CN1422292A - Polyurethane foams with reduced exothermy - Google Patents
Polyurethane foams with reduced exothermy Download PDFInfo
- Publication number
- CN1422292A CN1422292A CN01807891A CN01807891A CN1422292A CN 1422292 A CN1422292 A CN 1422292A CN 01807891 A CN01807891 A CN 01807891A CN 01807891 A CN01807891 A CN 01807891A CN 1422292 A CN1422292 A CN 1422292A
- Authority
- CN
- China
- Prior art keywords
- component
- foams
- acid
- polyol
- prepolymer
- 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
- 229920005830 Polyurethane Foam Polymers 0.000 title abstract description 3
- 239000011496 polyurethane foam Substances 0.000 title abstract description 3
- 239000011435 rock Substances 0.000 claims abstract description 14
- 238000005065 mining Methods 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims description 26
- 150000003077 polyols Chemical class 0.000 claims description 26
- 239000006260 foam Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 5
- -1 polyphenylene Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical class C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007596 consolidation process Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- UNVGBIALRHLALK-UHFFFAOYSA-N 1,5-Hexanediol Chemical compound CC(O)CCCCO UNVGBIALRHLALK-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- LOLANUHFGPZTLQ-UHFFFAOYSA-N 1-ethoxydecane Chemical compound CCCCCCCCCCOCC LOLANUHFGPZTLQ-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical class CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- IIVBUJGYWCCLNG-UHFFFAOYSA-N 3-(dimethylamino)propylurea Chemical compound CN(C)CCCNC(N)=O IIVBUJGYWCCLNG-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- GTJVPLGQFHDOAC-UHFFFAOYSA-N C(C(=O)O)(=O)O.C(CCCCCCC)[Sn]CCCCCCCC Chemical compound C(C(=O)O)(=O)O.C(CCCCCCC)[Sn]CCCCCCCC GTJVPLGQFHDOAC-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- RIEUTJOAEXVILC-UHFFFAOYSA-N P(O)(O)=O.C(C)C(C)CC Chemical compound P(O)(O)=O.C(C)C(C)CC RIEUTJOAEXVILC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- QVTWBMUAJHVAIJ-UHFFFAOYSA-N hexane-1,4-diol Chemical compound CCC(O)CCCO QVTWBMUAJHVAIJ-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- RLEFZEWKMQQZOA-UHFFFAOYSA-M potassium;octanoate Chemical compound [K+].CCCCCCCC([O-])=O RLEFZEWKMQQZOA-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 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
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/30—Polyisocyanates; 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention concerns polyurethane foams with reduced exothermy and to the use thereof for hardening rocks in mining and underground engineering.
Description
The present invention relates to the urethane foam system of low exothermicity and relate to they solidify the geology formulation in underground mining, in tunnel construction and in underground works (Tiefbau) purposes.
Two component polyurethane foams system is used at coal mining consolidated rock and coal and is used for sealing going into flowing water with opposing to a great extent.Is heat release from polyisocyanates and polyvalent alcohol formation urethane in principle.Under adverse environment, because the high reaction temperature that produces in foam makes coal dust on fire.Especially when reaction mixture flows in the big relatively spacious space, the core temperature of urethane foam can be brought up to spontaneous combustion that urethane takes place and the therefore a kind of degree of coal combustion in-situ of making.
For fear of this shortcoming of polyurethane system, EP-A 167 002 has advised using the reaction product of isocyanic ester and alkali metal silicate aqueous solution.EP A 636 154 discloses by polyisocyanates, the reaction of alkali metal silicate aqueous solution and cement.Yet these systems can't be succeedd in practice.
Have now found that by by some polyisocyanate prepolymers and selected polyvalent alcohol and appropriate filler blending, the heat release that urethane forms can be reduced to a kind of degree that no longer includes hazard of catch fire in the consolidation process of rock.
So, the present invention relates to contain polyurethanyl group and the foams that reaction obtained by following component:
1. have 20-30wt.%, the polyisocyanate component of the NCO content of preferred 23-28wt.%, it comprises the prepolymer that contains isocyanate group of the NCO content with 20-28wt% of 50wt.% at least,
2. have 120 to 350, the polyol component of preferred 180 to 300 OH value,
3. be dispersed in polyol component b) or prepolymer a) in, preferably at polyol component b) in, and have 4-100 μ m, preferred 4-25 μ m, the solid packing of 10-25 μ m mean particle size especially,
4. water,
5. Ren Xuan catalyzer,
6. Ren Xuan additional additives.
According to the present invention, this isocyanate component a) contains 20-30wt.%, the NCO group of preferred 23-28wt.% and contain 50wt.% at least contain 20-30wt.%, the prepolymer of the isocyanate group of preferred 23-28wt.%.Preferably by the isocyanic ester and functionality and 350-1 with 3-8 of diphenylmethane series, 000 OH value and 150-1, the polyether polyol of 000 number-average molecular weight react prepared to this prepolymer.Suitable prepolymer also is described among the EP-A 550 901.The isocyanic ester of employed diphenylmethane series is two nuclear diphenylmethanediisocyanates, as 4,4 '-and/or 2,4 '-diphenylmethanediisocyanate of ditan-vulcabond or their more higher homologue or two or more nuclears for example the mixture or have of polyphenylene polymethylene polyisocyanates (as by aniline-formaldehyde condensation reaction and the prepared product (" thick MDI ") of phosgenation subsequently) be higher than the industrial polyisocyanates (commodity are called " polymerization ditan-vulcabond ") that obtains of 2.0 functionality.
The product that comprises two nuclear isomers of 75-95wt% is preferred, especially in two nuclear isomers 2,4 '-content of isomer is that 15-40wt.% and 2,2 '-content of isomer is those products of 2-10wt%.
Except that prepolymer, this isocyanate component a) can comprise other isocyanic ester of the diphenylmethane series of 50wt% at the most.This is polymeric MDI preferably.Yet monomer M DI also can use, or the MDI type that is modified, and those that for example contain biuret, allophanate and isocyanurate group can use, if isocyanate component viscosity a) be unlikely raise too many.
In order to ensure isocyanate component good workability a), its viscosity preferably is adjusted at 200-6,000mPas, and preferred especially 500-3 is in the 000mPas scope.This type of isocyanate component can be usually used in the piston or the toothed gear pump of fixed rock mass by use, without any problem be transferred and inject the rock mass layer.
Polyol component b) has 120 to 350, preferred 180 to 300 OH value.This polyol component preferably comprise have 2-8, the functionality of preferred 2-4 and by alkylene oxide such as oxyethane, propylene oxide, butylene oxide ring, decyl oxyethane or phenyl ethylene oxide, the polyoxyalkylene polyol that optimization ethylene oxide and/or propylene oxide, addition polymerization are obtained to the initiator compound with active hydrogen atom.Employed initiator compound is the compound with two or more terminal hydroxy groups, for example, and water, trolamine, 1,1,2-propylene glycol, 1, ammediol, glycol ether, dipropylene glycol, triglycol, tripropylene glycol, 1,2-butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,2-hexylene glycol, 1, the 3-hexylene glycol, 1,4-hexylene glycol, 1,5-hexylene glycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane and Sorbitol Powder.These initiator compounds can use separately or use as mixture.
One or more polyester polyols also can be with components b) the amount of 10wt.% at the most of total amount be used for polyol component b jointly).Suitable polyester polyol has 200-6,000g/mol, and preferred 200-2, the number-average molecular weight of 400g/mol, and can obtain with the polyvalent alcohol that contains at least two hydroxyls from aromatics and/or aliphatic dicarboxylic acid.The example of dicarboxylic acid is a phthalic acid, m-phthalic acid, terephthalic acid, fumaric acid, toxilic acid, nonane diacid, pentanedioic acid, hexanodioic acid, suberic acid, sebacic acid, propanedioic acid and succsinic acid.Can use pure dicarboxylic acid and their any desirable mixture.The dicarboxylic acid that need not dissociate also can use corresponding dicarboxylic acid derivatives, for example has the dicarboxylic acid list or the diester class of the alcohols of 1-4 carbon atom.This type of ester class for example forms in the recycling of polyester waste material.Dicarboxylic anhydride as Tetra hydro Phthalic anhydride or maleic anhydride, also can be used as acid constituents.Following compound is preferably used as the alkoxide component of esterification: ethylene glycol, glycol ether, Tetraglycol 99,1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane or their mixture.Also might use from lactone for example 6-caprolactone, or hydroxycarboxylic acid, for example polyester polyol of 'omega '-hydroxy carboxylic acid formation.This polyol component can also comprise the polyether ester polyvalent alcohol, can and obtain with reacting ethylene oxide subsequently by Tetra hydro Phthalic anhydride and glycol ether reaction as it.
In the preparation of foams of the present invention, have 4-100 μ m, preferred 4-25 μ m, especially the solid packing of the mean particle size of 10-25 μ m is as amount of component b).Package stability dispersion with the viscosity that is suitable for processing can obtain with this filler.Appropriate filler is, for example, and three aluminium hydroxides, the urea-formaldehyde resin (condensation product of urea and formaldehyde, referring to Houben-Weyl, " Methoden der organi schen Chemie[organic chemistry method] ", the XIV volume, 1963, the 319-402 page or leaf), rock dust or pyrogenic silica; Three aluminium hydroxides are preferred.In order to prepare according to foams of the present invention, filler is dispersed or suspended in polyol component b) or prepolymer a) in, preferably at polyol component b) in.This filler is preferably with 30-55wt.%, and the amount of preferred especially 35-50wt.% is used, based on the amount of suspension agent.
If this filler is dispersed in polyol component b) in, the viscosity that then contains the polyol component of filler should preferably be no more than 6,000mPas, and they can utilize low-pressure pump to carry like this.The viscosity of isocyanate component and the polyol component that contains filler especially preferably is adjusted to approximately identical value, in order that help processing, the especially uniform mixing of each component.
In order to prepare foams of the present invention, water is as whipping agent d), preferably with 0.1-1wt%, the amount of preferred especially 0.6-0.9wt% is added, based on this polyol component b).Most preferably, the amount of water makes the foaming coefficient (Sch umfaktor) that reaches 2-6 through calculating the back, that is, the volume of prepared foams be starting ingredient cumulative volume 2-6 doubly.
In the preparation process of foams of the present invention, can randomly add and to quicken catalyst for reaction e between isocyanate component and polyol component).The example of suitable catalyst is an organo-tin compound, tin (II) salt as organic carboxylic-acid, tin acetate (II) salt for example, stannous octoate (II), thylhexoic acid tin (II) and tin laurate (II), and dialkyl tin (IV) salt, for example dibutyltin diacetate, dibutyl tin dilaurate and oxalic acid dioctyl tin.Other example of suitable catalyst is an amine, as the dimethylaminopropyl urea, and dimethylaminopropyl amine, two (dimethylaminopropyl) amine, diazabicyclo octane, dimethylethanolamine, triethylamine, dimethylcyclohexylam,ne, dimethyl benzyl amine, five methyl diethylentriamine, N, N, N ', N '-tetramethyl butane diamine, N-methylmorpholine, two (dimethyl aminoethyl) ethers and three (dialkyl aminoalkyl)-s-Hexahydrotriazines.
The example of producing the suitable catalyst of polyisocyanic acid ester structure is a sylvite, as potassium acetate or potassium octanoate.Also can use several mixture of catalysts.
Optional also have other additive f) be used for preparation according to foams of the present invention, pigment for example, dyestuff or softening agent are as dioctyl phthalate (DOP).These are usually with the 0-10 weight part, and the amount of preferred 0-5 weight part joins in the polyol component.
The also optional fire retardant that adds, preferably liquid and/or can dissolved in one or more of the component that is used for preparing foams those.Commercially available phosphonium flame retardant is preferred the use, lindol for example, tricresyl phosphate (2-chloropropyl) ester, tricresyl phosphate (2, the 3-dibromopropyl) ester, tricresyl phosphate (1,3-two chloropropyls) ester, bisphosphate four (2-chloroethyl) ethylidene ester, diethyl ethane phosphonic acid ester and diethanolamine ylmethyl diethyl phosphonate.Have fire retardation halogen-containing-and/or phosphorous-polyvalent alcohol also be suitable.Fire retardant is preferably with maximum 35wt.%, and the amount of preferred especially maximum 20wt.% is used, based on components b).
The present invention also provide foams of the present invention in mining and underground works, be used for rock fixed, for example be used for coal and rock fixed on every side and be used to seal to resist the various uses of underground hard coal mining inflow water.
Because geological fault section (St rungszonen) and by extracting caused hollow space out, rock avalanche from the wall has caused the serious interruption of producing and has caused sizable danger to the people of underground operation.
In the consolidation process of rock mass, urethane foam according to the present invention utilizes suitable syringe pump to flow in the fixed rock mass layer of needs via boring.The expansible reaction mixture makes the slit of filling and crack that gluing take place, and therefore causes forming once more the system strength of geology series of rocks; Rock or coal fall can prevent reliably.
According to the preparation of foams of the present invention preferably by with isocyanate component a) and comprise components b), c), d), e) and f) mixture mix by 1: 1 volume ratio and carry out.Preferably be defined as the NCO/OH ratio of 130-300 here, preferred especially 180-260.
The preferred prescription of selecting according to foams of the present invention makes the temperature that reaction mixture reached in the urethane forming process be no more than 120 ℃ top temperature.It is particularly preferred that maximum temperature is no more than 110 ℃ prescription.
Embodiment
Following starting ingredient is used for the following example:
Formulation A
Have the polyol blends of the OH value of 239mg KOH/g, form by following component: the 1) polyethers with OH value 190 of 20.9 weight parts, it is obtained by propylene glycol and reacting ethylene oxide,
2) polyethers with OH value 255mg KOH/g of 78 weight parts, it is obtained by TriMethylolPropane(TMP) and oxyethane and propylene oxide reaction,
3) 0.9 weight part as the water of whipping agent and
4) dibutyl tin laurate as catalyzer of 0.2 weight part.
Formulation B
Have the polyol blends of the OH value of 111mg KOH/g, form by following component:
1) polyethers with OH value 112 of 98.9 weight parts, it is obtained by propylene glycol and propylene oxide reaction,
2) 0.9 weight part as the water of whipping agent and
3) dibutyl tin laurate as catalyzer of 0.2 weight part.
Formulation C
Have the polyol blends of the OH value of 381mg KOH/g, form by following component:
1) polyethers with OH value 385 of 98.9 weight parts, it is obtained by TriMethylolPropane(TMP) and propylene oxide reaction,
2) 0.9 weight part as the water of whipping agent and
3) dibutyl tin laurate as catalyzer of 0.2 weight part.
Formulation D
Have the polyol blends of the OH value of 242mg KOH/g, form by following component:
1) polyethers with OH value 245 of 98.9 weight parts, it is obtained by glycerine and propylene oxide reaction,
2) 0.9 weight part as the water of whipping agent and
3) dibutyl tin laurate as catalyzer of 0.2 weight part.
Isocyanic ester I
Isocyanate prepolymer (Desmodur with NCO content of 25.6wt.%
VP.PU28HS07, Bayer AG, D-51368 Leverkusen); Contain 4 of 60wt.%, 2 of 4 '-two isocyano ditans and 22wt.%, 4 '-two isocyano ditans, with 2 of 3wt.%, the polyisocyanates of 2 '-two isocyano ditans is and by TriMethylolPropane(TMP) and propylene oxide reaction obtained, have OH value 865 the polyether polyol reaction product according to the amount ratio of 92.5wt%MDI/7.5wt% polyvalent alcohol.
Isocyanic ester II
Polyisocyanates (Desmodur with NCO content of 31wt%
44V70 L, BayerAG, D-51368 Leverkusen), it comprises the two isocyano ditan isomer of about 31wt.%, and wherein about 89wt.% is that 4,4 '-two isocyano ditans and about 11wt.% are 2,4 '-two isocyano ditans.
Aluminium hydroxide (Martinal with mean particle size of 15-25 μ m
ON-320, Martinswerk GmbH, D-50127 Bergheim) as solid matter (Feststoff).
These components are tested in the laboratory by known way: these components of about 200 grams are according to 1: 1 volume ratio of isocyanic ester and polyvalent alcohol and mix under 23 ℃ material temperature.This temperature of reaction of middle measurements at sample.After about four hours, the cropped and assess foam structure of sample.
Test-results is shown in the following table 1.
Table 1
| Embodiment | ????1 | ????2 * | ????3 * | ????4 | ????5 | ????6 * | ????7 * | ????8 |
| Polyol component | ||||||||
| A[weight part] | ????55 | ????- | ????- | ????- | ????75 | ????100 | ????55 | ????55 |
| B[weight part] | ????- | ????55 | ????- | ????- | ????- | ????- | ????- | ????- |
| C[weight part] | ????- | ????- | ????55 | ????- | ????- | ????- | ????- | ????- |
| D[weight part] | ????- | ????- | ????- | ????55 | ????- | ????- | ????- | ????- |
| Isocyanate component | ||||||||
| I[weight part] | ????90 | ????90 | ????90 | ????90 | ????90 | ????90 | ????- | ????45 |
| II[weight part] | ????- | ????- | ????- | ????- | ????- | ????- | ????90 | ????45 |
| The OH value of polyol component [mg KOH/g] | ????239 | ????111 | ????381 | ????242 | ????239 | ????239 | ????239 | ????239 |
| The NCO content [wt.%] of isocyanate component | ????25.6 | ????25.6 | ????25.6 | ????25.6 | ????25.6 | ????25.6 | ????31.0 | ????28.1 |
| ????Al(OH) 3[wt.％] | ????45 | ????45 | ????45 | ????45 | ????25 | ????0 | ????45 | ????45 |
| Foam structure | ????A | ????K | ????A | ????A | ????A | ????A | ????K | ????A |
| Maximum temperature [℃] | ????105 | ????68 | ????131 | ????103 | ????115 | ????121 | ????97 | ????99 |
*Not according to comparative example of the present invention
A: acceptable, K: subside
Claims (3)
1. the foams that contain polyurethanyl group can be obtained by following component reaction:
A) have the polyisocyanate component of the NCO content of 20-30wt.%, it comprises the prepolymer that contains isocyanate group of the NCO content with 20-28wt% of 50wt.% at least,
B) have the polyol component of 120 to 350 OH value,
C) be dispersed in polyol component b) or this prepolymer a) in and solid packing with 4-100 μ m mean particle size,
D) water,
E) Ren Xuan catalyzer,
F) Ren Xuan additional additives.
2. according to the preparation method of the foams that contain polyurethanyl group of claim 1, wherein isocyanate component a) with comprise components b), c), d) and optional e) and mixture f) react by 1: 1 volume ratio.
3. be used for purposes according to the foams of claim 1 at mining and underground works consolidated rock.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10018395A DE10018395B4 (en) | 2000-04-13 | 2000-04-13 | Low exothermic polyurethane foams |
| DE10018395.6 | 2000-04-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1422292A true CN1422292A (en) | 2003-06-04 |
| CN1167723C CN1167723C (en) | 2004-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018078915A Expired - Fee Related CN1167723C (en) | 2000-04-13 | 2001-04-02 | Polyurethane foams with reduced exothermy |
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| Country | Link |
|---|---|
| CN (1) | CN1167723C (en) |
| AU (2) | AU6017501A (en) |
| DE (1) | DE10018395B4 (en) |
| HK (1) | HK1054559B (en) |
| PL (1) | PL206612B1 (en) |
| UA (1) | UA73564C2 (en) |
| WO (1) | WO2001079321A1 (en) |
| ZA (1) | ZA200207411B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019001838A (en) * | 2017-06-12 | 2019-01-10 | 旭有機材株式会社 | Agent liquid composition for grouting |
| CN110790883A (en) * | 2019-11-15 | 2020-02-14 | 上海东大聚氨酯有限公司 | Low-heat-release combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070093602A1 (en) * | 2005-10-24 | 2007-04-26 | Bayer Materialscience Llc | Solid polyurethane compositions, infrastucture repair and geo-stabilization processes |
| CN102226088B (en) * | 2011-04-27 | 2013-03-06 | 南京大学 | Polyurethane-based ecological sand-fixing agent and preparation method thereof |
| CN102251517B (en) * | 2011-04-27 | 2013-03-13 | 南京大学 | Dust prevention and sand fixation method |
| EP2706148B1 (en) | 2012-08-30 | 2014-10-15 | TuTech Innovation GmbH | Method for improving the bearing capacity of open profiles placed in the foundation and system created using the same |
| AU2020220093A1 (en) * | 2019-08-26 | 2021-03-18 | Gcp Applied Technologies Inc. | Penetrating single component prepolymer system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1159865B (en) * | 1962-10-31 | 1963-12-19 | Peute Chemie G M B H & Co Kg | Procedures and sealing and consolidation of geological formations |
| CA999400A (en) * | 1972-04-28 | 1976-11-02 | General Tire And Rubber Company (The) | Flame retardant flexible polyurethane foams |
| US4114382A (en) * | 1974-07-26 | 1978-09-19 | Bayer Aktiengesellschaft | Process for the consolidation of geological formations and loosened rock and earth masses |
| DE2524191C3 (en) * | 1975-05-31 | 1980-04-03 | Bayer Ag, 5090 Leverkusen | Process for the production of hole-filled lightweight foams containing hydrophobic urea groups |
| US4454252A (en) * | 1981-03-02 | 1984-06-12 | Bergwerksverband Gmbh | Process of sealing and strengthening water-bearing geological formations by means of polyurethane-resin-forming compositions |
| DE3532387A1 (en) * | 1985-09-11 | 1987-04-23 | Bergwerksverband Gmbh | METHOD FOR STRENGTHENING GEOLOGICAL FORMATIONS |
| DE3704802A1 (en) * | 1987-02-16 | 1987-10-08 | Horst Ing Grad Kaiser | Process for modifying the mechanical properties of polyurethane foams |
-
2000
- 2000-04-13 DE DE10018395A patent/DE10018395B4/en not_active Expired - Fee Related
-
2001
- 2001-02-04 UA UA2002119023A patent/UA73564C2/en unknown
- 2001-04-02 PL PL358663A patent/PL206612B1/en not_active IP Right Cessation
- 2001-04-02 CN CNB018078915A patent/CN1167723C/en not_active Expired - Fee Related
- 2001-04-02 AU AU6017501A patent/AU6017501A/en active Pending
- 2001-04-02 AU AU2001260175A patent/AU2001260175B2/en not_active Ceased
- 2001-04-02 WO PCT/EP2001/003714 patent/WO2001079321A1/en active IP Right Grant
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019001838A (en) * | 2017-06-12 | 2019-01-10 | 旭有機材株式会社 | Agent liquid composition for grouting |
| CN110790883A (en) * | 2019-11-15 | 2020-02-14 | 上海东大聚氨酯有限公司 | Low-heat-release combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof |
| CN110790883B (en) * | 2019-11-15 | 2021-11-23 | 上海东大聚氨酯有限公司 | Low-heat-release combined polyether, polyurethane raw material composition, polyurethane foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| UA73564C2 (en) | 2005-08-15 |
| PL206612B1 (en) | 2010-08-31 |
| WO2001079321A1 (en) | 2001-10-25 |
| DE10018395A1 (en) | 2001-10-31 |
| ZA200207411B (en) | 2003-09-16 |
| DE10018395B4 (en) | 2004-07-15 |
| AU6017501A (en) | 2001-10-30 |
| PL358663A1 (en) | 2004-08-09 |
| HK1054559B (en) | 2005-05-27 |
| CN1167723C (en) | 2004-09-22 |
| HK1054559A1 (en) | 2003-12-05 |
| AU2001260175B2 (en) | 2005-07-21 |
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