CA1068450A - Process for the preparation of semi-rigid polyurethane foam having exceptional shock-absorbing properties and vehicle bumpers thereof - Google Patents
Process for the preparation of semi-rigid polyurethane foam having exceptional shock-absorbing properties and vehicle bumpers thereofInfo
- Publication number
- CA1068450A CA1068450A CA269,201A CA269201A CA1068450A CA 1068450 A CA1068450 A CA 1068450A CA 269201 A CA269201 A CA 269201A CA 1068450 A CA1068450 A CA 1068450A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- polyether polyol
- range
- polyol
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 49
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 2
- 229920005862 polyol Polymers 0.000 claims abstract description 61
- 150000003077 polyols Chemical class 0.000 claims abstract description 59
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 210000003850 cellular structure Anatomy 0.000 claims abstract description 4
- 238000007906 compression Methods 0.000 claims description 47
- 230000006835 compression Effects 0.000 claims description 47
- 239000005056 polyisocyanate Substances 0.000 claims description 35
- 229920001228 polyisocyanate Polymers 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000011541 reaction mixture Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000012948 isocyanate Substances 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002250 absorbent Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- -1 methylene, ethylene, propylene Chemical group 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 150000002902 organometallic compounds Chemical group 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 239000006260 foam Substances 0.000 description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 30
- 238000012360 testing method Methods 0.000 description 13
- 235000013877 carbamide Nutrition 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 229960002887 deanol Drugs 0.000 description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 5
- 229940043237 diethanolamine Drugs 0.000 description 5
- 238000009863 impact test Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000003750 conditioning effect Effects 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 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 3
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 3
- 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229930195725 Mannitol Natural products 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000594 mannitol Substances 0.000 description 3
- 235000010355 mannitol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 235000010356 sorbitol Nutrition 0.000 description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 3
- 239000000811 xylitol Substances 0.000 description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 3
- 235000010447 xylitol Nutrition 0.000 description 3
- 229960002675 xylitol Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 2
- 235000019414 erythritol Nutrition 0.000 description 2
- 229940009714 erythritol Drugs 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 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 2
- 229960001124 trientine Drugs 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- DGLFZUBOMRZNQX-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorocyclobutane Chemical compound FC1(F)CC(F)(F)C1(F)F DGLFZUBOMRZNQX-UHFFFAOYSA-N 0.000 description 1
- WGZYQOSEVSXDNI-UHFFFAOYSA-N 1,1,2-trifluoroethane Chemical compound FCC(F)F WGZYQOSEVSXDNI-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- KODLUXHSIZOKTG-UHFFFAOYSA-N 1-aminobutan-2-ol Chemical compound CCC(O)CN KODLUXHSIZOKTG-UHFFFAOYSA-N 0.000 description 1
- VEZJSKSPVQQGIS-UHFFFAOYSA-N 1-chloro-2-fluoroethane Chemical compound FCCCl VEZJSKSPVQQGIS-UHFFFAOYSA-N 0.000 description 1
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 239000004340 Chloropentafluoroethane Substances 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000764877 Parena Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960001855 mannitol Drugs 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- RIVIDPPYRINTTH-UHFFFAOYSA-N n-ethylpropan-2-amine Chemical compound CCNC(C)C RIVIDPPYRINTTH-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 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
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R19/00—Wheel guards; Radiator guards, e.g. grilles; Obstruction removers; Fittings damping bouncing force in collisions
- B60R19/02—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects
- B60R19/03—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects characterised by material, e.g. composite
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSlmE
A ___ _ _ _ A process ls provlded for produclng seml-rlgid polyurethane ioams havlng exceptional sboclc-abYorblng propert~es, even after repeated com-presslon, prepared ~y the reaction of a polylsocyanate; a polyether polyol haylng a molecubr we~ght wlthln the range trom about 2, 000 to about 10, OOO;from about 1 ~o about ~i~ by welght of water per part by we~ht of polyetber polyol;
from about 1 to about 6~c by ~velght of ~urea and/or thloures. per part by welght of polyether polyol; and a cross-1lnklng compour.d haYlng at least three actlve hydrogen atoms per molecule that are reactlve wlth lsocyanate grou~ and havlng a molecular we~ght below about 1000 ln an amount from about 5 to about 25g~ by welght per part by weight of polyether polyol; the amount of polylsocyanate belng selected to give an lsocyanate index wlthln the range from about 0. 7 to about 1. ~.
The process provldes polyurethane foams that have a cellular structure that remalns un~maged under compresslon as high as 60~ at temperatures wlthln the range from about ~ 60°C to about -40~C, and the consequent deformatlon Is 1ess than 1~ even after ten compresslons of at least 50~ In rapid succession.
Accordingly, tlle lnYention iurther pro~rides vehlcle bumpers haYing an impact-r~celvlng layer of thls polyurethane foam, and that meet th~
requlrements of FM~SS 215.
A ___ _ _ _ A process ls provlded for produclng seml-rlgid polyurethane ioams havlng exceptional sboclc-abYorblng propert~es, even after repeated com-presslon, prepared ~y the reaction of a polylsocyanate; a polyether polyol haylng a molecubr we~ght wlthln the range trom about 2, 000 to about 10, OOO;from about 1 ~o about ~i~ by welght of water per part by we~ht of polyetber polyol;
from about 1 to about 6~c by ~velght of ~urea and/or thloures. per part by welght of polyether polyol; and a cross-1lnklng compour.d haYlng at least three actlve hydrogen atoms per molecule that are reactlve wlth lsocyanate grou~ and havlng a molecular we~ght below about 1000 ln an amount from about 5 to about 25g~ by welght per part by weight of polyether polyol; the amount of polylsocyanate belng selected to give an lsocyanate index wlthln the range from about 0. 7 to about 1. ~.
The process provldes polyurethane foams that have a cellular structure that remalns un~maged under compresslon as high as 60~ at temperatures wlthln the range from about ~ 60°C to about -40~C, and the consequent deformatlon Is 1ess than 1~ even after ten compresslons of at least 50~ In rapid succession.
Accordingly, tlle lnYention iurther pro~rides vehlcle bumpers haYing an impact-r~celvlng layer of thls polyurethane foam, and that meet th~
requlrements of FM~SS 215.
Description
"" 1068450 SPECIFICATION
un;~ ;td~s iA The~llFederal Motor Vehicle Safety Standard FMVSS 215 establishes ``` ~ ^ requirements for safety bumpers for motor vehicles, and i.s applicable to all motor vehicles manufactured on or after September 1, 1973. The 5 objective of the standard is to prevent lo~v sl?eed collisions from impairing the safe operation of the vehicle. Certain requirements for impact resistance and the confi~uration of the front ànd rear surfaces oE the bumper system are prescribed, and the bumper must meet speciIied requirements during alld after impact by a pendlllum-type test device, followed by impact into a ~0 fixed collision barrier that is perpendicular to the line of movement of the vehicle, while the vehicle is travelling forward at a speed of five miles })er hour. The bumpe.r impact-receiving face must not have a permanent deformation greater than three-eights of an inch from its original con-figuration thirty minutes following each impact against the barrier~
15One way to meet the requirement is to incorporate a hydraulic system behind a rigid bumper structure. However, hydraulic systems are heavy, and require a considerable amount of space for proper operation.
Consequently, they are not favored by motor vehicle manufacturers.
An alternative way of meeting the requirement, interposition of à
20 shock-absorbent resin foa~ layer as the impact-receiving surface, has been the subject of considerable investi~ation. This approach contemplates a rigld bumper bar faced with a shock-absorbent layer of semi-rigid polyure-thane resin. The polyurethane resin foam layer receives and absorbs the impact~
25Prior to the promulgation of FMVSS 215, semi-rigid polyurethane foams had been in use for some time as shock~ab~orbing foams for ~068450 instrument panels, steering wheels, different types of bumpers, and shock-absorbent de~rices, as well as packing materials. These materials do not in general have the capability of resisting permanellt deformation after repeatecl compressions in excess of 50~c. Such resistance to permanent deformation or deformation set has not been a feature of polyurethane foam materials, l)ut for most purposes, where the material is not subjected to repeated compression, this has posed no problem.
The situation changed when FMV~S 215 was promulgated. Very few of the available semi-l igid polyurethane foams are capable of meeting the FM~SS 215 requirements.
The FMVSS 215 requirements are discussed in U. S. patent No.
3,q 39, 10~, ,~ 3, ~30,10~, issued February 17, 1976 to Dunleavy and Hawker. In their discussion of the art prlor to their invention, Dunleavy and Hawker point out that the polyurethane polymers providedby UO S. patent No. 3,493,257, patented February 3, 1970 to Fitzgerald, Haines, Harris and Kienle, are`
not capable of meeting the F~VSS 215 requirements. The polymers of this patent are too sensitive to temperature changes, and at cold temperatures the polyurethane foam is too hard.
Patellt No. 3, 939~106 provides an improved polyurethane foam ,~
using high molecular weight polyol starting materials. The polyurethane foam of that illvention is prepared by forming and curing a reaction mixture of: `
" a. a polymer polyol comprising a major liquid polyoxyalhylene polyol that has a molecular weig~ht of at least 1500 and a hydroxyl number from 20 to 120 and that contains therein a minor amount of film-forming organic polymer having a molecular weight of at least 5000, " b. an aromatic polyamine having at least two primary amine groups ( NH2) attached to carbon atoms of the same or different aromatic rings, at least one of such carbon atoms being adjacent to a carbon atom having a substituent other than hydrogen, '~ c. an aromatic glycol, "d. an organic polyisocyanate in an amount that provides from 0.8 to 1~ ~ (preferably from 0. 95 to 1.1) isocyanate groups per active hydrogen group in the reaction mixture, " e. a catalytic amount of catalyst for the curing of the reaction mlxture to produce the elastomer, and "f. a blowing a~ent in an amount sufficient to produce a cellular structure in the elastomer, "said reaction mixture containing from 97 to 65 (preferably from 97 to 85) parts by weight of (a) and from 3 to 35 (preferably from 3 to 15) parts by weight of (b) per 100 parts by weight of (a) and (b) and said reaction mixture containing from 1 to 35 (preferably from 1 to 20) parts by weight of (c) per 100 parts by weight of (a) and (c), with the proviso that the reaction mixture contains no more than 35 parts by weigllt of (b) and (c) per 100 parts by weight of (a), (b) and (c). "
13ven in the case of the polymers of that patent, however, the patentees point out that:
". . . a specific formulation (reaction mixture) for an energy absorb-ing impact elastomer cannot be described which would answer each and every application requirement. The reaction mixture used in a particular case will depend upon the speciEications necessary for satisfactory performance ~mder the given conditions. For e~ample, the particular operating temperature range, the final forces and deflections allowed during the impact cycle, cost requirements, processing re~uirements , etc., must be considered far each case. "
In accordance witll the invention, a series of semi-rigid polyurethane foams are provided having a high shock-absorbent capability over a wide range of temperatures, even after repeated compressions in excess of 50%, and which do not acquù e a permanent deformation or deformation set in excess of ~ ven after rapidly repeated compressions. The term "semi-rigid"
means that the polyurethane foam must be subjectecl to a pressure within the range from about 50 to about 200kPa to obtain a compression of ~k. ~, Consequently, the polyurethane foam in accordance with the invention can be used as the impact absorbent layer on bumpers which will meet the requirements of FMVSS 215.
The process for preparin~ semi-rigicl polyurethane foams of these properties in accordance with the invention comprises reacting a polyiso-cyanate; a polyether polyol having a molecular weight within the range from about 2, 000 to about 10, 000, preferably from about 3000 to about 7000; from about 1 to about 5~C, preferably from about 1. 5 to about 4~C,bY weight of water per part by weight of polyether polyol; from about 1 to about 6~k, A preferably from about 1. 5 to about~ by weight of urea and/or thiourea per part by weight of polyether polyol; a cross-linking compound having at least tbree active hydrogen atoms per molecule that are reactive with iso-cyanate groups and having a molecular weight below about 1000, preferably below about 500, in an amount from about 5 to about 25~c, preferably from :1068450 about 7 to ab~ut 20~C by weight per part by weight of polyether polyol; the amount of polyisocyanate being selected to give an isocyanate index within the range from about 0. ? to about 1. 4, preferably from about 0. 9 to about 1. 2.
The polyurethane foams obtained by this process hàve a cellular structure that remains undamaged by higll compression at temperatures within the range from about ~ 60C to about -40C, even after compressions as hi~h as 60O/C, and the consequent deformation is less than l~, even after ten compressions of at least 50~c~ in rapid succession~ ~ccordlngly, thls poly~u~ethalle foam is exceptionally suited for the manufacture of poly-urethane bumpers that meet the requirements of FMVSS 215~
The invention therefore further pro~ides a vehicle bumper ~.
comprising a bumper frame or support, and an impact-absorbing facing layer comprising a polyurethane foam of the invention having a density within the range from about 50 to about 150 g/dm3, preferably from about 70 to about 120 g/dm3, and a deformation (noted thirty minutes after compression) not e~ceeding 1~c over a temperature range from about 60 C to about -~0 C .
In the drawings:
Fi~,ures lA, lB, lC, lD and lE represent the force in kPa require~l 20 for compression and retrogression of the test foams of Example 1.
Figuxes 2~, 2B, 2C, 2D and 2E represent the force in kPa reg.uired for compression and retrogression of the test fGams of Example 2.
Fi~ure 3 represents the force ~n kPa required for compression and retrogression of the test foams of Example 3.
~068450 Fi~ure 4 represents the force in kPa required for compression and retrogression of the test foams of Example 4~
Figure 5 represents the force in kPa required for compression and retrogression of the test foams of Example 5.
Fi~u e 6 represents a view in cross-section of a motor vehicle bumper including a polyurethane foam of Example 2.
The shock-absorbellt capability of the polyurethane foam of the in~e~tion is attributed to the presence of u~ea and/or thio~u~ea, and the cross-linking compound~ In the absence of either Ol` both of these ingredients, 10 the shock-absorbing capability is greatly reduced.
The cross-linking compound can contain the active hydrogens reactive with isocyanate groups attached to nitrogen, for example, as a part of amino groups, or attached to oxygen, for example, as hydroxyl groups, or a mixture of amino and hydroxyl groups.
` Exemplary amines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, propylene diamine, dipropylene triamine, butylene diamine, dibutylene triamine.
Exemplary hydroxyamines include monoethanolamine, diethanol-amine, triethanolamine, monopropanolamine, dipropanolamine, dibutanol-20 amine, monobutanolamine, diiso~ropanolamine, tripropanolamine, andtributanolamine.
10684S~
Exemplary polyols include ethylene glycol, glycerol, penta-erythritol, trimethylol propane, trimethylol ethane, butanetriol, hexanetriol, arabitol,xylitol, sorbitol, mannitol,clulcitol, triethylolmethane, triethylol-ethane, and erythritol.
Also useful are the polyoxyalkylene polyols obtained by condensation of an alkylene oxide (such as ethylene oxide, propylene oxide, butylene aa~ide, and muxtures thereof) with any of the polyols just referred to above.
Illustrative aLkylelle oxide adducts of polyhydroxyall~anes include, among others, the alkylene oxide adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, ~,4~-, 1,5- and 1,6-dihydroYyhexalle, 1,2-,1,3-, 1,4-, 1,6- and 1,8-dihydro~yoctane, 1,10-dihydroxydecane, glycerol, 1, 2, 4-trihydroxybutane, 1, 2, 6-trihydroxyhexane, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane,pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, sorbitol, mannitol, and the like; preferably the adducts of ethylene oxide, propylene oxide, epoxybutane, or mi~xtures thereof. A preferred class of aLkylene ~xide adducts of polyhydr~xyalkanes are the ethylene oxide, propylene oxide, butylene ~xide,or mixtures thereof, adducts of trihydroxyaLkanes.
Ethylene oxide capped (~C2H4OH terminated) propylene oxide polyols are preferred because of their increased reactivity over noncapped propylene oxide polyols thus leadin~ to decreased demold times for the molded article.
Tllustrative hydrQYyl-terminated polyesters are those which are prepared by polymerizing a lactone in the presence of an active hydrogen-containing starter as disclosed in U.S. patent No. 2,914,556.
1~6~450 Tt is important that the amount of cross-linlcing compound be at least 5~c per part by weigrht of polyether polyol. An amoullt below 5~ gives a foam whose shock absorbency is too low. On the other hand, an amount in excess o abo~lt 2~/c of cross-linking compound resùlts in a foam that is S too rigid, and insuficiently compressible to meet the FMVSS standard.
Tt is generally preferred that the cross-linking compound contains a mixture of hydroxyl and amino groups, and that at least ~~c of the cross-linking~ compound be an amine having at least one hydroxyl group, such as triethanolamille, diethanolamine, and monoethanolamine. The amino 10 alcohols have a catalytic effect on the reaction between hydroxyl groups and isocyanate groups, and therefore can replace the conventional catalysts employed in the preparation of polyurethane foams, either in whole or in part.
Resista~lce of the polyurethane foam to development of compression 15 set can be enhanced if the reaction mixture contains a small amount of a strong base, usually within the range from about 0. 001 to about 1~c by weight of the polyether polyol. Strong bases which can be used include the inorganic bases, the aLkali metal and aL~aline earth metal hydroxides, alkaline-reacting inorganic salts of tllese metals, including the alkali 20 metal and alkaline earth metal carbonates, borates, phosphates, acetates, formates and isocyanates, as well as strong organic amine bases.
Exemplary are sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide~ barium oxide, calcium oxide, strontium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium formate, 25 sodium borate, potassium borate, sodium phosphate, potassium phosphate, SOdiUIll ben~oate, potassium benzoate, calcium phosphate, pyridine, tributylamine, morpholine, triethylamine, ethylisopropylamine, and tripropylamine. Strong bases have the capacity of rupturing cell walls in the course of foam formation without collapsing the foam, thus resulting 5 in a foam havingahigh proportion of open cells. This is important in increasing the compressibility of the foam, since an open cell foam does not develop high internal cellular gas` pressure upon compression.
The polyether polyol is an adduct of an alkylelle oxide to a polyol havin~ at least two and preferably at least three hydroxyl ~roups with 10 reactive hydrogen atoms. The alkylene oxide can be ethylene oxide, propylene oxide~ butylene oxide, and any mixture of two or thl~ee thereof.
The polyol can have from two to si~c hydroxyl groups and from two to six carbon atoms, and includes ethylene glycol, diethylene glycol, triethylene glycol, butanediol, pentanediol, propanediol, dipropylene glycol, hexanediol, 15 glycerol, trimethyloi propane, triethylolmethane, triethylolpropane, butanetriol, hexanetriol, pentaerythritol, erythritol, sorbitol, mannitol, xylitol, arabitol, dulcitol, trimethylolethane, and triethylolethane.
Also useful compounds having reactive hydrogen atoms which form adducts with alkylene oxides include amines and aminoalcohols, including, 20 for example, aliphatic, aromatic and heterocyclic polyamines and amino-alcohols having at least one amine and one hydroxyl group or two amine groups, such as monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene-tetramine, tetraetllylenepentamine, pentaethylenehexamine, dipropylene-25 triamine, and tripropylenetetramine.
As the all~rlene oxide, ethylene oxide and propylene oxide arepreferred. Mixtures of from 5 to 60~C ethylene o~ide and from 9S to 40~C
propylene oxide (calculated on the total weight of all;ylene oxide units derived from alkylerle oxide) are preEerred. If desired, a small amount of 5 butylene oxide, up to about 20~c by weight, can also be added. Amounts of ethylene oxide in excess of 60~c give relatively hydrophilic foams, which are capable of absorbing large amounts o~ water, which may be a disadvantage.
If several alkylene oxides are used, they can be added separately, in serles, in lncrernents, alternatingly, or together as a mixture, or any 10 combination of these alternatives.
In general, the polyether polyols should have from about 2. 2 to about 3. 5 reactive hydrogens per mole. A hydroxyl number within the range from about 25 to about 40, and a primary hydroxyl number within the range from about 10 to about 80~C, and preferably from about 60 to about 80~C, 15 are prefèrred.
The organic polyisocyanate should have at least two and preferabIy three or more isocyanate groups. The aromatic isocyanates are preferred but aliphatic, heterocyclic, cycloalipllatic, and mixed aliphatic aromatic, aliphatic heterocyclic, and aliphatic cycloaliphatic polyisocyanates can 20 alsobe used.
Exemplary are tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, 1-methyl-2, 6-phenylene diisocyanate, cyclohexane diisocyanate, diphenylmethane diisocyanate, and polyphenyl-
un;~ ;td~s iA The~llFederal Motor Vehicle Safety Standard FMVSS 215 establishes ``` ~ ^ requirements for safety bumpers for motor vehicles, and i.s applicable to all motor vehicles manufactured on or after September 1, 1973. The 5 objective of the standard is to prevent lo~v sl?eed collisions from impairing the safe operation of the vehicle. Certain requirements for impact resistance and the confi~uration of the front ànd rear surfaces oE the bumper system are prescribed, and the bumper must meet speciIied requirements during alld after impact by a pendlllum-type test device, followed by impact into a ~0 fixed collision barrier that is perpendicular to the line of movement of the vehicle, while the vehicle is travelling forward at a speed of five miles })er hour. The bumpe.r impact-receiving face must not have a permanent deformation greater than three-eights of an inch from its original con-figuration thirty minutes following each impact against the barrier~
15One way to meet the requirement is to incorporate a hydraulic system behind a rigid bumper structure. However, hydraulic systems are heavy, and require a considerable amount of space for proper operation.
Consequently, they are not favored by motor vehicle manufacturers.
An alternative way of meeting the requirement, interposition of à
20 shock-absorbent resin foa~ layer as the impact-receiving surface, has been the subject of considerable investi~ation. This approach contemplates a rigld bumper bar faced with a shock-absorbent layer of semi-rigid polyure-thane resin. The polyurethane resin foam layer receives and absorbs the impact~
25Prior to the promulgation of FMVSS 215, semi-rigid polyurethane foams had been in use for some time as shock~ab~orbing foams for ~068450 instrument panels, steering wheels, different types of bumpers, and shock-absorbent de~rices, as well as packing materials. These materials do not in general have the capability of resisting permanellt deformation after repeatecl compressions in excess of 50~c. Such resistance to permanent deformation or deformation set has not been a feature of polyurethane foam materials, l)ut for most purposes, where the material is not subjected to repeated compression, this has posed no problem.
The situation changed when FMV~S 215 was promulgated. Very few of the available semi-l igid polyurethane foams are capable of meeting the FM~SS 215 requirements.
The FMVSS 215 requirements are discussed in U. S. patent No.
3,q 39, 10~, ,~ 3, ~30,10~, issued February 17, 1976 to Dunleavy and Hawker. In their discussion of the art prlor to their invention, Dunleavy and Hawker point out that the polyurethane polymers providedby UO S. patent No. 3,493,257, patented February 3, 1970 to Fitzgerald, Haines, Harris and Kienle, are`
not capable of meeting the F~VSS 215 requirements. The polymers of this patent are too sensitive to temperature changes, and at cold temperatures the polyurethane foam is too hard.
Patellt No. 3, 939~106 provides an improved polyurethane foam ,~
using high molecular weight polyol starting materials. The polyurethane foam of that illvention is prepared by forming and curing a reaction mixture of: `
" a. a polymer polyol comprising a major liquid polyoxyalhylene polyol that has a molecular weig~ht of at least 1500 and a hydroxyl number from 20 to 120 and that contains therein a minor amount of film-forming organic polymer having a molecular weight of at least 5000, " b. an aromatic polyamine having at least two primary amine groups ( NH2) attached to carbon atoms of the same or different aromatic rings, at least one of such carbon atoms being adjacent to a carbon atom having a substituent other than hydrogen, '~ c. an aromatic glycol, "d. an organic polyisocyanate in an amount that provides from 0.8 to 1~ ~ (preferably from 0. 95 to 1.1) isocyanate groups per active hydrogen group in the reaction mixture, " e. a catalytic amount of catalyst for the curing of the reaction mlxture to produce the elastomer, and "f. a blowing a~ent in an amount sufficient to produce a cellular structure in the elastomer, "said reaction mixture containing from 97 to 65 (preferably from 97 to 85) parts by weight of (a) and from 3 to 35 (preferably from 3 to 15) parts by weight of (b) per 100 parts by weight of (a) and (b) and said reaction mixture containing from 1 to 35 (preferably from 1 to 20) parts by weight of (c) per 100 parts by weight of (a) and (c), with the proviso that the reaction mixture contains no more than 35 parts by weigllt of (b) and (c) per 100 parts by weight of (a), (b) and (c). "
13ven in the case of the polymers of that patent, however, the patentees point out that:
". . . a specific formulation (reaction mixture) for an energy absorb-ing impact elastomer cannot be described which would answer each and every application requirement. The reaction mixture used in a particular case will depend upon the speciEications necessary for satisfactory performance ~mder the given conditions. For e~ample, the particular operating temperature range, the final forces and deflections allowed during the impact cycle, cost requirements, processing re~uirements , etc., must be considered far each case. "
In accordance witll the invention, a series of semi-rigid polyurethane foams are provided having a high shock-absorbent capability over a wide range of temperatures, even after repeated compressions in excess of 50%, and which do not acquù e a permanent deformation or deformation set in excess of ~ ven after rapidly repeated compressions. The term "semi-rigid"
means that the polyurethane foam must be subjectecl to a pressure within the range from about 50 to about 200kPa to obtain a compression of ~k. ~, Consequently, the polyurethane foam in accordance with the invention can be used as the impact absorbent layer on bumpers which will meet the requirements of FMVSS 215.
The process for preparin~ semi-rigicl polyurethane foams of these properties in accordance with the invention comprises reacting a polyiso-cyanate; a polyether polyol having a molecular weight within the range from about 2, 000 to about 10, 000, preferably from about 3000 to about 7000; from about 1 to about 5~C, preferably from about 1. 5 to about 4~C,bY weight of water per part by weight of polyether polyol; from about 1 to about 6~k, A preferably from about 1. 5 to about~ by weight of urea and/or thiourea per part by weight of polyether polyol; a cross-linking compound having at least tbree active hydrogen atoms per molecule that are reactive with iso-cyanate groups and having a molecular weight below about 1000, preferably below about 500, in an amount from about 5 to about 25~c, preferably from :1068450 about 7 to ab~ut 20~C by weight per part by weight of polyether polyol; the amount of polyisocyanate being selected to give an isocyanate index within the range from about 0. ? to about 1. 4, preferably from about 0. 9 to about 1. 2.
The polyurethane foams obtained by this process hàve a cellular structure that remains undamaged by higll compression at temperatures within the range from about ~ 60C to about -40C, even after compressions as hi~h as 60O/C, and the consequent deformation is less than l~, even after ten compressions of at least 50~c~ in rapid succession~ ~ccordlngly, thls poly~u~ethalle foam is exceptionally suited for the manufacture of poly-urethane bumpers that meet the requirements of FMVSS 215~
The invention therefore further pro~ides a vehicle bumper ~.
comprising a bumper frame or support, and an impact-absorbing facing layer comprising a polyurethane foam of the invention having a density within the range from about 50 to about 150 g/dm3, preferably from about 70 to about 120 g/dm3, and a deformation (noted thirty minutes after compression) not e~ceeding 1~c over a temperature range from about 60 C to about -~0 C .
In the drawings:
Fi~,ures lA, lB, lC, lD and lE represent the force in kPa require~l 20 for compression and retrogression of the test foams of Example 1.
Figuxes 2~, 2B, 2C, 2D and 2E represent the force in kPa reg.uired for compression and retrogression of the test fGams of Example 2.
Fi~ure 3 represents the force ~n kPa required for compression and retrogression of the test foams of Example 3.
~068450 Fi~ure 4 represents the force in kPa required for compression and retrogression of the test foams of Example 4~
Figure 5 represents the force in kPa required for compression and retrogression of the test foams of Example 5.
Fi~u e 6 represents a view in cross-section of a motor vehicle bumper including a polyurethane foam of Example 2.
The shock-absorbellt capability of the polyurethane foam of the in~e~tion is attributed to the presence of u~ea and/or thio~u~ea, and the cross-linking compound~ In the absence of either Ol` both of these ingredients, 10 the shock-absorbing capability is greatly reduced.
The cross-linking compound can contain the active hydrogens reactive with isocyanate groups attached to nitrogen, for example, as a part of amino groups, or attached to oxygen, for example, as hydroxyl groups, or a mixture of amino and hydroxyl groups.
` Exemplary amines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, propylene diamine, dipropylene triamine, butylene diamine, dibutylene triamine.
Exemplary hydroxyamines include monoethanolamine, diethanol-amine, triethanolamine, monopropanolamine, dipropanolamine, dibutanol-20 amine, monobutanolamine, diiso~ropanolamine, tripropanolamine, andtributanolamine.
10684S~
Exemplary polyols include ethylene glycol, glycerol, penta-erythritol, trimethylol propane, trimethylol ethane, butanetriol, hexanetriol, arabitol,xylitol, sorbitol, mannitol,clulcitol, triethylolmethane, triethylol-ethane, and erythritol.
Also useful are the polyoxyalkylene polyols obtained by condensation of an alkylene oxide (such as ethylene oxide, propylene oxide, butylene aa~ide, and muxtures thereof) with any of the polyols just referred to above.
Illustrative aLkylelle oxide adducts of polyhydroxyall~anes include, among others, the alkylene oxide adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, ~,4~-, 1,5- and 1,6-dihydroYyhexalle, 1,2-,1,3-, 1,4-, 1,6- and 1,8-dihydro~yoctane, 1,10-dihydroxydecane, glycerol, 1, 2, 4-trihydroxybutane, 1, 2, 6-trihydroxyhexane, 1, 1, 1-trimethylolethane, 1, 1, 1-trimethylolpropane,pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, sorbitol, mannitol, and the like; preferably the adducts of ethylene oxide, propylene oxide, epoxybutane, or mi~xtures thereof. A preferred class of aLkylene ~xide adducts of polyhydr~xyalkanes are the ethylene oxide, propylene oxide, butylene ~xide,or mixtures thereof, adducts of trihydroxyaLkanes.
Ethylene oxide capped (~C2H4OH terminated) propylene oxide polyols are preferred because of their increased reactivity over noncapped propylene oxide polyols thus leadin~ to decreased demold times for the molded article.
Tllustrative hydrQYyl-terminated polyesters are those which are prepared by polymerizing a lactone in the presence of an active hydrogen-containing starter as disclosed in U.S. patent No. 2,914,556.
1~6~450 Tt is important that the amount of cross-linlcing compound be at least 5~c per part by weigrht of polyether polyol. An amoullt below 5~ gives a foam whose shock absorbency is too low. On the other hand, an amount in excess o abo~lt 2~/c of cross-linking compound resùlts in a foam that is S too rigid, and insuficiently compressible to meet the FMVSS standard.
Tt is generally preferred that the cross-linking compound contains a mixture of hydroxyl and amino groups, and that at least ~~c of the cross-linking~ compound be an amine having at least one hydroxyl group, such as triethanolamille, diethanolamine, and monoethanolamine. The amino 10 alcohols have a catalytic effect on the reaction between hydroxyl groups and isocyanate groups, and therefore can replace the conventional catalysts employed in the preparation of polyurethane foams, either in whole or in part.
Resista~lce of the polyurethane foam to development of compression 15 set can be enhanced if the reaction mixture contains a small amount of a strong base, usually within the range from about 0. 001 to about 1~c by weight of the polyether polyol. Strong bases which can be used include the inorganic bases, the aLkali metal and aL~aline earth metal hydroxides, alkaline-reacting inorganic salts of tllese metals, including the alkali 20 metal and alkaline earth metal carbonates, borates, phosphates, acetates, formates and isocyanates, as well as strong organic amine bases.
Exemplary are sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide~ barium oxide, calcium oxide, strontium hydroxide, sodium carbonate, potassium carbonate, sodium acetate, potassium formate, 25 sodium borate, potassium borate, sodium phosphate, potassium phosphate, SOdiUIll ben~oate, potassium benzoate, calcium phosphate, pyridine, tributylamine, morpholine, triethylamine, ethylisopropylamine, and tripropylamine. Strong bases have the capacity of rupturing cell walls in the course of foam formation without collapsing the foam, thus resulting 5 in a foam havingahigh proportion of open cells. This is important in increasing the compressibility of the foam, since an open cell foam does not develop high internal cellular gas` pressure upon compression.
The polyether polyol is an adduct of an alkylelle oxide to a polyol havin~ at least two and preferably at least three hydroxyl ~roups with 10 reactive hydrogen atoms. The alkylene oxide can be ethylene oxide, propylene oxide~ butylene oxide, and any mixture of two or thl~ee thereof.
The polyol can have from two to si~c hydroxyl groups and from two to six carbon atoms, and includes ethylene glycol, diethylene glycol, triethylene glycol, butanediol, pentanediol, propanediol, dipropylene glycol, hexanediol, 15 glycerol, trimethyloi propane, triethylolmethane, triethylolpropane, butanetriol, hexanetriol, pentaerythritol, erythritol, sorbitol, mannitol, xylitol, arabitol, dulcitol, trimethylolethane, and triethylolethane.
Also useful compounds having reactive hydrogen atoms which form adducts with alkylene oxides include amines and aminoalcohols, including, 20 for example, aliphatic, aromatic and heterocyclic polyamines and amino-alcohols having at least one amine and one hydroxyl group or two amine groups, such as monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene-tetramine, tetraetllylenepentamine, pentaethylenehexamine, dipropylene-25 triamine, and tripropylenetetramine.
As the all~rlene oxide, ethylene oxide and propylene oxide arepreferred. Mixtures of from 5 to 60~C ethylene o~ide and from 9S to 40~C
propylene oxide (calculated on the total weight of all;ylene oxide units derived from alkylerle oxide) are preEerred. If desired, a small amount of 5 butylene oxide, up to about 20~c by weight, can also be added. Amounts of ethylene oxide in excess of 60~c give relatively hydrophilic foams, which are capable of absorbing large amounts o~ water, which may be a disadvantage.
If several alkylene oxides are used, they can be added separately, in serles, in lncrernents, alternatingly, or together as a mixture, or any 10 combination of these alternatives.
In general, the polyether polyols should have from about 2. 2 to about 3. 5 reactive hydrogens per mole. A hydroxyl number within the range from about 25 to about 40, and a primary hydroxyl number within the range from about 10 to about 80~C, and preferably from about 60 to about 80~C, 15 are prefèrred.
The organic polyisocyanate should have at least two and preferabIy three or more isocyanate groups. The aromatic isocyanates are preferred but aliphatic, heterocyclic, cycloalipllatic, and mixed aliphatic aromatic, aliphatic heterocyclic, and aliphatic cycloaliphatic polyisocyanates can 20 alsobe used.
Exemplary are tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, 1-methyl-2, 6-phenylene diisocyanate, cyclohexane diisocyanate, diphenylmethane diisocyanate, and polyphenyl-
2~ polymethylene polyisocyanate.
`` 1068450 `
Of these polyisocyanates, toluene diisocyanate is preferred, either in its isomeric 2,4-form or 2,6-form, or as mixtures of these two isomeric forms. A suitable mi~ture is composed of about 80~C 2,4 - toluene diisocyanate and 20~/c 2, 6 - toluene diisocyanate.
5Another class of suitable polyisocyanates has at least two benzene rings, with one isocyanate group per ring, the benzene rings being inter~
connectedby ether, sulfone, sulfwcide, methylene, ethylene, propylene, or carb~nyl ~roups, and having tlle g,~eneral structure:
NCO NCO NCO
10 ~-Y L-~-Y! ~ , where Y is a linking group selected from the group consisting of 15 - ~CH2-, -C2H4-~ -C~H6- and - Il-, preferably -CH~-; and O ~) O
n is a number within the range from about 0. 2 to about 1. 5, it being understood that n represents an average of the species present, and therefore need not be an integer, in which species n is an integer and can 20 range from 0 to about 10.
The amount of polyisocyanate employed is stoichiometrically equivalent to the reactive hydrogens present that are reactive with isocyanate groups, taking into account the polyether polyol, carbamine compound, water and other reactants, so that the resulting polyurethane foam has an isocyanate 106~4S0 inde~;, i. e., a ratio between isocyanate groups and isocyanate-reactive hydrogen atoms present in the mixture, witbin the range from about 0. 7 to about 1. 4, and preferably from about 0. 9 to about 1. 2.
The reaction between the polyisocyanate and the polyether polyol 5 is carried out in the presence of a catalyst, the catalyst being any catalyst l~lown to catalyze this ~olymeri~ation ~eaction. The catalyst forms no part of the installt invention.
An amine catalyst can be used, particularly tertiary amines, such as diethylene t~iamine, dimethylami1loetllanol, and tetramethyl ethylene-10 dia mlne.
Also useful are org~anometallic compounds such as lead octoate,dibutyltin dilaurate, tin octoate, tin-2-ethylhexoate, lead naphthenate and col~alt naphthenate.
Only a small amount of the catalyst is required. The amount can be 15 within the range from about 0. 01 to about 5. ~c by weight of the polyether polyol, and preferably from about 0. 05 to about 1. ~c by weight.
The blowing agent is a compound capable of generating an inert gas under the reaction conditions used, by reaction to produce a gas, or by volatilization. According to the invention the blowing agent is water. If so 20 desired the water could be combined with other blowing agents like volatile halocarbons (especially chlorocarbons and chlorofluorocarbons) such as methylene chloride, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, bromo-trifluoromethane, chlorodifluoromethane, chloromethane, 1,1-dichloro-1, 1 ~06~3450 fluoromethane, 1,1-difllloro-1, 2,2-trichloroethane, chloropentafluoroethane, 1-chloro-1-fluol~oethane, 1-chloro-2-fluoroethane, 1,1,2-trifluoroethane, 2, -chloro-1, 1, 2, 3, 3, 4, 4-heptafluorobutane, hexafluorocyclobutane and oct~fluorobutane; ancl low-boiling hydrocarbons such as butane, pentane, 5 hexane, and cyclohexalle.
The amount of blowing ag~ent is determined by the desired foam properties. From about 1 to about 5 parts by weight of water and, if so desired, 0. 3 to 0.1 paI~t by wei~m of another blowing agent per part by weight o the }~olyether polyol is generally satisfactory~
Foam stabilizers such as silicone oils can be added, to improve foam stability in the course of foam formation, and the physical strength o~ the polymer.
The density of the foam is controlled by the addition of water and the blowinD agent.
The temperature of the reaction is in no way critical. The reaction proceeds at temperatures slightly above normal room temperature, such as 30C. The maximum temperature is that which leads to undesirably rapid decomposition of the blowing agellt, and loss of control of the foam properties~ In general, the reactio~ temperature is within the range from 20 about 30 to about 130C.
A prepolymer can first be prepared by reacting the polyether polyol with a stoichiometric excess of the multifunctional polyisocyanate, or, alternatively, of the polyisocyanate with a stoichiometric excess of the polyether polyol, under circumstances such that the prepolymer 25 contains isocyanate and/or hydroxyl terminal groups~
-`` 10684S0 The amounts of polyether polyol and polyisocyanate are so chosen that the isocyanate index is within the range from about 1. 5 to about 3, when the prepolymer contains isocyanate terminal gl`OUpS, and within the range from about 0.1 to about Q. 7, when the prepolymer contains hydroxyl 5 terminal groups.
The reactive prepolymer is then mixed with the remaining polyol Ol` polyisocyanate, cross-linking compound, carbamide compound, catalyst, foam stabilizer, filler, pigment, and any other reactant com~onent, and introduced into a mold.
It is also possible to mix all of the reactants together, and allow the reaction to proceed with this reaction mixture. This can be done by first mixing polyether, polyol, cross-linking agent and catalyst, and then adding polyisocyanate. It is also possible first to react polyisocyanate and the carbamide compolmd, and then add the remaining ingredients.
The following Examples in the opinion of the inventor represent preferred embodiments of the invention.
Five polyurethane foams were prepared, in accordance with the following procedure. The polyether polyol ~sed was prepared by 20 addition to glycerol of,first,propylene oxide, to a molecular weight of about 4300, and then ethylene oxide, to a molecular weight of about 5000.
The formulations ~ each of these polyurethane foams were as follows:
TABLE I
Exam~le No. lA lB lC _ lD _ lE
Ingredients Parts by Weight Polyether polyol 100 100 100 100 100 Triethanolamine 15 15 15 15 15 Water 3.0 3.0 3.0 3.0 3.0 Dimethylamilloethanol 0. 25 0. 25 0. 25 0. 25 0. 25 Polyphenylpolymethyle~le polyisocyanate (functionallty 2. 5) 95. 9 95. 9 95. 9 95. 9 95. 9 lû Urea 0 1 2 3 4 Isocyanate Index 1 0. 95 0. 91 0. 87 0. 84 The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, dimethylaminoethanol, and urea; and
`` 1068450 `
Of these polyisocyanates, toluene diisocyanate is preferred, either in its isomeric 2,4-form or 2,6-form, or as mixtures of these two isomeric forms. A suitable mi~ture is composed of about 80~C 2,4 - toluene diisocyanate and 20~/c 2, 6 - toluene diisocyanate.
5Another class of suitable polyisocyanates has at least two benzene rings, with one isocyanate group per ring, the benzene rings being inter~
connectedby ether, sulfone, sulfwcide, methylene, ethylene, propylene, or carb~nyl ~roups, and having tlle g,~eneral structure:
NCO NCO NCO
10 ~-Y L-~-Y! ~ , where Y is a linking group selected from the group consisting of 15 - ~CH2-, -C2H4-~ -C~H6- and - Il-, preferably -CH~-; and O ~) O
n is a number within the range from about 0. 2 to about 1. 5, it being understood that n represents an average of the species present, and therefore need not be an integer, in which species n is an integer and can 20 range from 0 to about 10.
The amount of polyisocyanate employed is stoichiometrically equivalent to the reactive hydrogens present that are reactive with isocyanate groups, taking into account the polyether polyol, carbamine compound, water and other reactants, so that the resulting polyurethane foam has an isocyanate 106~4S0 inde~;, i. e., a ratio between isocyanate groups and isocyanate-reactive hydrogen atoms present in the mixture, witbin the range from about 0. 7 to about 1. 4, and preferably from about 0. 9 to about 1. 2.
The reaction between the polyisocyanate and the polyether polyol 5 is carried out in the presence of a catalyst, the catalyst being any catalyst l~lown to catalyze this ~olymeri~ation ~eaction. The catalyst forms no part of the installt invention.
An amine catalyst can be used, particularly tertiary amines, such as diethylene t~iamine, dimethylami1loetllanol, and tetramethyl ethylene-10 dia mlne.
Also useful are org~anometallic compounds such as lead octoate,dibutyltin dilaurate, tin octoate, tin-2-ethylhexoate, lead naphthenate and col~alt naphthenate.
Only a small amount of the catalyst is required. The amount can be 15 within the range from about 0. 01 to about 5. ~c by weight of the polyether polyol, and preferably from about 0. 05 to about 1. ~c by weight.
The blowing agent is a compound capable of generating an inert gas under the reaction conditions used, by reaction to produce a gas, or by volatilization. According to the invention the blowing agent is water. If so 20 desired the water could be combined with other blowing agents like volatile halocarbons (especially chlorocarbons and chlorofluorocarbons) such as methylene chloride, trichloromonofluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, bromo-trifluoromethane, chlorodifluoromethane, chloromethane, 1,1-dichloro-1, 1 ~06~3450 fluoromethane, 1,1-difllloro-1, 2,2-trichloroethane, chloropentafluoroethane, 1-chloro-1-fluol~oethane, 1-chloro-2-fluoroethane, 1,1,2-trifluoroethane, 2, -chloro-1, 1, 2, 3, 3, 4, 4-heptafluorobutane, hexafluorocyclobutane and oct~fluorobutane; ancl low-boiling hydrocarbons such as butane, pentane, 5 hexane, and cyclohexalle.
The amount of blowing ag~ent is determined by the desired foam properties. From about 1 to about 5 parts by weight of water and, if so desired, 0. 3 to 0.1 paI~t by wei~m of another blowing agent per part by weight o the }~olyether polyol is generally satisfactory~
Foam stabilizers such as silicone oils can be added, to improve foam stability in the course of foam formation, and the physical strength o~ the polymer.
The density of the foam is controlled by the addition of water and the blowinD agent.
The temperature of the reaction is in no way critical. The reaction proceeds at temperatures slightly above normal room temperature, such as 30C. The maximum temperature is that which leads to undesirably rapid decomposition of the blowing agellt, and loss of control of the foam properties~ In general, the reactio~ temperature is within the range from 20 about 30 to about 130C.
A prepolymer can first be prepared by reacting the polyether polyol with a stoichiometric excess of the multifunctional polyisocyanate, or, alternatively, of the polyisocyanate with a stoichiometric excess of the polyether polyol, under circumstances such that the prepolymer 25 contains isocyanate and/or hydroxyl terminal groups~
-`` 10684S0 The amounts of polyether polyol and polyisocyanate are so chosen that the isocyanate index is within the range from about 1. 5 to about 3, when the prepolymer contains isocyanate terminal gl`OUpS, and within the range from about 0.1 to about Q. 7, when the prepolymer contains hydroxyl 5 terminal groups.
The reactive prepolymer is then mixed with the remaining polyol Ol` polyisocyanate, cross-linking compound, carbamide compound, catalyst, foam stabilizer, filler, pigment, and any other reactant com~onent, and introduced into a mold.
It is also possible to mix all of the reactants together, and allow the reaction to proceed with this reaction mixture. This can be done by first mixing polyether, polyol, cross-linking agent and catalyst, and then adding polyisocyanate. It is also possible first to react polyisocyanate and the carbamide compolmd, and then add the remaining ingredients.
The following Examples in the opinion of the inventor represent preferred embodiments of the invention.
Five polyurethane foams were prepared, in accordance with the following procedure. The polyether polyol ~sed was prepared by 20 addition to glycerol of,first,propylene oxide, to a molecular weight of about 4300, and then ethylene oxide, to a molecular weight of about 5000.
The formulations ~ each of these polyurethane foams were as follows:
TABLE I
Exam~le No. lA lB lC _ lD _ lE
Ingredients Parts by Weight Polyether polyol 100 100 100 100 100 Triethanolamine 15 15 15 15 15 Water 3.0 3.0 3.0 3.0 3.0 Dimethylamilloethanol 0. 25 0. 25 0. 25 0. 25 0. 25 Polyphenylpolymethyle~le polyisocyanate (functionallty 2. 5) 95. 9 95. 9 95. 9 95. 9 95. 9 lû Urea 0 1 2 3 4 Isocyanate Index 1 0. 95 0. 91 0. 87 0. 84 The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, dimethylaminoethanol, and urea; and
(3) polyphenylpolymethylene polyisocyanate.
Each of the reaction mixtures was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~c relative ~lumidity, 50 mm x 50 mm samples of each test foam lA to lE were taken~ The samples were com~
pressed at a rate of 150 mm per minute to a compression of 70~c. Com-pression was then released, at the same rate. The force in KpA required for compression and retro,,ression was registered by a recorcler, resulting in the dia~ams lA, lB, lC, lD and lE of the drawing. -~068450 It is apparent from the diagrams that the polyurethane foams in accordance with the invention, Examples lB, lC, lD and lE, have a very high shock-absorbing capability. The polyurethane foam lA without the urea was quite unsatisfactory in this respect.
Samples of foams lA to lE were àlso subjected to a dynamic impact test. Each of the test foam specimens was subjècted to a 60~/c compression at 25~C, the compression and retrogression being completed within this tin~e interval. The foams were then allowed to stantl for 30 minutes. Tn each case, the deformation remailling after this time was less than 1~ .
It is apparent that the polyurethane foams in accordance with the invention have a high shock~absorbent capability, together with an absence of deformation set.
Five polyurethane foams were prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, prowlene oxide to a molecular weight of about 4300, and then, ethylene oxide to a molecular weight of 500~. The formulations of each of these polyurethane foams were as follows:
TABLE II
Example No. 2A 2B 2C 2D 2E
.
dients Parts by Weigllt Polyether polyol 95.9 100 103.6 107.3 110.9 Triethanolamine 15 15 15 15 15 Water 3~0 3.0 3.0 3.0 3.0 Dimethylaminoethanol 0. 25 0. 25 0. 25 0. 25 0. 25 Polyphenylpolymethylerle 95- 9 95- 9 95- 9 95- 9 95- 9 polyisocyanate (futlctiouality 2.5) Thiourea 0 1 2 3 4 _ Isocyanate Index 1 1 1 1~ 1 The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, dimetllylaminoethanol, and thiourea; and (3) polyphenylpolymethylene polyisocyanate.
- Each of these mixtures was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~C ~elative humidity, 50 mm x 50 mm samples of 20 each test foam were taken. The samples were thell compressed at a rate of 150 mm per minute to a com~ression o~ 70~c. Compression was then released at the same rate. The force requirecl for compression and retrogression was re~isterecl by a recorder, resulting in the diagrams shown as 2A, 2B, 2C, 2D and 2E in the drawing.
106~450 It is a~parena rom tlle diagrams that the polyurethane foams in accordallce with tlle invention,Examples 2B, 2C, 2D and 2E:,have a very high shock-absorbing capability. The polyurethane foam without the thiourea (2A) was quite unsatisfactory in this respect.
Samples of the differellt polymers were also subjected to a dynamic impact test. Each of the test foam specimens were subjected to a 60~C
compression at 25~C~ the compression and retrogression belng completed within this time interval. The foams were then allowed to stand for 30 mil~uaes. In each case, the deformation remaining after this time was less than l~c-It is apparent that the polyurethane foams in accordance with the invention have a high shocl~-absorbent capability, together with an absence of deformation set.
EXA~IPLE 3 ~ polyurethane foam was prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, propylene oxide to a molecular weight of about 4300, alld then, ethylene o~ide to a molecular weic~,ht of 5000. The formulation of the poly~ethane foam was as ollows:
106~3450 T~BLE III
In~Jredients Parts by Wei~t Polyether polyol lO0 Triethanolamine 15 Water 3~ 0 Dimetllylaminoethallol 0. 25 Polyphellylpolymetllylene polyisocyanate (functionality 2. 5) 106. 5 Urea 2. 0 10 Isocyanate Index ~ . .
The reaction mixture was prepared by mixing together:
(l) polyether polyol and triethanolamine;
(2) water, dimethylaminoethanol, and urea; and (3) polyphellylpolymethylene polyisocyanate.
The reaction mixture was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~0 relative humidity, a 50 mm x 50 mm sample of the foam was tak~n. The sample was canpressed at a rate of 150 mm per minute to a compression of 70~Zo. Compression was then released at the same - 20 rate. The force required for compression and retrogression was registered by a recorder, resulting in the diagram 3 shown in the drawing.
It is app.~rent from the dia~ram that the polyurethane foam in accordance with the invention has a very high shock absorbent capability.
The sample was also subjected to a dynamic impact test. The test foam specimen was subjected to a 609ro compression at 25C, 5 the compression and retrogression being completed within this time interval. The foam was then allowed to stand for 30 minutes. The deformation`re~aining after this time was less tllan 1qb.
It is apparent that the polyurethane foa~n in accordance with the invention has a high shock-absorbent capability, together with an absence 10 of defol~n~ation set.
A polyurethane foam ~vas prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol oE, first, propylene oxide to a molecular weight of about 5000 and then, ethylene oxide to a molecular weight of 6000. The formulation of the polyurethane foam ~vas as follows:
TABLE IV
In~edients Parts by Weight Polyether polyol ` 100 ~:q :
Triethanolamine 15 Water 3. 0 Dimethylaminoethanol 0. 25 Polyphenylpolymethylene polyisocyanate (functionality 2 . 5) 105 . 2 Urea 2.0 25 Isocyanate Index The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamh~e, (2) water, dimethylaminoethanol, and urea; and (3) polyphenylpolymetllylene polyisocyanate.
The r eaction mi~;ture was poured into a mold 1800 mm x 150 mm x ~20 mm and allowed to react for 0. 5 hour. After conditiorling for 24 hours at room temperature and 50~c relat~re humidity, a 50 Irlm x 50 mm sample of the foam was taken. The sample was compressed at a rate of 150 mm per minute to a compression of 70/~c. Compression was then released at the same rate. The force reqLuired for compression and retrogression was registered by a recorder, resulting in the diagram ~ shown in the drawing.
It is apparent from the diagram that the polyurethane foam in accordance with the invention has a very high shock-absorbent capability.
The sample was also subjected to a dvnamic impact test. The test foam specimen was subjected to a 60~k compression at 25C, the compression and retrogression being completed within this time interval. The fo~m was then allowed to stand for 30 minutes. The deformation remaining after this time was less than l~c.
It is apparent that the polyurethane foam in accordance with the invention has a high shock-absorbent capability, together with an absence of deformation set.
.
A polyurethane foam was prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, propylelle oxide to a molecular weight of about4300, 5 and then, ethylene o2~ide to a molecular weight of 5000. The formulation of the polyurethane foam was as follows:
TABLE V
ngredients P rts by Wei~t Polyether polyol 100 Triethanolan~ e 10 Water 4 0 Diethanolamine 2. 0 NaOH 0. 1 Polyphenylpolymethylene polyisocyanate (functionality 2. S) 115. 0 Glycerol 2. 0 Urea 3 0 . . . _ . _ . . .
Isocyanate Index o. go .. .. . ~
The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, diethanolamine, Na~H, glycerol, and urea; and (~) polyphenylpolymethylene polyisocyanate.
The reaction mixture was poul~ed into a mold 1800 mm x 1500 mm x 120 mm and allo~ved to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50/c relative humidity, a 50 mm x 50 mm sample of the foam was taken. The sample was compressed at a rate of 150 mm per minute to a compression of 70/c. Compression was then released at the same rate. The force required iOl' compression and retrogression was registered by a recorder, resulting in the diagram 5 shown in the drawing.
It is apparent from the diagram that the polyurethane foam in accordance with the inventioll has very higll shock absorbent capability.
The sample was also subjected to a dynamic impact test. The test oam specimen ~vas ~ubjected to a 60~ compression at 25C, the compression and retrogression being completed within this time interval. The foam was then allowed to stand for 30 minutes. The deformation remaining after this time was less than 1~
The bumper shown in Figure 6 has a frame 1 and an impact-receiving facint, layer 2 of polyurethane foam mounted in the frame. The foam layer 2 has a density of 50-150 grs/dm and a remaining deformation of at most 1'~c at a dynamic compression of 60~c within the temperature range from -40C to +60C after 30 minutes. The bumper according to the invention can easily be given such dimensions that it complies with the ~n ~t~ s+Qt~5 "~ requirements oftFederal ~otor Vehicle Security Standard 215 (~MVSS 215).For a heavy vehicle, a polyurethane foam of a somewhat higher density is normally preferred to a lighter one.
The polyurethane foam layer 2 is attached to the frame 1 by a number of assembly screws 3 (of which only one screw is shown) which thread into a perforated aluminum sheet 4 molded in situ in the polyurethane foam layer. A protective cover 5 of a thin hydrophobic plastic film material such as polypropylelle or polyethylene keeps out moisture and dirt from the polyurethane foam layer 2.
The polyurethane foam was made of the same formulation as Example 2C, injected into a mold 14 cms ~16 cms x 172 cms. The mold 5 was closed, and the ~eaction mi.;t~u~e allowed to react at a mold tempera-t~u~e of ~0C. The ~olyurethane foam had a density of 96 grs/dm~. Further-more, before the casting of the polyurethane in the mold a perforated alumlnum sheet with assembly screws 3 and a cover 5 had previously been inserted, arranged in such a way that after the casting and assembling 10 of a frame, the structure shown in Figuxe 6 was obtained. The bumper was testèd accoxding to F~aVSS 215, and found to meet all requirements of the specification.
2a~
Each of the reaction mixtures was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~c relative ~lumidity, 50 mm x 50 mm samples of each test foam lA to lE were taken~ The samples were com~
pressed at a rate of 150 mm per minute to a compression of 70~c. Com-pression was then released, at the same rate. The force in KpA required for compression and retro,,ression was registered by a recorcler, resulting in the dia~ams lA, lB, lC, lD and lE of the drawing. -~068450 It is apparent from the diagrams that the polyurethane foams in accordance with the invention, Examples lB, lC, lD and lE, have a very high shock-absorbing capability. The polyurethane foam lA without the urea was quite unsatisfactory in this respect.
Samples of foams lA to lE were àlso subjected to a dynamic impact test. Each of the test foam specimens was subjècted to a 60~/c compression at 25~C, the compression and retrogression being completed within this tin~e interval. The foams were then allowed to stantl for 30 minutes. Tn each case, the deformation remailling after this time was less than 1~ .
It is apparent that the polyurethane foams in accordance with the invention have a high shock~absorbent capability, together with an absence of deformation set.
Five polyurethane foams were prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, prowlene oxide to a molecular weight of about 4300, and then, ethylene oxide to a molecular weight of 500~. The formulations of each of these polyurethane foams were as follows:
TABLE II
Example No. 2A 2B 2C 2D 2E
.
dients Parts by Weigllt Polyether polyol 95.9 100 103.6 107.3 110.9 Triethanolamine 15 15 15 15 15 Water 3~0 3.0 3.0 3.0 3.0 Dimethylaminoethanol 0. 25 0. 25 0. 25 0. 25 0. 25 Polyphenylpolymethylerle 95- 9 95- 9 95- 9 95- 9 95- 9 polyisocyanate (futlctiouality 2.5) Thiourea 0 1 2 3 4 _ Isocyanate Index 1 1 1 1~ 1 The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, dimetllylaminoethanol, and thiourea; and (3) polyphenylpolymethylene polyisocyanate.
- Each of these mixtures was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~C ~elative humidity, 50 mm x 50 mm samples of 20 each test foam were taken. The samples were thell compressed at a rate of 150 mm per minute to a com~ression o~ 70~c. Compression was then released at the same rate. The force requirecl for compression and retrogression was re~isterecl by a recorder, resulting in the diagrams shown as 2A, 2B, 2C, 2D and 2E in the drawing.
106~450 It is a~parena rom tlle diagrams that the polyurethane foams in accordallce with tlle invention,Examples 2B, 2C, 2D and 2E:,have a very high shock-absorbing capability. The polyurethane foam without the thiourea (2A) was quite unsatisfactory in this respect.
Samples of the differellt polymers were also subjected to a dynamic impact test. Each of the test foam specimens were subjected to a 60~C
compression at 25~C~ the compression and retrogression belng completed within this time interval. The foams were then allowed to stand for 30 mil~uaes. In each case, the deformation remaining after this time was less than l~c-It is apparent that the polyurethane foams in accordance with the invention have a high shocl~-absorbent capability, together with an absence of deformation set.
EXA~IPLE 3 ~ polyurethane foam was prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, propylene oxide to a molecular weight of about 4300, alld then, ethylene o~ide to a molecular weic~,ht of 5000. The formulation of the poly~ethane foam was as ollows:
106~3450 T~BLE III
In~Jredients Parts by Wei~t Polyether polyol lO0 Triethanolamine 15 Water 3~ 0 Dimetllylaminoethallol 0. 25 Polyphellylpolymetllylene polyisocyanate (functionality 2. 5) 106. 5 Urea 2. 0 10 Isocyanate Index ~ . .
The reaction mixture was prepared by mixing together:
(l) polyether polyol and triethanolamine;
(2) water, dimethylaminoethanol, and urea; and (3) polyphellylpolymethylene polyisocyanate.
The reaction mixture was poured into a mold 1800 mm x 150 mm x 120 mm and allowed to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50~0 relative humidity, a 50 mm x 50 mm sample of the foam was tak~n. The sample was canpressed at a rate of 150 mm per minute to a compression of 70~Zo. Compression was then released at the same - 20 rate. The force required for compression and retrogression was registered by a recorder, resulting in the diagram 3 shown in the drawing.
It is app.~rent from the dia~ram that the polyurethane foam in accordance with the invention has a very high shock absorbent capability.
The sample was also subjected to a dynamic impact test. The test foam specimen was subjected to a 609ro compression at 25C, 5 the compression and retrogression being completed within this time interval. The foam was then allowed to stand for 30 minutes. The deformation`re~aining after this time was less tllan 1qb.
It is apparent that the polyurethane foa~n in accordance with the invention has a high shock-absorbent capability, together with an absence 10 of defol~n~ation set.
A polyurethane foam ~vas prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol oE, first, propylene oxide to a molecular weight of about 5000 and then, ethylene oxide to a molecular weight of 6000. The formulation of the polyurethane foam ~vas as follows:
TABLE IV
In~edients Parts by Weight Polyether polyol ` 100 ~:q :
Triethanolamine 15 Water 3. 0 Dimethylaminoethanol 0. 25 Polyphenylpolymethylene polyisocyanate (functionality 2 . 5) 105 . 2 Urea 2.0 25 Isocyanate Index The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamh~e, (2) water, dimethylaminoethanol, and urea; and (3) polyphenylpolymetllylene polyisocyanate.
The r eaction mi~;ture was poured into a mold 1800 mm x 150 mm x ~20 mm and allowed to react for 0. 5 hour. After conditiorling for 24 hours at room temperature and 50~c relat~re humidity, a 50 Irlm x 50 mm sample of the foam was taken. The sample was compressed at a rate of 150 mm per minute to a compression of 70/~c. Compression was then released at the same rate. The force reqLuired for compression and retrogression was registered by a recorder, resulting in the diagram ~ shown in the drawing.
It is apparent from the diagram that the polyurethane foam in accordance with the invention has a very high shock-absorbent capability.
The sample was also subjected to a dvnamic impact test. The test foam specimen was subjected to a 60~k compression at 25C, the compression and retrogression being completed within this time interval. The fo~m was then allowed to stand for 30 minutes. The deformation remaining after this time was less than l~c.
It is apparent that the polyurethane foam in accordance with the invention has a high shock-absorbent capability, together with an absence of deformation set.
.
A polyurethane foam was prepared in accordance with the following procedure. The polyether polyol used was prepared by addition to glycerol of, first, propylelle oxide to a molecular weight of about4300, 5 and then, ethylene o2~ide to a molecular weight of 5000. The formulation of the polyurethane foam was as follows:
TABLE V
ngredients P rts by Wei~t Polyether polyol 100 Triethanolan~ e 10 Water 4 0 Diethanolamine 2. 0 NaOH 0. 1 Polyphenylpolymethylene polyisocyanate (functionality 2. S) 115. 0 Glycerol 2. 0 Urea 3 0 . . . _ . _ . . .
Isocyanate Index o. go .. .. . ~
The reaction mixture was prepared by mixing together:
(1) polyether polyol and triethanolamine;
(2) water, diethanolamine, Na~H, glycerol, and urea; and (~) polyphenylpolymethylene polyisocyanate.
The reaction mixture was poul~ed into a mold 1800 mm x 1500 mm x 120 mm and allo~ved to react for 0. 5 hour. After conditioning for 24 hours at room temperature and 50/c relative humidity, a 50 mm x 50 mm sample of the foam was taken. The sample was compressed at a rate of 150 mm per minute to a compression of 70/c. Compression was then released at the same rate. The force required iOl' compression and retrogression was registered by a recorder, resulting in the diagram 5 shown in the drawing.
It is apparent from the diagram that the polyurethane foam in accordance with the inventioll has very higll shock absorbent capability.
The sample was also subjected to a dynamic impact test. The test oam specimen ~vas ~ubjected to a 60~ compression at 25C, the compression and retrogression being completed within this time interval. The foam was then allowed to stand for 30 minutes. The deformation remaining after this time was less than 1~
The bumper shown in Figure 6 has a frame 1 and an impact-receiving facint, layer 2 of polyurethane foam mounted in the frame. The foam layer 2 has a density of 50-150 grs/dm and a remaining deformation of at most 1'~c at a dynamic compression of 60~c within the temperature range from -40C to +60C after 30 minutes. The bumper according to the invention can easily be given such dimensions that it complies with the ~n ~t~ s+Qt~5 "~ requirements oftFederal ~otor Vehicle Security Standard 215 (~MVSS 215).For a heavy vehicle, a polyurethane foam of a somewhat higher density is normally preferred to a lighter one.
The polyurethane foam layer 2 is attached to the frame 1 by a number of assembly screws 3 (of which only one screw is shown) which thread into a perforated aluminum sheet 4 molded in situ in the polyurethane foam layer. A protective cover 5 of a thin hydrophobic plastic film material such as polypropylelle or polyethylene keeps out moisture and dirt from the polyurethane foam layer 2.
The polyurethane foam was made of the same formulation as Example 2C, injected into a mold 14 cms ~16 cms x 172 cms. The mold 5 was closed, and the ~eaction mi.;t~u~e allowed to react at a mold tempera-t~u~e of ~0C. The ~olyurethane foam had a density of 96 grs/dm~. Further-more, before the casting of the polyurethane in the mold a perforated alumlnum sheet with assembly screws 3 and a cover 5 had previously been inserted, arranged in such a way that after the casting and assembling 10 of a frame, the structure shown in Figuxe 6 was obtained. The bumper was testèd accoxding to F~aVSS 215, and found to meet all requirements of the specification.
2a~
Claims (23)
1. A process for preparing semi-rigid polyurethane foam having a high shock-absorbent capability over a wide range of temperatures, even after repeated compressions in excess of 50%, and which do not acquire a permanent deformation or deformation set in excess of 1% even after rapidly repeated compressions, which comprises reacting a polyisocyanate;
a polyether polyol having a molecular weight within the range from about 2000 to about 10, 000; from about 1 to about 5% by weight of water per part by weight of polyether polyol; from about 1 to about 6% by weight of at least one member selected from the group consisting of urea and thiourea per part by weight of polyether polyol; and a cross-linking compound having at least three active hydrogen atoms per molecule that are reactive with isocyanate groups and having a molecular weight below about 1000 in an amount from about 5 to about 25% by weight per part by weight of polyether polyol; the amount of polyisocyanate being selected to give an isocyanate index within the range from about 0.7 to about 1.4 at a temperature at which reaction proceeds within the range from about 30 to about 130°C until a polyurethane foam is produced.
a polyether polyol having a molecular weight within the range from about 2000 to about 10, 000; from about 1 to about 5% by weight of water per part by weight of polyether polyol; from about 1 to about 6% by weight of at least one member selected from the group consisting of urea and thiourea per part by weight of polyether polyol; and a cross-linking compound having at least three active hydrogen atoms per molecule that are reactive with isocyanate groups and having a molecular weight below about 1000 in an amount from about 5 to about 25% by weight per part by weight of polyether polyol; the amount of polyisocyanate being selected to give an isocyanate index within the range from about 0.7 to about 1.4 at a temperature at which reaction proceeds within the range from about 30 to about 130°C until a polyurethane foam is produced.
2. A process according to claim 1, which comprises first preparing a prepolymer by reacting the polyether polyol with a stoichiometric excess of the polyisocyanate to form a prepolymer containing isocyanate terminal groups.
3. A process according to claim 1, which comprises first preparing a prepolymer by reacting the polyisocyanate with a stoichiometric excess of the polyether polyol to form a prepolymer containing hydroxyl terminal groups.
4. A process according to claim 1 in which the member is urea.
5. A process according to claim 1 in which the member is thiourea.
6. A process according to claim 1 in which the cross-linking compound contains the active hydrogens reactive with isocyanate groups attached to nitrogen as a part of amino groups.
7. A process according to claim 1 in which the cross-linking compound contains the active hydrogens reactive with isocyanate groups attached to oxygen as a part of hydroxyl groups.
8. A process according to claim 1 in which the cross-linking compound contains the active hydrogens reactive with isocyanate groups attached to nitrogen and oxygen as a mixture of amino and hydroxyl groups.
9. A process according to claim 1 in which the cross-linking compound is a polyol.
10. A process according to claim 1 in which the cross-linking compound is a polyoxyalkylene polyol obtained by condensation of an alkylene oxide with polyol.
11. A process according to claim 1 in which the reaction mixture also contains an amount of a strong base within the range from about 0. 001 to about 1% by weight of the polyether polyol.
12. A process according to claim 11 in which the base is selected from the group consisting of the alkali metal and alkaline earth metal hydroxides, alkaline-reacting inorganic salts of these metals, and organic amine bases.
13. A process according to claim 1 in which the polyether polyol is an adduct of an alkylene oxide to a polyol having at least two hydroxyl groups with reactive hydrogen atoms, the alkylene oxide having from two to four carbon atoms and the polyol having from two to six hydroxyl groups and from two to six carbon atoms.
14. A process according to claim 1 in which the polyether polyol is an adduct of an alkylene oxide to an amine or aminoalcohol having at least one amine and one hydroxyl group or at least two amine groups.
15. A process according to claim 1 in which the organic poly-isocyanate has at least two isocyanate groups and is selected from the group consisting of aliphatic, heterocyclic, cycloaliphatic, and mixed aliphatic aromatic, aliphatic heterocyclic, and aliphatic cycloaliphatic polyisocyanates.
16. A process according to claim 15, in which the polyisocyanate is toluene diisocyanate.
17. A process according to claim 15, in which the polyisocyanate has at least two benzene rings, with one isocyanate group per ring, the benzene rings being interconnected by a member selected from the group consisting of ether, sulfone, sulfoxide, methylene, ethylene, propylene, and carbonyl groups, and having the general structure:
where Y is a linking group selected from the group consisting of -O-, -?-, -?-, -CH2-, -C2H4-, -C3H6- and -?-; and n is a number within the range from about 0.2 to about 1.5 representing an average of the species present.
where Y is a linking group selected from the group consisting of -O-, -?-, -?-, -CH2-, -C2H4-, -C3H6- and -?-; and n is a number within the range from about 0.2 to about 1.5 representing an average of the species present.
18. A process according to claim 1 in which the reaction between the polyisocyanate and the polyether polyol is carried out in the presence of a catalyst.
19. A process according to claim 18 in which the catalyst is an amine.
20. A process according to claim 18 in which the catalyst is an organometallic compound.
21. A process according to claim 1 in which the reaction mixture also includes a blowing agent capable of generating an inert gas under the reaction conditions used.
22. A polyurethane foam obtained by the process of claim 1, having a cellular structure that remains undamaged by high compression at temperatures within the range from about + 60°C to about -40°C, even after compressions as high at 60%, and a consequent deformation of less than 1%, even after ten compressions of at least 50%, in rapid succession.
23. A vehicle bumper comprising a bumper support, and an impact-absorbing facing layer comprising a polyurethane foam of claim 22, having a density within the range from about 50 to about 150 g/dm3 and a deformation (noted thirty minutes after compression) not exceeding 1%
over a temperature range of from about + 60°C to about -40°C.
over a temperature range of from about + 60°C to about -40°C.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE7602076A SE7602076L (en) | 1976-02-23 | 1976-02-23 | BUMPER |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1068450A true CA1068450A (en) | 1979-12-18 |
Family
ID=20327075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA269,201A Expired CA1068450A (en) | 1976-02-23 | 1977-01-05 | Process for the preparation of semi-rigid polyurethane foam having exceptional shock-absorbing properties and vehicle bumpers thereof |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5349731A (en) |
CA (1) | CA1068450A (en) |
ES (1) | ES456116A1 (en) |
FI (1) | FI770548A (en) |
IT (1) | IT1072742B (en) |
SE (1) | SE7602076L (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55154837U (en) * | 1979-04-24 | 1980-11-07 | ||
JPS5730642A (en) * | 1980-07-29 | 1982-02-18 | Toyo Kagaku Kk | Car bumper |
JPS5740136A (en) * | 1980-08-21 | 1982-03-05 | Mitsuboshi Belting Ltd | Shock energy absorbing bumper for vehicle |
JP2538715Y2 (en) * | 1991-04-10 | 1997-06-18 | 日産自動車株式会社 | Impact absorbing structure of vehicle bumper |
-
1976
- 1976-02-23 SE SE7602076A patent/SE7602076L/en not_active Application Discontinuation
-
1977
- 1977-01-05 CA CA269,201A patent/CA1068450A/en not_active Expired
- 1977-02-21 FI FI770548A patent/FI770548A/fi not_active Application Discontinuation
- 1977-02-21 IT IT67386/77A patent/IT1072742B/en active
- 1977-02-21 JP JP1799077A patent/JPS5349731A/en active Pending
- 1977-02-21 ES ES456116A patent/ES456116A1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS5349731A (en) | 1978-05-06 |
IT1072742B (en) | 1985-04-10 |
FI770548A (en) | 1977-08-24 |
SE7602076L (en) | 1977-08-24 |
ES456116A1 (en) | 1978-02-01 |
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