CN101080428A - Method for producing microcellular polyurethane elastomers - Google Patents
Method for producing microcellular polyurethane elastomers Download PDFInfo
- Publication number
- CN101080428A CN101080428A CNA2005800431336A CN200580043133A CN101080428A CN 101080428 A CN101080428 A CN 101080428A CN A2005800431336 A CNA2005800431336 A CN A2005800431336A CN 200580043133 A CN200580043133 A CN 200580043133A CN 101080428 A CN101080428 A CN 101080428A
- Authority
- CN
- China
- Prior art keywords
- polyurethane elastomer
- microcellular polyurethane
- aii
- amine
- 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.)
- Granted
Links
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title description 2
- -1 amine compound Chemical class 0.000 claims abstract description 29
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 23
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 150000003512 tertiary amines Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004954 1-(2-hydroxyethyl)-imidazoles Chemical class 0.000 claims description 3
- OMDXZWUHIHTREC-UHFFFAOYSA-N 1-[2-(dimethylamino)ethoxy]ethanol Chemical compound CC(O)OCCN(C)C OMDXZWUHIHTREC-UHFFFAOYSA-N 0.000 claims description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical class NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 claims description 3
- BRKHZWFIIVVNTA-UHFFFAOYSA-N 4-cyclohexylmorpholine Chemical compound C1CCCCC1N1CCOCC1 BRKHZWFIIVVNTA-UHFFFAOYSA-N 0.000 claims description 3
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical class CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 3
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 239000012948 isocyanate Substances 0.000 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 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- FGFWCOVNCKWNLU-UHFFFAOYSA-N oxalic acid;tin Chemical compound [Sn].OC(=O)C(O)=O FGFWCOVNCKWNLU-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000002175 menstrual effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
- C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
- C08K5/5353—Esters of phosphonic acids containing also nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0066—≥ 150kg/m3
-
- 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
- C08G2410/00—Soles
Abstract
The invention relates to microcellular polyurethane elastomers which can be produced by reacting polyisocyanates with compounds having at least two hydrogen atoms which are reactive with isocyanate groups. Said elastomers are characterised in that they contains a combination a) made of ai) an aromatic phosphite having a phosphorus content of between 9,00 - 11,00 wt.- %, and aii) an amine compound. The molar ratio between ai) and aii) is between 0,005 - 4,0.
Description
The integral polyurethane foam usually is known as " microcellular polyurethane elastomer ", and also be called " MPE " hereinafter, and they are known for some time, for example are used to produce sole.They for example are described in Kunststoffhandbuch[plastics handbook], the 7th volume " urethane ", the 3rd edition, 376 pages and subsequently in each page.They are by making polyisocyanates and having at least two compound reactions that isocyanate group is reactive hydrogen atom and prepare.The compound that is used for this reaction usually is polyesterols.This makes material have outstanding use properties such as snappiness, high tensile and tear propagation strength or low abrasion.Simultaneously, this system can be processed with high process reliability.The hydrolytic resistance that is material based on a shortcoming of the microcellular polyurethane elastomer of polyesterols is low.Described low hydrolytic resistance is caused by the tropism that ester group has hydrolytic deterioration.The fracture of ester group causes the decline of polymkeric substance molar mass and causes the deterioration of use properties, may cause the completely destroy of material under extreme case.
Therefore in the past taked various effort to improve the stability to hydrolysis of such material.
The improvement that has proposed is to use special polyesterols based on a kind of method of the stability to hydrolysis of the microcellular polyurethane elastomer of polyesterols.Here should mention for example DE 3 144 968, wherein use, 4-butyleneglycol, 1, the polyesterols of 6-hexylene glycol and neopentyl glycol based on hexanodioic acid, 1.In addition, have more hydrolytic resistance in order to make polyesterols, replacement or the part of having described polyesterols replace.
The another kind of method of improving hydrolytic resistance is for using special additive, and its consumption is less than 10 weight % usually.For example, EP 965 582 has described the use acid anhydrides, and DE 19 710 978 has described the combination of using lactone and carbodiimide.
Yet, can have shortcoming usually by the solution that prior art obtains.In some cases, realize higher hydrolytic resistance really, but before aging, only obtained inadequate use properties simultaneously.In addition, some solution can not realize actually owing to higher raw materials cost.This may for example take place under the situation of the special additive that uses particular polyesters alcohol or higher consumption.Another shortcoming of many solutions that can be obtained by prior art is the decline of component stability in storage.In addition, especially when stability to hydrolysis was had high the requirement, the efficient of many solutions was low excessively.
In microcellular polyurethane elastomer, use phosphorous acid ester normally known and for example be described in Kunststoffhandbuch, the 7th volume, " urethane ", the 3rd edition, the 120th page and subsequently in each page.At this moment, phosphorous acid ester is used as the antioxidant auxiliary.Caused synergistic function with being used in combination of typical antioxidant (as sterically hindered phenol), prevented that simultaneously the efficient of thermal oxidation process is able to remarkable increase.
The phosphorous acid ester that JP 61128904 has described 4-14 weight % is based on the use in the microcellular polyurethane elastomer of polyesterols.To be used as the jaundice inhibitor based on the phosphorous acid ester of phenol and chain alkyl.Described phosphorous acid ester is used for prepolymer.JP 63278962 described will be based on polyester the stable MPE of UV is used for sole.Phosphorous acid ester is used with the sterically hindered phenol as antioxidant as the antioxidant auxiliary.Weight ratio is 1 weight %.JP 63305162 has described the stable bag of UV that is used for based on the MPE of polyesterols.Here especially mention triphenyl phosphite (TPP) is used in combination with sterically hindered phenol as the antioxidant auxiliary.Weight ratio is 0.5 weight %.JP 05214240 has described the UV protection that is used for the PU sole, and it especially comprises consumption and is about 1% thiophosphite.JP2003147057 has described the purposes of polycarbonate diol in footwear.For example, the TPP that has mentioned about 2 weight % adds in the prepolymer.
Document JP 61128904, JP 63278962 and JP 05214240 have described phosphorous acid ester purposes as the antioxidant auxiliary in based on the MPE of polyester usually.File JP 63278962 and JP63305162 mention and can be especially aromatic phosphite be used as antioxidant in that isocyanic ester is in reactive component.File JP 2003147057 has described aromatic phosphite based on the purposes in the microcellular polyurethane elastomer of polyether carbonate alcohol.
The purpose of this invention is to provide the hydrolysis inhibitor that is used for based on the MPE of polyesterols, this inhibitor can have high-level efficiency under low consumption, and no matter uses which kind of polyesterols all to guarantee efficient.
This purpose a) realizes by using special hydrolysis inhibitor, wherein said hydrolysis inhibitor is a) by ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %, preferred 9.90-10.10 weight %, especially 9.95-10.05 weight %) composition of amine compound such as triethylenediamine forms, ai wherein) and mol ratio aii) be preferably 0.005-4.0, more preferably 0.1-3.0, especially 0.5-2.0.Preferably in containing the component of isocyanic ester (B component), use component ai) and isocyanic ester is being use aii in reactive component (A component)).
Therefore, the invention provides can be by making polyisocyanates and having at least two isocyanate group is the MPE that the compound reaction of reactive hydrogen atom prepares, it comprises by ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) composition formed of amine compound a), ai) and aii) mol ratio be 0.005-4.0.
It is a kind of by making polyisocyanates and having the method that at least two compound reactions that isocyanate group is reactive hydrogen atom prepare MPE that the present invention also provides, it is included in a) to exist down and reacts, and wherein said a) is by ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) the amine compound composition and the ai that form) and mol ratio aii) be 0.005-4.0.
The present invention also provides ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) composition of amine compound is as the purposes of MPE hydrolysis inhibitor.
The present invention also provides the sole that comprises microcellular polyurethane elastomer of the present invention.
Ai) and mol ratio aii) preferred 0.1-3.0, especially 0.5-2.0.
Component ai) the preferred 9.90-10.10 weight of phosphorus content %, especially 9.95-10.05 weight %.
Used component ai) preferred triphenyl phosphite (TPP).
Used amine compound aii) can be primary amine, secondary amine, preferred tertiary amine.Preferred usually as the amine for preparing catalyst of polyurethane.
Amine compound is preferably and is selected from following tertiary amine: triethylamine; triethylenediamine; Tributylamine; dimethyl benzylamine; N; N; N '; N '-Tetramethyl Ethylene Diamine; N; N; N '; N '-tetramethyl butane diamine; N; N; N '; N '-tetramethyl--1; the 6-hexanediamine; dimethylcyclohexylamine; the pentamethyl-dipropylenetriamine; five methyl diethylentriamine; 3-methyl-6-dimethylamino-3-azepine amylalcohol (3-Methyl-6-dimethylamino-3-azapentol); dimethylamino propylamine; 1; 3-two (dimethylamino) butane; two (2-dimethyl aminoethyl) ether; N-ethylmorpholine; N-methylmorpholine; N-cyclohexyl morpholine; 2-dimethylamino ethoxy ethanol; dimethylethanolamine; the tetramethyl-hexamethylene-diamine; dimethylamino-N-Mono Methyl Ethanol Amine; the N-Methylimidazole; N-(3-aminopropyl) imidazoles; N-(3-aminopropyl)-glyoxal ethyline; 1-(2-hydroxyethyl) imidazoles; N-formyl radical-N; N '-diamine dimethyl butyrate; N-dimethyl aminoethyl morpholine; 3; 3 '-two-dimethylamino di-n-propyl amine and/or 2; 2 '-two piperazine Di Iso Propyl Ethers; lupetazin; N; N '-two (3-aminopropyl) quadrol and/or three (N; the N-dimethylaminopropyl)-s-Hexahydrotriazine or comprise the mixture of at least two kinds of described amine, but also can use the more high-molecular weight tertiary amine that for example is described among the DE-A 28 12 256.Especially preferably use triethylenediamine.
As a rule, tertiary amine as catalyzer with aromatic phosphite ai) consumption when being used in combination should be enough to the stabilization that reaches required.Yet, when the catalyzer that uses except that amine catalyst, perhaps during less than the required amount of sufficient stabilization, can also use other amine at the consumption of amine catalyst.In order to get rid of the fracture in the catalyzer, then they are not the tertiary amines that is used as catalyzer in the method.
Preferably use weight to be 0.0001-3 weight % based on MPE, 0.0005-2 weight %, the hydrolysis inhibitor of 0.001-1.6 weight % is a).
For the raw material that is used to prepare MPE of the present invention, should be described below especially.
The polyisocyanates that is used for the inventive method comprises aliphatic series well known in the prior art, alicyclic and aromatic isocyanate and any mixture thereof.Example is a ditan 4,4 '-vulcabond, monomer diphenylmethanediisocyanate and have the more mixture of the homologue of the diphenylmethanediisocyanate of epipodium number (polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI) or its mixture.
Preferred use 4,4 '-MDI and/or HDI.4 of preferred especially use, 4 '-MDI can comprise the allophanate of a small amount of and about at the most 10 weight % or the polyisocyanates of uretonimine (uretonimin) modification.Can use a spot of polyphenylene polymethylene polyisocyanates (thick MDI) in addition.The total amount of the polyisocyanates of these high functionalities should not surpass 5 weight % of used isocyanic ester.In addition, 4,4 '-MDI can comprise on a small quantity, preferably is at most 2 of 10 weight %, 4 '-MDI.
Polyisocyanates can also use with the form of polyisocyanate prepolymers.These prepolymers are known in the prior art.They in a manner known way by make above-mentioned polyisocyanates with have isocyanic ester is reactive hydrogen atom compound as described below for example under about 80 ℃ temperature reaction prepare to form prepolymer.It is 8-25 weight % that the selection of the ratio of polyvalent alcohol and polyisocyanates should make the NCO content of prepolymer usually, preferred 10-22 weight %, more preferably 13-20 weight %.
Used have isocyanic ester is reactive hydrogen atom compound as described be polyesterols like that.
Usually by having 2-12 polyvalent alcohol individual, preferably 2-6 carbon atom, preferred dibasic alcohol and having the condensation prepared of the polycarboxylic acid of 2-12 carbon atom, wherein said polycarboxylic acid for example is Succinic Acid, pentanedioic acid, hexanodioic acid, phthalic acid, m-phthalic acid and/or terephthalic acid and composition thereof to polyesterols.Suitable dibasic alcohol and examples of polyhydric alcohols are ethylene glycol, glycol ether, 1,4-butyleneglycol, 1,5-pentanediol and/or 1,6-hexylene glycol and composition thereof.
Polyesterols can also be a branching.The functionality of branched polyester alcohol is preferably greater than 2 to 3, especially 2.2-2.8.In addition, branched polyester alcohol preferably has 500-5000g/mol, the more preferably number-average molecular weight of 2000-3000g/mol.
Usually, the polyesterols that is used for the inventive method has 2-4, is preferably greater than 2 to less than 3 average theory functionality and above-mentioned number-average molecular weight.
Polyesterols in principle can also be to use with the mixture of Aethoxy Sklerol.Yet,, thereby not too preferably use such mixture because such mixture often has inadequate phase stability.
Compound with two reactive hydrogen atoms also comprises suitable words and the chain extension agent that uses.Suitable chain extension agent is known in the prior art.Preferably use molecular weight less than 400g/mol, especially the difunctional alcohol of 60-150g/mol.Example is an ethylene glycol, 1, ammediol, glycol ether, 1,4-butyleneglycol, glycerine or TriMethylolPropane(TMP) and composition thereof.Preferably make spent glycol.
Chain extension agent is if use, usually being 1-15 weight % based on having two gross weights that isocyanate group are the compound of reactive hydrogen atom, and preferred 3-12 weight %, the more preferably amount of 4-10 weight % and using.
Polyisocyanates reacts with the compound with two reactive hydrogen atoms in the presence of whipping agent usually.Used whipping agent can be the compound of known chemically reactive or physical activity.Chemically active whipping agent can be preferably water.The example of pneumatogen is inertia (ring) aliphatic hydrocrbon that has 4-8 carbon atom and evaporate under the formation condition of urethane.The consumption of whipping agent depends on the foamy desired density.
Suitable words, at catalyzer and auxiliary agent and/or additive such as abscess conditioning agent, releasing agent, pigment, toughener such as glass fibre, surface active cpd and/or in the presence of, make polyisocyanates and compound reaction with two reactive hydrogen atoms to anti-oxidant, heat or microbiological deterioration or aged stablizer.
The catalyzer that is used to prepare microcellular polyurethane elastomer of the present invention can be conventional and known catalyst for preparing polyurethane, for example organometallic compound such as oxalic acid tin, two stannous octoates, dibutyl tin dilaurate, and/or strong basicity amine such as diazabicyclooctane, two (N, N-dimethyl aminoethyl) ether or above-mentioned amine.It is 0.01-10 weight % that catalyst consumption is preferably based on reaction mixture, preferred 0.02-5 weight %.
As mentioned above, preferably with amine, particularly tertiary amine is as catalyzer.As mentioned above, amine can use separately or as using with each other any mixture.They are simultaneously as the component aii in the microcellular polyurethane elastomer).For this reason, the preferred described amine that reaches as the effectiveness aequum of stablizer that only uses.If this is for the catalytic effect deficiency, then tertiary amine can combine use with other catalyzer.
Operable organic amine is by tertiary amine well known in the prior art.Useful tertiary amine for example comprises: organic amine such as triethylamine; triethylenediamine; Tributylamine; dimethyl benzylamine; N; N; N '; N '-Tetramethyl Ethylene Diamine; N; N; N '; N '-tetramethyl butane diamine; N; N; N '; N '-tetramethyl--1; the 6-hexanediamine; dimethylcyclohexylamine; the pentamethyl-dipropylenetriamine; five methyl diethylentriamine; 3-methyl-6-dimethylamino-3-azepine amylalcohol (3-Methyl-6-dimethylamino-3-azapentol); dimethylamino propylamine; 1; 3-two (dimethylamino) butane; two (2-dimethyl aminoethyl) ether; N-ethylmorpholine; N-methylmorpholine; N-cyclohexyl morpholine; 2-dimethylamino ethoxy ethanol; dimethylethanolamine; the tetramethyl-hexamethylene-diamine; dimethylamino-N-Mono Methyl Ethanol Amine; the N-Methylimidazole; N-(3-aminopropyl) imidazoles; N-(3-aminopropyl)-glyoxal ethyline; 1-(2-hydroxyethyl) imidazoles; N-formyl radical-N; N '-diamine dimethyl butyrate; N-dimethyl aminoethyl morpholine; 3; 3 '-two-dimethylamino di-n-propyl amine and/or 2; 2 '-two piperazine Di Iso Propyl Ethers; lupetazin; N; N '-two (3-aminopropyl) quadrol and/or three (N; the N-dimethylaminopropyl)-s-Hexahydrotriazine or comprise the mixture of at least two kinds of described amine, but also can use the more high-molecular weight tertiary amine that for example is described among the DE 28 12 256.Especially preferably use triethylenediamine.
The catalyzer that can use with the mixture with tertiary amine is mainly organometallic compound as mentioned above, especially tin compound such as oxalic acid tin, two stannous octoates, dibutyl tin dilaurate and/or bismuth compound.
Catalyzer preferably with have at least two compound that isocyanate group are reactive hydrogen atom.Organometallic compound is mixed with polyisocyanates.
Usually, polyisocyanates is called " isocyanate component ", and will be usually with catalyzer and suitable, the mixture of whipping agent and additive uses has at least two compounds that isocyanate group is reactive hydrogen atom and is called " polyol component ".
Be the production polyurethane foam, it is 1 that the amount that isocyanate component and polyol component react usually should make the equivalence ratio of NCO group and hydrogen atoms summation: 0.8-1: 1.25, preferred 1: 0.9-1: 1.15.In the present context, 1: 1 ratio is 100 corresponding to nco index.
The reaction that forms microcellular polyurethane elastomer is preferably carried out under compression in mould.Mould preferably by metal such as steel or aluminium, perhaps form by plastics such as Resins, epoxy.Under 15-90 ℃, preferred 20-35 ℃ temperature starting ingredient mixing and introducing are preferably in the airtight mould, suitable words are introduced under elevated pressure.Can stimulate the menstrual flow in introducing process high pressure well known in the prior art or low pressure mixed gear end of mixing carries out.Die temperature is generally 20-90 ℃, preferred 30-60 ℃.
Reaction mixture is incorporated into amount in the mould, and should to make the density of gained moulded product be 250-600g/l or 800-1200g/l, preferred 400-600g/l or 820-1050g/l.The degree of compactness of gained microcellular polyurethane elastomer is 1.1-8.5, preferred 1.2-5, more preferably 1.5-4.
Microcellular polyurethane elastomer of the present invention can be used for bearing circle, safety clothes and be preferred for sole.
The present invention is elaborated by following embodiment.
Comparative Examples C1-C3 and embodiment 1-4
The isocyanate component of weight part shown in 100 weight part polyol components and the following table 1 is acutely mixed down at 23 ℃, and this mixture be incorporated into be heated to 50 ℃ and be of a size of in the tabular aluminium matter mould of 20 * 20 * 1cm, the amount of being introduced should make in closed mold foaming and solidify after obtain the microcellular polyurethane elastomer plate that overall consistency is 550g/L.
Store after 24 hours, use punch die from the elastomeric sheets of producing thus, to stamp out dumbbell specimen.Before the beginning senile experiment, measure the initial value of tensile strength according to DIN 53543.Then with sample according to DIN 53543 70 ℃ carry out senile experiment under water.After 14 days, take out sample then.The results are summarized in the table 2.
After the hydrolysising aging in two weeks, the residual tensile strength of sample 1-4 and elongation are apparently higher than comparative sample C1-C3.
Raw materials used:
PESOL 1: available from Elastogran GmbH by hexanodioic acid, 1, the polyesterols (Lupraphen that 4-butyleneglycol and ethylene glycol make
8108), OHN=56mg KOH/g, functionality=2
Amine catalyst: available from the 33 weight % solution (Lupragens of triethylenediamine in ethylene glycol of BASF AG
N 202)
Foaming stabilizer: available from the Dabco of Air Products
DC 193
Isocyanate prepolymer: based on 4,4 '-prepolymer of MDI and PESOL1, NCO content=17.4%
Hydrolysis inhibitor ai): triphenyl phosphite
Hydrolysis inhibitor aii): triethylenediamine
The composition of table 1: system C1-C3 (Comparative Examples) and 1-4 (inventive embodiments)
| C1 | C2 | C3 | 1 | 2 | 3 | 4 | |
| A | |||||||
| PESOL1 | 89.24 | 89.24 | 89.24 | 89.24 | 89.24 | 89.24 | 89.24 |
| Monoethylene glycol | 8.6 | 8.6 | 8.6 | 8.6 | 8.6 | 8.6 | 8.6 |
| Water | 0.475 | 0.475 | 0.475 | 0.475 | 0.475 | 0.475 | 0.475 |
| Amine catalyst | 1.63 | 1.63 | 1.63 | 1.63 | 1.63 | 1.63 | 1.63 |
| Foaming stabilizer | 0.14 | 0.14 | 0.14 | 0.14 | 0.14 | 0.14 | 0.14 |
| B | |||||||
| Isocyanate prepolymer | 104 | 104 | 104 | 104 | 104 | 104 | 104 |
| Hydrolysis inhibitor ai) | 0 | 6.5 | 13.05 | 0.014 | 0.135 | 0.677 | 1.3 |
| The mol ratio of [hydrolysis inhibitor ai)/hydrolysis inhibitor aii)] | 0.0 | 5 | 10 | 0.01 | 0.1 | 0.5 | 1.0 |
Table 2: the aging result of sample C1-C3 and 1-4
| C1 | C2 | C3 | 1 | 2 | 3 | 4 | |
| Tensile strength [N/mm 2] | |||||||
| t＝0 | 8 | 6.7 | 5.5 | 7.9 | 7.8 | 8 | 7.4 |
| t＝14 | 2.8 | n.m. | n.m. | 3.2 | 3.2 | 4.6 | 2.9 |
| Residual tensile strength [%] a) | 35 | 0 | 0 | 40 | 41 | 57 | 39 |
| Elongation [%] | |||||||
| t＝0 | 429 | 431 | 392 | 441 | 452 | 444 | 452 |
| t＝14 | 291 | n.m | n.m. | 362 | 359 | 438 | 321 |
| Residual elongation rate [%] a) | 67 | 0 | 0 | 82 | 79 | 98 | 71 |
A)=after two weeks aging, in the residual tensile strength or the residual elongation rate of the percentage ratio of initial value.
N.m.=can't measure (decomposed sample)
T=is in the digestion time in sky
Claims (13)
- One kind can be by making polyisocyanates and having at least two isocyanate group is the microcellular polyurethane elastomer that the compound reaction of reactive hydrogen atom prepares, it comprises by ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) composition formed of amine compound a), ai wherein) and mol ratio aii) be 0.005-4.0.
- 2. according to the microcellular polyurethane elastomer of claim 1, wherein said ai) and mol ratio aii) be 0.1-3.0.
- 3. according to the microcellular polyurethane elastomer of claim 1, wherein said ai) and mol ratio aii) be 0.5-2.0.
- 4. according to the microcellular polyurethane elastomer of claim 1, the phosphorus content of wherein said aromatic phosphite is 9.90-10.10 weight %.
- 5. according to the microcellular polyurethane elastomer of claim 1, the phosphorus content of wherein said aromatic phosphite is 9.95-10.05 weight %.
- 6. according to the microcellular polyurethane elastomer of claim 1, wherein said aromatic phosphite is a triphenyl phosphite.
- 7. according to the microcellular polyurethane elastomer of claim 1, wherein used amine aii) be tertiary amine.
- 8. according to the microcellular polyurethane elastomer of claim 1; wherein said tertiary amine is selected from triethylamine; triethylenediamine; Tributylamine; dimethyl benzylamine; N; N; N '; N '-Tetramethyl Ethylene Diamine; N; N; N '; N '-tetramethyl butane diamine; N; N; N '; N '-tetramethyl--1; the 6-hexanediamine; dimethylcyclohexylamine; the pentamethyl-dipropylenetriamine; five methyl diethylentriamine; 3-methyl-6-dimethylamino-3-azepine amylalcohol; dimethylamino propylamine; 1; 3-two (dimethylamino) butane; two (2-dimethyl aminoethyl) ether; N-ethylmorpholine; N-methylmorpholine; N-cyclohexyl morpholine; 2-dimethylamino ethoxy ethanol; dimethylethanolamine; the tetramethyl-hexamethylene-diamine; dimethylamino-N-Mono Methyl Ethanol Amine; the N-Methylimidazole; N-(3-aminopropyl) imidazoles; N-(3-aminopropyl)-glyoxal ethyline; 1-(2-hydroxyethyl) imidazoles; N-formyl radical-N; N '-diamine dimethyl butyrate; N-dimethyl aminoethyl morpholine; 3; 3 '-two-dimethylamino di-n-propyl amine and/or 2; 2 '-two piperazine Di Iso Propyl Ethers; lupetazin; N; N '-two (3-aminopropyl) quadrol and/or three (N, N-dimethylaminopropyl)-s-Hexahydrotriazine or comprise the mixture of at least two kinds of described amine.
- 9. according to the microcellular polyurethane elastomer of claim 1, wherein said tertiary amine is a triethylenediamine.
- 10. one kind by making polyisocyanates and having the method that at least two compound reactions that isocyanate group is reactive hydrogen atom prepare microcellular polyurethane elastomer, it is included in hydrolysis inhibitor and a) reacts under existing, described a) for by ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) composition formed of amine compound, wherein ai) and mol ratio aii) be 0.005-4.0.
- 11. according to each the purposes of microcellular polyurethane elastomer in producing sole among the claim 1-9.
- 12.ai) phosphorus content is aromatic phosphite and the aii of 9.00-11.00 weight %) amine compound is as the purposes of the hydrolysis inhibitor of microcellular polyurethane elastomer.
- 13. sole that comprises according to each microcellular polyurethane elastomer among the claim 1-9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004061609.4A DE102004061609B4 (en) | 2004-12-17 | 2004-12-17 | Microcellular polyurethane elastomers preparable by reaction of polyisocyanates containing 4,4'-diphenylmethane diisocyanate, process for the preparation of such microcellular polyurethane elastomers and their use |
| DE102004061609.4 | 2004-12-17 | ||
| PCT/EP2005/013405 WO2006066763A1 (en) | 2004-12-17 | 2005-12-14 | Method for producing microcellular polyurethane elastomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101080428A true CN101080428A (en) | 2007-11-28 |
| CN101080428B CN101080428B (en) | 2011-02-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800431336A Active CN101080428B (en) | 2004-12-17 | 2005-12-14 | Method for producing microcellular polyurethane elastomers |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20070100937A (en) |
| CN (1) | CN101080428B (en) |
| DE (1) | DE102004061609B4 (en) |
| WO (1) | WO2006066763A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005008242A1 (en) | 2005-02-22 | 2006-08-24 | Basf Ag | Cylindrical molded bodies, useful in automobile parts e.g. auxiliary springs, buffer, short arm-bearing, comprises cellular polyurethane elastomers with determined density, tensile strength, breach extension and tear resistance |
| KR20090116712A (en) | 2006-12-20 | 2009-11-11 | 바스프 에스이 | Anisotropic cellular elastomers |
| WO2008074705A1 (en) * | 2006-12-20 | 2008-06-26 | Basf Se | Anisotropic cellular elastomers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU74540A1 (en) * | 1976-03-12 | 1977-09-27 | ||
| LU81024A1 (en) * | 1979-03-09 | 1980-09-24 | Prb Sa | PROCESS FOR THE PREPARATION OF FULL-SKIN POLYURETHANE AND POLYURETHANE OBTAINED |
| US4477600A (en) * | 1983-09-23 | 1984-10-16 | Stauffer Chemical Company | Polyurethane foams having low scorch discoloration |
-
2004
- 2004-12-17 DE DE102004061609.4A patent/DE102004061609B4/en not_active Expired - Fee Related
-
2005
- 2005-12-14 WO PCT/EP2005/013405 patent/WO2006066763A1/en not_active Application Discontinuation
- 2005-12-14 CN CN2005800431336A patent/CN101080428B/en active Active
- 2005-12-14 KR KR1020077015957A patent/KR20070100937A/en not_active Application Discontinuation
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| Publication number | Publication date |
|---|---|
| DE102004061609B4 (en) | 2014-06-26 |
| DE102004061609A1 (en) | 2006-07-06 |
| KR20070100937A (en) | 2007-10-15 |
| WO2006066763A1 (en) | 2006-06-29 |
| CN101080428B (en) | 2011-02-02 |
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