CA2177347A1 - Production of moldings containing ester and urethane groups, isocyanate semiprepolymers containing ester groups for this purpose and their use - Google Patents
Production of moldings containing ester and urethane groups, isocyanate semiprepolymers containing ester groups for this purpose and their useInfo
- Publication number
- CA2177347A1 CA2177347A1 CA002177347A CA2177347A CA2177347A1 CA 2177347 A1 CA2177347 A1 CA 2177347A1 CA 002177347 A CA002177347 A CA 002177347A CA 2177347 A CA2177347 A CA 2177347A CA 2177347 A1 CA2177347 A1 CA 2177347A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- isocyanate
- molecular weight
- groups
- aiii
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012948 isocyanate Substances 0.000 title claims abstract description 74
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 74
- 125000004185 ester group Chemical group 0.000 title claims abstract description 34
- 238000000465 moulding Methods 0.000 title claims abstract description 28
- 150000002148 esters Chemical class 0.000 title claims abstract description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title 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 abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 15
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000004971 Cross linker Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000001413 cellular effect Effects 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 8
- 238000005056 compaction Methods 0.000 claims abstract description 6
- -1 neopentyl glycol ester Chemical class 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 38
- 239000004814 polyurethane Substances 0.000 description 23
- 229920002635 polyurethane Polymers 0.000 description 21
- 239000006260 foam Substances 0.000 description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 229920001228 polyisocyanate Polymers 0.000 description 13
- 239000005056 polyisocyanate Substances 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 150000002009 diols Chemical class 0.000 description 10
- 150000002334 glycols Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000010097 foam moulding Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010107 reaction injection moulding Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000518994 Conta Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002605 large molecules Chemical class 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 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 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012766 organic filler Substances 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
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- DJZRNMVJDPIQIO-UHFFFAOYSA-N (1,4-dimethylcyclohexa-2,4-dien-1-yl)methanamine Chemical compound CC1=CCC(C)(CN)C=C1 DJZRNMVJDPIQIO-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 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
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- ZFDWWDZLRKHULH-UHFFFAOYSA-N 1,2-dimethyl-5,6-dihydro-4h-pyrimidine Chemical compound CN1CCCN=C1C ZFDWWDZLRKHULH-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- FCQPNTOQFPJCMF-UHFFFAOYSA-N 1,3-bis[3-(dimethylamino)propyl]urea Chemical compound CN(C)CCCNC(=O)NCCCN(C)C FCQPNTOQFPJCMF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- OREGNAGKJMVGKA-UHFFFAOYSA-N 2,2,5-trimethylhexane-1,6-diol Chemical compound OCC(C)CCC(C)(C)CO OREGNAGKJMVGKA-UHFFFAOYSA-N 0.000 description 1
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- UYZUYVVDLFXCCV-UHFFFAOYSA-N 2,2-dimethylhexane-1,6-diol Chemical compound OCC(C)(C)CCCCO UYZUYVVDLFXCCV-UHFFFAOYSA-N 0.000 description 1
- CVFRFSNPBJUQMG-UHFFFAOYSA-N 2,3-bis(2-hydroxyethyl)benzene-1,4-diol Chemical compound OCCC1=C(O)C=CC(O)=C1CCO CVFRFSNPBJUQMG-UHFFFAOYSA-N 0.000 description 1
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
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- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 150000003606 tin compounds Chemical class 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- DHNUXDYAOVSGII-UHFFFAOYSA-N tris(1,3-dichloropropyl) phosphate Chemical compound ClCCC(Cl)OP(=O)(OC(Cl)CCCl)OC(Cl)CCCl DHNUXDYAOVSGII-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Classifications
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/30—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
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- 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
- C08G2110/0016—Foam properties semi-rigid
-
- 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
- C08G2110/0033—Foam properties having integral skins
-
- 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
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- C08G2390/00—Containers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
A process for producing moldings containing ester and urethane groups and having a cellular core and a compacted surface zone, preferably shoe soles, comprises reacting a) isocyanate semiprepolymers containing ester groups and having an isocyanate content of from 10 to 26% by weight, which in turn are prepared by reacting ai) 4,4'-MDI or mixtures of 4,4'-MDI and modified or unmodified MDI isomers, with aii) difunctional to trifunctional polyester polyols having molecular weights of from 600 to 3000 and aiii)at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500, with b) at least one relatively high molecular weight polyhydroxyl compound and, if desired, c) low molecular weight chain extenders and/or crosslinkers in the presence of d) blowing agents, e) catalysts and, if desired, f) additives in a closed mold with compaction. The isocyanate semiprepolymers containing ester groups which can be used in this process are liquid at room temperature.
Description
Production of moldings containing ester and urethane groups, isocyanate semiprepolymers containing ester groups for this purpose and their use The invention relates to a process for producing moldings containing ester and urethane groups and having a cellular core and a compacted surface zone, known as polyurethane (PU) integral foams, by reacting isocyanate semiprepolymers containing ester 10 groups (a) with relatively high molecular weight polyhydroxyl compounds (b), preferably polyester polyols, and, if desired, low molecular weight chain extenders and/or crosslinkers (c) in the presence of blowing agents (d), preferably water, catalysts (e) and, if desired, additives (f) in a closed mold, using isocyanate semiprepolymers according to the invention, which are liquid at room temperature, contain ester groups and have an isocyanate content of from 10 to 26~ by weight, which semiprepolymer~ are prepared by reacting 20 ai) diphenylmethane 4,4'-diisocyanate, also abbreviated to MDI, or mixtures of 4,4'-MDI and modified or unmodified MDI
isomers with aii) difunctional to trifunctional polyester polyols having molecular weights of from 600 to 3000 and aiii) at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500.
The invention also relates to the use of the moldings produced as shoe soles and the novel, eg. usable according to the invention, isocyanate semiprepolymers which are liquid at room temperature and contain ester groups.
The production of moldings having a cellular core and a compacted surface zone by reacting organic polyisocyanates, relatively high molecular weight compounds having at least two reactive hydrogens and, if desired, chain extenders in the pre~ence of blowing 40 agents, preferably physically acting blowing agents, catalysts, auxiliaries and/or additives in a closed, heated or unheated mold with compaction has been known for a long time and i8 degcribed, for example, in DE-A-16 94 138 (GB-A-1 209 243), DE-A-19 55 891 (G~-A-1 321 679) and DE-A-17 69 886 (US-A-3 824 l99).
.
Also known is the production of sole material by the polyisocyanate polyaddition process and the use of shoe soles containing urethane groups in the shoe industry. Significant application areas for polyisocyanate polyaddition products in the shoe industry are the direct foaming on of soles and the production of ready-made polyurethane (PU) soles. Such PU shoe soles can be produced by the low-pressure or high-pressure technique (RIM) (Schuh-Technik ~ abc, 10/1980, pages 822 ff).
10 A summary overview of polyurethane integral foams has been published, for example, in Integralschaumstoffe by Dr. H. Piechota and Dr. H. Rohr, Carl-Hanser-Verlag, Munich, Vienna, 1975 and in Kunststoff-Handbuch, volume 7, Polyurethane by Dr. G. Oertel, Carl-Hanser-Verlag, Munich, Vienna, 2nd. edition, 1983, pages 333 ff, which also gives information about the use of inteqral foams in the shoe industry (pages 362 to 366).
4,4'-MDI and 2,4'-MDI have melting points of 39.5 C and 34.5 C
20 respectively and are therefore usually solid at room temperature and can be processed only with difficulty. There have therefore been many attempts to prepare polyisocyanate compositions which are based on MDI and are liguid at room temperature by modification of 4,4'- and/or 2,4'-MDI. For this purpose, 4,4'-and/or 2,4'-MDI are customarily reacted with substoichiometric amounts of alkylene glycols, dialkylene glycols, low molecular weight and/or relatively high molecular weight difunctional and/or trifunctional polyoxyalkylene polyols to give isocyanate semiprepolymers which are liquid at room temperature.
For example, according to DE-C-16 18 380 (US-A-3 644 457), an MDI
preparation which iB liquid at room temperature i9 prepared by reacting 1 mol of 4,4'- and/or 2,4'-MDI with from 0.1 to 0.3 mol of tri-1,2-propylene ether glycol and/or poly-1,2-propylene ether glycol having a molecular weight of up to 700. 4,4'-MDI partially reacted with dipropylene glycol or partially reacted mixtures of MDI isomers and polyphenyl-polymethylene polyisocyanates, known as raw MDI, are used according to EP-B-O 364 854 (CA-A-2 000 019 r for producing moldings having a compacted surface zone and a 40 cellular core, known as integral foams, preferably shoe soles.
Liquid polyisocyanate mixtures based on MDI, containing bonded urethane groups and having an isocyanate content of from 22 to 30% by weight can, according to EP-A-O 557 792 (US-A-5 374 667), be obtained, inter alia, by partial reaction of raw MDI with a polyoxypropylene-polyoxyethylene polyol having a functionality of from 2.5 to 3.5, a hydroxyl number of from 50 to 90 and a 2~ 77347 polymerized ethylene oxide group content of from more than 30 to less than 50%,by weight, based on the weight of polymerized ethylene oxide and 1,2-propylene oxide groups. The isocyanate semiprepolymers are preferably used for producing CFC-free PU
(molded) flexible foams.
Polyester polyurethanes can be prepared in a similar manner by reacting MDI and/or raw MDI with polyester polyols to give isocyanate semiprepolymers and these can be used for producing 10 moldings.
According to US-A-4 857 561, for example MDI and/or polyphenyl-polymethylene polyisocyanates are reacted with a polyneopentyl glycol adipate having a molecular weight of from 750 to 3500 and a functionality of from 2 to 3 to give an isocyanate semiprepolymer having an isocyanate content of from 14 to 28% by weight and this is used to produce a molding by the RIM
process in a closed mold. According to CA-A-l 096 181, polyadipates based on tripropylene glycol, butanediol and 20 ethylene glycol are used in place of neopentyl glycol for modifying 4,4'-MDI. According to DE-A-3 831 681 (US-A-5 053 528), dihydroxy compounds containing bonded ester groups and having the formula HOH2C-C(CH3)2-CO-O-R-O-CO-C(CH3)2-CH20H, where R is a branched or unbranched alkylene radical or a polyoxyalkylene radical, are reacted with 4,4'- and 2,4'-MDI or mixtures of 4,4'-MDI, 2,4'-MDI and raw MDI to give isocyanate 30 semiprepolymers. The use of ester diols or polyester diols having methyl side groups enabled the storage stability of the isocyanate semiprepolymers to be improved. However, obviously because of the high content of branched diols in the isocyanate semiprepolymers, the mechanical properties of the PU integral foams produced therefrom were adversely affected.
US-A-4 182 898 describes storage-stable isocyanate prepolymers which are liquid at room temperature and are prepared by reacting diisocyanates such as HDI, JPDI, TDI and MDI with mixtures of 40 compatible polyether and polyester polyols in a ratio of 15 to 85:85 to 15% by weight and in a ratio of NCO:OH groups of from 1.5:1 to 2:1.
According to US-A-4 647 596, microcellular PU elastomers are produced from an isocyanate prepolymer whose polyol component comprises a polyester-polyether polyol from polyoxytetramethylene glycol and ~-caprolactone in a weight ratio of from 20:80 to 80:20 and having a molecular weight of from 1000 to 3000 and a polyester polyol based on adipic acid and having a molecular weight of from lO00 to 3000 and whose isocyanate component is 4,4'-MDI. PU integral foams produced using water as blowing agent are, according to US-A-5 166 183, obtained by reacting an isocyanate prepolymer having an isocyanate content of from 16 to 25% by weight, prepared from MDI and a polyester diol having a molecular weight of from 1000 to 3000 and mixed, if desired, with an isocyanate prepolymer based on MDI and polyoxypropylene glycol 10 having a molecular weight of from 134 to 700 and a specific mixture of relatively high molecular weight polyether diols, polyether polyols, 1,4-butanediol and ethylene glycol.
US-A-4 986 929 describes polyisocyanate mixtures having an isocyanate content of from 16 to 25% by weight and consist~ng essentially of an isocyanate prepolymer from MDI and a polyoxypropylene glycol having a molecular weight of from 134 to 700 and an isocyanate prepolymer prepared by reacting a mixture of MDI and MDI containing carbodiimide groups with a polyester diol having a molecular weight of from lO00 to 3000. A
20 disadvantage of the isocyanate prepolymers described is the formation of flaws at the surface of PU integral foam~ produced therefrom, which flaws can be caused by insufficient compatibility of polyether and polyester isocyanate prepolymers.
It is an object of the present invention to produce moldings contAi~;ng ester and urethane groups, having a cellular core and a compacted surface zone and having mechanical properties which are at least equally good, but advantageously improved, using isocyanate semiprepolymers which are liquid at room temperature, 30 are based on a polyester polyol and have improved storage stability, even at about 0 C.
We have found that this object is achieved by using new isocyanate semiprepolymers which contain ester groups and are liquid at room temperature for producing the PU-ester integral foams.
The invention accordingly provides a process for producing moldings conta;ning ester and urethane groups and having a gO cellular core and a compacted surface zone by reacting a) isocyanate semiprepolymers contA; n; ng ester groups with b) at least one relatively high molecular weight polyhydroxyl compound and, if desired, 2~ 77347 .- 5 c) low molecular weight chain extenders, crosslinkers or mixtures of chain extenders and crosslinkers in the presence of d) blowing agents, e) catalysts and in the presence or absence of f) additives in a closed mold with compaction, wherein the isocyanate semiprepolymers (a) used are reaction products having an isocyanate content of from 10 to 26% by weight prepared from ai) 4,4'-MDI or mixtures of 4,4'-MDI and modified or unmodified MDI isomers, aii) at least one polyester polyol having a functionality of from 2 to 3 and a molecular weight of from 600 to 3000 and aiii) at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500.
The invention also provides isocyanate semiprepolymers which contain ester groups, are liquid at room temperature and have an 30 isocyanate content of from 10 to 26% by weight, which semiprepolymers are prepared by reacting ai) 4,4~-MDI or mixtures of 4,4'-MDI and modified or unmodified MDI isomers with aii) at least one polyester polyol having a functionality of fro~
2 to 3 and a molecular weight of from 600 to 3000 and aiii) at least one dihydroxy compound containing at least one bonded ester unit as bridge and lateral alkyl groups and having a molecular weight of up to 500.
For the purposes of the present ïnvention, isocyanate semiprepolymers which contain ester groups and are liquid at room temperature are reaction products prepared from (ai) to (aiii) which have a viscosity at 45 C of from 200 to 2500 mPas measured using a rotation viscometer in accordance with DIN 53018 and can be processed in liquid form above 10 C.
The novel isocyanate semiprepolymers having an isocyanate content of from 10 to 26~ by weight, preferably from 15 to 22% by weight, are al~o storage stable at 15 C for at least one month, preferably more than 3 months, ie. they form no crystalline sediments during this time.
10 Despite the preferred use of water as blowing agent, the moldings containing ester and urethane groups and produced by the process of the invention have a pronounced surface zone of higher density with an essentially smooth external skin. The Shore A hardness of the surface zone corresponds, like the other mechanical properties, to the PU integral foam moldings foamed using CFC~.
Furthermore, the system components have very good flowability and can be processed without difficulty by conventional methods, eg.
by the RIM or low-pressure technique, to give moldings, preferably shoe soles.
a) The following may be specifically said about the preparation of the novel isocyanate semiprepolymer~ (a) which contain ester groups, are liquid at room temperature and have an isocyanate content of from 10 to 26% by weight, preferably from 15 to 22~ by weight, and about the formative components (b) to (f) which can be used for the process of the invention for producing the moldings cont~ining ester and urethane groups:
30 ai) the polyisocyanate (ai) used for preparing the isocyanate semiprepolymers (a) is in particular 4,4'-MDI. Mixtures of 4,4~- and 2,4'-MDI, advantageously those having a 4,4'-MDI
content of at least 40% by weight, preferably at least 80%
by weight, have also been found to be very useful, so that such mixtures are also preferred. However, other suitable mixtures are those of 4,4'-MDI, 2,4'-MDI and 4,4'- and 2,4'-HDI in which the isocyanate groups have been reacted at least partially in a previous reaction stage to give carbodiimide groups, urethane groups and/or urethanimine groups.
aii) The polyester polyols (aii) which are suitable according to the invention as modifiers advantageously have a functionality of from 2 to 3, preferably from 2.0 to 2.5, and a mo~ecular weight of from 600 to 3000, preferably from 1000 to 3000 and in particular from 1200 to 2400. The molecular weights specified in the patent description for the polyhydroxyl compounds were calc~lated according to the formula 56100 x functionality molecular weight =
hydroxyl number where the hydroxyl number was experimentally measured in a known manner.
Suitable polyester polyols can be prepared, for example, from orqanic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. Examples of suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can here be ~0 used either individually or in admixture with one another.
In place of the free dicarboxylic acids, it i8 al~o possible to use the corresponding dicarboxylic acid derivatives such as dicarboxylic monoesters and~or diesters of alcohols having from 1 to 4 carbon atoms or dicarboxylic anhydrides.
Preference is given to using dicarboxylic acid mixtures of succinic, glutaric and adipic acid in weight ratios of, for example, 20 to 35:35 to 50:20 to 32, and particularly adipic acid. Examples of dihydric and higher-hydric alcohols, in particlar alkanediols and alkylene glycols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,10-decanediol, glycerol and trimethylolpropane. Preference is given to using ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol or mixtures of at least two of the specified diols, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol and/or glycerol. It is also possible to use polyester polyols from lactones, eg. E-caprolactone or hydroxycarboxylic acids, eg. ~-hydroxycaproic acid.
To prepare the polyester polyols, the organic, preferably aliphatic, polycarboxylic acids and/or derivatives and polyhydric alcohols can be polycondensed in the absence of catalyst or preferably in the presence of esterification catalysts, advantageously in an atmosphere of inert gases, eg. nitrogen, helium, argon, etc., in the melt at from 150 to 250 C, preferably from 180 to 220 C, at atmo~pheric 2 l 77347 pressure or under reduced pressure to the desired acid number which is advantageously less than 10, preferably less than 2. According to a preferred embodiment, the esterification mixture is polycondensed at the abovementioned temperatures to an acid number of from 80 to 30, preferably from 40 to 30, at atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably from 50 to 150 mbar. Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of diluents and/or entrainers such as benzene, toluene, xylene or chlorobenzene to azeotropically distill off the water of condensation.
To prepare the polyester polyols, the organic polycarboxylic acids and/or derivatives are polycondensed with polyhydric alcohols advantageously in a molar ratio of from 1:1 to 1.8, preferably from 1:1.05 to 1.2. To remove cyclic volatile byproducts, the polyester polyols can subsequently be additionally subjected to a distillation under reduced pressure, eg. by means of a thin-film evaporator. The polyester polyols can be used individually or as mixtures.
aiii)According to the invention, the polyisocyanates (ai) for preparing the isocyanate semiprepolymers (a) containing ester groups are partially reacted with polyester polyols (aii) and dihydroxy c~r.~younds (aiii) having a molecular weight of up to 500, preferably from 180 to 320, with the proviso that the dihydroxy compounds, preferably aliphatic dihydroxy compounds, contain at least one bonded ester unit, preferably one or 2 ester units, as bridge and have a branched chain. To form the branches, the dihydroxy compounds cont~i~;ng ester groups have at least 2, preferably from 2 to 12 and in particular from 4 to 8, lateral substituents, with preference being given to alkoxy groups and/or particularly alkyl groups having from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, as substituents. Examples of suitable sub~tituents which may be mentioned are the methoxy, ethoxy, isopropoxy, ethyl, n- and iso-propyl, n-butyl and, in particular, methyl groups. The dihydroxy compounds are advantageously prepared u~ing linear or branched aliphatic hydroxycarboxylic acids having from 2 to 6, preferably from 2 to 5 carbon atoms, eg. glycolic acid, lactic acid, a-, ~-, y-hydroxybutyric acid, ~-hydroxycaproic acid and, in particular, hydroxypivalic .
g acid. However, hydroxybenzoic acids are also suitable.
Examples of diols for preparing the dihydroxy compounds (aiii) contA;n;ng ester groups are dialkylene glycols, eg. diethylene and dipropylene glycol, oligomeric polyoxyalkylene glycols having molecular weights of up to 300 and based on ethylene oxide and/or 1,2-propylene oxide, eg. polyoxypropylene and polyoxyethylene-polyoxypropylene glycol, linear alkanediols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, eg. ethanediol, 1,3-propanediol, 1!4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, and preferably branched-chain alkanediols having from 3 to 15 carbon atoms, preferably from 3 to lO carbon atoms, eg. 1,2-propanediol, 1,2- and 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-, 2-methyl-2-ethyl-, 2-ethyl-2-butyl-, 2-ethoxy-pentane-1,5-diol, 2,2-dimethylhexane-1,6-diol, 2,2,5-trimethylhexane-1,6-diol, 1,2-pentanediol, 2,5-dimethylhexane-2,5-diol and, in particular, 2,2-dimethylpropane-1,3-diol. Branched-chain dihydroxy compounds containing ester groups (aiii) which have been found to be useful are, for example, transesterification products of 2 mol of alkyl hydroxypivalate~ with one mole of dialkylene glycol, polyoxyalkylene glycol, linear alkanediol and preferably branched alkanediol, as are described, for example, in US-A-5 053 528, whose entire di~closure is incorporated in this description by reference, esters of 2 mol of a linear hydroxycarboxylic acid and one mole of a branched alkanediol and preferably esters of one mole of a branched hydroxycarboxylic acid and one mole of a branched alkanediol. Particular preference is given to using the neopentyl glycol ester of hydroxypivalic acid.
To prepare the novel isocyanate semiprepolymers (a) contAin~ng ester group~ and having an isocyanate content of from 10 to 26 by weight, the formative components can be reacted in the following amounts, based on the total weight of the semiprepolymer, at from lS to 120 C, preferably from 45 to 90 C:
40 ai) from 94 to 25% by weight, preferably from 77 to 53% by weight, of (ai), aii) from 5 to 60% by weight, preferably from 20 to 40% by weight, of (aii) and aiii)from 1 to 15% by weight, preferably from 3 to 7% by weight, of (aiii).
For this purpose, the modified or unmodified 4,4'-MDI and/or 2,4'-MDI can, if they are not already liquid at room temperature, be liquified by heating and then reacted while stirring with the polyester polyols (aii) and the branched-chain dihydroxy compounds containing ester groups (aiii) individually in succession or with a mixture of (aii) and (aiii). According to a preferred embodiment, the polyisocyanates (ai) are first reacted with at least one polyester polyol (aii) and then with at least one low molecular weight dihydroxy compound (aiii). To complete 10 the reaction, it has been found to be advantageous to stir the reaction mixture for from 0.5 to 6 hours, preferably from 1 to 3 hours, in the abovementioned temperature range, eg. at from 45 to sO-C, and then to allow it to cool to room temperature while stirring.
To produce the CFC-free moldings containing ester and urethane groups and having a cellular core and a compacted surface zone, the novel liquid, storage-stable isocyanate semiprepolymers (a) containing ester groups are, as already indicated, allowed to 20 foam with customary relatively high molecular weight polyhydroxyl compounds (b) and, if desired, low molecular weight chain extenders and/or crosslinkers (c) in the presence of blowing agents (d), catalysts (e) and, if desired, additives (f) in a closed mold with compaction and allowed to cure.
(b) Suitable relatively high molecular weight polyhydroxyl compounds for this purpose advantageously have a functionality of from 2 to 4, preferably from 2 to 3, and a molecular weight of from 1200 to 7000, preferably from 1200 to 3600. Examples of suitable polyhydroxyl compounds are the polyether polyols, polyoxytetramethylene glycols, polymer-modified polyether polyols, polyether polyol dispersions, hydroxyl-con~;n;ng polyesteramides and hydroxyl-containing polyacetals known per se. Polyhydroxyl compounds which have been found to be particularly useful and are therefore preferably used are hydroxyl-cont~i n; ng polycarbonates, advantageously those prepared from 1,6-hexanediol and/or 1,4-butanediol and diphenyl carbonate by transesterification, polyether-polyester polyols prepared by esterification of polyoxytetramethylene glycols having molecular weights of from 250 to 1600, preferably from 250 to 600, or of mixtures of the specified polyoxytetra-methylene glycols and alkanediols having from 2 to 6 carbon atoms and/or dialkylene glycols having from 4 to 6 caron atoms with alkanedicarboxylic acids having from 4 to 6 carbon atoms, eg. succinic, glutaric or adipic acid or mixtures of at least 2 of the specified dicarboxylic acids, and, in particular, polyester polyols prepared from the abovementioned polycarboxylic acids and polyhydric alcohol~
and/or dialkylene glycols which can be used for preparing the polyester polyols (aii).
c) The for example semirigid and preferably flexible moldings containing ester and urethane groups and having a compacted surface zone and cellular core, known as PV integral foams, can be produced by the process of the invention with or without use of chain extenders and/or crosslinkers (c).
However, in the case of flexible and semirigid PU integral foams, the addition of chain extenders, crosslinkers or, if desired, mixtures thereof can be found to be advantageous for modifying the mechanical properties, eg. the hardness.
Chain extenders and/or crosslinkers which can be used are, for example, low molecular weight, polyhydric alcohols, preferably diol~ and/or triols, having molecular weights of less than 400, preferably from 60 to 300. Suitable chain extenders are, for example, aliphatic, cycloaliphatic and/or araliphatic diols such as alkanediols having from 2 to 14, preferably from 2 to 6, carbon atoms and/or dialkylene glycols having from 4 to 8, preferably from 4 to 6, carbon atoms, eg. ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and preferably 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, and suitable crosslinkers are, for example, triols such as 1,2,4- or 1,3,5-trihydroxycyclohexane, trimethylolethane, glycerol and trimethylolpropane.
If compounds of the component (c) are used, these can be used in the form of mixtures or individually and are advantageously employed in amounts of from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, bsed on 100 parts by weight of the relatively high molecular weight compounds (b).
d) The blowing agent (d) used is preferably water which reacts in situ with the isocyanate semiprepolymer~ (a) cont~;n~ng ester groups to form carbon dioxide and amino groups which in turn react further with the isocyanate semiprepolymers (a) to give urea groups and can thereby influence the compressive strength of the PU integral foam moldings. Since the formative components (b) and, if used, (c) can contain water as a result of their preparation and/or chemical composition, in some cases it is not necessary to separately _ add water to the formative components (b) and, if applicable, (c) or to the reaction mixture. However, if water has to be additionally incorporated into the polyurethane formulation to achieve the desired bulk density, this is usually used in amounts of from 0.05 to 4.0% by weight, preferably from 0.1 to 3.0% by weight and in particular from 0.3 to 2.5% by weight, based on the weight of the formative components (a) to (c).
As blowing agent (d) it is also possible to use, in place of water or preferably in combination with water, low-boiling liquids which vaporize under the influence of the exothermic polyaddition reaction and advantageously have a boiling point at atmospheric pressure in the range from -40 to 120 C, preferably from 10 to 90 C, or gases.
The liquids of the abovementioned type and gases suitable as blowing agent can, for example, be selected from the group of alkanes such as propane, n- and iso-butane, n- and iso-pentane and preferably the industrial pentane mixtures, cycloalkanes and cycloalkenes such as cyclobutane, cyclopentene, cyclohexene and preferably cyclopentane and/or cyclohexane, dialkyl ethers such as dimethyl ether, methyl ethyl ether or diethyl ether, tert-butyl methyl ether, cycloalkylene ethers such as furan, ketones such as acetone, methyl ethyl ketone, acetals and~or ketals such as formaldehyde dimethyl acetal, 1,3-dioxolane and acetone dimethyl acetal, carboxylic esters such as ethyl acetate, methyl formate and ethylene-acrylic acid tert-butyl ester, tertiary alcohols such as tertiary butanol, carboxylic acids such as formic acid, acetic acid and propionic acid, fluoroalkanes which are degraded in the troposphere and therefore do not damage the ozone layer, eg.
trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and heptafluoroethane, chloroalkanes such as 2-chloropropane, and gases such as nitrogen, carbon monoxide and noble gases such as helium, neon and krypton.
Among the liquids which are inert toward NC0 groups and are suitable as blowing agent (d), preference is given to using alkanes, cycloalkanes or mixtures of alkanes and cycloalkanes having a boiling point of from -40 to 50 C at atmospheric pressure.
Suitable blowing agents also include salts which decompose thermally, eg. ammonium bicarbonate and/or ammonium carbamate or compounds which form such salts in situ, eg.
-aqueou~ ammonia and/or amines and carbon dioxide, and ammonium salts of organic carboxylic acids, eg. the monoammonium salts of malonic acid, boric acid, formic acid or acetic acid.
The most advantageous amount of solid blowing aqents, low-boiling liquids and gases which can be used either individually or in the form of mixtures, eg. as liquid or gas mixtures or as gas-liquid mixtures, depends on the density which is to be achieved and the amount of water used. The amounts required can be easily determined by simple experiments. Satisfactory results are usually given by amounts of solid of from 0.5 to 35 parts by weight, preferably from 2 to 15 parts by weight, amounts of liquid of from 1 to 30 parts by weight, preferably from 3 to 18 parts by weight, and/or amounts of gas of from 0.01 to 80 parts by weight, preferably from 10 to 35 parts by weight, in each case based on the weight of the formative components (a), (b) and, if applicable, (c). The charge with gas, eg.
air, carbon dioxide, nitrogen and/or helium, can be carried out via the relatively high molecular weight compounds (b) and, if applicable, low molecular weight chain extenders and/or crosslinkers (c) or via the polyisocyanates (a) or via (a) and (b) and, if applicable, (c).
Blowing agents which are not used are, as already indicated, fully halogenated CFCs.
e) Catalysts (e) used for producing the PU foam moldings are, in particular, compounds which strongly accelerate the reaction of the hydroxyl-cont~1 n ~ ng compounds of the formative component (b) and, if used, (c) with the isocyanate semiprepolymers (a) containing ester groups.
~uitable examples are organic metal compounds, eg. zinc stearate, zinc oleate and preferably organic tin compounds such as tin(II) salts of organic carboxylic acids, eg.
tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate, and the dialkyltin(IV) salts of organic carboxylic acid~ eg. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, organic amidines such as 2,3-dimethyl-3,4,5,6-tetra-hydropyrimidine, tertiary amines such as triethylamine, tributylamine, methyldicyclohexylamine, 1,4-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, dimethylaminopropylamine, N,N-bis(dimethylaminopropyl)methylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N'N'-tetramethylbutane-1,4-diamine, N,N,N'N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, 2-hydroxyethyl 2'-dimethylaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine and dimethylethanolamine. Preference is given to using 1,4-diazabicyclo[2.2.2]octane, particularly in the form of a solution in ethylene glycol or 1,4-butanediol, dimethylaminopropylamine and also combinations of these tertiary amines with tin salts. Preference is given to using from 0.01 to 3~ by weight, in particular from 0.8 to 1.4~ by weight, of catalyst or catalyst combination, based on the weight of the component (b). The organic metal compounds and strongly basic amines, preferably tertiary amines, can, for example, each be used as sole catalyst or in combination with one another.
(f) If desired, additives (f) can also be incorporated into the reaction mixture for producing the preferably flexible moldings cont~i ni ng ester and urethane groups and having a cellular core and a compacted surface zone. Examples which may be mentioned are surface-active substances, foam stabilizers, cell regulators, lubricants, fillers, dyes, pigments, flame retardants, internal mold release agents, hydrolysis inhibitors, fungistatic and bacteriostatic substances.
Suitable surface-active substances are, for example, compounds which serve to aid the homogenization of the starting materials and may also be suitable for regulating the cell structure. Examples which may be mentioned are emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and also salts of fatty acids with amines, eg. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, eg.
~lkAli metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic esters, Turkey red oil and peanut oil and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
2~ 77347 Oligomeric polyacrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying action, the cell structure and/or stabilizing the foam. The surface-active substances are usually used in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of the component (b).
As lubricant, the addition of a ricinoleic polyester having a molecular weight of from 1500 to 3500, preferably from 2000 to 3000, has been found to be particularly useful and this is advantageously used in an amount of from 0;5 to 10%
by weight, preferably from 5 to 8% by weight, based on the weight of the component (b) or the components (b) and (c).
For the purposes of the present invention, fillers, in particular reinforcing fillers, are the customary organic and inorganic fillQrs and reinforcements known per se.
Specific examples are: inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, serpentine, hornblendes, amphiboles, chrysotile, talc; metal oxides such as kaolin, aluminum oxides, aluminum silicate, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide, and also glass particles. Examples of suitable organic fillers are: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers.
The inorganic and organic fillers can be used individually or as mixtures and are advantageously incorporated into the reaction mixture in amounts of from 0.5 to 50~ by weight, preferably from 1 to 40% by weight, based on the wei~ht of the components (a) to (c).
Suitable flame retardants are, for example, tricresyl phosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(1,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate and tetrakis(2-chloroethyl)ethylene diphosphate.
Apart from the abovementioned halogen-substituted phosphates, it is also possible to use inorganic flame retardants such as red phosphorus, expanded graphite, hydrated aluminum oxide, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine or mixtures of at least two flame retardants such as expanded graphite and ammonium polyphosphate, ammonium polyphosphates and melamine and also, if desired, expanded graphite and/or starch for making the moldings produced according to the invention flame resistant. In gQneral, it has been found to be advantageous to use from 2 to 50 parts by weight, preferably from 5 to 25 parts by weight, of the specified flame retardants or mixtures per 100 parts by weight of the components (a) to ( c ) .
Further details about the abovementioned other customary auxiliaries and additives can be found in the specialist literature, for example the monography by ~.H. Saunders and K.C. Frisch "High polymersn volume XVI, Polyurethane~, parts 1 and 2, Interscience Publishers 1962 or 1964, or Kunststoff-Handbuch, Polyurethane, volume VII, Carl-Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, lg66 and 1983.
To produce the moldings, the isocyanate semiprepolymers (a) cont~;ning ester groups, relatively high molecular weight 20 polyhydroxyl compounds (b) and, if desired, low molecular weight chain extenders and/or crosslinkers (c) are usually reacted in such amounts that the equivalence ratio of NC0 groups of the semiprepolymers (a) to the sum of the reactive hydrogens of the components (b) and, if applicable, (c) i8 from 0.45 to 1.80:1, preferably from 0.95 to 1.15:1 and in particular from 0.9 to 1 . 1 : 1 .
The novel for example semirigid or preferably flexible moldings containing ester and urethane groups can be produced by the 30 one-shot process using the low-pressure technique or the high-pressure technique in clo~ed, advantageously heatable molds, for example metal molds of, for example, aluminum, cast iron or steel, or molds of fiber-reinforced polyester or epoxide molding compositions. However, owing to the good flowability and improved processibility of the formulations, the moldings are produced in particular by means of reaction injection molding (RIM). These methods are de~cribed, for example, by Dr. Piechota and Dr. Rohr in "Integralschaumstoff", Carl-Hanser-Verlag, Munich, Vienna 1975; D.J. Prepelka and J.L. Wharton in Journal of Cellular 40 Plastics, March/April 1975, pages 87 to 98, U. Knipp in Journal of Cellular Plastics, March/April 1973, pages 76 to 84 and in Kunststoff-Handbuch, volume 7, Polyurethane, 2nd edition, 1983, pages 333 ff.
It has been found to be particularly advantageous to work according to the two-component process and combine the formative components (b), (d), (e) and, if used, (c) and (f) in the ` 2177347 -component (A) and use the novel isocyanate semiprepolymers (a) containing ester groups as component (~)~
The starting components are advantageously mixed at from 15 to 80 C, preferably from 25 to 55 C, and introduced, if desired under increased pressure, into the closed mold. Mixing can be carried out mechanically by means of a stirrer or a stirring spiral or under high pressure by the countercurrent in~ection method. The mold temperature is advantageously from 20 to 120 C, preferably 10 from 30 to 80 C and in particular from 45 to 60 C. The degrees of compaction are in the range from 1.4 to 8.3, preferably from 2 to 7 and in particular from 2.4 to 4.5.
The amount of reaction mixture introduced into the mold i8 advantageously such that the moldings obtained have a total density of from 0.06 to 0.9 g/cm3, with, for example, the semirigid moldings preferably having a total density of from 0.1 to 0.9 g/cm3, in particular from 0.35 to 0.7 g/cm3, and the flexible moldings preferably having a total density of from 0.2 20 to 0.7 g/cm3, preferably from 0.3 to 0.5 g/cm3.
The flexible moldings produced by the process of the invention are used, for example, as armrests, headrests and safety linings in motor vehicle interiors, as sports goods and as bicycle or motorcycle saddles. They are also suitable a~ steering wheels for vehicles, preferably motor vehicles, and as inner boot for ski boots, and al~o, in particular, as shoe soles. The semirigid moldings are suitable, for example, as dashboards and side linings in vehicles, as ski cores and for the cladding of metal 30 containers, preferably of metal barrels for beverages, for example alcoholic or nonalcoholic beverages such as beer or fruit juices.
Examples Preparation of the isocyanate semiprepolymers containing ester groups Starting materials:
Polyisocyanate (ai): 4,4'-MDI
Polyester polyol (aiiI): difunctional polyester polyol having a molecular weight of 2000 and a vi~cosity at 75-C of 615 mPas, measured using a rotation viscome~er in accordance with DIN 53018, prepared by polycondensation of adipic acid with ethylene glycol and 1,4-butanediol in a molar ratio of 3:2:1.
2 1 ~7347 .
Polyester polyol (aiiII): polyester polyol having a molecular weight of 2200, a functionality of 2.15 and a viscosity at 75 C of 700 mPas, measured using a rotation viscometer in accordance with DIN 53018, prepared by polycondensation of adipic acid, ethylene glycol, diethylene glycol, 1,4-butanediol and trimethylolpropane in a molar ratio of 9.1:5:3:120.1.
Branched-chain dihydroxy compound (aiii) cont~;n~ng at least one ester unit: neopentyl glycol ester of hydroxypivalic acid having 10 the formula HOH2C-C(CH3) 2 -CO-O-CH2-C(CH3)2-CH2OH, thereinafter abbreviated to "HPN").
General preparative procedure In a three-neck flask fitted with stirrer, reflux condenser and gas inlet and outlet facilities, 4,4'-MDI was heated to 50 C under 20 an atmosphere of dry nitrogen and reacted while stirring with a polyester polyol (aii) and then with HPN (aiii) to produce the isocyanate semiprepolymers (a) of the invention. The heat liberated during the polyaddition reaction caused the temperature of the reaction mixture to rise to about 75 C. To complete the isocyanate semiprepolymer formation, the reaction mixture was heated to 80 C, stirred for one hour at this temperature and then allowed to cool.
The amount and type of the formative components used and the 30 properties determined on the isocyanate semiprepolymers prepared are summarized in Table 1 below. Here, nstability(+)" means that the isocyanate semiprepolymers are a clear li~uid after storage for 7 days at 15 C and "stability(-)" means that the isocyanate semiprepolymers have crystallized under the same storage conditions.
Table 1 Example Isocyanate semiprepolymer prepared by reaction of Properties 4,4'-HDI polyester polyol HPN NCO content Viscosit.y 7Stdabi/ilt5YC
Type Amount [parts by [parts by [parts by [parts by [mPa s]
weight] weight] weight] weight]
1 66 aiiI 30 4 19.3 410 (+) 2 64 aiiI 30 6 17.8 670 (+) 3 66 aiiII 30 4 19.3 380 (+) 4 64 aiiII 30 6 17.8 630 (+) 58 aiiII 40 2 16.9 690 (+) 6 56 aiiII 40 4 15.5 1300 (+) Cr~n~rarative ~YA~r e I 85 - - 15 21.5 200 (-) ~~
II 70 aiiI 30 - 22.3 250 ( III 60 aiiII 40 - 18.5 380 (-) * measured using a rotation viscometer in accordance with DIN 53018 2~ 77347 Production of PU integral foams Example 7 A component: mixture comprising 90.7 parts by weight of polyester polyol (aiiI), 7.8 parts by weight of ethylene glycol, 0 0.3 parts by weight of a foam stabilizer based on silicone (Tegostab~ 84S0, from Goldschmidt AG, Essen) 0.4 parts by weight of triethylenediamine and 0.8 parts by weight of water B component: isocyanate semiprepolymer prepared as described in Example 2.
20 100 parts by weight of the A component and 99 parts by weight of the B component were intensively mixed at 23 C. 140 g of the reaction mixture were placed in an aluminum mold heated to 45 C and having the internal dimensions 20 x 20 x 1 cm, the mold was closed and the mixture was allowed to foam and cure. This gave a PU foam plate having a pronounced, essentially compact surface zone and a cellular core.
The mechanical properties measured on the PU foam plate are shown in Table 2.
30 Example 8 A component: as in Example 7 B component: isocyanate semiprepolymer prepared as described in Example 3 The PU integral foam plate was produced by a method similar to Example 7, but 91 parts by weight of the B c~- ,,onent were used for 100 parts by weight of the A component. The mechanical 40 properties measured on the PU integral foam plate produced are shown in Table 2.
Table 2 -Mechanical properties of the PU integral foam plates Example 7 8 Mechanical properties:
Total density [g/l] 350 350 Shore A hardness in accordance 41 42 10 with DIN 53505 Tensile strength in accordance 4.5 4.1 with DIN 53504 [N/mm2]
Elongation in accordance with 350 400 DIN 53504 t%]
Tear propagation resistance in 5.5 6.3 accordance with DIN 53507 [N/mm]
Free-foamed density [g/l] 191 185 C ,~-rative Example No PU integral foam moldings could be produced from the isocyanate semiprepolymers described in Comparative Examples I, II and III under the abovementioned reaction conditions, since these isocyanate semiprepolymers were crystAll;ne at room temperature and therefore could not be processed by the abovedescribed method.
isomers with aii) difunctional to trifunctional polyester polyols having molecular weights of from 600 to 3000 and aiii) at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500.
The invention also relates to the use of the moldings produced as shoe soles and the novel, eg. usable according to the invention, isocyanate semiprepolymers which are liquid at room temperature and contain ester groups.
The production of moldings having a cellular core and a compacted surface zone by reacting organic polyisocyanates, relatively high molecular weight compounds having at least two reactive hydrogens and, if desired, chain extenders in the pre~ence of blowing 40 agents, preferably physically acting blowing agents, catalysts, auxiliaries and/or additives in a closed, heated or unheated mold with compaction has been known for a long time and i8 degcribed, for example, in DE-A-16 94 138 (GB-A-1 209 243), DE-A-19 55 891 (G~-A-1 321 679) and DE-A-17 69 886 (US-A-3 824 l99).
.
Also known is the production of sole material by the polyisocyanate polyaddition process and the use of shoe soles containing urethane groups in the shoe industry. Significant application areas for polyisocyanate polyaddition products in the shoe industry are the direct foaming on of soles and the production of ready-made polyurethane (PU) soles. Such PU shoe soles can be produced by the low-pressure or high-pressure technique (RIM) (Schuh-Technik ~ abc, 10/1980, pages 822 ff).
10 A summary overview of polyurethane integral foams has been published, for example, in Integralschaumstoffe by Dr. H. Piechota and Dr. H. Rohr, Carl-Hanser-Verlag, Munich, Vienna, 1975 and in Kunststoff-Handbuch, volume 7, Polyurethane by Dr. G. Oertel, Carl-Hanser-Verlag, Munich, Vienna, 2nd. edition, 1983, pages 333 ff, which also gives information about the use of inteqral foams in the shoe industry (pages 362 to 366).
4,4'-MDI and 2,4'-MDI have melting points of 39.5 C and 34.5 C
20 respectively and are therefore usually solid at room temperature and can be processed only with difficulty. There have therefore been many attempts to prepare polyisocyanate compositions which are based on MDI and are liguid at room temperature by modification of 4,4'- and/or 2,4'-MDI. For this purpose, 4,4'-and/or 2,4'-MDI are customarily reacted with substoichiometric amounts of alkylene glycols, dialkylene glycols, low molecular weight and/or relatively high molecular weight difunctional and/or trifunctional polyoxyalkylene polyols to give isocyanate semiprepolymers which are liquid at room temperature.
For example, according to DE-C-16 18 380 (US-A-3 644 457), an MDI
preparation which iB liquid at room temperature i9 prepared by reacting 1 mol of 4,4'- and/or 2,4'-MDI with from 0.1 to 0.3 mol of tri-1,2-propylene ether glycol and/or poly-1,2-propylene ether glycol having a molecular weight of up to 700. 4,4'-MDI partially reacted with dipropylene glycol or partially reacted mixtures of MDI isomers and polyphenyl-polymethylene polyisocyanates, known as raw MDI, are used according to EP-B-O 364 854 (CA-A-2 000 019 r for producing moldings having a compacted surface zone and a 40 cellular core, known as integral foams, preferably shoe soles.
Liquid polyisocyanate mixtures based on MDI, containing bonded urethane groups and having an isocyanate content of from 22 to 30% by weight can, according to EP-A-O 557 792 (US-A-5 374 667), be obtained, inter alia, by partial reaction of raw MDI with a polyoxypropylene-polyoxyethylene polyol having a functionality of from 2.5 to 3.5, a hydroxyl number of from 50 to 90 and a 2~ 77347 polymerized ethylene oxide group content of from more than 30 to less than 50%,by weight, based on the weight of polymerized ethylene oxide and 1,2-propylene oxide groups. The isocyanate semiprepolymers are preferably used for producing CFC-free PU
(molded) flexible foams.
Polyester polyurethanes can be prepared in a similar manner by reacting MDI and/or raw MDI with polyester polyols to give isocyanate semiprepolymers and these can be used for producing 10 moldings.
According to US-A-4 857 561, for example MDI and/or polyphenyl-polymethylene polyisocyanates are reacted with a polyneopentyl glycol adipate having a molecular weight of from 750 to 3500 and a functionality of from 2 to 3 to give an isocyanate semiprepolymer having an isocyanate content of from 14 to 28% by weight and this is used to produce a molding by the RIM
process in a closed mold. According to CA-A-l 096 181, polyadipates based on tripropylene glycol, butanediol and 20 ethylene glycol are used in place of neopentyl glycol for modifying 4,4'-MDI. According to DE-A-3 831 681 (US-A-5 053 528), dihydroxy compounds containing bonded ester groups and having the formula HOH2C-C(CH3)2-CO-O-R-O-CO-C(CH3)2-CH20H, where R is a branched or unbranched alkylene radical or a polyoxyalkylene radical, are reacted with 4,4'- and 2,4'-MDI or mixtures of 4,4'-MDI, 2,4'-MDI and raw MDI to give isocyanate 30 semiprepolymers. The use of ester diols or polyester diols having methyl side groups enabled the storage stability of the isocyanate semiprepolymers to be improved. However, obviously because of the high content of branched diols in the isocyanate semiprepolymers, the mechanical properties of the PU integral foams produced therefrom were adversely affected.
US-A-4 182 898 describes storage-stable isocyanate prepolymers which are liquid at room temperature and are prepared by reacting diisocyanates such as HDI, JPDI, TDI and MDI with mixtures of 40 compatible polyether and polyester polyols in a ratio of 15 to 85:85 to 15% by weight and in a ratio of NCO:OH groups of from 1.5:1 to 2:1.
According to US-A-4 647 596, microcellular PU elastomers are produced from an isocyanate prepolymer whose polyol component comprises a polyester-polyether polyol from polyoxytetramethylene glycol and ~-caprolactone in a weight ratio of from 20:80 to 80:20 and having a molecular weight of from 1000 to 3000 and a polyester polyol based on adipic acid and having a molecular weight of from lO00 to 3000 and whose isocyanate component is 4,4'-MDI. PU integral foams produced using water as blowing agent are, according to US-A-5 166 183, obtained by reacting an isocyanate prepolymer having an isocyanate content of from 16 to 25% by weight, prepared from MDI and a polyester diol having a molecular weight of from 1000 to 3000 and mixed, if desired, with an isocyanate prepolymer based on MDI and polyoxypropylene glycol 10 having a molecular weight of from 134 to 700 and a specific mixture of relatively high molecular weight polyether diols, polyether polyols, 1,4-butanediol and ethylene glycol.
US-A-4 986 929 describes polyisocyanate mixtures having an isocyanate content of from 16 to 25% by weight and consist~ng essentially of an isocyanate prepolymer from MDI and a polyoxypropylene glycol having a molecular weight of from 134 to 700 and an isocyanate prepolymer prepared by reacting a mixture of MDI and MDI containing carbodiimide groups with a polyester diol having a molecular weight of from lO00 to 3000. A
20 disadvantage of the isocyanate prepolymers described is the formation of flaws at the surface of PU integral foam~ produced therefrom, which flaws can be caused by insufficient compatibility of polyether and polyester isocyanate prepolymers.
It is an object of the present invention to produce moldings contAi~;ng ester and urethane groups, having a cellular core and a compacted surface zone and having mechanical properties which are at least equally good, but advantageously improved, using isocyanate semiprepolymers which are liquid at room temperature, 30 are based on a polyester polyol and have improved storage stability, even at about 0 C.
We have found that this object is achieved by using new isocyanate semiprepolymers which contain ester groups and are liquid at room temperature for producing the PU-ester integral foams.
The invention accordingly provides a process for producing moldings conta;ning ester and urethane groups and having a gO cellular core and a compacted surface zone by reacting a) isocyanate semiprepolymers contA; n; ng ester groups with b) at least one relatively high molecular weight polyhydroxyl compound and, if desired, 2~ 77347 .- 5 c) low molecular weight chain extenders, crosslinkers or mixtures of chain extenders and crosslinkers in the presence of d) blowing agents, e) catalysts and in the presence or absence of f) additives in a closed mold with compaction, wherein the isocyanate semiprepolymers (a) used are reaction products having an isocyanate content of from 10 to 26% by weight prepared from ai) 4,4'-MDI or mixtures of 4,4'-MDI and modified or unmodified MDI isomers, aii) at least one polyester polyol having a functionality of from 2 to 3 and a molecular weight of from 600 to 3000 and aiii) at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500.
The invention also provides isocyanate semiprepolymers which contain ester groups, are liquid at room temperature and have an 30 isocyanate content of from 10 to 26% by weight, which semiprepolymers are prepared by reacting ai) 4,4~-MDI or mixtures of 4,4'-MDI and modified or unmodified MDI isomers with aii) at least one polyester polyol having a functionality of fro~
2 to 3 and a molecular weight of from 600 to 3000 and aiii) at least one dihydroxy compound containing at least one bonded ester unit as bridge and lateral alkyl groups and having a molecular weight of up to 500.
For the purposes of the present ïnvention, isocyanate semiprepolymers which contain ester groups and are liquid at room temperature are reaction products prepared from (ai) to (aiii) which have a viscosity at 45 C of from 200 to 2500 mPas measured using a rotation viscometer in accordance with DIN 53018 and can be processed in liquid form above 10 C.
The novel isocyanate semiprepolymers having an isocyanate content of from 10 to 26~ by weight, preferably from 15 to 22% by weight, are al~o storage stable at 15 C for at least one month, preferably more than 3 months, ie. they form no crystalline sediments during this time.
10 Despite the preferred use of water as blowing agent, the moldings containing ester and urethane groups and produced by the process of the invention have a pronounced surface zone of higher density with an essentially smooth external skin. The Shore A hardness of the surface zone corresponds, like the other mechanical properties, to the PU integral foam moldings foamed using CFC~.
Furthermore, the system components have very good flowability and can be processed without difficulty by conventional methods, eg.
by the RIM or low-pressure technique, to give moldings, preferably shoe soles.
a) The following may be specifically said about the preparation of the novel isocyanate semiprepolymer~ (a) which contain ester groups, are liquid at room temperature and have an isocyanate content of from 10 to 26% by weight, preferably from 15 to 22~ by weight, and about the formative components (b) to (f) which can be used for the process of the invention for producing the moldings cont~ining ester and urethane groups:
30 ai) the polyisocyanate (ai) used for preparing the isocyanate semiprepolymers (a) is in particular 4,4'-MDI. Mixtures of 4,4~- and 2,4'-MDI, advantageously those having a 4,4'-MDI
content of at least 40% by weight, preferably at least 80%
by weight, have also been found to be very useful, so that such mixtures are also preferred. However, other suitable mixtures are those of 4,4'-MDI, 2,4'-MDI and 4,4'- and 2,4'-HDI in which the isocyanate groups have been reacted at least partially in a previous reaction stage to give carbodiimide groups, urethane groups and/or urethanimine groups.
aii) The polyester polyols (aii) which are suitable according to the invention as modifiers advantageously have a functionality of from 2 to 3, preferably from 2.0 to 2.5, and a mo~ecular weight of from 600 to 3000, preferably from 1000 to 3000 and in particular from 1200 to 2400. The molecular weights specified in the patent description for the polyhydroxyl compounds were calc~lated according to the formula 56100 x functionality molecular weight =
hydroxyl number where the hydroxyl number was experimentally measured in a known manner.
Suitable polyester polyols can be prepared, for example, from orqanic dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having from 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms. Examples of suitable dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can here be ~0 used either individually or in admixture with one another.
In place of the free dicarboxylic acids, it i8 al~o possible to use the corresponding dicarboxylic acid derivatives such as dicarboxylic monoesters and~or diesters of alcohols having from 1 to 4 carbon atoms or dicarboxylic anhydrides.
Preference is given to using dicarboxylic acid mixtures of succinic, glutaric and adipic acid in weight ratios of, for example, 20 to 35:35 to 50:20 to 32, and particularly adipic acid. Examples of dihydric and higher-hydric alcohols, in particlar alkanediols and alkylene glycols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, l,10-decanediol, glycerol and trimethylolpropane. Preference is given to using ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerol or mixtures of at least two of the specified diols, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol and/or glycerol. It is also possible to use polyester polyols from lactones, eg. E-caprolactone or hydroxycarboxylic acids, eg. ~-hydroxycaproic acid.
To prepare the polyester polyols, the organic, preferably aliphatic, polycarboxylic acids and/or derivatives and polyhydric alcohols can be polycondensed in the absence of catalyst or preferably in the presence of esterification catalysts, advantageously in an atmosphere of inert gases, eg. nitrogen, helium, argon, etc., in the melt at from 150 to 250 C, preferably from 180 to 220 C, at atmo~pheric 2 l 77347 pressure or under reduced pressure to the desired acid number which is advantageously less than 10, preferably less than 2. According to a preferred embodiment, the esterification mixture is polycondensed at the abovementioned temperatures to an acid number of from 80 to 30, preferably from 40 to 30, at atmospheric pressure and subsequently under a pressure of less than 500 mbar, preferably from 50 to 150 mbar. Suitable esterification catalysts are, for example, iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts. However, the polycondensation can also be carried out in the liquid phase in the presence of diluents and/or entrainers such as benzene, toluene, xylene or chlorobenzene to azeotropically distill off the water of condensation.
To prepare the polyester polyols, the organic polycarboxylic acids and/or derivatives are polycondensed with polyhydric alcohols advantageously in a molar ratio of from 1:1 to 1.8, preferably from 1:1.05 to 1.2. To remove cyclic volatile byproducts, the polyester polyols can subsequently be additionally subjected to a distillation under reduced pressure, eg. by means of a thin-film evaporator. The polyester polyols can be used individually or as mixtures.
aiii)According to the invention, the polyisocyanates (ai) for preparing the isocyanate semiprepolymers (a) containing ester groups are partially reacted with polyester polyols (aii) and dihydroxy c~r.~younds (aiii) having a molecular weight of up to 500, preferably from 180 to 320, with the proviso that the dihydroxy compounds, preferably aliphatic dihydroxy compounds, contain at least one bonded ester unit, preferably one or 2 ester units, as bridge and have a branched chain. To form the branches, the dihydroxy compounds cont~i~;ng ester groups have at least 2, preferably from 2 to 12 and in particular from 4 to 8, lateral substituents, with preference being given to alkoxy groups and/or particularly alkyl groups having from 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms, as substituents. Examples of suitable sub~tituents which may be mentioned are the methoxy, ethoxy, isopropoxy, ethyl, n- and iso-propyl, n-butyl and, in particular, methyl groups. The dihydroxy compounds are advantageously prepared u~ing linear or branched aliphatic hydroxycarboxylic acids having from 2 to 6, preferably from 2 to 5 carbon atoms, eg. glycolic acid, lactic acid, a-, ~-, y-hydroxybutyric acid, ~-hydroxycaproic acid and, in particular, hydroxypivalic .
g acid. However, hydroxybenzoic acids are also suitable.
Examples of diols for preparing the dihydroxy compounds (aiii) contA;n;ng ester groups are dialkylene glycols, eg. diethylene and dipropylene glycol, oligomeric polyoxyalkylene glycols having molecular weights of up to 300 and based on ethylene oxide and/or 1,2-propylene oxide, eg. polyoxypropylene and polyoxyethylene-polyoxypropylene glycol, linear alkanediols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, eg. ethanediol, 1,3-propanediol, 1!4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, and preferably branched-chain alkanediols having from 3 to 15 carbon atoms, preferably from 3 to lO carbon atoms, eg. 1,2-propanediol, 1,2- and 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-, 2-methyl-2-ethyl-, 2-ethyl-2-butyl-, 2-ethoxy-pentane-1,5-diol, 2,2-dimethylhexane-1,6-diol, 2,2,5-trimethylhexane-1,6-diol, 1,2-pentanediol, 2,5-dimethylhexane-2,5-diol and, in particular, 2,2-dimethylpropane-1,3-diol. Branched-chain dihydroxy compounds containing ester groups (aiii) which have been found to be useful are, for example, transesterification products of 2 mol of alkyl hydroxypivalate~ with one mole of dialkylene glycol, polyoxyalkylene glycol, linear alkanediol and preferably branched alkanediol, as are described, for example, in US-A-5 053 528, whose entire di~closure is incorporated in this description by reference, esters of 2 mol of a linear hydroxycarboxylic acid and one mole of a branched alkanediol and preferably esters of one mole of a branched hydroxycarboxylic acid and one mole of a branched alkanediol. Particular preference is given to using the neopentyl glycol ester of hydroxypivalic acid.
To prepare the novel isocyanate semiprepolymers (a) contAin~ng ester group~ and having an isocyanate content of from 10 to 26 by weight, the formative components can be reacted in the following amounts, based on the total weight of the semiprepolymer, at from lS to 120 C, preferably from 45 to 90 C:
40 ai) from 94 to 25% by weight, preferably from 77 to 53% by weight, of (ai), aii) from 5 to 60% by weight, preferably from 20 to 40% by weight, of (aii) and aiii)from 1 to 15% by weight, preferably from 3 to 7% by weight, of (aiii).
For this purpose, the modified or unmodified 4,4'-MDI and/or 2,4'-MDI can, if they are not already liquid at room temperature, be liquified by heating and then reacted while stirring with the polyester polyols (aii) and the branched-chain dihydroxy compounds containing ester groups (aiii) individually in succession or with a mixture of (aii) and (aiii). According to a preferred embodiment, the polyisocyanates (ai) are first reacted with at least one polyester polyol (aii) and then with at least one low molecular weight dihydroxy compound (aiii). To complete 10 the reaction, it has been found to be advantageous to stir the reaction mixture for from 0.5 to 6 hours, preferably from 1 to 3 hours, in the abovementioned temperature range, eg. at from 45 to sO-C, and then to allow it to cool to room temperature while stirring.
To produce the CFC-free moldings containing ester and urethane groups and having a cellular core and a compacted surface zone, the novel liquid, storage-stable isocyanate semiprepolymers (a) containing ester groups are, as already indicated, allowed to 20 foam with customary relatively high molecular weight polyhydroxyl compounds (b) and, if desired, low molecular weight chain extenders and/or crosslinkers (c) in the presence of blowing agents (d), catalysts (e) and, if desired, additives (f) in a closed mold with compaction and allowed to cure.
(b) Suitable relatively high molecular weight polyhydroxyl compounds for this purpose advantageously have a functionality of from 2 to 4, preferably from 2 to 3, and a molecular weight of from 1200 to 7000, preferably from 1200 to 3600. Examples of suitable polyhydroxyl compounds are the polyether polyols, polyoxytetramethylene glycols, polymer-modified polyether polyols, polyether polyol dispersions, hydroxyl-con~;n;ng polyesteramides and hydroxyl-containing polyacetals known per se. Polyhydroxyl compounds which have been found to be particularly useful and are therefore preferably used are hydroxyl-cont~i n; ng polycarbonates, advantageously those prepared from 1,6-hexanediol and/or 1,4-butanediol and diphenyl carbonate by transesterification, polyether-polyester polyols prepared by esterification of polyoxytetramethylene glycols having molecular weights of from 250 to 1600, preferably from 250 to 600, or of mixtures of the specified polyoxytetra-methylene glycols and alkanediols having from 2 to 6 carbon atoms and/or dialkylene glycols having from 4 to 6 caron atoms with alkanedicarboxylic acids having from 4 to 6 carbon atoms, eg. succinic, glutaric or adipic acid or mixtures of at least 2 of the specified dicarboxylic acids, and, in particular, polyester polyols prepared from the abovementioned polycarboxylic acids and polyhydric alcohol~
and/or dialkylene glycols which can be used for preparing the polyester polyols (aii).
c) The for example semirigid and preferably flexible moldings containing ester and urethane groups and having a compacted surface zone and cellular core, known as PV integral foams, can be produced by the process of the invention with or without use of chain extenders and/or crosslinkers (c).
However, in the case of flexible and semirigid PU integral foams, the addition of chain extenders, crosslinkers or, if desired, mixtures thereof can be found to be advantageous for modifying the mechanical properties, eg. the hardness.
Chain extenders and/or crosslinkers which can be used are, for example, low molecular weight, polyhydric alcohols, preferably diol~ and/or triols, having molecular weights of less than 400, preferably from 60 to 300. Suitable chain extenders are, for example, aliphatic, cycloaliphatic and/or araliphatic diols such as alkanediols having from 2 to 14, preferably from 2 to 6, carbon atoms and/or dialkylene glycols having from 4 to 8, preferably from 4 to 6, carbon atoms, eg. ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and preferably 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, and suitable crosslinkers are, for example, triols such as 1,2,4- or 1,3,5-trihydroxycyclohexane, trimethylolethane, glycerol and trimethylolpropane.
If compounds of the component (c) are used, these can be used in the form of mixtures or individually and are advantageously employed in amounts of from 1 to 50 parts by weight, preferably from 3 to 40 parts by weight, bsed on 100 parts by weight of the relatively high molecular weight compounds (b).
d) The blowing agent (d) used is preferably water which reacts in situ with the isocyanate semiprepolymer~ (a) cont~;n~ng ester groups to form carbon dioxide and amino groups which in turn react further with the isocyanate semiprepolymers (a) to give urea groups and can thereby influence the compressive strength of the PU integral foam moldings. Since the formative components (b) and, if used, (c) can contain water as a result of their preparation and/or chemical composition, in some cases it is not necessary to separately _ add water to the formative components (b) and, if applicable, (c) or to the reaction mixture. However, if water has to be additionally incorporated into the polyurethane formulation to achieve the desired bulk density, this is usually used in amounts of from 0.05 to 4.0% by weight, preferably from 0.1 to 3.0% by weight and in particular from 0.3 to 2.5% by weight, based on the weight of the formative components (a) to (c).
As blowing agent (d) it is also possible to use, in place of water or preferably in combination with water, low-boiling liquids which vaporize under the influence of the exothermic polyaddition reaction and advantageously have a boiling point at atmospheric pressure in the range from -40 to 120 C, preferably from 10 to 90 C, or gases.
The liquids of the abovementioned type and gases suitable as blowing agent can, for example, be selected from the group of alkanes such as propane, n- and iso-butane, n- and iso-pentane and preferably the industrial pentane mixtures, cycloalkanes and cycloalkenes such as cyclobutane, cyclopentene, cyclohexene and preferably cyclopentane and/or cyclohexane, dialkyl ethers such as dimethyl ether, methyl ethyl ether or diethyl ether, tert-butyl methyl ether, cycloalkylene ethers such as furan, ketones such as acetone, methyl ethyl ketone, acetals and~or ketals such as formaldehyde dimethyl acetal, 1,3-dioxolane and acetone dimethyl acetal, carboxylic esters such as ethyl acetate, methyl formate and ethylene-acrylic acid tert-butyl ester, tertiary alcohols such as tertiary butanol, carboxylic acids such as formic acid, acetic acid and propionic acid, fluoroalkanes which are degraded in the troposphere and therefore do not damage the ozone layer, eg.
trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and heptafluoroethane, chloroalkanes such as 2-chloropropane, and gases such as nitrogen, carbon monoxide and noble gases such as helium, neon and krypton.
Among the liquids which are inert toward NC0 groups and are suitable as blowing agent (d), preference is given to using alkanes, cycloalkanes or mixtures of alkanes and cycloalkanes having a boiling point of from -40 to 50 C at atmospheric pressure.
Suitable blowing agents also include salts which decompose thermally, eg. ammonium bicarbonate and/or ammonium carbamate or compounds which form such salts in situ, eg.
-aqueou~ ammonia and/or amines and carbon dioxide, and ammonium salts of organic carboxylic acids, eg. the monoammonium salts of malonic acid, boric acid, formic acid or acetic acid.
The most advantageous amount of solid blowing aqents, low-boiling liquids and gases which can be used either individually or in the form of mixtures, eg. as liquid or gas mixtures or as gas-liquid mixtures, depends on the density which is to be achieved and the amount of water used. The amounts required can be easily determined by simple experiments. Satisfactory results are usually given by amounts of solid of from 0.5 to 35 parts by weight, preferably from 2 to 15 parts by weight, amounts of liquid of from 1 to 30 parts by weight, preferably from 3 to 18 parts by weight, and/or amounts of gas of from 0.01 to 80 parts by weight, preferably from 10 to 35 parts by weight, in each case based on the weight of the formative components (a), (b) and, if applicable, (c). The charge with gas, eg.
air, carbon dioxide, nitrogen and/or helium, can be carried out via the relatively high molecular weight compounds (b) and, if applicable, low molecular weight chain extenders and/or crosslinkers (c) or via the polyisocyanates (a) or via (a) and (b) and, if applicable, (c).
Blowing agents which are not used are, as already indicated, fully halogenated CFCs.
e) Catalysts (e) used for producing the PU foam moldings are, in particular, compounds which strongly accelerate the reaction of the hydroxyl-cont~1 n ~ ng compounds of the formative component (b) and, if used, (c) with the isocyanate semiprepolymers (a) containing ester groups.
~uitable examples are organic metal compounds, eg. zinc stearate, zinc oleate and preferably organic tin compounds such as tin(II) salts of organic carboxylic acids, eg.
tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate, and the dialkyltin(IV) salts of organic carboxylic acid~ eg. dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate and dioctyltin diacetate, organic amidines such as 2,3-dimethyl-3,4,5,6-tetra-hydropyrimidine, tertiary amines such as triethylamine, tributylamine, methyldicyclohexylamine, 1,4-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, dimethylaminopropylamine, N,N-bis(dimethylaminopropyl)methylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N'N'-tetramethylbutane-1,4-diamine, N,N,N'N'-tetramethylhexane-1,6-diamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, 2-hydroxyethyl 2'-dimethylaminoethyl ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo[3.3.0]octane and preferably 1,4-diazabicyclo[2.2.2]octane and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine and dimethylethanolamine. Preference is given to using 1,4-diazabicyclo[2.2.2]octane, particularly in the form of a solution in ethylene glycol or 1,4-butanediol, dimethylaminopropylamine and also combinations of these tertiary amines with tin salts. Preference is given to using from 0.01 to 3~ by weight, in particular from 0.8 to 1.4~ by weight, of catalyst or catalyst combination, based on the weight of the component (b). The organic metal compounds and strongly basic amines, preferably tertiary amines, can, for example, each be used as sole catalyst or in combination with one another.
(f) If desired, additives (f) can also be incorporated into the reaction mixture for producing the preferably flexible moldings cont~i ni ng ester and urethane groups and having a cellular core and a compacted surface zone. Examples which may be mentioned are surface-active substances, foam stabilizers, cell regulators, lubricants, fillers, dyes, pigments, flame retardants, internal mold release agents, hydrolysis inhibitors, fungistatic and bacteriostatic substances.
Suitable surface-active substances are, for example, compounds which serve to aid the homogenization of the starting materials and may also be suitable for regulating the cell structure. Examples which may be mentioned are emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and also salts of fatty acids with amines, eg. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, eg.
~lkAli metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic esters, Turkey red oil and peanut oil and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes.
2~ 77347 Oligomeric polyacrylates having polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying action, the cell structure and/or stabilizing the foam. The surface-active substances are usually used in amounts of from 0.01 to 5 parts by weight, based on 100 parts by weight of the component (b).
As lubricant, the addition of a ricinoleic polyester having a molecular weight of from 1500 to 3500, preferably from 2000 to 3000, has been found to be particularly useful and this is advantageously used in an amount of from 0;5 to 10%
by weight, preferably from 5 to 8% by weight, based on the weight of the component (b) or the components (b) and (c).
For the purposes of the present invention, fillers, in particular reinforcing fillers, are the customary organic and inorganic fillQrs and reinforcements known per se.
Specific examples are: inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, serpentine, hornblendes, amphiboles, chrysotile, talc; metal oxides such as kaolin, aluminum oxides, aluminum silicate, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide, zinc sulfide, and also glass particles. Examples of suitable organic fillers are: carbon black, melamine, rosin, cyclopentadienyl resins and graft polymers.
The inorganic and organic fillers can be used individually or as mixtures and are advantageously incorporated into the reaction mixture in amounts of from 0.5 to 50~ by weight, preferably from 1 to 40% by weight, based on the wei~ht of the components (a) to (c).
Suitable flame retardants are, for example, tricresyl phosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(1,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate and tetrakis(2-chloroethyl)ethylene diphosphate.
Apart from the abovementioned halogen-substituted phosphates, it is also possible to use inorganic flame retardants such as red phosphorus, expanded graphite, hydrated aluminum oxide, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives such as melamine or mixtures of at least two flame retardants such as expanded graphite and ammonium polyphosphate, ammonium polyphosphates and melamine and also, if desired, expanded graphite and/or starch for making the moldings produced according to the invention flame resistant. In gQneral, it has been found to be advantageous to use from 2 to 50 parts by weight, preferably from 5 to 25 parts by weight, of the specified flame retardants or mixtures per 100 parts by weight of the components (a) to ( c ) .
Further details about the abovementioned other customary auxiliaries and additives can be found in the specialist literature, for example the monography by ~.H. Saunders and K.C. Frisch "High polymersn volume XVI, Polyurethane~, parts 1 and 2, Interscience Publishers 1962 or 1964, or Kunststoff-Handbuch, Polyurethane, volume VII, Carl-Hanser-Verlag, Munich, Vienna, 1st and 2nd editions, lg66 and 1983.
To produce the moldings, the isocyanate semiprepolymers (a) cont~;ning ester groups, relatively high molecular weight 20 polyhydroxyl compounds (b) and, if desired, low molecular weight chain extenders and/or crosslinkers (c) are usually reacted in such amounts that the equivalence ratio of NC0 groups of the semiprepolymers (a) to the sum of the reactive hydrogens of the components (b) and, if applicable, (c) i8 from 0.45 to 1.80:1, preferably from 0.95 to 1.15:1 and in particular from 0.9 to 1 . 1 : 1 .
The novel for example semirigid or preferably flexible moldings containing ester and urethane groups can be produced by the 30 one-shot process using the low-pressure technique or the high-pressure technique in clo~ed, advantageously heatable molds, for example metal molds of, for example, aluminum, cast iron or steel, or molds of fiber-reinforced polyester or epoxide molding compositions. However, owing to the good flowability and improved processibility of the formulations, the moldings are produced in particular by means of reaction injection molding (RIM). These methods are de~cribed, for example, by Dr. Piechota and Dr. Rohr in "Integralschaumstoff", Carl-Hanser-Verlag, Munich, Vienna 1975; D.J. Prepelka and J.L. Wharton in Journal of Cellular 40 Plastics, March/April 1975, pages 87 to 98, U. Knipp in Journal of Cellular Plastics, March/April 1973, pages 76 to 84 and in Kunststoff-Handbuch, volume 7, Polyurethane, 2nd edition, 1983, pages 333 ff.
It has been found to be particularly advantageous to work according to the two-component process and combine the formative components (b), (d), (e) and, if used, (c) and (f) in the ` 2177347 -component (A) and use the novel isocyanate semiprepolymers (a) containing ester groups as component (~)~
The starting components are advantageously mixed at from 15 to 80 C, preferably from 25 to 55 C, and introduced, if desired under increased pressure, into the closed mold. Mixing can be carried out mechanically by means of a stirrer or a stirring spiral or under high pressure by the countercurrent in~ection method. The mold temperature is advantageously from 20 to 120 C, preferably 10 from 30 to 80 C and in particular from 45 to 60 C. The degrees of compaction are in the range from 1.4 to 8.3, preferably from 2 to 7 and in particular from 2.4 to 4.5.
The amount of reaction mixture introduced into the mold i8 advantageously such that the moldings obtained have a total density of from 0.06 to 0.9 g/cm3, with, for example, the semirigid moldings preferably having a total density of from 0.1 to 0.9 g/cm3, in particular from 0.35 to 0.7 g/cm3, and the flexible moldings preferably having a total density of from 0.2 20 to 0.7 g/cm3, preferably from 0.3 to 0.5 g/cm3.
The flexible moldings produced by the process of the invention are used, for example, as armrests, headrests and safety linings in motor vehicle interiors, as sports goods and as bicycle or motorcycle saddles. They are also suitable a~ steering wheels for vehicles, preferably motor vehicles, and as inner boot for ski boots, and al~o, in particular, as shoe soles. The semirigid moldings are suitable, for example, as dashboards and side linings in vehicles, as ski cores and for the cladding of metal 30 containers, preferably of metal barrels for beverages, for example alcoholic or nonalcoholic beverages such as beer or fruit juices.
Examples Preparation of the isocyanate semiprepolymers containing ester groups Starting materials:
Polyisocyanate (ai): 4,4'-MDI
Polyester polyol (aiiI): difunctional polyester polyol having a molecular weight of 2000 and a vi~cosity at 75-C of 615 mPas, measured using a rotation viscome~er in accordance with DIN 53018, prepared by polycondensation of adipic acid with ethylene glycol and 1,4-butanediol in a molar ratio of 3:2:1.
2 1 ~7347 .
Polyester polyol (aiiII): polyester polyol having a molecular weight of 2200, a functionality of 2.15 and a viscosity at 75 C of 700 mPas, measured using a rotation viscometer in accordance with DIN 53018, prepared by polycondensation of adipic acid, ethylene glycol, diethylene glycol, 1,4-butanediol and trimethylolpropane in a molar ratio of 9.1:5:3:120.1.
Branched-chain dihydroxy compound (aiii) cont~;n~ng at least one ester unit: neopentyl glycol ester of hydroxypivalic acid having 10 the formula HOH2C-C(CH3) 2 -CO-O-CH2-C(CH3)2-CH2OH, thereinafter abbreviated to "HPN").
General preparative procedure In a three-neck flask fitted with stirrer, reflux condenser and gas inlet and outlet facilities, 4,4'-MDI was heated to 50 C under 20 an atmosphere of dry nitrogen and reacted while stirring with a polyester polyol (aii) and then with HPN (aiii) to produce the isocyanate semiprepolymers (a) of the invention. The heat liberated during the polyaddition reaction caused the temperature of the reaction mixture to rise to about 75 C. To complete the isocyanate semiprepolymer formation, the reaction mixture was heated to 80 C, stirred for one hour at this temperature and then allowed to cool.
The amount and type of the formative components used and the 30 properties determined on the isocyanate semiprepolymers prepared are summarized in Table 1 below. Here, nstability(+)" means that the isocyanate semiprepolymers are a clear li~uid after storage for 7 days at 15 C and "stability(-)" means that the isocyanate semiprepolymers have crystallized under the same storage conditions.
Table 1 Example Isocyanate semiprepolymer prepared by reaction of Properties 4,4'-HDI polyester polyol HPN NCO content Viscosit.y 7Stdabi/ilt5YC
Type Amount [parts by [parts by [parts by [parts by [mPa s]
weight] weight] weight] weight]
1 66 aiiI 30 4 19.3 410 (+) 2 64 aiiI 30 6 17.8 670 (+) 3 66 aiiII 30 4 19.3 380 (+) 4 64 aiiII 30 6 17.8 630 (+) 58 aiiII 40 2 16.9 690 (+) 6 56 aiiII 40 4 15.5 1300 (+) Cr~n~rarative ~YA~r e I 85 - - 15 21.5 200 (-) ~~
II 70 aiiI 30 - 22.3 250 ( III 60 aiiII 40 - 18.5 380 (-) * measured using a rotation viscometer in accordance with DIN 53018 2~ 77347 Production of PU integral foams Example 7 A component: mixture comprising 90.7 parts by weight of polyester polyol (aiiI), 7.8 parts by weight of ethylene glycol, 0 0.3 parts by weight of a foam stabilizer based on silicone (Tegostab~ 84S0, from Goldschmidt AG, Essen) 0.4 parts by weight of triethylenediamine and 0.8 parts by weight of water B component: isocyanate semiprepolymer prepared as described in Example 2.
20 100 parts by weight of the A component and 99 parts by weight of the B component were intensively mixed at 23 C. 140 g of the reaction mixture were placed in an aluminum mold heated to 45 C and having the internal dimensions 20 x 20 x 1 cm, the mold was closed and the mixture was allowed to foam and cure. This gave a PU foam plate having a pronounced, essentially compact surface zone and a cellular core.
The mechanical properties measured on the PU foam plate are shown in Table 2.
30 Example 8 A component: as in Example 7 B component: isocyanate semiprepolymer prepared as described in Example 3 The PU integral foam plate was produced by a method similar to Example 7, but 91 parts by weight of the B c~- ,,onent were used for 100 parts by weight of the A component. The mechanical 40 properties measured on the PU integral foam plate produced are shown in Table 2.
Table 2 -Mechanical properties of the PU integral foam plates Example 7 8 Mechanical properties:
Total density [g/l] 350 350 Shore A hardness in accordance 41 42 10 with DIN 53505 Tensile strength in accordance 4.5 4.1 with DIN 53504 [N/mm2]
Elongation in accordance with 350 400 DIN 53504 t%]
Tear propagation resistance in 5.5 6.3 accordance with DIN 53507 [N/mm]
Free-foamed density [g/l] 191 185 C ,~-rative Example No PU integral foam moldings could be produced from the isocyanate semiprepolymers described in Comparative Examples I, II and III under the abovementioned reaction conditions, since these isocyanate semiprepolymers were crystAll;ne at room temperature and therefore could not be processed by the abovedescribed method.
Claims (12)
1. A process for producing moldings containing ester and urethane groups and having a cellular core and a densified surface zone by reacting a) isocyanate semiprepolymers containing ester groups with b) at least one relatively high molecular weight polyhydroxyl compound and, if desired, c) low molecular weight chain extenders, crosslinkers or mixtures of chain extenders and crosslinkers in the presence of d) blowing agents, e) catalysts and in the presence or absence of f) additives in a closed mold with compaction, wherein the isocyanate semiprepolymers (a) used are reaction products having an isocyanate content of from 10 to 26% by weight prepared from ai) diphenylmethane 4,4'-diisocyanate or mixtures of diphenylmethane 4,4'-diisocyanate and modified or unmodified diphenylmethane diisocyanate isomers, aii) at least one polyester polyol having a functionality of from 2 to 3 and a molecular weight of from 600 to 3000 and aiii)at least one branched-chain dihydroxy compound containing at least one bonded ester unit as bridge and having a molecular weight of up to 500.
2. A process as claimed in claim 1, wherein the dihydroxy compounds (aiii) contain at least one bonded ester unit as bridge and at least one bonded lateral alkyl group having from 1 to 4 carbon atoms.
3. A process as claimed in claim 1, wherein the dihydroxy compound (aiii) is the neopentyl glycol ester of hydroxypivalic acid.
4. A process as claimed in claim 1, wherein the isocyanate semiprepolymers (a) are reaction products prepared using diphenylmethane 4,4'-diisocyanate or mixtures of diphenylmethane 4,4'- and 2,4'-diisocyanate (ai).
5. A process as claimed in claim 1, wherein the isocyanate semiprepolymers (a) containing ester groups and having an isocyanate content of from 10 to 26% by weight are reaction products prepared by reaction of, based on the total weight, (ai) from 94 to 25% by weight of (ai), (aii) from 5 to 60% by weight of (aii) and (aiii) from 1 to 15% by weight of (aiii).
6. A process as claimed in claim 1, wherein the polyhydroxyl compounds (b) have a functionality of from 2 to 4 and a molecular weight of from 1200 to 3600 and are selected from the group of polyester polyols, polyether-polyester polyols and hydroxyl-containing polycarbonates.
7. A process as claimed in claim 1, wherein the blowing agent (d) is formed in situ from water and the isocyanate semiprepolymers (a).
8. An isocyanate semiprepolymer which is liquid at room temperature, contains ester groups and has an isocyanate content of from 10 to 26% by weight, prepared by reacting ai) diphenylmethane 4,4'-diisocyanate or mixtures of diphenylmethane 4,4'-diisocyanate and modified or unmodified diphenylmethane diisocyanate isomers with aii) at least one polyester polyol having a functionality of from 2 to 3 and a molecular weight of from 600 to 3000 and aiii)at least one dihydroxy compound containing at least one bonded ester unit as bridge and bonded lateral alkyl groups and having a molecular weight of up to 500.
9. An isocyanate semiprepolymer as claimed in claim 8, which is liquid at room temperature and contains ester groups, which is prepared using ai) diphenylmethane 4,4'-diisocyanate and aii) neopentyl glycol ester of hydroxypivalic acid.
10. An isocyanate semiprepolymer as claimed in claim 8, which is liquid at room temperature and contains ester groups, which is prepared by reacting, based on the total weight, (ai) from 94 to 25% by weight of (ai), (aii) from 5 to 60% by weight of (aii) and (aiii) from 1 to 15% by weight of (aiii).
11. An isocyanate semiprepolymer containing ester groups as claimed in claim 8, which has a viscosity at 45°C of from 200 to 2500 mPas measured using a rotation viscometer in accordance with DIN 53 018 and is processible in liquid form above 10°C.
12. Shoe soles when prepared by the process claimed in claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19519335A DE19519335A1 (en) | 1995-05-26 | 1995-05-26 | Process for the production of molded articles containing ester and urethane groups, isocyanate semiprepolymers therefor containing them and their use |
DE19519335.0 | 1995-05-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2177347A1 true CA2177347A1 (en) | 1996-11-27 |
Family
ID=7762920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002177347A Abandoned CA2177347A1 (en) | 1995-05-26 | 1996-05-24 | Production of moldings containing ester and urethane groups, isocyanate semiprepolymers containing ester groups for this purpose and their use |
Country Status (6)
Country | Link |
---|---|
US (2) | US5585409A (en) |
EP (1) | EP0745626B1 (en) |
CN (1) | CN1149597A (en) |
AT (1) | ATE186925T1 (en) |
CA (1) | CA2177347A1 (en) |
DE (2) | DE19519335A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19701074A1 (en) * | 1997-01-15 | 1998-07-16 | Bayer Ag | Flexible to semi-rigid integral polyurethane foam production |
DE19706030C2 (en) * | 1997-02-17 | 2000-07-06 | Bayer Ag | Method and device for producing filler-containing polyurethanes |
DE19721220C1 (en) * | 1997-05-21 | 1998-08-20 | Bayer Ag | Soft to half hard polyurethane foam articles, used in production of e.g. bicycle saddles |
US5889068A (en) * | 1997-07-24 | 1999-03-30 | Bayer Corporation | Water blown polyurethane soling systems |
US7101956B2 (en) * | 2001-11-14 | 2006-09-05 | Medtronic, Inc. | Compounds containing quaternary carbons, medical devices, and methods |
US6753357B2 (en) * | 2001-12-18 | 2004-06-22 | Foam Supplies, Inc. | Rigid foam compositions and method employing methyl formate as a blowing agent |
JP4225252B2 (en) * | 2004-07-30 | 2009-02-18 | サンスター技研株式会社 | Shoe sole repair agent |
BRPI0513070B1 (en) * | 2004-08-04 | 2018-01-16 | Foam Supplies, Inc. | Method and component for retaining catalyst activity, and polyurethane foam |
CN101296958B (en) * | 2005-09-20 | 2012-07-18 | 宝利诺沃生物材料有限公司 | Chain extenders |
ITMI20052257A1 (en) * | 2005-11-25 | 2007-05-26 | Basf Ag | INTERMEDIATE SOLES FOR SHOES GOD SAFETY FROM EXPANDED POLYURETHANE OF LOW DENSITY |
AR069314A1 (en) * | 2007-11-14 | 2010-01-13 | Basf Se | FOAMED POLYURETHANE WITH IMPROVED FLEXION RESISTANCE PROPERTIES |
WO2012065299A1 (en) * | 2010-11-16 | 2012-05-24 | Basf Se | Dimensionally stable low-density polyurethane moldings |
US9023910B2 (en) * | 2012-01-18 | 2015-05-05 | Basf Se | Low-density polyurethane shoe soles or sole parts with high rebound resilience and low compression set |
BR112015000928B1 (en) * | 2012-07-18 | 2021-02-23 | Dow Global Technologies Llc | polyol composition, process for preparing a flame retardant and a dissipative polyurethane elastomer and flame retardant and static dissipative polyurethane elastomer |
EP3022244B2 (en) | 2013-07-16 | 2020-02-05 | Basf Se | Isocyanate prepolymer composition and crosslinked polyurethane prepared therefrom |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4132839A (en) * | 1976-10-12 | 1979-01-02 | W. R. Grace & Co. | Biodegradable hydrophilic foams and method |
JPS61250019A (en) * | 1985-04-27 | 1986-11-07 | Bridgestone Corp | Production of fine foam of polyurethane elastomer |
DE3831681A1 (en) * | 1988-09-17 | 1990-03-22 | Basf Ag | NEW ESTER GROUPS CONTAINED DIHYDROXY COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
DE3914718A1 (en) * | 1989-05-04 | 1990-11-08 | Bayer Ag | PROCESS FOR PREPARING URETHANOUS GROUP POLYURNIC ELASTOMERS |
DE4122872A1 (en) * | 1991-07-11 | 1993-01-14 | Bayer Ag | MOLDED FOAMS |
GB9216631D0 (en) * | 1992-08-05 | 1992-09-16 | Ici Plc | Reaction system for preparing microcellular elastomers |
US5389693A (en) * | 1994-05-31 | 1995-02-14 | The Dow Chemical Company | Integral skin polyurethane foams and process for the preparation thereof |
-
1995
- 1995-05-26 DE DE19519335A patent/DE19519335A1/en not_active Withdrawn
-
1996
- 1996-05-17 DE DE59603697T patent/DE59603697D1/en not_active Expired - Lifetime
- 1996-05-17 EP EP96107839A patent/EP0745626B1/en not_active Expired - Lifetime
- 1996-05-17 AT AT96107839T patent/ATE186925T1/en not_active IP Right Cessation
- 1996-05-24 CA CA002177347A patent/CA2177347A1/en not_active Abandoned
- 1996-05-24 US US08/653,527 patent/US5585409A/en not_active Expired - Fee Related
- 1996-05-25 CN CN96110085A patent/CN1149597A/en active Pending
- 1996-08-29 US US08/705,277 patent/US5710185A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US5710185A (en) | 1998-01-20 |
DE59603697D1 (en) | 1999-12-30 |
CN1149597A (en) | 1997-05-14 |
ATE186925T1 (en) | 1999-12-15 |
US5585409A (en) | 1996-12-17 |
DE19519335A1 (en) | 1996-11-28 |
EP0745626A1 (en) | 1996-12-04 |
EP0745626B1 (en) | 1999-11-24 |
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