(sec)
(kg/m.sup.3)
1692-68
Direction
Direction
__________________________________________________________________________
K-3
50 I-38
50 -- -- -- 10 95 41.6 38 30.1 25.3
K-3
50 I-38
50 -- -- -- 15 98 37.2 34 15.2 14.0
K-3
50 I-38
50 -- -- -- 20 97 32.4 36 6.7 5.1
K-3
50 I-38
50 -- -- -- 25 100 27.2 24 4.1 2.7
K-3
50 I-38
50 -- -- -- 30 102 22.5 11 2.5 1.2
K-3
50 Y-1 50 P-1
15 -- 10 94 42.0 37 29.4 23.0
K-3
50 Y-2 50 P-1
15 -- 15 92 37.8 46 14.1 12.0
K-3
50 Y-3 50 P-1
15 -- 20 88 32.2 61 4.8 3.9
K-3
50 Y-4 50 P-1
15 -- 25 84 27.5 85 3.0 1.5
K-3
50 Y-5 50 P-1
15 -- 30 81 22.2 95 1.8 0.7
K-3
100 -- -- P-1
15 1.8 10 94 43.1 36 28.2 22.5
K-3
100 -- -- P-1
15 1.8 15 98 49.0 48 14.2 12.2
K-3
100 -- -- P-1
15 1.8 20 105 33.0 72 3.9 2.8
K-3
100 -- -- P-1
15 1.8 25 111 28.5 100 3.0 1.5
K-3
100 -- -- P-1
15 1.8 30 120 24.2 100 1.7 0.6
K-1
65 I-41-A
35 P-2
2 0.8 25 92 27.2 14 4.0 2.7
K-1
65 I-41-A
35 P-2
4 0.8 25 95 26.9 2 4.1 2.7
K-1
65 I-41-A
35 P-2
6 0.8 25 93 27.3 0 3.8 2.9
K-1
65 I-41-A
35 P-2
8 0.8 25 89 27.8 0 4.0 2.7
K-1
65 Y-2 35 P-2
2 0.8 25 94 27.5 100 3.5 2.0
K-1
65 Y-2 35 P-2
4 0.8 25 93 28.0 100 3.8 1.8
K-1
65 Y-2 35 P-2
6 0.8 25 88 28.2 100 3.3 1.8
K-1
65 Y-2 35 P-2
8 0.8 25 93 27.9 96 3.6 1.9
__________________________________________________________________________
Same as in Example 1.
Same as in Example 1.
The test results obtained are shown in TAble 4. As shown in the table, the amine compounds of this invention make it possible to provide a good flame-resisting property to the polyurethane foam without causing any deterioration of physical properties of the foam.
Rigid polyurethane foams were prepared using the combination of two kinds of the amine compounds and the polyetherpolyols previously described. The composition of the foaming mixtures, the foaming procedures, and the flame resistance test employed in this example were as follows:
______________________________________
Composition parts by weight
______________________________________
Polyetherpolyol.sup.(1)
variable
Water 1.0
Freon II 35
Silicone Oil DC-195.sup.(2)
1.0
Dimethylethanolamine
1.5
Amine Compound.sup.(1)
variable
Millionate MR 105 (index)
______________________________________
Note:
.sup.(1) As shown in Table 5.
.sup.(2) Trademark of silicone oil, produced by Dow Corning Co.
Same as in Example 1.
The results obtained are shown in Table 5. That is, as shown in Table 5, the polyurethane foams prepared showed sufficient flame-resisting effect in the case of using the combination of two kinds of the amine compounds of this invention without using a phosphorus-containing compound.
TABLE 5
__________________________________________________________________________
Amine Compound
Amine Compound ASTM
Experiments
Polyetherpolyol
[I] [II] Foam Density
Burning Distance
No. No. Part
No. Part
No. Part
(kg/m.sup.3)
(mm)
__________________________________________________________________________
1-1 K-1 60 I-4 5 I-35 35 32.5 10
1-2 K-1 60 I-6 5 I-39 35 31.5 8
1-3 K-1 60 II-2 5 I-42 35 32.4 12
1-4 K-1 60 III-3
5 I-46 35 31.8 6
1-5 K-1 60 IV-3 5 I-49 35 31.8 0
1-6 K-1 60 V-3 10 I-55 30 32.0 12
1-7 K-1 60 VI-1 10 I-52 30 32.2 9
1-8 K-1 60 VI-4 10 I-40 30 31.6 7
1-9 K-1 60 II-2 10 I-35 30 32.3 6
1-10 K-1 60 II-2 10 II-1 30 32.6 2
1-11 K-2 40 I-2 20 III-5
40 31.5 18
1-12 K-2 40 II-2 20 VI-2 40 31.4 21
1-13 K-2 40 II-2 20 V-2 40 31.6 16
1-14 K-2 40 II-2 20 VI-3 40 32.0 18
1-15 K-2 40 II-2 20 VI-5 40 32.2 14
1-16 K-3 35 III-2
2.5 I-47 62.5
31.5 2
1-17 K-3 35 III-3
2.5 II-1 62.5
31.7 4
1-18 K-3 35 II-4 2.5 III-5
62.5
32.6 2
1-19 K-3 50 III-2
2.5 IV-1 47.5
31.3 6
1-20 K-3 50 III-3
2.5 V-1 47.5
33.0 5
1-21 K-4 65 III-4
5 VI-4 30 31.3 22
1-22 K-4 65 IV-2 10 VI-5 25 31.2 24
1-23 K-4 65 IV-3 15 I-43 20 32.6 22
1-24 K-1 100 -- -- -- -- 32.1 100
__________________________________________________________________________
Rigid polyurethane foams were prepared using the polyetherpolyols, the silicone oils, and the combination of two kinds of the amine compounds, and the phosphorus-containing compounds as previously described. The compositions of the foaming mixtures, the foaming procedure, and the flame test results were as follows:
______________________________________
Composition parts by weight
______________________________________
Polyetherpolyol.sup.(1)
variable
Freon 11 45
Silicone Oil L5340 1.2
Dimethylethanolamine 1.5
Phosphorus-Containing Compound.sup.(1)
variable
Amine Compound.sup.(1)
variable
polyisocyanate.sup.(2)
105 (index)
______________________________________
Note:
.sup.(1) As shown in Table 6.
.sup.(2) A prepolymer of TDI80 (trademark of tolylene diisocyanate,
produced by Nippon Soda Co., Ltd.) and a polyetherpolyol; isocyanate grou
content, 30%.
Foaming procedure and flame test procedure were the same as in Example 1.
The results obtained are shown in Table 6.
TABLE 6
__________________________________________________________________________
Amine Compound
Amine Compound ASTM
Experiments
Polyetherpolyol
[I] [II] Flame Retardant
Foam Density
Burning Distance
No. No. Part No. Part No. Part No. Part
(kg/m.sup.3)
(mm)
__________________________________________________________________________
2-1 K-1 60 I-7 5 Y-1 35 -- -- 22.6 100
2-2 K-1 60 I-8 5 Y-2 35 -- -- 23.1 100
2-3 K-1 60 I-9 5 Y-3 35 -- -- 21.5 100
2-4 K-1 60 I-10 5 Y-4 35 -- -- 22.0 100
2-5 K-1 60 I-11 5 Y-5 35 -- -- 24.0 100
2-6 K-1 60 I-13 3 Y-6 37 -- -- 22.4 100
2-7 K-1 60 I-14 3 Y-7 37 P-1 2 22.5 100
2-8 K-1 60 I-15 3 I-46 37 P-1 4 22.6 2
2-9 K-1 60 I-16 3 I-47 37 P-1 6 22.8 0
2-10 K-1 60 I-17 3 I-48 37 P-1 8 22.8 0
2-11 K-3 40 I-18 10 I-49 50 P-2 10 22.6 0
2-12 K-3 40 II-2 5 I-52 55 -- -- 21.2 10
2-13 K-3 40 III-2
5 I-53 55 P-3 2 21.5 6
2-14 K-3 40 IV-3 5 II-1 55 P-3 4 21.7 0
2-15 K-3 40 V-3 5 III-5
55 P-3 6 21.7 0
2-16 K-3 40 VI-1 5 IV-2 55 P-3 8 22.0 0
2-17 K-1 20 VII-3
2 V-1 78 -- -- 21.3 100
2-18 K-1 20 VI-4 2 V-3 78 -- -- 21.6 100
2-19 K-1 100 -- -- -- -- P-1 6 21.8 100
2-20 K-1 100 -- -- -- -- P-1 8 22.0 83
2-21 K-1 100 -- -- -- -- P-1 12 22.8 36
2-22 K-1 100 -- -- -- -- P-1 14 23.2 24
2-23 K-1 100 -- -- -- -- P-1 16 23.5 4
__________________________________________________________________________
As shown in Table 6, when the combination of two kinds of amine compounds of this invention was used together with phosphorus-containing compound more excellent flame-resisting effects were obtained as compared with the cases of using the amine compound individually and a combination of the two kinds of amine compounds without phosphorus-containing compound.
The physical properties of the foam are shown in Table 7.
TABLE 7
__________________________________________________________________________
Experiment No. 3-1 3-2 3-3 3-4 3-5
Polyetherpolyol K-1
60
60 60 100 70
__________________________________________________________________________
Amine I-8 10
Compound
I-10 10 30
[I] VI-6 10
Amine I-42 30
Compound
II-2 30
[II] I-39 30
Rise Time (sec)
54 60 58 90 65
Density (kg/m.sup.3)
22.0
23.2
22.5
24.0
24.3
10% Compression Strength
* 2.6 2.8 2.4 1.6 1.7
(Kg/cm.sup.2)
**
1.3 1.4 1.2 0.7 0.7
Foam Dimension Stability (%)
Properties
Volume Change
100° C. 1 day
+2.1
+2.0
°2.3
+2.5
+2.4
100° C. 7 days
+3.8
+3.7
+3.9
+4.8
+5.0
100° C. 14 days
+3.9
+4.0
+4.2
+5.2
+5.5
-20° C. 1 day
0.0 0.0 0.0 -0.2
-0.1
-20° C. 7 days
0.0 0.0 0.0 -0.5
-0.4
-20° C. 14 days
0.0 -0.1
0.0 -0.6
-0.7
Burning Test
ASTM 1692-68 8 4 7 100 88
Burning Distance (mm)
__________________________________________________________________________
*Parallel to Rise Direction
**Perpendicular to Rise Direction
with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (16)
1. A process for producing a flame resistant rigid polyurethane foam comprising reacting a mixture consisting of (i) a polyetherpolyol .[.and.]. .Iadd.or .Iaddend.a polyesterpolyol, each having an active hydrogen atom, (ii) a polyisocyanate, said polyisocyanate being used in an amount of 0.5 to 3 equivalents per 1 equivalent of said polyetherpolyol .[.and.]. .Iadd.or .Iaddend.polyesterpolypol, (iii) at least one blowing agent selected from water and a volatile foaming agent, said water when present being used in an amount of less than about 5% by weight and said volatile foaming agent when present being used in an amount of less than about 70% by weight, said weights being based on the total weight of the starting materials, (iv) an emulsifying agent, said emulsifying agent being used in an amount of less than about 2% by weight based on the total weight of the starting materials, and (v) at least one amine compound selected from general formulae (I), (II), (III), (IV), (V), (VI), and (VII): ##STR88## wherein A1, A2, A3, A4, and A5 each represents a hydrogen atom or a monovalent organic group, wherein at least one of A1 to A5 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R1 is a divalent organic group, a trivalent organic group or a tetravalent organic group; R2 represents a divalent organic group; m1 represents 0 or a positive integer smaller than 8; and n1 represents 1, 2 or 3; ##STR89## wherein A6, A7, and A8 each represents a hydrogen atom or a monovalent organic group, with at least one of A6 to A8 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R3, R4 and R5 each represents a divalent organic group; ##STR90## wherein A9, A10, A11, and A12 each represents a hydrogen atom or a monovalent organic group, with at least one of A9 to A12 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; ##STR91## wherein A13 and A14 each represents a hydrogen atom or a monovalent organic group, with at least one of A13 and A14 being a hydrogen atom or an organic group which contains a hydrogen atom active to a isocyanate group and R6 and R7 each represents a divalent organic group; ##STR92## wherein A15, A16, A17, A18, and A19 each represents a hydrogen atom or a monovalent organic group, with at least one of A15 to A19 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; ##STR93## wherein A20, A21 and A22 each represents a hydrogen atom or a monovalent organic group, with at least one of A20 to A22 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; and ##STR94## wherein R8 represents a hydrogen atom, a monovalent organic group, a divalent organic group, or a trivalent organic group; A23 and A24 each represents a hydrogen atom or a monovalent organic group, at least one of said R8, A23, and A24 being a hydrogen atom or a group having a hydrogen atom active to an isocyanate group; Z represents an oxygen atom or a sulfur atom; and n2 is an integer of 1 to 3, the weight ratio of said amine compound to said polyetherpolyol .[.and.]. .Iadd.or .Iaddend.polyesterpolyol being from 7:3 to 3:7, said polyurethane foam being self-extinguishing with a burning distance of 14 to 22 mm as tested in accordance with ASTM D 1692-68.
2. The process as claimed in claim 1, wherein said groups for A1 to A24 are selected from the group consisting of a saturated or unsaturated alkyl group, aryl group, or alicyclic group.
3. The process as claimed in claim 2, wherein said alkyl, aryl or alicyclic groups are substituted with substituents, said substituents being an amino group, a hydroxyl group, a cyano group, a mercapto group or a halogen atom.
4. The process as claimed in 1, wherein said monovalent organic group contains therein a ##STR95## grouping.
5. The process as claimed in claim 1, wherein A1 to A24 ##STR96## or --R'--O--R, wherein R represents a lower alkyl group or an aryl group and R' represents a lower alkylene group.
6. The process as claimed in claim 1, wherein R1 is a divalent saturated or unsaturated alkylene group, arylene group, or alicyclic group, or a tri- or tetra-valent saturated or unsaturated aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic hydrocarbon group or a heterocyclic group.
7. The process as claimed in claim 1, wherein R1 and R2 is selected from the group consisting of a saturated or unsaturated alkylene group, an arylene group, or a divalent alicyclic group.
8. The process as claimed in claim 1, wherein R' or R2 is ##STR97## wherein R9 and R10 each represents a hydrogen atom or a lower alkyl group and R11 represents an alkylene group.
9. The process as claimed in claim 1, wherein the divalent organic group represented by said R3, R4, R5, R6 and R7 is a saturated or unsaturated alkylene group, an arylene group or a divalent alicyclic group.
10. The process as claimed in claim 1, wherein the organic group represented by said R8 in the general formula (VII) is a monovalent, divalent or trivalent saturated or unsaturated aliphatic hydrocarbon group; an aromatic hydrocarbon group; an alicyclic group; in which each of said groups may be substituted by a saturated or unsaturated alkyl group, a hydroxyl group, or an aryl group; a ##STR98## group; a --N═N-- group; or a ##STR99## group; wherein A29 to A33 each represents an unsubstituted or substituted, saturated or unsaturated alkyl group, an aryl group, or an alicyclic group, said substituents for each of said alkyl, aryl, and alicyclic groups being a halogen atom, a hydroxyl group, a mercapto group, an amino group or a cyano group.
11. The process as claimed in claim 1, wherein said amine compounds is represented by the formulae (I), (II), (III) or (IV) wherein at least two groups of the monovalent groups represented by A1 to A14 are hydroxyl-containing groups.
12. The process as claimed in claim 1, wherein said amine compound is a mixture of an amine compound selected from the compounds (i) represented by the formulae (I), (II), (III), (IV), (V), (VI) and (VII) wherein at least one group of the monovalent organic groups represented by A1 to A24 is a hydrogen atom, and an amine compound selected from the compounds (ii) represented by the formulae (I), (II), (III), (IV), (V), (VI) and (VII) wherein all monovalent organic groups represented by A1 to A24 are hydroxyl-containing groups.
13. The process as claimed in claim 1, wherein said emulsifying agent is a silicone oil.
14. The process as claimed in claim 1, wherein said emulsifying agent is used in an amount less than about 2% by weight based on the weight of the total amount of starting materials.
15. The process as claimed in claim 1, wherein said mixture further contains at least one catalyst.
16. A flame resistant rigid polyurethane foam produced by the process as claimed in claim 1. .Iadd. 17. A process for producing a flame resistant rigid polyurethane foam comprising reacting a mixture consisting of (i) a polyetherpolyol or a polyesterpolyol, each having an active hydrogen atom, (ii) a polyisocyanate, said polyisocyanate being used in an amount of 0.5 to 3 equivalents per 1 equivalent of said polyetherpolyol or polyesterpolyl, (iii) at least one blowing agent selected from water and a volatile foaming agent, said water when present being used in an amount of less than about 5% by weight and said volatile foaming agent when present being used in an amount of less than about 70% by weight, said weights being based on the total weight of the starting materials, (iv) an emulsifying agent, said emulsifying agent being used in an amount of less than about 2% by weight based on the total weight of the starting materials, and (v) at least one amine compound selected from general formula (I): ##STR100## wherein A1, A2, A3, A4, and A5 each represents a hydrogen atom or a monovalent organic group, wherein at least one of A1 to A5 being a hydrogen atom or an organic group which contains a hydrogen atom active to an isocyanate group; R1 is a divalent organic group, a trivalent organic group or a tetravalent organic group; R2 represents a divalent organic group; m1 represents 0 or a positive integer smaller than 8; and n1 represents 1, 2 or 3; the weight ratio of said amine compound to said polyetherpolyol or polyesterpolyol being from 7:3 to 3:7, said polyurethane foam being self-extinguishing with a burning distance of 14 to 22 mm as tested in accordance with ASTM D 1692-68. .Iaddend.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP48-72463 | 1973-06-26 | ||
| JP48072463A JPS5215118B2 (en) | 1973-06-26 | 1973-06-26 | |
| JP48-110799 | 1973-10-01 | ||
| JP48110799A JPS5215119B2 (en) | 1973-10-01 | 1973-10-01 |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US48333974A Continuation | 1973-06-26 | 1974-06-26 | |
| US05/645,172 Reissue US4088614A (en) | 1973-06-26 | 1975-12-29 | Flame resistant polyurethane foam and process for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE30676E true USRE30676E (en) | 1981-07-14 |
Family
ID=26413597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/110,501 Expired - Lifetime USRE30676E (en) | 1973-06-26 | 1980-01-08 | Flame resistant polyurethane foam and process for producing the same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | USRE30676E (en) |
| DE (1) | DE2430589A1 (en) |
| FR (1) | FR2235146B1 (en) |
| GB (1) | GB1480392A (en) |
| IT (1) | IT1016145B (en) |
| NL (1) | NL7408510A (en) |
| PH (1) | PH14717A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722942A (en) | 1986-05-30 | 1988-02-02 | The Dow Chemical Company | Flexible polyurethane foams which exhibit excellent flame resistance |
| US5336696A (en) * | 1993-12-10 | 1994-08-09 | Nisshinbo Industries, Inc. | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US5776992A (en) * | 1995-11-03 | 1998-07-07 | Hoechst Aktiengesellschaft | Halogen-free, flame retardant rigid polyurethane foam |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948825A (en) * | 1974-07-05 | 1976-04-06 | Basf Wyandotte Corporation | Curing agent for use in making cellular polyurethane compositions |
| DE2523633C2 (en) * | 1975-05-28 | 1982-12-16 | Bayer Ag, 5090 Leverkusen | Process for the production of polyurethane foams and catalysts for carrying out the process |
| CN115537171A (en) * | 2022-09-27 | 2022-12-30 | 江苏华大新材料有限公司 | Low-temperature-resistant polyurethane composite adhesive and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953533A (en) * | 1958-04-04 | 1960-09-20 | Allied Chem | Highly cross-linked non flammable polyurethane foams and preparation of same |
| US3175030A (en) * | 1963-03-07 | 1965-03-23 | Chemotronics International Inc | Process for the preparation of reticulated materials |
| US3175025A (en) * | 1963-04-05 | 1965-03-23 | Chemotronics International Inc | Process for bonding and/or reticulation |
| US3221016A (en) * | 1962-07-16 | 1965-11-30 | Jefferson Chem Co Inc | Piperazine derivatives and method of preparation |
| US3476933A (en) * | 1966-10-21 | 1969-11-04 | Westinghouse Electric Corp | Large-celled polyurethane foam |
| US3681273A (en) * | 1969-10-14 | 1972-08-01 | Scott Paper Co | Nonburning,intumescent flexible polyurethane foam |
| US3730919A (en) * | 1970-03-09 | 1973-05-01 | Uniroyal Inc | Process for production of rigid self-skinning polyurethane foam |
| US4143003A (en) * | 1976-06-01 | 1979-03-06 | Bayer Aktiengesellschaft | Polyurethanes made with linear polyamines |
-
1974
- 1974-06-24 IT IT51685/74A patent/IT1016145B/en active
- 1974-06-25 NL NL7408510A patent/NL7408510A/xx not_active Application Discontinuation
- 1974-06-26 GB GB28463/74A patent/GB1480392A/en not_active Expired
- 1974-06-26 FR FR7422333A patent/FR2235146B1/fr not_active Expired
- 1974-06-26 PH PH15979A patent/PH14717A/en unknown
- 1974-06-26 DE DE2430589A patent/DE2430589A1/en not_active Ceased
-
1980
- 1980-01-08 US US06/110,501 patent/USRE30676E/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2953533A (en) * | 1958-04-04 | 1960-09-20 | Allied Chem | Highly cross-linked non flammable polyurethane foams and preparation of same |
| US3221016A (en) * | 1962-07-16 | 1965-11-30 | Jefferson Chem Co Inc | Piperazine derivatives and method of preparation |
| US3175030A (en) * | 1963-03-07 | 1965-03-23 | Chemotronics International Inc | Process for the preparation of reticulated materials |
| US3175025A (en) * | 1963-04-05 | 1965-03-23 | Chemotronics International Inc | Process for bonding and/or reticulation |
| US3476933A (en) * | 1966-10-21 | 1969-11-04 | Westinghouse Electric Corp | Large-celled polyurethane foam |
| US3681273A (en) * | 1969-10-14 | 1972-08-01 | Scott Paper Co | Nonburning,intumescent flexible polyurethane foam |
| US3730919A (en) * | 1970-03-09 | 1973-05-01 | Uniroyal Inc | Process for production of rigid self-skinning polyurethane foam |
| US4143003A (en) * | 1976-06-01 | 1979-03-06 | Bayer Aktiengesellschaft | Polyurethanes made with linear polyamines |
Non-Patent Citations (2)
| Title |
|---|
| Billmeyer, "Textbook of Polymer Science," 2nd Ed., (Wiley, N.Y.) 1971, pp. 480-482. * |
| Vollmert, "Polymer Chemistry," (Springer-Verlag) 1973, p. 240. * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4722942A (en) | 1986-05-30 | 1988-02-02 | The Dow Chemical Company | Flexible polyurethane foams which exhibit excellent flame resistance |
| US5336696A (en) * | 1993-12-10 | 1994-08-09 | Nisshinbo Industries, Inc. | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US5776992A (en) * | 1995-11-03 | 1998-07-07 | Hoechst Aktiengesellschaft | Halogen-free, flame retardant rigid polyurethane foam |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1480392A (en) | 1977-07-20 |
| DE2430589A1 (en) | 1975-01-16 |
| FR2235146B1 (en) | 1982-02-19 |
| PH14717A (en) | 1981-11-13 |
| IT1016145B (en) | 1977-05-30 |
| AU7051274A (en) | 1976-01-15 |
| NL7408510A (en) | 1974-12-30 |
| FR2235146A1 (en) | 1975-01-24 |
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