US20010003122A1 - Preparation of polyisocyanate polyaddition products - Google Patents
Preparation of polyisocyanate polyaddition products Download PDFInfo
- Publication number
- US20010003122A1 US20010003122A1 US09/305,946 US30594699A US2001003122A1 US 20010003122 A1 US20010003122 A1 US 20010003122A1 US 30594699 A US30594699 A US 30594699A US 2001003122 A1 US2001003122 A1 US 2001003122A1
- Authority
- US
- United States
- Prior art keywords
- particles
- polyisocyanate polyaddition
- wear
- compounds
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 58
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title description 6
- 239000012948 isocyanate Substances 0.000 claims abstract description 54
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 9
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 239000006260 foam Substances 0.000 claims description 23
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 14
- 239000011496 polyurethane foam Substances 0.000 claims description 14
- 239000001993 wax Substances 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 7
- 230000007774 longterm Effects 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 39
- 229920005862 polyol Polymers 0.000 description 23
- 150000003077 polyols Chemical class 0.000 description 22
- -1 polyethylene Polymers 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 229920001971 elastomer Polymers 0.000 description 17
- 239000000806 elastomer Substances 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 229920002379 silicone rubber Polymers 0.000 description 13
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004945 silicone rubber Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 235000019589 hardness Nutrition 0.000 description 9
- 239000004970 Chain extender Substances 0.000 description 8
- 239000004971 Cross linker Substances 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229910001651 emery Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 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 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 150000004072 triols Chemical class 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001412 amines 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
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000009835 boiling 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000004872 foam stabilizing agent Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
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- 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
- ZOWKLYKKECRQRR-UHFFFAOYSA-N 1,3-bis(3-amino-3-methylbutyl)urea Chemical compound CC(C)(N)CCNC(=O)NCCC(C)(C)N ZOWKLYKKECRQRR-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 1
- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-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
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- RZEWIYUUNKCGKA-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanol;octadecanoic acid Chemical compound OCCNCCO.CCCCCCCCCCCCCCCCCC(O)=O RZEWIYUUNKCGKA-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- CJWBPEYRTPGWPF-UHFFFAOYSA-N 2-[bis(2-chloroethoxy)phosphoryloxy]ethyl bis(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCOP(=O)(OCCCl)OCCCl CJWBPEYRTPGWPF-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
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- 235000019759 Maize starch Nutrition 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
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- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- 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
- 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
- ZYMLPCYLTMMPQE-UHFFFAOYSA-J tris(2,2-diethylhexanoyloxy)stannyl 2,2-diethylhexanoate Chemical compound [Sn+4].CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O.CCCCC(CC)(CC)C([O-])=O ZYMLPCYLTMMPQE-UHFFFAOYSA-J 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- C08G2110/0025—Foam properties 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Definitions
- the present invention relates to a process for preparing polyisocyanate polyaddition products by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, and also to polyisocyanate polyaddition products which can be prepared by this process.
- the invention further relates to the use of thermoplastic particles which have a size of ⁇ 200 ⁇ m and a melting point in the range from 50 to 300° C. for producing usually foamed polyisocyanate polyaddition products which have greatly reduced the dust formation during sawing.
- the invention relates to a process for preparing a low-wear polyisocyanate polyaddition product, in particular a foamed or compact elastomer of this type, by reacting isocyanate components with components comprising compounds which are reactive toward isocyanates in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives and to polyisocyanate polyaddition products which can be prepared by this process.
- the invention also relates to low-wear compositions, storage-stable components, a process for setting particular properties in polyisocyanate polyaddition products or compositions and to the use of polyisocyanate polyaddition products or compositions for improving the wear behavior and to articles which comprise at least one of the abovementioned materials.
- polyisocyanate polyaddition products usually polyurethane and possibly polyisocyanurate products, for example polyurethane foams and compact or foamed elastomers
- polyurethane and possibly polyisocyanurate products for example polyurethane foams and compact or foamed elastomers
- particles (i) use is made of generally known compounds or mixtures which have the melting point specified according to the invention and can be brought to the size specified according to the present invention by customary methods, for example by known milling methods or spray drying, or are commercially available in this size.
- particles (i) which can be used are polyolefins, polyolefin copolymers and/or waxes, for example polyethylene, polypropylene, polyolefins comprising polyethylene and polypropylene units, which have been copolymerized with maleic acid and/or vinyl acetate, for example EVA, polystyrenes, modified polystyrenes and/or modified polyolefins, Fischer-Tropsch waxes (synthetic paraffin), montan waxes, camauba wax, candilla wax, vegetable and/or animal waxes, e.g. esters of fatty acids having from 20 to 53 carbon atoms which are esterified with organic alcohols having from 1 to 5 hydroxyl groups, for example glycerol.
- polyolefins for example polyethylene, polypropylene, polyolefins comprising polyethylene and polypropylene units, which have been copolymerized with maleic acid and/or vinyl acetate
- AF-31 wax micronized polyethylene wax
- the size of the particles (i) is the diameter which the particles (i) would have if they were present as spheres having the corresponding volume.
- silicone rubber has drawbacks, since it can be mixed only in very small amounts and with great technical difficulty with compounds (component A) which are reactive toward isocyanates.
- component A which are reactive toward isocyanates.
- This poor miscibility leads, for example, to the silicone rubber and the component A very quickly undergoing phase separation.
- the occurrence of phase separation makes it necessary for the component A comprising silicone rubber to be stirred again immediately before preparation of the polyisocyanate polyaddition adduct to achieve sufficient mixing of the silicone rubber with the component A.
- silicone rubbers leads only to an apparent improvement in the wear behavior.
- the materials modified with a silicone rubber produce a wax-like layer on the surface of the article rubbing along the surface of the silicone-modified material. This layer allows better sliding.
- the surface of emery paper becomes covered with wax when the material modified with a silicone rubber is rubbed across the emery paper.
- the wax-layer formed on the emery paper robs the surface of the emery paper of its roughness and thus allows the surface of the emery paper and the surface of the material modified with silicone rubber to slide over one another more readily.
- the silicone rubbers are comparatively expensive materials.
- a further object of the present invention is to overcome the abovementioned disadvantages associated with the silicone rubber and, in particular, to provide a low-wear polyisocyanate polyaddition product or a low-wear composition and a storage-stable component, particularly one which has less tendency toward phase separation.
- the polyaddition product preferably has a wear of less than 250 mg in accordance with DIN 53516.
- the polyaddition product preferably contains thermoset particles (ii), either alone or in combination with particles (i).
- thermoset particles (ii) either alone or in combination with particles (i).
- thermoset means that materials having these properties are not fusible.
- Thermoset particles can, according to the present invention, be either polymers or inorganic materials. In the case of polymers, it is preferred that they be crosslinked. Particularly preferred polymers are polycondensates, for example bakelites, polyamides, polyimides and the like. Inorganic thermosets are preferably mineral materials. Among these, particular preference is given to the fillers described further below in the present application.
- thermoset particles (ii) preferably have the same size as the fusible particles (i), said size being identically defined.
- the particles (i) it is preferred according to the present invention for the particles (i) to have a melting point and, in particular, be wax-like.
- a low-wear composition comprising at least one polyisocyanate polyaddition product according to the present invention or at least one foamed or compact elastomer according to the present invention or at least two thereof.
- a storage-stable component A comprising compounds which are reactive toward isocyanates and at least one type of particles (i) and/or (ii).
- the particles (i) and/or (ii) can also be present in the component B, as a result of which this component likewise gains a greater storage stability compared to components admixed with silicone rubbers.
- the particles (i) and/or (ii) enable the storage stability of the components used to be increased.
- the low-wear compositions of the present invention comprise at least one polyisocyanate addition product or at least one foam or compact elastomer or at least two thereof as constituents in an amount in the range from 0.1 to 100% by weight, preferably from 1 to 30% by weight and particularly preferably from 1.1 to 8% by weight, based on the low-wear composition.
- the weight ratio of the compounds which are reactive towards isocyanates to the particles (i) and/or (ii) is from 5:1 to 300:1, preferably from 5:1 to 200:1, particularly preferably from 5:1 to 100:1 and even more preferably from 5:1 to 20:1.
- the low-wear composition may comprise, as further constituents, all polymers, additives and auxiliaries known to those skilled in the art.
- the polyisocyanate polyaddition products, in particular the compact or foamed elastomers, and the low-wear composition obtainable by means of the process of the present invention have at least one of the following properties: Shore A hardness in the range from 10 to 90, preferably from 30 to 80 and particularly preferably from 40 to 70, or Shore D hardness in the range from 10 to 60, preferably from 20 to 50 and particularly preferably from 30 to 40; long-term flexural strength in the range from 1 to 8, preferably from 2 to 7; wear in accordance with DIN 53516 of less than 250 mg, preferably less than 150 mg and particularly preferably less than 100 mg.
- the compact or foamed elastomers or the low-wear compositions have Shore hardnesses and wear values in the abovementioned ranges. Further preference is given to compact or foamed elastomers and low-wear compositions which have Shore hardnesses, long-term flexural strengths and wear values within the abovementioned ranges.
- the compact elastomers have, either alone or in combination with the other properties, a Shore D hardness in the abovementioned ranges.
- the Shore D hardness is determined in accordance with DIN 53505.
- low-wear polyisocyanate polyaddition products which contain from 0.1 to 10% by weight, preferably from 0.5 to 9% by weight and in particular from 1 to 5% by weight, in each case based on the polyisocyanate polyaddition product, of at least one type of particles (i) and/or (ii).
- the storage life of the component comprising at least one type of particles (i) and/or (ii) is at least 3 days, preferably at least 5 days and particularly preferably at least 14 days.
- emulsifiers or auxiliaries as are described in EP A 0 368 217 are preferably added.
- Suitable isocyanates are the aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates known per se, preferably diisocyanates, which may have been, if desired, biuretized and/or isocyanuratized by generally known methods.
- alkylene diisocyanate having from 4 to 12 carbon atoms in the alkylene radical, for example dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, lysine ester diisocyanates (LDI), hexamethylene 1,6-diisocyanate (HDI), cyclohexane 1,3- and/or 1,4-diisocyanate, hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, dicyclohexylmethane 4,4′-, 2,2′- and 2,4′-diisocyanate and also the corresponding isomer mixtures and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPD
- polyols selected from the group consisting of polyether polyols, for example polytetrahydrofuran, polyester polyols, polythioether polyols, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the polyols mentioned. Preference is given to using polyester polyols and/or polyether polyols.
- the hydroxyl number of the polyhydroxyl compounds is generally from 28 to 850 mg KOH/g and preferably from 35 to 600 mg KOH/g.
- EP-A 0 451 559 urethane- and carbodimide-modified MDI is reacted with polyetherols to produce cellular polyurethane integral foams.
- EP-A 0 582 385 describes an NCO-terminated prepolymer of MDI and polyetherols having an NCO content of from 17 to 21% by weight which can be reacted to form microcellular elastomers.
- DE-A 16 18 380 describes NCO-terminated prepolymers which are derived from MDI and branched aliphatic dihydroxy compounds, have molecular weights up to 700 and are liquid at room temperature. The NCO content of these prepolymers is from 15 to 25% by weight.
- WO 91/17197 describes the preparation of microcellular polyurethane elastomers which are used, for example, for shoe soles.
- isocyanate component use is here made of prepolymers of MDI and polytetramethylene glycol which have NCO contents of from 7 to 30% by weight, preferably from 10 to 22% by weight.
- the storage stability of such prepolymers based on polytetramethylene glycol is, however, unsatisfactory.
- WO 92/22595 describes prepolymers derived from MDI and a polyol mixture comprising a branched diol or triol and at least one 2- to 4-functional polyoxyalkylene glycol.
- the NCO contents of the prepolymers are in the range from 15 to 19% by weight.
- prepolymers in which the polyol:polyisocyanate ratio is selected so that the NCO content of the prepolymer is >15% by weight, preferably >13% by weight, have been found to be particularly useful, especially in the case of low-wear polyisocyanate polyaddition products.
- Polyol components generally used, in particular for low-wear polyisocyanate polyaddition products and for rigid polyurethane foams, which may, if desired, contain isocyanurate structures, are high-functionality polyols, in particular polyether polyols based on high-functionality alcohols, sugar alcohols and/or saccharides as initiator molecules, and polyol components used for flexible foams are 2- and/or 3-functional polyether polyols and/or polyester polyols based on glycerol and/or trimethylolpropane and/or glycols as initiator molecules or alcohols to be esterified.
- the preparation of the polyether polyols is carried out by known methods.
- Suitable alkylene oxides for preparing the polyols are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
- the alkylene oxides can be used individually, alternatively in succession or as mixtures. Preference is given to using alkylene oxides which lead to primary hydroxyl groups in the polyol.
- Polyols which are particularly preferably used are those which have been alkoxylated with ethylene oxide at the conclusion of the alkoxylation and thus have primary hydroxyl groups.
- the polyether polyols have a functionality of preferably from 2 to 6 and in particular from 2 to 4 and molecular weights of from 400 to 3000, preferably from 400 to 2000.
- Suitable polyester polyols can be prepared, for example from organic 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.
- the polyester polyols preferably have a functionality of from 2 to 4, in particular from 2 to 3, and a molecular weight of from 480 to 3000, preferably from 600 to 2000 and in particular from 600 to 1500.
- chain extenders and/or crosslinkers As compounds which are reactive toward isocyanates, it is possible to use, if desired, diols and/or triols having molecular weights of from 60 to ⁇ 400 as chain extenders and/or crosslinkers in the process of the present invention.
- chain extenders, crosslinkers or, if desired, mixtures thereof can prove to be advantageous for modifying the mechanical properties, e.g. the hardness.
- the chain extenders and/or crosslinkers preferably have a molecular weight of from 60 to 300.
- suitable chain extenders/crosslinkers are aliphatic, cycloaliphatic and/or araliphatic diols having from 2 to 14, preferably from 4 to 10, carbon atoms, e.g.
- chain extenders, crosslinkers or mixtures thereof are employed for preparing the polyisocyanate polyaddition products, they are advantageously used in an amount of from 0 to 20% by weight, preferably from 2 to 8% by weight, based on the total weight of all the isocyanate-reactive compounds used.
- blowing agents in particular for producing polyurethane foams, it is possible to use customary chemically active blowing agents, for example water, and/or physically acting blowing agents.
- Suitable physically acting blowing agents are liquids which are inert toward the organic, modified or unmodified polyisocyanates and have boiling points below 100° C., preferably below 50° C., in particular from ⁇ 50° C. to 30° C., at atmospheric pressure so that they vaporize under the action of the exothermic polyaddition reaction.
- alkanes such as heptane, hexane, n- and iso-pentane, preferably industrial mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes such as cyclopentane and/or cyclohexane, ethers such as furan, dimethyl ether and diethyl ether, ketones such as acetone and methyl ethyl ketone, alkyl carboxylates such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons such as customary fluorinated hydrocarbons and/or chlorinated hydrocarbons, e.g.
- dichloromethane Mixtures of these low-boiling liquids with one another and/or with other substituted or unsubstituted hydrocarbons can also be used.
- organic carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl-containing compounds.
- the blowing agents are usually added to the compounds which are reactive toward isocyanates. However, they can be added to the isocyanate component or, as a combination, both to the polyol component and the isocyanate component or to premixtures of these components with the other formative components.
- the amount of physically acting blowing agent used is preferably from 0.5 to 25% by weight, particularly preferably from 3 to 15% by weight, in each case based on the weight of all the isocyanate-reactive compounds used. If water is used as blowing agent, preferably in an amount of from 0.5 to 10% by weight, particularly preferably in an amount of from 0.6 to 7% by weight, in each case based on the weight of all the isocyanate-reactive compounds used, it is preferably added to the polyol component.
- catalysts it is possible to use generally known compounds which strongly accelerate the reaction of isocyanates with the compounds which are reactive toward isocyanates. Preference is given to using a total catalyst content of from 0.001 to 15% by weight, in particular from 0.05 to 6% by weight, based on the weight of all the isocyanate-reactive compounds used.
- Examples of compounds which can be used are: triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclo-hexylamine, bis(N,N-dimethylaminoethyl) ether, bis(dimethyl-aminopropyl)urea, N-methylmorpholine and N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N′,N′-tetramethylethylene-diamine, N,N,N′,N′-tetramethylbutanediamine, N,N,N′,N′-tetramethylhexane-1,6-diamine, pentamethyl-diethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo[2.2.0]octane, 1,4-diazabicyclo[2.2.2]oc
- tin salts such as tin dioctoate, tin
- auxiliaries and/or additives can be incorporated into the reaction mixture for preparing the polyisocyanate polyaddition products.
- surface-active substances foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, 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 of the plastics.
- emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and also amine salts of fatty acids, e.g.
- foam stabilizers such as siloxane-oxyalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil
- oligomeric acrylates 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 employed in amounts of from 0.01 to 5% by weight, based on 100% by weight of all the isocyanate-reactive compounds used.
- fillers, in particular reinforcing fillers are the customary organic and inorganic fillers, reinforcing materials, weighting agents, agents for improving the wear behavior in paints, coatings, etc., known per se.
- inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, serpentine, hornblendes, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, and also glass, etc.
- kaolin china clay
- aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and also natural and synthetic fibrous minerals such as wollastonite, metal fibers and in particular glass fibers of various lengths which may be coated with a size.
- Suitable organic fillers are: carbon melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and, in particular, carbon fibers.
- 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 weight of the isocyanates and on the weight of all the isocyanate-reactive compounds used, although the content of mats, nonwovens and woven fabrics of natural and synthetic fibers may reach values up to 80% by weight.
- 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, tetrakis(2-chloroethyl) ethylene diphosphate, dimethyl methanephosphonate, diethyl dianolaminophosphonate and also commercial halogen-containing flame retardant polyols.
- inorganic or organic flame retardants such as red phosphorus, hydrated aluminum oxide, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and also, if desired, maize starch or ammonium polyphosphate, melamine and expandable graphite and/or aromatic or aliphatic polyesters for making the polyisocyanate polyaddition products flame resistant.
- the isocyanates and the compounds which are reactive toward isocyanates are reacted in such amounts that the equivalence ratio of NCO groups of the isocyanates to the sum of the reactive hydrogen atoms of the compounds which are reactive toward isocyanates is 0.85-1.25:1, preferably 0.95-1.15:1 and in particular 1-1.05:1. If, in particular, at least some bound isocyanurate groups are present in the rigid polyurethane foams, it is usual to employ a ratio of NCO groups to the sum of the reactive hydrogen atoms of 1.5-60:1, preferably 1.5-8:1.
- the isocyanates and the compounds which are reactive toward isocyanates are reacted in such amounts that the equivalence ratio of NCO groups of the isocyanates to the sum of the reactive hydrogen atoms of the compounds which are reactive toward isocyanates is 0.85-1.25:1, preferably 0.95-1.15:1 and in particular 1-1.05:1.
- polyurethane elastomers of the present invention in particular those comprising low-wear polyisocyanate polyaddition products, preference is given to using the customary and known formative components which are also employed in open-cell, flexible polyurethane foams.
- Polyisocyanates used are (cyclo)aliphatic and/or, in particular, aromatic polyisocyanates.
- suitable polyisocyanates are diisocyanates, preferably diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI).
- MDI diphenylmethane diisocyanate
- TDI tolylene diisocyanate
- the isocyanates can be used in the form of the pure compound or in modified form, for example in the form of uretdiones, isocyanurates, allophanates and biurets, preferably in the form of reaction products containing urethane and isocyanate groups, known as isocyanate prepolymers.
- polyols having a functionality of from 2 to 4, in particular from 2 to 3, and a molecular weight of from 1000 to 10,000, in particular from 2000 to 6000.
- Possible polyols are polycarbonate diols, polyesterols and polyetherols, with particular preference being given to polyetherols because of their greater hydrolysis stability.
- the polyetherols used for producing the flexible polyurethane foams of the present invention are usually prepared by base-catalyzed addition of lower alkylene oxides, in particular ethylene oxide and/or propylene oxide, onto 2- to 4-functional, in particular 2- and 3-functional, initiator substances.
- Initiator substances used are, in particular, 2- to 4-functional alcohols having molecular weights up to 400, for example ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol.
- the compounds having at least two hydroxyl groups which are reactive toward isocyanate also include chain extenders and/or crosslinkers.
- the chain extenders are predominantly 2- or three-functional alcohols having molecular weights of less than 400, for example ethylene glycol, propylene glycol, 1,4-butanediol or 1,5-pentanediol.
- the crosslinkers are compounds having molecular weights of less than 400 and containing 3 or more active H atoms, preferably amines and particularly preferably alcohols, for example glycerol, trimethylolpropane and/or pentaerythritol.
- the elastomers of the present invention can be produced either in the presence or in the absence of chain extenders and/or crosslinkers.
- the foamed elastomers of the present invention are produced using blowing agents.
- the blowing agent used for producing them is nowadays usually water which forms carbon dioxide with reaction with the isocyanate groups, if desired in admixture with physical blowing agents, viz. inert compounds which vaporize under the conditions of polyurethane formation.
- physical blowing agents are (cyclo)aliphatic hydrocarbons, preferably those having from 4 to 8, particularly preferably from 4 to 6 and in particular 5, carbon atoms, partially halogenated hydrocarbons or ethers, ketones or acetates. The amount of blowing agents used depends on the intended density of the foams.
- the elastomers are usually prepared in the presence of catalysts, for example tertiary amines or organic metal compounds which have been described above, in particular tin compounds such as tin mercaptide.
- catalysts for example tertiary amines or organic metal compounds which have been described above, in particular tin compounds such as tin mercaptide.
- the reaction is carried out in the presence or absence of auxiliaries and/or additives such as fillers, cell regulators and surface-active compounds.
- auxiliaries and/or additives such as fillers, cell regulators and surface-active compounds.
- the polyisocyanate polyaddition products are advantageously prepared by the one-shot process, for example by means of the high-pressure or low-pressure technique in open or closed molds, for example metal molds.
- the continuous application of the reaction mixture to suitable conveyor belts for producing panels or block foams is also customary.
- the compounds or particles (i) employed according to the present invention are preferably used in the process of the present invention in admixture with the polyol component, i.e. in admixture with compounds which are reactive toward isocyanates, for example in the above-described component A.
- the compounds (i) can also be mixed into the component (B). This applies also to particles (ii).
- the weight ratio of the compounds which are reactive toward isocyanates to particles (i) and/or (ii) is preferably from 5: 1 to 20:1.
- the index which indicates the mixing ratio of the component A and the component B, is from 90 to 100, preferably from 95 to 99.5 and particularly preferably from 96 to 99.
- the wear resistance can be increased by increasing the index in addition to the use of wear improvers.
- the starting components are mixed at from 0 to 100° C., preferably from 20 to 60° C., and introduced into the open mold or under atmospheric or superatmospheric pressure into the closed mold or, in the case of a continuous processing station, applied to a belt which accommodates the reaction mixture.
- Mixing can, as has already been described, be carried out mechanically by means of a stirrer or a stirring screw.
- the reaction temperature in the mold i.e. the temperature at which the reaction occurs, is usually >20° C., preferably from 40 to 80° C.
- the process of the present invention can be used, as a function of the starting materials, to produce all customary polyisocyanate polyaddition products, but in particular rigid polyurethane foams which may contain isocyanurate structures.
- the rigid polyurethane foams produced by the process of the present invention usually have a density of from 15 to 300 kg/m 3 , preferably from 20 to 240 kg/m 3 and in particular from 25 to 100 kg/m 3 . They are suitable, for example, as insulation in the building and refrigeration appliance sectors, e.g. as intermediate layer in sandwich elements or for filling the housings of refrigerators and freezer chests with foam, and in particular as foams in which materials can be fixed by pressing in; the latter foams preferably have a density of from 20 to 50 kg/m 3 .
- the flexible polyurethane foams produced by the process of the present invention usually have a density of from 15 to 100 kg/m 3 and are preferably used in the furniture and automobile sectors, particularly preferably as upholstery material.
- the process of the present invention is preferably employed for producing rigid polyurethane foams, which may contain isocyanurate groups, since the advantages of the invention (smooth surface after cutting where the action of heat is involved and also no dust formation on cutting) become particularly apparent in the case of rigid foams.
- the foamed elastomers produced by the process of the present invention usually have a density of from 15 to 800 kg/m 3 , preferably from 20 to 240 kg/m 3 and in particular from 25 to 100 kg/m 3 .
- the compact elastomers produced by the process of the present invention usually have a density of more than 800 kg/m 3 , preferably up to a maximum of 1200 kg/m 3 .
- the wear or, in addition, the Shore A or D hardness or the long-term flexural strength can be set in a low-wear polyisocyanate polyaddition product or in a composition comprising this by means of a process according to the present invention by incorporating particles (i) and/or (ii) into the polyisocyanate polyaddition product in an amount of from 0.1 to 10% by weight, based on the polyisocyanate polyaddition product.
- low-wear polyisocyanate polyaddition adducts or compact or foamed elastomers or low-wear compositions or at least two thereof for improving the wear behavior in articles, in particular foams, films, fibers, molding compositions and coatings.
- articles comprise a low-wear polyisocyanate polyaddition product or a compact or foamed elastomer or a low-wear composition or at least two thereof.
- Particularly preferred articles are shoe soles, automobile tires, conveyor belts, industrial seals and rollers subjected to mechanical loads.
- Example 2 The A component of Example 2 was not stable, so that no foam could be produced.
- the reaction parameters for Examples 1, 3 and 4 are shown in Table 2. TABLE 2 Example 1 (co) 3 (in) 4 (in) Cream time [s] 36 37 35 Fiber time [s] 118 120 118 Rise time [s] 180 165 175
Abstract
In a process for preparing polyisocyanate polyaddition products by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, the reaction is carried out in the presence of (i) particles which have a size of <200 μm and a melting point in a range from 50 to 300° C., or in the presence of thermoset particles (ii) or in the presence of particles (i) and (ii).
Description
- The present invention relates to a process for preparing polyisocyanate polyaddition products by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, and also to polyisocyanate polyaddition products which can be prepared by this process. The invention further relates to the use of thermoplastic particles which have a size of <200 μm and a melting point in the range from 50 to 300° C. for producing usually foamed polyisocyanate polyaddition products which have greatly reduced the dust formation during sawing.
- Furthermore, the invention relates to a process for preparing a low-wear polyisocyanate polyaddition product, in particular a foamed or compact elastomer of this type, by reacting isocyanate components with components comprising compounds which are reactive toward isocyanates in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives and to polyisocyanate polyaddition products which can be prepared by this process. The invention also relates to low-wear compositions, storage-stable components, a process for setting particular properties in polyisocyanate polyaddition products or compositions and to the use of polyisocyanate polyaddition products or compositions for improving the wear behavior and to articles which comprise at least one of the abovementioned materials.
- The preparation of polyisocyanate polyaddition products, usually polyurethane and possibly polyisocyanurate products, for example polyurethane foams and compact or foamed elastomers, by reacting an isocyanate component B with a component A comprising compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, has been described many times.
- In further processing of, for example, polyurethane foams, in particular rigid polyurethane foams which may contain polyisocyanurate structures, sawing the moldings or cutting them by means of a hot wire results in undesirable dust formation and a rough surface.
- It is an object of the present invention to develop a process for preparing polyisocyanate polyaddition products by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, which makes it possible to obtain polyisocyanate polyaddition products which have greatly reduced dust formation during further processing involving local action of heat, for example sawing with generation of frictional heat or, in particular, cutting by means of a hot wire, and subsequently have a pleasantly smooth surface.
- We have found that this object is achieved by carrying out the reaction of isocyanates with isocyanate-reactive compounds, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, in the presence of particles (i) which have a size of <200 μm, preferably ≦100 μm, particularly preferably from 2 to 100 μm, in particular from 10 to 100 μm, and have a melting point in a range from 50 to 300° C., preferably from 70 to 200° C., or in the presence of particles (ii), which are thermoset, or in the presence of particles (i) and (ii). The particle size of particles (ii) is in the same range as the particle size of particles (i).
- As particles (i), use is made of generally known compounds or mixtures which have the melting point specified according to the invention and can be brought to the size specified according to the present invention by customary methods, for example by known milling methods or spray drying, or are commercially available in this size. Examples of particles (i) which can be used are polyolefins, polyolefin copolymers and/or waxes, for example polyethylene, polypropylene, polyolefins comprising polyethylene and polypropylene units, which have been copolymerized with maleic acid and/or vinyl acetate, for example EVA, polystyrenes, modified polystyrenes and/or modified polyolefins, Fischer-Tropsch waxes (synthetic paraffin), montan waxes, camauba wax, candilla wax, vegetable and/or animal waxes, e.g. esters of fatty acids having from 20 to 53 carbon atoms which are esterified with organic alcohols having from 1 to 5 hydroxyl groups, for example glycerol.
- Preference is given to using polyolefins which may be modified or unmodified and/or waxes.
- Appropriate waxes are commercially available, for example micronized polyethylene wax (AF-31 wax) from BASF Aktiengesellschaft.
- For the purposes of the present invention, the size of the particles (i) is the diameter which the particles (i) would have if they were present as spheres having the corresponding volume.
- A further problem which frequently gives rise to complaints in the case of articles, particularly foams, films, fibers, moldings and coatings, in particular shoe soles, which comprise at least some polyisocyanate polyaddition products, in particular polyurethanes, is excessively high wear.
- This wear has previously been reduced in the case of shoe soles by adding silicone rubber to the polyisocyanate polyaddition products or polyurethanes.
- However, the use of silicone rubber has drawbacks, since it can be mixed only in very small amounts and with great technical difficulty with compounds (component A) which are reactive toward isocyanates. This poor miscibility leads, for example, to the silicone rubber and the component A very quickly undergoing phase separation. This leads, for example, to the problem that the mixture of component A and silicone rubber cannot be stored for a prolonged period or cannot be transported over long distances. In general, the occurrence of phase separation makes it necessary for the component A comprising silicone rubber to be stirred again immediately before preparation of the polyisocyanate polyaddition adduct to achieve sufficient mixing of the silicone rubber with the component A.
- Furthermore, the addition of silicone rubbers leads only to an apparent improvement in the wear behavior. The materials modified with a silicone rubber produce a wax-like layer on the surface of the article rubbing along the surface of the silicone-modified material. This layer allows better sliding. Thus, for example, the surface of emery paper becomes covered with wax when the material modified with a silicone rubber is rubbed across the emery paper. The wax-layer formed on the emery paper robs the surface of the emery paper of its roughness and thus allows the surface of the emery paper and the surface of the material modified with silicone rubber to slide over one another more readily. In addition, the silicone rubbers are comparatively expensive materials.
- A further object of the present invention is to overcome the abovementioned disadvantages associated with the silicone rubber and, in particular, to provide a low-wear polyisocyanate polyaddition product or a low-wear composition and a storage-stable component, particularly one which has less tendency toward phase separation.
- Furthermore, it is preferred according to the present invention for the polyaddition product to have a wear of less than 250 mg in accordance with DIN 53516. For this purpose, the polyaddition product preferably contains thermoset particles (ii), either alone or in combination with particles (i). These polyaddition products will hereinafter be referred to as “low-wear” polyisocyanate polyaddition products.
- For the purposes of the present invention, thermoset means that materials having these properties are not fusible. Thermoset particles can, according to the present invention, be either polymers or inorganic materials. In the case of polymers, it is preferred that they be crosslinked. Particularly preferred polymers are polycondensates, for example bakelites, polyamides, polyimides and the like. Inorganic thermosets are preferably mineral materials. Among these, particular preference is given to the fillers described further below in the present application.
- The thermoset particles (ii) preferably have the same size as the fusible particles (i), said size being identically defined.
- However, it is preferred according to the present invention for the particles (i) to have a melting point and, in particular, be wax-like.
- Furthermore, we have found that the abovementioned objects are achieved by a low-wear composition comprising at least one polyisocyanate polyaddition product according to the present invention or at least one foamed or compact elastomer according to the present invention or at least two thereof.
- In addition, the objects of the invention are achieved by a storage-stable component A comprising compounds which are reactive toward isocyanates and at least one type of particles (i) and/or (ii). In another embodiment of the present invention, the particles (i) and/or (ii) can also be present in the component B, as a result of which this component likewise gains a greater storage stability compared to components admixed with silicone rubbers. Thus, the particles (i) and/or (ii) enable the storage stability of the components used to be increased.
- The low-wear compositions of the present invention comprise at least one polyisocyanate addition product or at least one foam or compact elastomer or at least two thereof as constituents in an amount in the range from 0.1 to 100% by weight, preferably from 1 to 30% by weight and particularly preferably from 1.1 to 8% by weight, based on the low-wear composition.
- According to the present invention it is preferred that the weight ratio of the compounds which are reactive towards isocyanates to the particles (i) and/or (ii) is from 5:1 to 300:1, preferably from 5:1 to 200:1, particularly preferably from 5:1 to 100:1 and even more preferably from 5:1 to 20:1.
- Apart from the abovementioned constituents, the low-wear composition may comprise, as further constituents, all polymers, additives and auxiliaries known to those skilled in the art.
- According to the present invention, it is preferred that the polyisocyanate polyaddition products, in particular the compact or foamed elastomers, and the low-wear composition obtainable by means of the process of the present invention have at least one of the following properties: Shore A hardness in the range from 10 to 90, preferably from 30 to 80 and particularly preferably from 40 to 70, or Shore D hardness in the range from 10 to 60, preferably from 20 to 50 and particularly preferably from 30 to 40; long-term flexural strength in the range from 1 to 8, preferably from 2 to 7; wear in accordance with DIN 53516 of less than 250 mg, preferably less than 150 mg and particularly preferably less than 100 mg. It is particularly preferred that the compact or foamed elastomers or the low-wear compositions have Shore hardnesses and wear values in the abovementioned ranges. Further preference is given to compact or foamed elastomers and low-wear compositions which have Shore hardnesses, long-term flexural strengths and wear values within the abovementioned ranges.
- According to the present invention, it is particularly preferred that the compact elastomers have, either alone or in combination with the other properties, a Shore D hardness in the abovementioned ranges. The Shore D hardness is determined in accordance with DIN 53505.
- In a further embodiment of the present invention, preference is given to low-wear polyisocyanate polyaddition products which contain from 0.1 to 10% by weight, preferably from 0.5 to 9% by weight and in particular from 1 to 5% by weight, in each case based on the polyisocyanate polyaddition product, of at least one type of particles (i) and/or (ii).
- The storage life of the component comprising at least one type of particles (i) and/or (ii) is at least 3 days, preferably at least 5 days and particularly preferably at least 14 days.
- To further reduce the tendency toward phase separation, emulsifiers or auxiliaries as are described in EP A 0 368 217 are preferably added.
- Storage stability of the component is ensured when there is no occurrence of phase separation of the remaining components and the particles (i) and/or (ii) which results in inhomogeneous distribution of the particles (i) and/or (ii) in the component.
- The further starting materials for the process of the present invention are described below by way of example:
- Suitable isocyanates are the aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates known per se, preferably diisocyanates, which may have been, if desired, biuretized and/or isocyanuratized by generally known methods. Specific examples are: alkylene diisocyanate having from 4 to 12 carbon atoms in the alkylene radical, for example dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate, lysine ester diisocyanates (LDI), hexamethylene 1,6-diisocyanate (HDI), cyclohexane 1,3- and/or 1,4-diisocyanate, hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, dicyclohexylmethane 4,4′-, 2,2′- and 2,4′-diisocyanate and also the corresponding isomer mixtures and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), and also tolylene 2,4- and/or 2,6-diisocyanate, diphenylmethane 4,4′-, 2,4′- and/or 2,2′-diisocyanate, polyphenylpoly-methylene polyisocyanates and/or mixtures comprising at least two of the abovementioned isocyanates. Furthermore, diisocyanates and/or polyisocyanates containing ester, urea, allophanate, carbodiimide, uretdione and/or urethane groups can be used in the process of the present invention.
- As compounds which are reactive toward isocyanates, use can advantageously be made of those having a functionality of from 2 to 8, preferably from 2 to 6, and a molecular weight of from 60 to 10,000 and having hydroxyl, thiol and/or primary and/or secondary amino groups as groups which are reactive toward isocyanates. Compounds which have been found to be useful are, for example, polyols selected from the group consisting of polyether polyols, for example polytetrahydrofuran, polyester polyols, polythioether polyols, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of the polyols mentioned. Preference is given to using polyester polyols and/or polyether polyols. The hydroxyl number of the polyhydroxyl compounds is generally from 28 to 850 mg KOH/g and preferably from 35 to 600 mg KOH/g.
- Furthermore, it has been found to be advantageous generally and in particular in the preparation of low-wear polyisocyanate polyaddition products to use prepolymers containing isocyanate groups. Such prepolymers are known in the prior art. Thus, EP-A 0 013 487 describes uretonimine-modified MDI prepolymers. The prepolymers have NCO contents of about 18% by weight. EP-A 0 235 888 describes microcellular elastomers based on polyesterols comprising alkanolamines. As isocyanate component, use is made of prepolymers of MDI and the amine-containing polyester alcohols having an NCO content of about 18% by weight. In EP-A 0 451 559, urethane- and carbodimide-modified MDI is reacted with polyetherols to produce cellular polyurethane integral foams. EP-A 0 582 385 describes an NCO-terminated prepolymer of MDI and polyetherols having an NCO content of from 17 to 21% by weight which can be reacted to form microcellular elastomers. DE-A 16 18 380 describes NCO-terminated prepolymers which are derived from MDI and branched aliphatic dihydroxy compounds, have molecular weights up to 700 and are liquid at room temperature. The NCO content of these prepolymers is from 15 to 25% by weight. WO 91/17197 describes the preparation of microcellular polyurethane elastomers which are used, for example, for shoe soles. As isocyanate component, use is here made of prepolymers of MDI and polytetramethylene glycol which have NCO contents of from 7 to 30% by weight, preferably from 10 to 22% by weight. The storage stability of such prepolymers based on polytetramethylene glycol is, however, unsatisfactory. WO 92/22595 describes prepolymers derived from MDI and a polyol mixture comprising a branched diol or triol and at least one 2- to 4-functional polyoxyalkylene glycol. The NCO contents of the prepolymers are in the range from 15 to 19% by weight.
- As disclosed in DE 19618392 A1, prepolymers in which the polyol:polyisocyanate ratio is selected so that the NCO content of the prepolymer is >15% by weight, preferably >13% by weight, have been found to be particularly useful, especially in the case of low-wear polyisocyanate polyaddition products.
- Polyol components generally used, in particular for low-wear polyisocyanate polyaddition products and for rigid polyurethane foams, which may, if desired, contain isocyanurate structures, are high-functionality polyols, in particular polyether polyols based on high-functionality alcohols, sugar alcohols and/or saccharides as initiator molecules, and polyol components used for flexible foams are 2- and/or 3-functional polyether polyols and/or polyester polyols based on glycerol and/or trimethylolpropane and/or glycols as initiator molecules or alcohols to be esterified. The preparation of the polyether polyols is carried out by known methods. Suitable alkylene oxides for preparing the polyols are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternatively in succession or as mixtures. Preference is given to using alkylene oxides which lead to primary hydroxyl groups in the polyol. Polyols which are particularly preferably used are those which have been alkoxylated with ethylene oxide at the conclusion of the alkoxylation and thus have primary hydroxyl groups. The polyether polyols have a functionality of preferably from 2 to 6 and in particular from 2 to 4 and molecular weights of from 400 to 3000, preferably from 400 to 2000.
- Suitable polyester polyols can be prepared, for example from organic 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. The polyester polyols preferably have a functionality of from 2 to 4, in particular from 2 to 3, and a molecular weight of from 480 to 3000, preferably from 600 to 2000 and in particular from 600 to 1500.
- As compounds which are reactive toward isocyanates, it is possible to use, if desired, diols and/or triols having molecular weights of from 60 to <400 as chain extenders and/or crosslinkers in the process of the present invention. However, the addition of chain extenders, crosslinkers or, if desired, mixtures thereof can prove to be advantageous for modifying the mechanical properties, e.g. the hardness. The chain extenders and/or crosslinkers preferably have a molecular weight of from 60 to 300. Examples of suitable chain extenders/crosslinkers are aliphatic, cycloaliphatic and/or araliphatic diols having from 2 to 14, preferably from 4 to 10, carbon atoms, e.g. ethylene glycol, 1,3-propanediol, 1,10-decanediol, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably 1,4-butanediol, 1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone, triols such as 1,2,4- and/or 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene oxide and/or 1,2-propylene oxide and the abovementioned diols and/or triols as initiator molecules.
- If chain extenders, crosslinkers or mixtures thereof are employed for preparing the polyisocyanate polyaddition products, they are advantageously used in an amount of from 0 to 20% by weight, preferably from 2 to 8% by weight, based on the total weight of all the isocyanate-reactive compounds used.
- As blowing agents, in particular for producing polyurethane foams, it is possible to use customary chemically active blowing agents, for example water, and/or physically acting blowing agents. Suitable physically acting blowing agents are liquids which are inert toward the organic, modified or unmodified polyisocyanates and have boiling points below 100° C., preferably below 50° C., in particular from −50° C. to 30° C., at atmospheric pressure so that they vaporize under the action of the exothermic polyaddition reaction. Examples of such preferably used liquids are alkanes such as heptane, hexane, n- and iso-pentane, preferably industrial mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes such as cyclopentane and/or cyclohexane, ethers such as furan, dimethyl ether and diethyl ether, ketones such as acetone and methyl ethyl ketone, alkyl carboxylates such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons such as customary fluorinated hydrocarbons and/or chlorinated hydrocarbons, e.g. dichloromethane. Mixtures of these low-boiling liquids with one another and/or with other substituted or unsubstituted hydrocarbons can also be used. Also suitable are organic carboxylic acids such as formic acid, acetic acid, oxalic acid, ricinoleic acid and carboxyl-containing compounds. The blowing agents are usually added to the compounds which are reactive toward isocyanates. However, they can be added to the isocyanate component or, as a combination, both to the polyol component and the isocyanate component or to premixtures of these components with the other formative components. The amount of physically acting blowing agent used is preferably from 0.5 to 25% by weight, particularly preferably from 3 to 15% by weight, in each case based on the weight of all the isocyanate-reactive compounds used. If water is used as blowing agent, preferably in an amount of from 0.5 to 10% by weight, particularly preferably in an amount of from 0.6 to 7% by weight, in each case based on the weight of all the isocyanate-reactive compounds used, it is preferably added to the polyol component.
- As catalysts, it is possible to use generally known compounds which strongly accelerate the reaction of isocyanates with the compounds which are reactive toward isocyanates. Preference is given to using a total catalyst content of from 0.001 to 15% by weight, in particular from 0.05 to 6% by weight, based on the weight of all the isocyanate-reactive compounds used. Examples of compounds which can be used are: triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclo-hexylamine, bis(N,N-dimethylaminoethyl) ether, bis(dimethyl-aminopropyl)urea, N-methylmorpholine and N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N′,N′-tetramethylethylene-diamine, N,N,N′,N′-tetramethylbutanediamine, N,N,N′,N′-tetramethylhexane-1,6-diamine, pentamethyl-diethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo[2.2.0]octane, 1,4-diazabicyclo[2.2.2]octane (Dabco) and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine and N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N′,N″-tris(dialkylaminoalkyl)hexahydrotriazines, e.g. N,N′,N″-tris(dimethylaminopropyl)-s-hexahydrotriazine, iron(II) chloride, zinc chloride, lead octoate and preferably tin salts such as tin dioctoate, tin diethylhexanoate, dibutyltin dilaurate and/or dibutyltin dilauryl mercaptide, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide, alkali metal alkoxides such as sodium methoxide and potassium isopropoxide, and/or alkali metal salts of long-chain fatty acids having from 10 to 20 carbon atoms and possibly lateral OH groups.
- If desired, further auxiliaries and/or additives can be incorporated into the reaction mixture for preparing the polyisocyanate polyaddition products. Examples which may be mentioned are surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, flame retardants, 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 of the plastics. Examples which may be mentioned are emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and also amine salts of fatty acids, e.g. diethylamine oleate, diethanolamine stearate, diethanolamine ricinoleate, salts of sulfonic acids, e.g. alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid; foam stabilizers such as siloxane-oxyalkylene 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. The above-described oligomeric acrylates 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 employed in amounts of from 0.01 to 5% by weight, based on 100% by weight of all the isocyanate-reactive compounds used. For the purposes of the present invention, fillers, in particular reinforcing fillers, are the customary organic and inorganic fillers, reinforcing materials, weighting agents, agents for improving the wear behavior in paints, coatings, etc., known per se. Specific examples are: inorganic fillers such as siliceous minerals, for example sheet silicates such as antigorite, serpentine, hornblendes, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, and also glass, etc. Preference is given to using kaolin (china clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and also natural and synthetic fibrous minerals such as wollastonite, metal fibers and in particular glass fibers of various lengths which may be coated with a size. Examples of suitable organic fillers are: carbon melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide fibers, polyacrylonitrile fibers, polyurethane fibers, polyester fibers based on aromatic and/or aliphatic dicarboxylic esters and, in particular, carbon fibers. 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 weight of the isocyanates and on the weight of all the isocyanate-reactive compounds used, although the content of mats, nonwovens and woven fabrics of natural and synthetic fibers may reach values up to 80% by weight.
- 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, tetrakis(2-chloroethyl) ethylene diphosphate, dimethyl methanephosphonate, diethyl dianolaminophosphonate and also commercial halogen-containing flame retardant polyols. Apart from the abovementioned halogen-substituted phosphates, it is also possible to use inorganic or organic flame retardants such as red phosphorus, hydrated aluminum oxide, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives such as melamine, or mixtures of at least two flame retardants such as ammonium polyphosphates and melamine and also, if desired, maize starch or ammonium polyphosphate, melamine and expandable graphite and/or aromatic or aliphatic polyesters for making the polyisocyanate polyaddition products flame resistant. In general, it has been found to be advantageous to use from 5 to 50% by weight, preferably from 5 to 25% by weight, of the flame retardants mentioned, based on the weight of all the isocyanate-reactive compounds used.
- To prepare the polyisocyanate polyaddition products of the present invention, the isocyanates and the compounds which are reactive toward isocyanates are reacted in such amounts that the equivalence ratio of NCO groups of the isocyanates to the sum of the reactive hydrogen atoms of the compounds which are reactive toward isocyanates is 0.85-1.25:1, preferably 0.95-1.15:1 and in particular 1-1.05:1. If, in particular, at least some bound isocyanurate groups are present in the rigid polyurethane foams, it is usual to employ a ratio of NCO groups to the sum of the reactive hydrogen atoms of 1.5-60:1, preferably 1.5-8:1.
- To prepare the low-wear polyisocyanate polyaddition products of the present invention, the isocyanates and the compounds which are reactive toward isocyanates are reacted in such amounts that the equivalence ratio of NCO groups of the isocyanates to the sum of the reactive hydrogen atoms of the compounds which are reactive toward isocyanates is 0.85-1.25:1, preferably 0.95-1.15:1 and in particular 1-1.05:1.
- As starting materials for the polyurethane elastomers of the present invention, in particular those comprising low-wear polyisocyanate polyaddition products, preference is given to using the customary and known formative components which are also employed in open-cell, flexible polyurethane foams.
- Polyisocyanates used are (cyclo)aliphatic and/or, in particular, aromatic polyisocyanates. To produce the flexible polyurethane foams of the present invention, particularly suitable polyisocyanates are diisocyanates, preferably diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI). The isocyanates can be used in the form of the pure compound or in modified form, for example in the form of uretdiones, isocyanurates, allophanates and biurets, preferably in the form of reaction products containing urethane and isocyanate groups, known as isocyanate prepolymers.
- As compounds containing at least two hydrogen atoms which are reactive toward isocyanate, use is made, in particular, of polyols having a functionality of from 2 to 4, in particular from 2 to 3, and a molecular weight of from 1000 to 10,000, in particular from 2000 to 6000. Possible polyols are polycarbonate diols, polyesterols and polyetherols, with particular preference being given to polyetherols because of their greater hydrolysis stability. The polyetherols used for producing the flexible polyurethane foams of the present invention are usually prepared by base-catalyzed addition of lower alkylene oxides, in particular ethylene oxide and/or propylene oxide, onto 2- to 4-functional, in particular 2- and 3-functional, initiator substances. Initiator substances used are, in particular, 2- to 4-functional alcohols having molecular weights up to 400, for example ethylene glycol, propylene glycol, glycerol, trimethylolpropane or pentaerythritol. As stated above, preference is given to using polyetherols having an ethylene oxide content, preferably one in the range of 10-80% by weight, based on the weight of the polyetherol, to achieve a further increase in the hydrophilicity of the foams.
- The compounds having at least two hydroxyl groups which are reactive toward isocyanate also include chain extenders and/or crosslinkers. The chain extenders are predominantly 2- or three-functional alcohols having molecular weights of less than 400, for example ethylene glycol, propylene glycol, 1,4-butanediol or 1,5-pentanediol. The crosslinkers are compounds having molecular weights of less than 400 and containing 3 or more active H atoms, preferably amines and particularly preferably alcohols, for example glycerol, trimethylolpropane and/or pentaerythritol.
- The elastomers of the present invention can be produced either in the presence or in the absence of chain extenders and/or crosslinkers.
- The foamed elastomers of the present invention are produced using blowing agents. The blowing agent used for producing them is nowadays usually water which forms carbon dioxide with reaction with the isocyanate groups, if desired in admixture with physical blowing agents, viz. inert compounds which vaporize under the conditions of polyurethane formation. Examples of physical blowing agents are (cyclo)aliphatic hydrocarbons, preferably those having from 4 to 8, particularly preferably from 4 to 6 and in particular 5, carbon atoms, partially halogenated hydrocarbons or ethers, ketones or acetates. The amount of blowing agents used depends on the intended density of the foams.
- The elastomers are usually prepared in the presence of catalysts, for example tertiary amines or organic metal compounds which have been described above, in particular tin compounds such as tin mercaptide.
- The reaction is carried out in the presence or absence of auxiliaries and/or additives such as fillers, cell regulators and surface-active compounds.
- Further details regarding the starting materials, catalysts and auxiliaries and additives used may be found, for example, in the Kunststoff-Handbuch, volume 7, Polyurethane, Carl-Hanser-Verlag, Munich, 1st edition 1966, 2nd edition 1983 and 3rd edition 1993 and in the above disclosures.
- The polyisocyanate polyaddition products are advantageously prepared by the one-shot process, for example by means of the high-pressure or low-pressure technique in open or closed molds, for example metal molds. The continuous application of the reaction mixture to suitable conveyor belts for producing panels or block foams is also customary.
- It has been found to be particularly advantageous to employ the two-component process and to combine the compounds which are reactive toward isocyanates, if desired the blowing agent or agents, the catalysts and/or auxiliaries and/or additives in component (A) and to use the isocyanates or mixtures of the isocyanates and, if desired, blowing agents as component (B).
- The compounds or particles (i) employed according to the present invention are preferably used in the process of the present invention in admixture with the polyol component, i.e. in admixture with compounds which are reactive toward isocyanates, for example in the above-described component A. However, the compounds (i) can also be mixed into the component (B). This applies also to particles (ii).
- The weight ratio of the compounds which are reactive toward isocyanates to particles (i) and/or (ii) is preferably from 5: 1 to 20:1.
- For the low-wear polyisocyanate polyaddition products, it is preferred that the index, which indicates the mixing ratio of the component A and the component B, is from 90 to 100, preferably from 95 to 99.5 and particularly preferably from 96 to 99. In general, the wear resistance can be increased by increasing the index in addition to the use of wear improvers.
- Depending on the application, the starting components are mixed at from 0 to 100° C., preferably from 20 to 60° C., and introduced into the open mold or under atmospheric or superatmospheric pressure into the closed mold or, in the case of a continuous processing station, applied to a belt which accommodates the reaction mixture. Mixing can, as has already been described, be carried out mechanically by means of a stirrer or a stirring screw. The reaction temperature in the mold, i.e. the temperature at which the reaction occurs, is usually >20° C., preferably from 40 to 80° C.
- The process of the present invention can be used, as a function of the starting materials, to produce all customary polyisocyanate polyaddition products, but in particular rigid polyurethane foams which may contain isocyanurate structures.
- The rigid polyurethane foams produced by the process of the present invention usually have a density of from 15 to 300 kg/m3, preferably from 20 to 240 kg/m3 and in particular from 25 to 100 kg/m3. They are suitable, for example, as insulation in the building and refrigeration appliance sectors, e.g. as intermediate layer in sandwich elements or for filling the housings of refrigerators and freezer chests with foam, and in particular as foams in which materials can be fixed by pressing in; the latter foams preferably have a density of from 20 to 50 kg/m3.
- The flexible polyurethane foams produced by the process of the present invention usually have a density of from 15 to 100 kg/m3 and are preferably used in the furniture and automobile sectors, particularly preferably as upholstery material.
- The process of the present invention is preferably employed for producing rigid polyurethane foams, which may contain isocyanurate groups, since the advantages of the invention (smooth surface after cutting where the action of heat is involved and also no dust formation on cutting) become particularly apparent in the case of rigid foams.
- The foamed elastomers produced by the process of the present invention usually have a density of from 15 to 800 kg/m3, preferably from 20 to 240 kg/m3 and in particular from 25 to 100 kg/m3. The compact elastomers produced by the process of the present invention usually have a density of more than 800 kg/m3, preferably up to a maximum of 1200 kg/m3.
- Furthermore, the wear or, in addition, the Shore A or D hardness or the long-term flexural strength can be set in a low-wear polyisocyanate polyaddition product or in a composition comprising this by means of a process according to the present invention by incorporating particles (i) and/or (ii) into the polyisocyanate polyaddition product in an amount of from 0.1 to 10% by weight, based on the polyisocyanate polyaddition product.
- In this context, particular preference is given according to the present invention to reducing the wear by increasing the amount of particles (i) and/or (ii) used.
- According to the present invention, preference is given to using the low-wear polyisocyanate polyaddition adducts or compact or foamed elastomers or low-wear compositions or at least two thereof for improving the wear behavior in articles, in particular foams, films, fibers, molding compositions and coatings.
- Furthermore, it is preferred according to the present invention that articles comprise a low-wear polyisocyanate polyaddition product or a compact or foamed elastomer or a low-wear composition or at least two thereof.
- Particularly preferred articles are shoe soles, automobile tires, conveyor belts, industrial seals and rollers subjected to mechanical loads.
- The invention is illustrated by the following examples.
- In the individual examples, the A components indicated in Table 1 were intensively mixed by stirring with Lupranat® M 50 (BASF Aktiengesellschaft) as B component at an isocyanate index of 185. Immediately afterwards, 50 g in each case were placed in a tub having a capacity of 1000 ml and reacted. The figures in the table are parts by weight.
TABLE 1 Example A component 1 (co) 2 (co) 3 (in) 4 (in) AF31 wax — — 5 10 A wax — 10 — — Merginat ® PV235 52 52 52 52 Castor oil 25 25 25 25 Lupranol ® 3530 18 18 18 18 Tegostab ® B 1903 0.5 0.5 0.5 0.5 n-Pentane 11.6 11.6 11.6 11.6 Water 3.5 3.5 3.5 3.5 Lupragen ® N 206 0.13 0.13 0.13 0.13 20% strength potassium formate 3.7 3.7 3.7 3.7 solution in ethylene glycol Lupragen ® N 600 0.55 0.55 0.55 0.55 - The A component of Example 2 was not stable, so that no foam could be produced. The reaction parameters for Examples 1, 3 and 4 are shown in Table 2.
TABLE 2 Example 1 (co) 3 (in) 4 (in) Cream time [s] 36 37 35 Fiber time [s] 118 120 118 Rise time [s] 180 165 175 - To assess the processability of the rigid foams, they were cut by means of a hot-wire cutting apparatus (from Dingeldein). The rigid foams produced according to the present invention using the micronized waxes did not form any dust on cutting with the hot wire. The cut surface was pleasantly smooth. In contrast, the rigid foam of Example 1 which had been produced without micronized wax produced dust during cutting with the hot wire and, in addition, had an unpleasantly rough, visually unsatisfactory surface after cutting.
- The various wear improvers were added to the component A.
- Component A
- 30 parts by weight of a trifunctional polyetherol based on propylene oxide, having an ethylene oxide end block of 21%, an OH number of 26 mg KOH/g and a mean functionality of 3,
- 57.3 parts by weight of a bifunctional polyetherol based on propylene oxide, having an ethylene oxide end block of 19%, an OH number of 28 mg KOH/g and a mean functionality of 2,
- 7.5 parts by weight of 1,4-butanediol,
- 4.5 parts by weight of a 25% strength solution of Dabco in 1,4-butanediol,
- 0.2 part by weight of a tin mercaptide,
- 0.47 part by weight of water.
- Component B
- Prepolymer of 4,4′-MDI (76%), a polymeric MDI (4%) and a bifunctional polyol having an OHN of 104 and based on propylene oxide (16.5%) and dipropylene glycol (6.0%), having an NCO content of 20.5%.
- Using a model F 20 low-pressure processing machine from Elastogran-Maschinenbau GmbH, the components were combined at 25° C. and processed to produce test plates having dimensions of 20 cm×20 cm×1 cm. Details are given in Table 3 below.
TABLE 3 Comparison of various wear improvers The component A contains 0.5% of emulsifier Special Shore A Expt. No. A:B = 100 Wear imp. in A DIN wear, mg wear, μm Long-term flexure hardness 1 104 2% AF31 246 515 7.0; 4.5; 6.5; 5.5 45 2 106 2% AF31 143 245 6.5; 7.5; 6.0; 8.5 45 3 108 2% AF31 134 180 rupture 45 4 110 2% AF31 104 145 rupture 45 5 112 2% AF31 94 120 rupture 44 6 102 2% AF29 128 410 4.2; 5.3; 6.0; 5.8 45 7 104 2% AF29 98 245 4.0; 4.5; 5.2; 4.6 45 8 106 2% AF29 84 135 5.2; 4.5; 4.4; 5.2 46 9 108 2% AF29 70 165 9.5; 6.8; 7.8; 7.9 47 10 110 2% AF29 59 135 rupture 46 11 112 2% AF29 50 110 rupture 44 12 102 2% AF32 151 290 7.0; 7.1; 8.5; 7.5 43 13 104 2% AF32 117 245 4.2; 4.3; 3.5; 3.5 45 14 106 2% AF32 79 200 5.0; 3.6; 4.5; 6.0 47 15 108 2% AF32 69 170 5.6; 5.8; 4.2; 7.5 47 16 110 2% AF32 60 125 rupture 47 17 112 2% AF32 55 140 rupture 45 18 (comp.) 102 1% Q2 40 m 100%* 205 4.5; 4.5; 5.5; 4.5 43 19 (comp.) 104 1% Q2 234 185 6.5; 7.0; 8.2; 4.5 45 20 (comp.) 106 1% Q2 124 155 8.5; 5.0; 6.5; 4.2 46 21 (comp.) 108 1% Q2 102 100 rupture 46 22 (comp.) 110 1% Q2 89 120 rupture 45 23 (comp.) 112 1% Q2 98 125 rupture 46 24 (comp.) 102 none 5.5; 5.9; 5.6; 6.8 43 25 (comp.) 104 none 14.6; 4.5; 11.7; 8.1 42 26 (comp.) 106 none 100% wear 580 rupture 43 27 (comp.) 108 none 100% wear 475 rupture 44 28 (comp.) 110 none 100% wear 505 rupture 44
Claims (20)
1. A process for preparing polyisocyanate polyaddition products by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, wherein the reaction is carried out in the presence of particles (i) which have a size of <200 μm and a melting point in the range from 50 to 300° C., or in the presence of thermoset particles (ii) or in the presence of particles (i) and (ii).
2. A process as claimed in , wherein the polyaddition product has a wear of less than 250 mg in accordance with DIN 53516.
claim 1
3. A process as claimed in , wherein polyolefins and/or waxes are used as particles (i).
claim 1
4. A process as claimed in , wherein the particles (i) have a size of ≦100 μm.
claim 1
5. A process as claimed in , wherein the particles (i) and/or (ii) are used in admixture with compounds which are reactive toward isocyanates.
claim 1
6. A process as claimed in , wherein the weight ratio of the compounds which are reactive toward isocyanates to (i) and/or (ii) is from 5:1 to 300:1.
claim 1
7. A process as claimed in , wherein the process is carried out in the presence of blowing agents and the polyisocyanate polyaddition products are polyisocyanate polyaddition product foams.
claim 1
8. A process as claimed in , wherein the foam is a rigid polyurethane foam.
claim 7
9. A polyisocyanate polyaddition product obtainable by reacting isocyanates with compounds which are reactive toward isocyanates, in the presence or absence of blowing agents, catalysts, auxiliaries and/or additives, wherein the reaction is carried out in the presence of particles (i) which have a size of <200 μm and a melting point in the range from 50 to 300° C., or in the presence of thermoset particles (ii) or in the presence of particles (i) and (ii).
10. A foam obtainable by reacting iso cyanates with compounds which are reactive toward isocyanates, in the presence of blowing agents, and in the absence or presence of catalysts, auxiliaries and/or additives, wherein the reaction is carried out in the presence of particles (i) which have a size of <200 μm and a melting point in the range from 50 to 300° C., or in the presence of thermoset particles (ii) or in the presence of particles (i) and (ii).
11. A low-wear composition comprising at least one polyisocyanate polyaddition product as defined in .
claim 9
12. A low-wear composition comprising at least one foam as defined in .
claim 10
13. A composition as claimed in having at least one of the following properties:
claim 11
Shore A hardness in the range from 10 to 90 or Shore D hardness in the range from 10 to 60,
long-term flexural strength in the range from 1 to 8,
wear of less than 250 mg in accordance with DIN 53516.
14. A composition as claimed in having at least one of the following properties:
claim 12
Shore A hardness in the range from 10 to 90 or Shore D hardness in the range from 10 to 60,
long-term flexural strength in the range from 1 to 8,
wear of less than 250 mg in accordance with DIN 53516.
15. A storage-stable component for preparing polyurethanes, comprising at least one type of particles (i) and/or (ii) as defined in .
claim 1
16. A process for setting at least the wear defined in or additionally the Shore A hardness or Shore D hardness defined in or the long-term flexural strength defined in in a polyisocyanate polyaddition product or in a composition comprising this polyisocyanate polyaddition product, wherein particles (i) and/or (ii) as defined in are incorporated into the polyisocyanate polyaddition product in an amount of from 0.1 to 10% by weight, based on the polyisocyanate polyaddition product.
claim 2
claim 13
claim 13
claim 1
17. Method of using a polyisocyanate polyaddition product as defined in for improving the wear behavior in articles, in particular foams, films, fibers, molding compositions, coatings and shoe soles.
claim 1
18. An article comprising at least one polyisocyanate polyaddition product as defined in .
claim 1
19. An article comprising at least one foam as defined in .
claim 10
20. Method of using thermoplastic particles (i) which have a size of <200 μm and a melting point in the range from 50 to 300° C. for preparing foamed polyisocyanate polyaddition products which have greatly reduced the dust formation during processing involving local action of heat, for example sawing with generation of frictional heat or, in particular, cutting by means of a hot wire.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19820917 | 1998-05-09 | ||
DE19820917A DE19820917A1 (en) | 1998-05-09 | 1998-05-09 | Polyisocyanate -polyaddition product, useful for the production of foam, for upholstery and insulation applications |
DE19820917.7 | 1998-05-09 | ||
DE19851880 | 1998-11-10 | ||
DE19851880A DE19851880A1 (en) | 1998-11-10 | 1998-11-10 | Polyisocyanate-polyaddition product, useful for the production of foam, sheet, fibers, shoe soles, car tires and belts |
Publications (2)
Publication Number | Publication Date |
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US20010003122A1 true US20010003122A1 (en) | 2001-06-07 |
US6329440B2 US6329440B2 (en) | 2001-12-11 |
Family
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Family Applications (1)
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US09/305,946 Expired - Fee Related US6329440B2 (en) | 1998-05-09 | 1999-05-06 | Preparation of polyisocyanate polyaddition products |
Country Status (7)
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US (1) | US6329440B2 (en) |
EP (1) | EP0957130B1 (en) |
KR (1) | KR19990088131A (en) |
CN (1) | CN1241583A (en) |
BR (1) | BR9901986A (en) |
DE (1) | DE59912944D1 (en) |
ES (1) | ES2253846T3 (en) |
Cited By (5)
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EP1321492A1 (en) * | 2001-12-21 | 2003-06-25 | Basf Corporation | Polyurethane foam composition and additive useful in shoe sole applications and method of making same |
US6649667B2 (en) | 2001-06-07 | 2003-11-18 | Bayer Polymers Llc | Polyurethane foams having improved heat sag and a process for their production |
CN112442160A (en) * | 2020-11-04 | 2021-03-05 | 黎明化工研究设计院有限责任公司 | Environment-friendly sand fixing agent and preparation method thereof |
WO2023186714A1 (en) * | 2022-04-01 | 2023-10-05 | Basf Se | A panel construction, a process for preparing the same and use thereof as an automotive part |
JP7459081B2 (en) | 2018-07-06 | 2024-04-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Elastomeric polyurethane foam and its production method |
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US6265457B1 (en) | 1998-12-11 | 2001-07-24 | Woodbridge Foam Corporation | Isocyanate-based polymer foam and process for production thereof |
DE10041162A1 (en) * | 2000-08-21 | 2002-03-07 | Basf Ag | Composite elements containing polyisocyanate polyaddition products |
EP1942122B1 (en) * | 2000-10-05 | 2015-08-12 | Dow Global Technologies LLC | Dispersion of a preformed polymer in a polyol |
KR100835550B1 (en) | 2000-10-05 | 2008-06-09 | 다우 글로벌 테크놀로지스 인크. | Dispersion of a polymer in a polyol, a process for making it and a polyurethane foam formulation comprising the same |
US20060014000A1 (en) * | 2004-04-30 | 2006-01-19 | Dai Nippon Printing Co., Ltd. | Plastic substrate and method for processing the same |
JP2008509247A (en) * | 2004-08-04 | 2008-03-27 | フォーム・サプライズ・インコーポレイテッド | Reactive drift and catalytic degradation in polyurethane foam |
US20090127195A1 (en) * | 2007-11-20 | 2009-05-21 | Allison Foss Calabrese | Purification of isocyanate functional polymers |
US8349987B2 (en) | 2009-02-19 | 2013-01-08 | Covidien Lp | Adhesive formulations |
EP2226344B1 (en) | 2009-03-02 | 2017-08-02 | Basf Se | Friction-resistant polyurethane form body with improved long-term bend resistance |
CN101805559A (en) * | 2010-04-07 | 2010-08-18 | 杭州东科建筑节能材料有限公司 | Polyurethane paint |
CN105199067A (en) * | 2015-09-21 | 2015-12-30 | 东港市华瑞彩钢有限公司 | Method for producing polyurethane foam |
WO2018018462A1 (en) * | 2016-07-27 | 2018-02-01 | Basf Se | Stabiliser for polyolefin-in-polyether polyol dispersions |
EP3553106A1 (en) * | 2018-04-13 | 2019-10-16 | Covestro Deutschland AG | Method for the preparation of polyurethane/polyisocyanurate (pur/pir) rigid foams |
CN109400839B (en) * | 2018-10-16 | 2021-06-04 | 上海东大聚氨酯有限公司 | Flame-retardant combined polyether, flame-retardant polyisocyanurate foam and preparation method thereof |
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NL260202A (en) * | 1960-01-19 | 1900-01-01 | ||
US3808129A (en) | 1972-02-07 | 1974-04-30 | Minnesota Mining & Mfg | Low friction,high load bearing compositions |
US4439548A (en) * | 1973-02-03 | 1984-03-27 | Morey Weisman | Modified polyurethane product having improved load-bearing characteristics |
JPS5321439B2 (en) * | 1973-09-11 | 1978-07-03 | ||
US3935132A (en) * | 1974-04-15 | 1976-01-27 | Union Carbide Corporation | Thermoplastic urethane polymer filled with cross-linked urethane polymer |
US4127515A (en) * | 1974-10-21 | 1978-11-28 | Colgate-Palmolive Company | Waxing sponge |
US4525386A (en) * | 1982-09-03 | 1985-06-25 | Morey Weisman | Technique for property enhancement of open-cell foam material |
US4980445A (en) | 1989-01-17 | 1990-12-25 | The Dow Chemical Company | Thermoplastic polyurethanes |
EG20399A (en) | 1991-06-13 | 1999-02-28 | Dow Chemical Co | A soft segment isocyanate terminate prepolymer and polyurethane elastomer therefrom |
TW293022B (en) * | 1992-07-27 | 1996-12-11 | Takeda Pharm Industry Co Ltd | |
JP3342758B2 (en) | 1993-11-26 | 2002-11-11 | 鬼怒川ゴム工業株式会社 | Smooth surface structure of rubber molded product |
JP2853547B2 (en) * | 1993-12-15 | 1999-02-03 | 日本鋼管株式会社 | Galvanized steel sheet with excellent press formability, appearance after press forming, and corrosion resistance |
DE19649290A1 (en) | 1996-11-28 | 1998-06-04 | Bayer Ag | Thermoplastic processable polyurethanes containing special wax mixtures |
-
1999
- 1999-05-06 US US09/305,946 patent/US6329440B2/en not_active Expired - Fee Related
- 1999-05-07 ES ES99108598T patent/ES2253846T3/en not_active Expired - Lifetime
- 1999-05-07 CN CN99107678A patent/CN1241583A/en active Pending
- 1999-05-07 EP EP99108598A patent/EP0957130B1/en not_active Expired - Lifetime
- 1999-05-07 DE DE59912944T patent/DE59912944D1/en not_active Expired - Lifetime
- 1999-05-07 BR BR9901986-8A patent/BR9901986A/en not_active IP Right Cessation
- 1999-05-08 KR KR1019990016422A patent/KR19990088131A/en not_active Application Discontinuation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6649667B2 (en) | 2001-06-07 | 2003-11-18 | Bayer Polymers Llc | Polyurethane foams having improved heat sag and a process for their production |
EP1321492A1 (en) * | 2001-12-21 | 2003-06-25 | Basf Corporation | Polyurethane foam composition and additive useful in shoe sole applications and method of making same |
JP7459081B2 (en) | 2018-07-06 | 2024-04-01 | ビーエーエスエフ ソシエタス・ヨーロピア | Elastomeric polyurethane foam and its production method |
CN112442160A (en) * | 2020-11-04 | 2021-03-05 | 黎明化工研究设计院有限责任公司 | Environment-friendly sand fixing agent and preparation method thereof |
WO2023186714A1 (en) * | 2022-04-01 | 2023-10-05 | Basf Se | A panel construction, a process for preparing the same and use thereof as an automotive part |
Also Published As
Publication number | Publication date |
---|---|
ES2253846T3 (en) | 2006-06-01 |
US6329440B2 (en) | 2001-12-11 |
EP0957130B1 (en) | 2005-12-21 |
KR19990088131A (en) | 1999-12-27 |
DE59912944D1 (en) | 2006-01-26 |
CN1241583A (en) | 2000-01-19 |
BR9901986A (en) | 2000-04-11 |
EP0957130A1 (en) | 1999-11-17 |
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