USRE33609E - Production of polyurethane moldings by the reaction injection molding process - Google Patents
Production of polyurethane moldings by the reaction injection molding process Download PDFInfo
- Publication number
- USRE33609E USRE33609E US07/331,874 US33187489A USRE33609E US RE33609 E USRE33609 E US RE33609E US 33187489 A US33187489 A US 33187489A US RE33609 E USRE33609 E US RE33609E
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- US
- United States
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- 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 - Lifetime
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- 238000000465 moulding Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000004814 polyurethane Substances 0.000 title claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 6
- 238000010107 reaction injection moulding Methods 0.000 title description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 32
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 32
- 229920005862 polyol Polymers 0.000 claims abstract description 30
- 150000003077 polyols Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000011368 organic material Substances 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004604 Blowing Agent Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 239000012783 reinforcing fiber Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- -1 polymethylene Polymers 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000006082 mold release agent Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 150000004665 fatty acids Chemical group 0.000 description 5
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical group CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-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
- UUSVDJBYMWOMCY-UHFFFAOYSA-N 1,2-dibromobutane-1,1-diol Chemical compound CCC(Br)C(O)(O)Br UUSVDJBYMWOMCY-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ZMESHQOXZMOOQQ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZMESHQOXZMOOQQ-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GGPLWEZGITVTJX-UHFFFAOYSA-N 2,2,4-trimethyl-1,4,2-oxazasilinane Chemical compound CN1CCO[Si](C)(C)C1 GGPLWEZGITVTJX-UHFFFAOYSA-N 0.000 description 1
- RZEWIYUUNKCGKA-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanol;octadecanoic acid Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCCC(O)=O RZEWIYUUNKCGKA-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- VFDYEMVVNIPATA-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;propane-1,2,3-triol Chemical compound OCC(O)CO.CCC(CO)(CO)CO VFDYEMVVNIPATA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- CEZWFBJCEWZGHX-UHFFFAOYSA-N 4-isocyanato-n-(oxomethylidene)benzenesulfonamide Chemical class O=C=NC1=CC=C(S(=O)(=O)N=C=O)C=C1 CEZWFBJCEWZGHX-UHFFFAOYSA-N 0.000 description 1
- BXZMYXFIMCKTTQ-UHFFFAOYSA-N 4-methylbenzene-1,2,3,5-tetrol Chemical compound CC1=C(O)C=C(O)C(O)=C1O BXZMYXFIMCKTTQ-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- 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 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- TXOFSCODFRHERQ-UHFFFAOYSA-N N,N-Dimethylphenethylamine Chemical compound CN(C)CCC1=CC=CC=C1 TXOFSCODFRHERQ-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- USKJMUFHXCJSGV-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O Chemical compound N=C=O.N=C=O.N=C=O USKJMUFHXCJSGV-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- RCZKTFHQZNLYAR-UHFFFAOYSA-N bis(2-hydroxyethyl) hexanedioate Chemical compound OCCOC(=O)CCCCC(=O)OCCO RCZKTFHQZNLYAR-UHFFFAOYSA-N 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- RGAMPJYGTCSRAG-UHFFFAOYSA-N bis[2-(diethylamino)ethyl] hexanedioate Chemical compound CCN(CC)CCOC(=O)CCCCC(=O)OCCN(CC)CC RGAMPJYGTCSRAG-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XFLSMWXCZBIXLV-UHFFFAOYSA-N n,n-dimethyl-2-(4-methylpiperazin-1-yl)ethanamine Chemical compound CN(C)CCN1CCN(C)CC1 XFLSMWXCZBIXLV-UHFFFAOYSA-N 0.000 description 1
- MJNLXAZOTQSLTM-UHFFFAOYSA-N n-[[[ethylaminomethyl(dimethyl)silyl]oxy-dimethylsilyl]methyl]ethanamine Chemical compound CCNC[Si](C)(C)O[Si](C)(C)CNCC MJNLXAZOTQSLTM-UHFFFAOYSA-N 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001590 sorbitan monolaureate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2120/00—Compositions for reaction injection moulding processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2130/00—Compositions of compatibilising agents used in mixtures of high-molecular-weight compounds having active hydrogen with other compounds having active hydrogen
Definitions
- Reaction injection molding has become an important process for the manufacture of a wide variety of moldings.
- the RIM process is a so-called “one-shot” process which involves the intimate mixing of a polyisocyanate component and an isocyanate-reactive component followed by the injection (generally under high pressure) of the mixture into a mold with subsequent rapid curing.
- the polyisocyanate component is generally a liquid isocyanate.
- the isocyanate-reactive component generally contains a high molecular weight isocyanate-reactive component (generally a polyol), and usually contains a chain extender or cross-linker containing amine or hydroxyl groups.
- 4,218,543 describes one particularly commercially significant RIM system, which requires the use of a specific type of aromatic amine as a cross-linker/chain extender.
- the preferred amine described in the '543 patent is diethyl toluene diamine (DETDA).
- DETDA diethyl toluene diamine
- Formulations based on DETDA are generally restricted to the lower flexural modulus range (i.e., less than about 70,000 psi at room temperature). While it is known to use DETDA in combination with other co-chain extenders in order to increase the flexural modulus of the resultant molding, the use of such co-chain extender generally adversely affects the thermal properties of the resultant part.
- U.S. Pat. No. 4,065,410 describes a RIM process wherein the reaction mixture comprises a polyisocyanate, a polyol having a molecular weight of from 1800 to 10,000, a blowing agent, and a chain extender mixture comprising ethylene glycol and another polyol having a molecular weight below 1800.
- the chain extender mixture comprises from 10 to 30% by weight based on the weight of the high molecular polyol.
- a similar system is described in U.S. Pat. No. 4,341,875.
- the present invention is directed to a process for the production of polyurethane moldings by reacting a reaction mixture comprising
- At least one polyether polyol having an hydroxy functionality of from 2 to 8, preferably 2 to 4, and a molecular weight of from 350 to below 1800, preferably from 350 to 1100, and
- component (iii) no more than 45% by weight based on the total weight of component (b), of an active hydrogen containing compound having a molecular weight of 1800 or more,
- reaction mixture being processed as a one-shot system by the RIM process at an isocyanate index of from about 70 to about 130.
- the compatible polyol blend have a viscosity at 25° C. of 200 mPa.s or less.
- the room temperature flexural modulus of the resultant part has been found to range from about 100,000 psi to as high as about 380,000 psi.
- a reinforcing fiber mat is placed in the mold cavity prior to introduction of the reaction mixture.
- the room temperature flexural modulus of the molded part can range from about 600,000 psi to as high as about 2,000,000 psi. Additionally, none of the flow problems generally seen in art are encountered.
- compatible is meant that no more than 1 percent by weight of the mixture separates after twelve hours storage at room temperature.
- Starting polyisocyanate components suitable for use in the present invention include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Specific examples of these compounds are ethylene diisocyanate: 1,4-tetramethylene diisocyanate: 1,6-hexamethylene diisocyanate: 1,12-dodecane diisocyanate: cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and mixtures of these isomers.
- Diphenylmethane-2,4- and/or -4,4'-diisocyanate diphenylmethane-2,4- and/or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate: triphenyl methane-4,4',4"-triisocyanate; polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation and described, for example, in British Pat. Nos. 874,430 and 848,671 may also be used in the present invention; m- and p-isocyanato-phenylsulfonyl isocyanates according to U.S. Pat. No. 3,454,606.
- perchlorinated aryl polyisocyanates of the type described, for example, in German Auslegeschrift No. 1,157,601 (U.S. Pat. No. 3,277,138); polyisocyanates containing carbodiimide groups of the type described in German Pat. No. 1,902,007 (U.S. Pat. No. 3,152,162); diisocyanates of the type described in U.S. Pat. No. 3,492,330; and polyisocyanates containing allophanate groups of the type described, for example, in British Pat. No. 993,890, in Belgian Pat. No. 761,626 and in published Dutch Patent Application No. 7,102,524 are still further examples of suitable isocyanates.
- Aromatic polyisocyanates which are liquid at the processing temperature are preferably used.
- the particularly preferred starting polyisocyanates include derivatives of 4,4'-diisocyanato-diphenylmethane which are liquid at room temperature, for example, liquid polyisocyanates containing urethane groups of the type obtainable in accordance with German Pat. No. 1,618,380 (U.S. Pat. No. 3,644,457). These may be produced for example, by reacting 1 mol of 4,4'-diisocyanatodiphenylmethane with from 0.05 to 0.3 mols of low molecular weight diols or triols, preferably polypropylene glycols having a molecular weight below 700.
- diisocyanates based on diphenylmethane diisocyanate containing carbodiimide and/or uretone imine groups of the type obtainable, for example, in accordance with German Pat. No. 1,092,007 (U.S. Pat. No. 3,152,162). Mixtures of these preferred polyisocyanates can also be used. In general, aliphatic and cycloaliphatic isocyanates are less suitable for the purposes of the instant invention.
- polyphenylpolymethylene polyisocyanates obtained by the phosgenation of an aniline/formaldehyde condensate. Where reinforcing fiber mats are used, it is particularly preferred that such polyisocyanates have viscosities of 200 mPa. or less at 25° C.
- the compatible polyol blend used according to the present invention must include (i) a polyether polyol having a molecular weight of from 350 to below 1800 and (ii) a polyhydroxy material having a molecular weight below 350.
- Polyethers containing two to four hydroxy groups are preferred.
- Useful polyethers are known and are obtained, for example, by the polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin alone, for example in the presence of BF 3 , or by the chemical addition of these epoxides, optionally in admixture with or in succession to starter components having reactive hydrogen atoms.
- Such starter compounds include water, alcohols, or amines, such as ethylene glycol, 1,3- or 1,2-propylene glycol, trimethylol propane glycerine, 4,4'-dihydroxy diphenyl propane, aniline, ammonia, ethanolamine and ethylene diamine.
- Compounds containing at least two hydroxyl groups and having molecular weights of below 350 are also used in the present invention. These materials preferably contain 2 or 3 hydroxyl groups. Mixtures of different compounds containing at least two hydroxyl groups and having molecular weight of less than 350 may also be used.
- low molecular weight compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, 1,4-bishydroxymethyl cyclohexane, 2-methyl-1,3-propane diol, dibromobutane diol (U.S. Pat. No.
- glycerol trimethylol propane, 1,2,6-hexane triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols having molecular weights of less than 350, dipropylene glycol, higher polypropylene glycols having molecular weights of less than 350, dibutylene glycol, higher polybutylene glycols having a molecular weight of less than 400, 4,4'-dihydroxydiphenyl propane, dihydroxy methyl hydroquinone, and the like.
- ester diols diol urethanes and diol ureas.
- Suitable ester diols correspond to the general formula
- R represents an alkylene radical containing from 1 to 10, (preferably from 2 to 6) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 10 carbon atoms:
- x 2 to 6
- y 3 to 5.
- Examples of compounds corresponding to these formulae are ⁇ -hydroxybutyl- ⁇ -hydroxycaproic acid ester, ⁇ -hydroxy-hexyl- ⁇ -hydroxybutyric acid ester, adipic acid-bis-( ⁇ -hydroxyethyl)-ester and terephthalic acid-bis(- ⁇ -hydroxy-ethyl)-ester.
- Diol urethanes which may be used in the present invention correspond to the general formula:
- R' represents an alkylene radical containing from 2 to 15 (preferably from 2 to 6) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 15 carbon atoms, and
- x represents a number of from 2 to 6.
- Diol urethanes suitable to the present invention correspond to the general formula: ##STR1## wherein R" represents an alkylene radical containing from 2 to 15 (preferably from 2 to 9) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 15 carbon atoms,
- R"' represents hydrogen or a methyl group
- x represents the number 2 or 3.
- diol ureas examples include 4,4'-diphenyl methane-bis-( ⁇ -hydroxyethyl urea) and the compound ##STR2##
- polyols containing sulfonate and/or phosphonate groups German Offenlegungsschrift No. 2,719,372
- polyols containing sulfonate and/or phosphonate groups German Offenlegungsschrift No. 2,719,372
- the adduct of bisulfite with 1,4-butene diol or the alkoxylation product thereof such as the adduct of bisulfite with 1,4-butene diol or the alkoxylation product thereof.
- the reinforcing mats useful in this invention comprise glass mats, graphite mats, polyester mats, polyaramide mats such as KEVLAR mats and mats made from any fibrous material. Also, although the particular mats used in the examples are random continuous strand mats made of glass fiber bundles, woven mats and oriented mats such as uniaxial or triaxial mats may also be used.
- Suitable organic blowing agents include halogen-substituted alkanes, such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, difluorochloromethane and difluorodichloromethane, and butane, hexane, heptane, or diethyl ether.
- a blowing effect may also be obtained by adding compounds which decompose spontaneously at temperatures above room temperature, giving off gases such as nitrogen. Examples of such compounds are azo compounds, such as azoisobutyronitrile.
- blowing agents and details on the use of blowing agents may be found in Kunststoff-Handbuch, Vol. VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Kunststoff (1966) on pages 108 and 109 453-455 and 507-510.
- Catalysts may also be used in the invention.
- Suitable catalysts include those known per se, for example tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N,N,N',N"-tetramethylethylene diamine, 1,4-diazabicyclo-(2,2,2)-octane, N-methyl-N'-dimethylaminoethyl piperazine, N,N-dimethylbenzylamine, bis-(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylene triamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butane diamine, N,N-dimethyl- -phenylethylamine, 1,2-
- tertiary amines containing hydrogen atoms capable of reacting with isocyanate groups are triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine and their reaction products with alkylene oxides, such as propylene oxide and/or ethylene oxide.
- Suitable catalysts are silaamines having carbon silicon bonds of the kind described in German Pat. No. 1,299,290. These include 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl tetramethyl disiloxane.
- Nitrogen-containing bases such as tetraalkyl ammonium hydroxides: alkali hydroxides such as sodium hydroxide; alkali phenolates such as sodium phenolate; alkali alcoholates such as sodium methylate, and hexahydrotriazines may also be used as catalysts.
- Organometallic compounds especially organotin compounds may also be used as catalysts.
- Preferred organotin compounds include tin-(II)-salts of carboxylic acids, such as tin-(II)-acetate, tin-(II)-octoate, tin-(II)-ethylhexoate and tin-(II)-laurate and the dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate.
- the catalysts are generally used in quantities of from about 0.001 to 10% by weight, based on the quantity of compounds (b).
- emulsifiers and foam stabilizers can also be used.
- emulsifiers are the sodium salts of castor oil sulphonates or even of fatty acids or salts of fatty acids with amines such as diethylamine oleate or diethanolamine stearate.
- Alkali or ammonium salts of sulphonic acids such as those of dodecylbenzene sulphonic acid or dinaphthylmethane disulphonic acid or even of fatty acids, such as ricinoleic acid, or of polymeric fatty acids, can also be used as surface-active additives.
- Suitable foam stabilizers include water-soluble polyether siloxanes. These compounds are generally of such structure that a copolymer of ethylene oxide and propylene oxide is attached to a polydimethylsiloxane radical. Foam stabilizers of this kind are described, for example, in U.S. Pat. No. 2,764,565.
- reaction retarders for example, substances with an acid reaction such as hydrochloric acid or organic acid halides.
- Cell regulators known per se such as paraffins or fatty alcohols or dimethyl polysiloxanes may also be used.
- Pigments or dyes and flameproofing agents known per se such as tris-chloroethyl phosphate or ammonium phosphate and polyphosphate and Mobil's Antiblaze 19 flame retardant may be used.
- Stabilizers against the effects of aging and weather, plasticizers and substances with fungistatic and bacteriostatic effects, fillers such as barium sulphate, kieselguhr, carbon black or prepared chalk may also be used.
- Suitable internal mold release agents include those described in U.S. Pat. Nos. 4,585,803, 4,581,386 and 4,519,965, the disclosures of which are herein incorporated by reference. Also useful are those internal mold release agents described in German Offenlegungsschriften 1,953,637 and 2,121,670.
- One particularly preferred mold release is a mixture of Silicone DC-193 (available from Dow Corning) and the adduct formed by reacting one mole of N,N'-dimethylpropylamine with two moles of tall oil.
- high molecular weight compounds having active hydrogen can be used in amounts of up to 45% by weight based on the total weight of the compatible blend, it is generally preferred that no more than 15% by weight be used and it is most preferred that such use be avoided.
- POLYOL A a glycerine/propylene oxide adduct having an OH number of 250 (molecular weight 670)
- POLYOL B an ethylene diamine/propylene oxide adduct having an OH number of 630 (molecular weight 360).
- POLYOL C a poly(oxypropyleneoxyethylene) glycol having an OH number of 28 (molecular weight 4000) (weight ratio of propylene oxide to ethylene oxide of about 4:1).
- ISOCYANATES all of the isocyanates used were polyphenylpolymethylene polyisocyanates having varying isocyanate group contents, diisocyanate contents, 2,4-isomer contents, equivalent weights, and viscosities, as set forth in TABLE I:
- Zn zinc laurate.
- DC-193 a silicone surfactant available from Dow Corning.
- T-12 dibutyltindilaurate.
- PC-8 Polycat 8, N,N-dimethylcyclohexylamine, available from Air Products.
- DBM dibutyltindimercaptide
- 8608 and 8610 continuous strand fiberglass mats available from Owens Corning Fiberglass. The mats are available in 3 oz. or 2 oz. per square foot sizes.
- RIM plaques were prepared using a laboratory piston metering unit and clamping unit.
- the metering unit was a two component instrument having a maximum metering capacity of 0.6 liters.
- a rectangular mold, 300 mm ⁇ 200 mm ⁇ 3 mm was used to mold the samples under the following conditions:
Abstract
The present invention is directed to a process for the production of polyurethane moldings by reacting a reaction mixture comprising
(a) an organic polyisocyanate
(b) a compatible polyol blend comprising
(i) at least one polyether polyol having a hydroxyl functionality of from 2 to 8, and a molecular weight of from 350 to below 1800, and
(ii) at least one hydroxyl functional organic material containing from 2 to 8 hydroxyl groups and having a molecular weight below 350, components (i) and (ii) being used in a weight ratio of component (b)(i) to (b)(ii) of from about 10:1 to about 1:10, and
(iii) no more than 45% by weight based on the weight of component (b) of an active hydrogen containing compound having a molecular weight of 1800 or more,
said reaction mixture being processed as a one-shot system by the RIM process at an isocyanate index of from about 70 to about 130.
Description
Reaction injection molding (RIM) has become an important process for the manufacture of a wide variety of moldings. The RIM process is a so-called "one-shot" process which involves the intimate mixing of a polyisocyanate component and an isocyanate-reactive component followed by the injection (generally under high pressure) of the mixture into a mold with subsequent rapid curing. The polyisocyanate component is generally a liquid isocyanate. The isocyanate-reactive component generally contains a high molecular weight isocyanate-reactive component (generally a polyol), and usually contains a chain extender or cross-linker containing amine or hydroxyl groups. U.S. Pat. No. 4,218,543 describes one particularly commercially significant RIM system, which requires the use of a specific type of aromatic amine as a cross-linker/chain extender. The preferred amine described in the '543 patent is diethyl toluene diamine (DETDA). Formulations based on DETDA are generally restricted to the lower flexural modulus range (i.e., less than about 70,000 psi at room temperature). While it is known to use DETDA in combination with other co-chain extenders in order to increase the flexural modulus of the resultant molding, the use of such co-chain extender generally adversely affects the thermal properties of the resultant part.
In general, the art has looked to various techniques for enhancing the flexural modulus of a RIM part, including use of different aromatic amines (see, e.g. U.S. Pat. No. 4,442,235), use of an aliphatic amine co-chain extender (see, e.g. U.S. Pat. No. 4,269,945), and the use of reinforcements such as fibers, particulate fillers and flakes (see, e.g., Journal of Cellular Plastics, September/October 1981, pages 268-273).
Another technique for enhancing the flexural modulus of RIM parts is to use a reinforcing fiber mat. Problems have been seen in using such mats in the RIM process including displacement of the mat in the mold. incomplete filling of the mold, and part distortion. It is believed that these problems are caused in part by the RIM reactants reaching a high viscosity in too short a time to completely impregnate the mat. One solution to this problem was described in U.S. Pat. No. 4,435,349. The '349 patent describes the use of a reaction mixture of a polyisocyanate, a polyol having an equivalent eeight above 500, a relatively low molecular weight chain extender (such as ethylene glycol), and a delayed action catalyst. In all the examples of the '349 patent, an excess of a polyol was used which had an equivalent weight in excess of 1800 and a molecular weight of no less than about 5500.
U.S. Pat. No. 4,065,410 describes a RIM process wherein the reaction mixture comprises a polyisocyanate, a polyol having a molecular weight of from 1800 to 10,000, a blowing agent, and a chain extender mixture comprising ethylene glycol and another polyol having a molecular weight below 1800. As disclosed in the '410 patent the chain extender mixture comprises from 10 to 30% by weight based on the weight of the high molecular polyol. A similar system is described in U.S. Pat. No. 4,341,875.
The present invention is directed to a process for the production of polyurethane moldings by reacting a reaction mixture comprising
(a) an organic polyisocyanate,
(b) a compatible polyol blend comprising
(i) at least one polyether polyol having an hydroxy functionality of from 2 to 8, preferably 2 to 4, and a molecular weight of from 350 to below 1800, preferably from 350 to 1100, and
(ii) at least one hydroxyl functional organic material containing from 2 to 8 hydroxyl groups, preferably 2 or 3 and having a molecular weight of below 350, components (b)(i) and (b)(ii) being used in a weight ratio of (b)(i) to (b)(ii) of from about 10:1 to about 1:10, and
(iii) no more than 45% by weight based on the total weight of component (b), of an active hydrogen containing compound having a molecular weight of 1800 or more,
said reaction mixture being processed as a one-shot system by the RIM process at an isocyanate index of from about 70 to about 130.
It is preferred that the compatible polyol blend have a viscosity at 25° C. of 200 mPa.s or less. The room temperature flexural modulus of the resultant part has been found to range from about 100,000 psi to as high as about 380,000 psi. In the most preferred embodiment of the present invention, a reinforcing fiber mat is placed in the mold cavity prior to introduction of the reaction mixture. When using reinforcing fiber mats, it has been found that the room temperature flexural modulus of the molded part can range from about 600,000 psi to as high as about 2,000,000 psi. Additionally, none of the flow problems generally seen in art are encountered.
By compatible is meant that no more than 1 percent by weight of the mixture separates after twelve hours storage at room temperature.
Starting polyisocyanate components suitable for use in the present invention include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Specific examples of these compounds are ethylene diisocyanate: 1,4-tetramethylene diisocyanate: 1,6-hexamethylene diisocyanate: 1,12-dodecane diisocyanate: cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and mixtures of these isomers. Additional examples are 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl cyclohexane (German Auslegeschrift No. 1,202,785, U.S. Pat. No. 3,401,190), 2,4- and 2,6-hexahydro-tolylene diisocyanate and mixtures of these isomers. Hexahydro-1,3- and/or -1,4-phenylene diisocyanate; perhydro-2,4'- and/or -4,4'-diphenylmethane diisocyanate; 1,3- and 1,4-phenylene diisocyanate; 1,4- and 2,6-tolylene diisocyanate and mixtures of these isomers are also suitable in the instant invention. Diphenylmethane-2,4- and/or -4,4'-diisocyanate; naphthylene-1,5-diisocyanate: triphenyl methane-4,4',4"-triisocyanate; polyphenyl polymethylene polyisocyanates of the type obtained by condensing aniline with formaldehyde, followed by phosgenation and described, for example, in British Pat. Nos. 874,430 and 848,671 may also be used in the present invention; m- and p-isocyanato-phenylsulfonyl isocyanates according to U.S. Pat. No. 3,454,606. perchlorinated aryl polyisocyanates of the type described, for example, in German Auslegeschrift No. 1,157,601 (U.S. Pat. No. 3,277,138); polyisocyanates containing carbodiimide groups of the type described in German Pat. No. 1,902,007 (U.S. Pat. No. 3,152,162); diisocyanates of the type described in U.S. Pat. No. 3,492,330; and polyisocyanates containing allophanate groups of the type described, for example, in British Pat. No. 993,890, in Belgian Pat. No. 761,626 and in published Dutch Patent Application No. 7,102,524 are still further examples of suitable isocyanates. Additionally, polyisocyanates containing isocyanurate groups of the type described, for example, in U.S. Pat. No. 3,001,973; in German Pat. Nos. 1,022,789; 1,222,067 and 1,027,394 and in German Offenlegungsschriften Nos. 1,929,034 and 2,004,408; polyisocyanates containing urethane groups of the type described, for example, in Belgian Pat. No. 752,261 or in U.S. Pat. No. 3,394,164: polyisocyanates containing acylated urea groups according to German Pat. No. 1,230,778 and polyisocyanates containing biuret groups of the type described, for example, in German Pat. No. 1,101,394 (U.S. Pat. No. 3,124,605 and 3,201,372) and in British Pat. No. 889,050 are also suitable.
Polyisocyanates produced by telomerization reactions of the type described, for example, in U.S. Pat. No. 3,654,106; polyisocyanates containing ester groups of the type described for example, in British Pat. Nos. 965,474 and 1,072,956, in U.S. Pat. No. 3,567,763 and in German Pat. No. 1,231,688; reaction products of the above-mentioned isocyanates with acetals according to German Pat. No. 1,072,385 and polyisocyanates containing polymeric fatty acid residues, according to U.S. Pat. No. 3,455,883 are still further examples of suitable isocyanate.
Aromatic polyisocyanates which are liquid at the processing temperature are preferably used. The particularly preferred starting polyisocyanates include derivatives of 4,4'-diisocyanato-diphenylmethane which are liquid at room temperature, for example, liquid polyisocyanates containing urethane groups of the type obtainable in accordance with German Pat. No. 1,618,380 (U.S. Pat. No. 3,644,457). These may be produced for example, by reacting 1 mol of 4,4'-diisocyanatodiphenylmethane with from 0.05 to 0.3 mols of low molecular weight diols or triols, preferably polypropylene glycols having a molecular weight below 700. Also useful are diisocyanates based on diphenylmethane diisocyanate containing carbodiimide and/or uretone imine groups of the type obtainable, for example, in accordance with German Pat. No. 1,092,007 (U.S. Pat. No. 3,152,162). Mixtures of these preferred polyisocyanates can also be used. In general, aliphatic and cycloaliphatic isocyanates are less suitable for the purposes of the instant invention.
Also preferred are the polyphenylpolymethylene polyisocyanates obtained by the phosgenation of an aniline/formaldehyde condensate. Where reinforcing fiber mats are used, it is particularly preferred that such polyisocyanates have viscosities of 200 mPa. or less at 25° C.
The compatible polyol blend used according to the present invention must include (i) a polyether polyol having a molecular weight of from 350 to below 1800 and (ii) a polyhydroxy material having a molecular weight below 350. Polyethers containing two to four hydroxy groups are preferred. Useful polyethers are known and are obtained, for example, by the polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin alone, for example in the presence of BF3, or by the chemical addition of these epoxides, optionally in admixture with or in succession to starter components having reactive hydrogen atoms. Such starter compounds include water, alcohols, or amines, such as ethylene glycol, 1,3- or 1,2-propylene glycol, trimethylol propane glycerine, 4,4'-dihydroxy diphenyl propane, aniline, ammonia, ethanolamine and ethylene diamine.
Compounds containing at least two hydroxyl groups and having molecular weights of below 350 are also used in the present invention. These materials preferably contain 2 or 3 hydroxyl groups. Mixtures of different compounds containing at least two hydroxyl groups and having molecular weight of less than 350 may also be used. Examples of such low molecular weight compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4- and 2,3-butylene glycol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane diol, neopentyl glycol, 1,4-bishydroxymethyl cyclohexane, 2-methyl-1,3-propane diol, dibromobutane diol (U.S. Pat. No. 3,723,392), glycerol, trimethylol propane, 1,2,6-hexane triol, trimethylol ethane, pentaerythritol, quinitol, mannitol, sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, higher polyethylene glycols having molecular weights of less than 350, dipropylene glycol, higher polypropylene glycols having molecular weights of less than 350, dibutylene glycol, higher polybutylene glycols having a molecular weight of less than 400, 4,4'-dihydroxydiphenyl propane, dihydroxy methyl hydroquinone, and the like.
Other low molecular weight polyols having a molecular weight of less than 350 which may be used in accordance with the present invention are ester diols, diol urethanes and diol ureas. Suitable ester diols correspond to the general formula
HO--(CH.sub.2).sub.x -CO-O-(CH.sub.2).sub.y --OH and
HO--(CH.sub.2).sub.x --O--CO--R--CO--O--(CH.sub.2).sub.x --OH
wherein
R represents an alkylene radical containing from 1 to 10, (preferably from 2 to 6) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 10 carbon atoms:
x represents 2 to 6; and
y represents 3 to 5.
Examples of compounds corresponding to these formulae are δ-hydroxybutyl-ε-hydroxycaproic acid ester, ω-hydroxy-hexyl-γ-hydroxybutyric acid ester, adipic acid-bis-(β-hydroxyethyl)-ester and terephthalic acid-bis(-β-hydroxy-ethyl)-ester.
Diol urethanes which may be used in the present invention correspond to the general formula:
HO--(CH.sub.2).sub.x --O--CO--NH--R'--N--H--CO--O--(CH.sub.2).sub.x --OH
wherein
R' represents an alkylene radical containing from 2 to 15 (preferably from 2 to 6) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 15 carbon atoms, and
x represents a number of from 2 to 6.
Examples of such diol urethanes are 1,6-hexamethylene-bis-(hydroxybutyl urethane) and 4,4'-diphenylmethane-bis-(-hydroxybutyl urethane). Diol ureas suitable to the present invention correspond to the general formula: ##STR1## wherein R" represents an alkylene radical containing from 2 to 15 (preferably from 2 to 9) carbon atoms or a cycloalkylene or arylene radical containing from 6 to 15 carbon atoms,
R"' represents hydrogen or a methyl group, and
x represents the number 2 or 3.
Examples of such diol ureas are 4,4'-diphenyl methane-bis-(β-hydroxyethyl urea) and the compound ##STR2##
For certain purposes, it may be advantageous to use polyols containing sulfonate and/or phosphonate groups (German Offenlegungsschrift No. 2,719,372), such as the adduct of bisulfite with 1,4-butene diol or the alkoxylation product thereof.
The reinforcing mats useful in this invention comprise glass mats, graphite mats, polyester mats, polyaramide mats such as KEVLAR mats and mats made from any fibrous material. Also, although the particular mats used in the examples are random continuous strand mats made of glass fiber bundles, woven mats and oriented mats such as uniaxial or triaxial mats may also be used.
Water and/or readily volatile organic substances can be used as blowing agents in the invention. Suitable organic blowing agents include halogen-substituted alkanes, such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, difluorochloromethane and difluorodichloromethane, and butane, hexane, heptane, or diethyl ether. A blowing effect may also be obtained by adding compounds which decompose spontaneously at temperatures above room temperature, giving off gases such as nitrogen. Examples of such compounds are azo compounds, such as azoisobutyronitrile. Further examples of blowing agents and details on the use of blowing agents may be found in Kunststoff-Handbuch, Vol. VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich (1966) on pages 108 and 109 453-455 and 507-510.
Catalysts may also be used in the invention. Suitable catalysts include those known per se, for example tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N,N,N',N"-tetramethylethylene diamine, 1,4-diazabicyclo-(2,2,2)-octane, N-methyl-N'-dimethylaminoethyl piperazine, N,N-dimethylbenzylamine, bis-(N,N-diethylaminoethyl)-adipate, N,N-diethylbenzylamine, pentamethyldiethylene triamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethyl-1,3-butane diamine, N,N-dimethyl- -phenylethylamine, 1,2-dimethylimidazole and 2-methylimidazole.
Examples of tertiary amines containing hydrogen atoms capable of reacting with isocyanate groups are triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine and their reaction products with alkylene oxides, such as propylene oxide and/or ethylene oxide.
Other suitable catalysts are silaamines having carbon silicon bonds of the kind described in German Pat. No. 1,299,290. These include 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyl tetramethyl disiloxane.
Nitrogen-containing bases such as tetraalkyl ammonium hydroxides: alkali hydroxides such as sodium hydroxide; alkali phenolates such as sodium phenolate; alkali alcoholates such as sodium methylate, and hexahydrotriazines may also be used as catalysts.
Organometallic compounds especially organotin compounds may also be used as catalysts. Preferred organotin compounds include tin-(II)-salts of carboxylic acids, such as tin-(II)-acetate, tin-(II)-octoate, tin-(II)-ethylhexoate and tin-(II)-laurate and the dialkyl tin salts of carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate.
Further examples of suitable catalysts and details on the way in which the catalysts work can be found in Kunststoff-Handbuch, Vol. VII, published by Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966 page 96-102.
The catalysts are generally used in quantities of from about 0.001 to 10% by weight, based on the quantity of compounds (b).
Surface-active additives (emulsifiers and foam stabilizers) can also be used. Examples of emulsifiers are the sodium salts of castor oil sulphonates or even of fatty acids or salts of fatty acids with amines such as diethylamine oleate or diethanolamine stearate. Alkali or ammonium salts of sulphonic acids, such as those of dodecylbenzene sulphonic acid or dinaphthylmethane disulphonic acid or even of fatty acids, such as ricinoleic acid, or of polymeric fatty acids, can also be used as surface-active additives.
Suitable foam stabilizers include water-soluble polyether siloxanes. These compounds are generally of such structure that a copolymer of ethylene oxide and propylene oxide is attached to a polydimethylsiloxane radical. Foam stabilizers of this kind are described, for example, in U.S. Pat. No. 2,764,565.
It is also possible to use reaction retarders, for example, substances with an acid reaction such as hydrochloric acid or organic acid halides. Cell regulators known per se such as paraffins or fatty alcohols or dimethyl polysiloxanes may also be used. Pigments or dyes and flameproofing agents known per se, such as tris-chloroethyl phosphate or ammonium phosphate and polyphosphate and Mobil's Antiblaze 19 flame retardant may be used. Stabilizers against the effects of aging and weather, plasticizers and substances with fungistatic and bacteriostatic effects, fillers such as barium sulphate, kieselguhr, carbon black or prepared chalk may also be used.
It is also preferred that so-called internal mold release agents be used. Suitable internal mold release agents include those described in U.S. Pat. Nos. 4,585,803, 4,581,386 and 4,519,965, the disclosures of which are herein incorporated by reference. Also useful are those internal mold release agents described in German Offenlegungsschriften 1,953,637 and 2,121,670. One particularly preferred mold release is a mixture of Silicone DC-193 (available from Dow Corning) and the adduct formed by reacting one mole of N,N'-dimethylpropylamine with two moles of tall oil. Although high molecular weight compounds having active hydrogen can be used in amounts of up to 45% by weight based on the total weight of the compatible blend, it is generally preferred that no more than 15% by weight be used and it is most preferred that such use be avoided.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
In the examples, the following materials were used:
DEG: diethylene glycol.
EG ethylene glycol.
BD: 1,4-butanediol.
POLYOL A: a glycerine/propylene oxide adduct having an OH number of 250 (molecular weight 670)
POLYOL B: an ethylene diamine/propylene oxide adduct having an OH number of 630 (molecular weight 360).
POLYOL C: a poly(oxypropyleneoxyethylene) glycol having an OH number of 28 (molecular weight 4000) (weight ratio of propylene oxide to ethylene oxide of about 4:1).
ISOCYANATES: all of the isocyanates used were polyphenylpolymethylene polyisocyanates having varying isocyanate group contents, diisocyanate contents, 2,4-isomer contents, equivalent weights, and viscosities, as set forth in TABLE I:
TABLE 1 __________________________________________________________________________ % by weight % of the diisocyanate % by weight Equivalent Viscosity at Isocyanate diisocyanate 2,4' isomer NCO Groups Weight 25° C. __________________________________________________________________________ A 58 2.5 32.4 129.6 45 mPa.s B 78 25 32.5 129.2 25 mPa.s C 55 13 32.2 130.5 60 mPa.s D 61 19 32.4 129.6 45 mPa.s __________________________________________________________________________
Zn: zinc laurate.
DC-193: a silicone surfactant available from Dow Corning.
T-12: dibutyltindilaurate.
PC-8: Polycat 8, N,N-dimethylcyclohexylamine, available from Air Products.
DBM: dibutyltindimercaptide.
8608 and 8610: continuous strand fiberglass mats available from Owens Corning Fiberglass. The mats are available in 3 oz. or 2 oz. per square foot sizes.
RIM plaques were prepared using a laboratory piston metering unit and clamping unit. The metering unit was a two component instrument having a maximum metering capacity of 0.6 liters. A rectangular mold, 300 mm×200 mm×3 mm was used to mold the samples under the following conditions:
______________________________________ Component A temperature 25° C. Component B temperature 25° C. Isocyanate index 105 Mold Temperature 60° C. Impingement pressure 2646 psi Demold time 2 minutes ______________________________________
The formulation used and the physical properties obtained were as indicated in the Tables. In those examples having the letter P, the molded part was post cured at 120° C. for one hour. The samples were tested for density (ASTM D-792), notched Izod (ASTM D-256), flex modulus (ASTM D-790), tensile strength (ASTM D-638) and heat distortion (ASTM D-648). In Examples 1 through 40, a silicone spray sold as Chemtrend MR-515 was used as an external mold release agent. In Example 41, a soap spray sold as Chemtrend RCTW-2006 was used as an external mold release agent, while in Example 42, a wax spray sold as Chemtrend 2007 was used as the external mold release agent. In those examples where glass mats were used, they were cut and placed in the mold. The column labelled % glass is the % by weight of glass in the final molded product.
TABLE II __________________________________________________________________________ EXAMPLES 1-12 Component Component A Glass Flex Notched Heat B Pbw Iso Pbw Number % by Density Modulus Izod Distortion Example Polyol A EG DBM A B C D Type Sheets wt. (lb/ft.sup.3) (Psi) (ft-lb/in) Temp. __________________________________________________________________________ (°C.) 1 90 10 0.25 -- -- -- 100 8610 2 43 86.3 1,090,000 13.2 197 3 oz. 2 ↓ ↓ ↓ 100 -- -- -- 70.9 376,000 1.17 54 3 ↓ ↓ ↓ 100 8610 2 43 86.5 1,220,000 14.0 200 3 oz. 4 ↓ ↓ ↓ 100 -- -- -- 73 366,000 1.66 55 5-P ↓ ↓ ↓ 98 8610 3 43 80.1 1,170,000 13.4 189 2 oz. 6 ↓ ↓ ↓ 98 8610 3 43 77.3 1,190,000 13.7 180 2 oz. 7 ↓ ↓ ↓ 98 -- -- -- 72.6 324,000 0.95 45 8-P ↓ ↓ ↓ 98 -- -- -- 70.9 373,000 0.98 47.5 9-P ↓ ↓ ↓ 100 8610 3 43 76.8 1,110,000 10.9 198 2 oz. 10 ↓ ↓ ↓ 100 8610 3 43 82.5 1,250,000 13.3 191 2 oz. 11-P ↓ ↓ ↓ 100 -- -- -- 70.9 353,000 1.35 52 12 ↓ ↓ ↓ 100 -- -- -- 71.9 365,000 1.52 48 __________________________________________________________________________
TABLE III __________________________________________________________________________ EXAMPLES 13-27 Component Den- Heat Ex- B Pbw Component A Glass % sity Flex Notched Distortion am- Polyol Polyol Iso Pbw Number by (lb/ Modulus Izod Temp. ple A C EG DBM A B C D Type Sheets wt. ft.sup.3) (Psi) (ft-lb/in) (°C.) __________________________________________________________________________ 13 44 40 16 0.25 100 8610 2 43 86.2 1,120,000 13.8 194 3 oz. 14 ↓ ↓ ↓ ↓ 100 2 43 84.9 950,000 11.9 200 15 ↓ ↓ ↓ ↓ 100 -- -- -- 73.5 191,000 2.2 50 16-P ↓ ↓ ↓ ↓ 100 8610 3 43 85.0 1,160,000 13.3 194 2 oz. 17 ↓ ↓ ↓ ↓ 100 8610 3 43 91.5 921,000 14.4 168 2 oz. 18-P ↓ ↓ ↓ ↓ 100 -- -- -- 72.6 199,000 2.0 50 19 ↓ ↓ ↓ ↓ 100 -- -- -- 72.8 182,000 1.9 43.5 20-P ↓ ↓ ↓ ↓ 100 8610 3 43 83.0 959,000 14.1 184 2 oz. 21 ↓ ↓ ↓ ↓ 100 8610 3 43 85.4 805.000 13.9 -- 2 oz. 22-P ↓ ↓ ↓ ↓ 100 -- -- -- 73.0 131,000 1.9 46 23 ↓ ↓ ↓ ↓ 100 -- -- -- 73.2 117,000 2.0 47.5 24-P ↓ ↓ ↓ ↓ 100 8610 3 43 68.0 874,000 12.2 182 2 oz. 25 ↓ ↓ ↓ ↓ 100 8610 3 43 83.9 1,290,000 13.0 185 2 oz. 26-P ↓ ↓ ↓ ↓ 100 -- -- -- 73.4 178,000 1.8 50 27 ↓ ↓ ↓ ↓ 100 -- -- -- 73.0 162,000 2.0 46 __________________________________________________________________________
TABLE IV __________________________________________________________________________ EXAMPLES 28-31 Glass Flex Notched Comp. B Pbw Comp. A Number % by Density Modulus Izod Heat Distortion Example Polyol A EG DBM Iso Pbw A Type Sheets weight (lb/ft.sup.3) (psi) (ft-lb/in) Temp. __________________________________________________________________________ (°C.) 28-P 85 15 0.25 100 8610 3 43 88.8 1,220,000 11.5 181 2 oz. 29 ↓ ↓ ↓ ↓ 8610 3 43 87.5 1,160,000 12.7 186 2 oz. 30-P ↓ ↓ ↓ ↓ -- -- -- 72.3 350,000 1.3 46 31 ↓ ↓ ↓ ↓ -- -- -- 73.9 328,000 0.9 45 __________________________________________________________________________
TABLE V __________________________________________________________________________ EXAMPLES 32-37 Glass Flex Notched Comp. B Pbw Comp. A Number % by Density Modulus Izod Heat Distortion Example Polyol A BD DBM Iso Pbw A Type Sheets weight (lb/ft.sup.3) (psi) (ft-lb/in) Temp. __________________________________________________________________________ (°C.) 32-P 78 22 0.25 100 8610 3 43 87.6 1,110,000 11.6 200 2 oz. 33 ↓ ↓ ↓ ↓ 8610 3 43 88.8 1,290,000 12.1 172 2 oz. 34 ↓ ↓ ↓ ↓ 8610 3 43 91.7 1,040,000 13.1 133 2 oz. 35-P ↓ ↓ ↓ ↓ -- -- -- 69.4 310,000 0.8 46 36 ↓ ↓ ↓ ↓ -- -- -- 72.5 289,000 0.8 43 37 ↓ ↓ ↓ ↓ -- -- -- 72.2 297,000 0.9 44 __________________________________________________________________________
TABLE VI __________________________________________________________________________ EXAMPLES 38-42 __________________________________________________________________________ Component B, Pbw Examples DEG EG Polyol A Polyol B Za E-493 DC-193 T-12 PC-8 __________________________________________________________________________ 38 72 -- 28 -- -- -- -- 0.25 -- 39 -- 10 90 -- -- -- -- 0.25 -- 40 -- 10 90 -- -- -- -- 0.25 -- 41 -- 10 80.6 5.6 3.8 -- -- 0.1 -- 42 70 -- 20 -- -- 5 5 -- 0.8 __________________________________________________________________________ Comp. A Glass Flex Tensile N Iso. Pbw Number % by Density Modulus Strength Examples A Type Sheets weight (lb/ft.sup.3) (psi) (psi) __________________________________________________________________________ 38 202 8610 3 51 96 1,320,000 31,600 3 oz. 39 100 8610 3 42 88.5 1,110,000 23,000 2 oz. 40 100 8608 3 40 85.9 1,200,000 26,000 2 oz. 41 101 8610 3 39 84.3 1,200,000 23,000 2 oz. 42 192 8610 3 52 97.1 1,670,000 32,300 3 oz. __________________________________________________________________________
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (12)
1. A process for the production of polyurethane moldings by reacting a reaction mixture comprising
(a) an organic polyisocyanate
(b) a compatible polyol blend comprising
(i) at least one polyether polyol having an hydroxyl functionality of from 2 to 8, and a molecular weight of from .[.350.]. 360 to .[.below 1800.]. .Iadd.670.Iaddend., and
(ii) at least one hydroxyl functional organic material containing from 2 to 8 hydroxyl groups and having a molecular weight below 350, components (i) and (ii) being used in a weight ratio of component (b)(i) to (b)(ii) of from about 10:1 to about 1:10, and
(iii) no more than 45% by weight based on the weight of component (b) of an active hydrogen containing compound having a molecular weight of 1800 or more,
said reaction mixture being processed as a one-shot system by the RIM process at an isocyanate index of from about 70 to about 130.
2. The process of claim 1 wherein said organic polyisocyanate is selected from the group consisting of 4,4'-diisocyanatodiphenylmethane, polyisocyanates based on 4,4'-diisocyanatodiphenylmethane, .[.or.]. .Iadd.and .Iaddend.mixtures thereof.
3. The process of claim 1, further comprising the step of placing a reinforcing fiber mat in the mold cavity prior to introduction of the reaction mixture.
4. The process of claim 3, wherein component (a) is a polyphenylpolymethylene polyisocyanate obtained by the phosgenation of an aniline/formaldehyde condensate, said polyisocyanate having a viscosity at 25° C. of 200 mPa.s or less, and wherein the viscosity of said compatible polyol blend is 200 mPa.s or less at 25° C.
5. The process of claim 1 wherein said reaction mixture contains a blowing agent.
6. The process of claim 1 wherein component (b)(i) has a hydroxy functionality of from 2 to 4 .[.and a molecular weight of from 350 to 1100.]..
7. The process of claim 6 wherein said organic material contains 2 or 3 hydroxyl groups.
8. The process of claim 1 wherein component (b)(iii) is present in an amount of no more than 15% by weight.
9. The process of claim 8 wherein component (b)(iii) is excluded.
10. The process of claim 1 wherein said reaction mixture contains a release agent.
11. A polyurethane molding made according to the process of claim 1. .Iadd.
12. A process for the production of polyurethane moldings by reacting a reaction mixture comprising
(a) an organic polyisocyanate
(b) a compatible polyol blend comprising
(i) at least one polyether polyol having an hydroxyl functionality of from 2 to 8, and a molecular weight of from 350 to below 1800, and
(ii) at least one hydroxyl functional organic material containing from 2 to 8 hydroxyl groups and having a molecular weight below 350, components (i) and (ii) being used in a weight ratio of component (b)(i) to (b)(ii) of from about 10:1 to about 1:10, and
(iii) no active hydrogen containing compound having a molecular weight of 1800 or more,
said reaction mixture being processed as a one-shot system by the RIM process at an isocyanate index of from about 70 to about 130. .Iaddend.
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US07/331,874 USRE33609E (en) | 1987-07-23 | 1989-03-31 | Production of polyurethane moldings by the reaction injection molding process |
Applications Claiming Priority (2)
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US07/076,827 US4792576A (en) | 1987-07-23 | 1987-07-23 | Production of polyurethane moldings by the reaction injection molding process |
US07/331,874 USRE33609E (en) | 1987-07-23 | 1989-03-31 | Production of polyurethane moldings by the reaction injection molding process |
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US07/076,827 Reissue US4792576A (en) | 1987-07-23 | 1987-07-23 | Production of polyurethane moldings by the reaction injection molding process |
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US07/331,874 Expired - Lifetime USRE33609E (en) | 1987-07-23 | 1989-03-31 | Production of polyurethane moldings by the reaction injection molding process |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5151483A (en) * | 1991-03-13 | 1992-09-29 | Miles Inc. | Process for the production of reinforced polyurethane moldings by the reaction injection molding process |
US5368806A (en) * | 1992-11-05 | 1994-11-29 | Miles Inc. | Production of moldings by the reaction injection molding process |
US5478494A (en) * | 1993-09-22 | 1995-12-26 | Basf Corporation | Polyol composition having good flow and formic acid blown rigid polyurethane foams made thereby having good dimensional stability |
US5536465A (en) * | 1994-02-09 | 1996-07-16 | Bayer Corporation | Long-gelling internal mold release compositions for structural rim processes |
US5622777A (en) * | 1995-05-17 | 1997-04-22 | Bayer Corporation | Heat-resistant reinforced foam |
US5688590A (en) * | 1995-08-21 | 1997-11-18 | Bayer Corporation | High heat resistant molded parts produced by structural reaction injection molding |
US5739247A (en) * | 1996-08-05 | 1998-04-14 | Bayer Corporation | Production of structural reaction injection molded polyurethane products of high flex modulus and high elongation |
US5798533A (en) * | 1993-09-23 | 1998-08-25 | Basf Corporation | Polyol compositions having good flow and water blown rigid polyurethane foams made thereby having good dimensional stability |
US20050038222A1 (en) * | 2002-03-29 | 2005-02-17 | Joshi Ravi R. | Process for filament winding |
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Cited By (10)
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---|---|---|---|---|
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US20050038222A1 (en) * | 2002-03-29 | 2005-02-17 | Joshi Ravi R. | Process for filament winding |
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