AU2013322928A1 - Method for producing porous materials on the basis of isocyanate - Google Patents
Method for producing porous materials on the basis of isocyanate Download PDFInfo
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- AU2013322928A1 AU2013322928A1 AU2013322928A AU2013322928A AU2013322928A1 AU 2013322928 A1 AU2013322928 A1 AU 2013322928A1 AU 2013322928 A AU2013322928 A AU 2013322928A AU 2013322928 A AU2013322928 A AU 2013322928A AU 2013322928 A1 AU2013322928 A1 AU 2013322928A1
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- Prior art keywords
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- components
- gel
- Prior art date
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- 239000011148 porous material Substances 0.000 title claims abstract description 77
- 239000012948 isocyanate Substances 0.000 title claims abstract description 44
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 35
- 238000009413 insulation Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 20
- -1 alkali metal carboxylates Chemical class 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 4
- OAGGYKVXVKGZOZ-UHFFFAOYSA-N 2-amino-1-(dimethylamino)ethanol Chemical compound CN(C)C(O)CN OAGGYKVXVKGZOZ-UHFFFAOYSA-N 0.000 claims description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- WVFDUZNAUQLQQP-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-a][1,3]diazepine Chemical compound N1CCCCN2CCCC=C21 WVFDUZNAUQLQQP-UHFFFAOYSA-N 0.000 claims description 3
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 claims description 3
- OMDXZWUHIHTREC-UHFFFAOYSA-N 1-[2-(dimethylamino)ethoxy]ethanol Chemical compound CC(O)OCCN(C)C OMDXZWUHIHTREC-UHFFFAOYSA-N 0.000 claims description 3
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 claims description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 3
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical class C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims description 3
- HQNOODJDSFSURF-UHFFFAOYSA-N 3-(1h-imidazol-2-yl)propan-1-amine Chemical compound NCCCC1=NC=CN1 HQNOODJDSFSURF-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QJSCFMXSIVOKPS-UHFFFAOYSA-N azane ethyl hexanoate Chemical class N.CCCCCC(=O)OCC QJSCFMXSIVOKPS-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical class CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 claims description 2
- 150000003141 primary amines Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 52
- 239000000499 gel Substances 0.000 description 47
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 32
- 239000011521 glass Substances 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 15
- 125000003277 amino group Chemical group 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 12
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 11
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000005829 trimerization reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000004964 aerogel Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 150000003512 tertiary amines Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 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 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- HYTRYEXINDDXJK-UHFFFAOYSA-N Ethyl isopropyl ketone Chemical compound CCC(=O)C(C)C HYTRYEXINDDXJK-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-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
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 239000012971 dimethylpiperazine Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- 150000004998 toluenediamines Chemical class 0.000 description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- QUPKOUOXSNGVLB-UHFFFAOYSA-N 1,8-diisocyanatooctane Chemical compound O=C=NCCCCCCCCN=C=O QUPKOUOXSNGVLB-UHFFFAOYSA-N 0.000 description 1
- FJWZMLSQLCKKGV-UHFFFAOYSA-N 1-(2-ethylphenyl)propane-1,1-diamine Chemical class CCC1=CC=CC=C1C(N)(N)CC FJWZMLSQLCKKGV-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- HOSWFGMPYWBJMK-UHFFFAOYSA-N 1-benzyl-4-methyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)CC1=CC=CC=C1 HOSWFGMPYWBJMK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RQUBQBFVDOLUKC-UHFFFAOYSA-N 1-ethoxy-2-methylpropane Chemical compound CCOCC(C)C RQUBQBFVDOLUKC-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- IUUONVQOMMQAEH-UHFFFAOYSA-N 1-methyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound CP1(=O)CCC=C1 IUUONVQOMMQAEH-UHFFFAOYSA-N 0.000 description 1
- YUQUHJGNZFFDAA-UHFFFAOYSA-N 1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C=1C=CC=CC=1P1(=O)CCC=C1 YUQUHJGNZFFDAA-UHFFFAOYSA-N 0.000 description 1
- JIEJJGMNDWIGBJ-UHFFFAOYSA-N 1-propan-2-yloxypropane Chemical compound CCCOC(C)C JIEJJGMNDWIGBJ-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 1
- DYVJZCIYRQUXBA-UHFFFAOYSA-N 2,5-dimethyl-3,4-dihydropyran-2-carbaldehyde Chemical compound CC1=COC(C)(C=O)CC1 DYVJZCIYRQUXBA-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- IEMMBWWQXVXBEU-UHFFFAOYSA-N 2-acetylfuran Chemical compound CC(=O)C1=CC=CO1 IEMMBWWQXVXBEU-UHFFFAOYSA-N 0.000 description 1
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- TYEYBOSBBBHJIV-UHFFFAOYSA-M 2-oxobutanoate Chemical compound CCC(=O)C([O-])=O TYEYBOSBBBHJIV-UHFFFAOYSA-M 0.000 description 1
- NPWYTMFWRRIFLK-UHFFFAOYSA-N 3,4-dihydro-2h-pyran-2-carbaldehyde Chemical compound O=CC1CCC=CO1 NPWYTMFWRRIFLK-UHFFFAOYSA-N 0.000 description 1
- UXECSYGSVNRHFN-UHFFFAOYSA-M 3-hydroxypropyl(trimethyl)azanium;formate Chemical compound [O-]C=O.C[N+](C)(C)CCCO UXECSYGSVNRHFN-UHFFFAOYSA-M 0.000 description 1
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 1
- ZMMOYIXZGHJMNI-UHFFFAOYSA-N 3-oxopropanenitrile Chemical compound O=CCC#N ZMMOYIXZGHJMNI-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 1
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- BOPCAWBPVSVBMM-UHFFFAOYSA-N 6-methylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1CC=CCC1C=O BOPCAWBPVSVBMM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical class [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- BRDWIEOJOWJCLU-LTGWCKQJSA-N GS-441524 Chemical compound C=1C=C2C(N)=NC=NN2C=1[C@]1(C#N)O[C@H](CO)[C@@H](O)[C@H]1O BRDWIEOJOWJCLU-LTGWCKQJSA-N 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KAEIHZNNPOMFSS-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1CCC1=CC=CC=C1 KAEIHZNNPOMFSS-UHFFFAOYSA-N 0.000 description 1
- BKAKFCXOCHNIIP-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 Chemical compound N=C=O.N=C=O.CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 BKAKFCXOCHNIIP-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives 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
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- DCFDVJPDXYGCOK-UHFFFAOYSA-N cyclohex-3-ene-1-carbaldehyde Chemical compound O=CC1CCC=CC1 DCFDVJPDXYGCOK-UHFFFAOYSA-N 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- GCHCGDFZHOEXMP-UHFFFAOYSA-L potassium adipate Chemical compound [K+].[K+].[O-]C(=O)CCCCC([O-])=O GCHCGDFZHOEXMP-UHFFFAOYSA-L 0.000 description 1
- 239000001608 potassium adipate Substances 0.000 description 1
- 235000011051 potassium adipate Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- CUNPJFGIODEJLQ-UHFFFAOYSA-M potassium;2,2,2-trifluoroacetate Chemical compound [K+].[O-]C(=O)C(F)(F)F CUNPJFGIODEJLQ-UHFFFAOYSA-M 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 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 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08G2110/0091—Aerogels; Xerogels
Abstract
The invention relates to a method for producing porous materials, comprising the reaction of at least one polyfunctional isocyanate with at least one polyfunctional aromatic amine in the presence of at least one catalyst and one solvent. The invention further relates to the porous materials thus obtained and the use of the porous materials as insulating material in particular for applications in the construction sector and in vacuum insulation panels.
Description
1 Method for producing porous materials on the basis of isocyanate Description 5 The present invention relates to a process for producing porous materials, which comprises reaction of at least one polyfunctional isocyanate with at least one polyfunctional aromatic amine in the presence of at least one catalyst and a solvent. The invention further relates to the porous materials which can be obtained in this way and the use of the porous materials as insulation material, in particular for applications 10 in the building sector and in vacuum insulation panels. Porous materials, for example polymer foams, having pores in the size range of a few microns or significantly below and a high porosity of at least 70% are particularly good thermal insulators on the basis of theoretical considerations. 15 Such porous materials having a small average pore diameter can be, for example, in the form of organic aerogels or xerogels which are produced with a sol-gel process and subsequent drying. In the sol-gel process, a sol based on a reactive organic gel precursor is first produced and the sol is then gelled by means of a crosslinking reaction to form a gel. To obtain a porous material, for example an aerogel, from the 20 gel, the liquid has to be removed. This step will hereinafter be referred to as drying in the interests of simplicity. WO 2011/069959, WO 2012/000917 and WO 2012/059388 describe porous materials based on polyfunctional isocyanates and polyfunctional aromatic amines, where the 25 amine component comprises polyfunctional substituted aromatic amines. The porous materials described are produced by reacting isocyanates with the desired amount of amine in a solvent which is inert toward the isocyanates. The use of catalysts is known from WO 2012/000917 and WO 2012/059388. However, these documents disclose the use of formulations comprising conventional, merely small amounts of catalysts. 30 However, the materials properties, in particular the mechanical stability and/or the compressive strength and also the thermal conductivity, of the known porous materials based on polyurea are not satisfactory for all applications. In particular, the thermal conductivities in the ventilated state are not sufficiently low. In the case of open-cell 35 materials, the ventilated state is the state under ambient pressure of air, whereas in the case of partially or completely closed-cell materials such as rigid polyurethane foams this state is reached only after aging, after the cell gas has gradually been completely replaced. 40 A particular problem associated with the formulations based on isocyanates and amines which are known from the prior art are mixing defects. Mixing defects occur as a result of the high reaction rate between isocyanates and amino groups, since the gelling reaction has already proceeded a long way before complete mixing. Mixing 2 defects lead to porous materials having heterogeneous and unsatisfactory materials properties. A concept for reducing the phenomenon of mixing defects is thus generally desirable. 5 It was therefore an object of the invention to avoid the abovementioned disadvantages. In particular, a porous material which does not have the abovementioned disadvantages, or has them to a reduced extent, should be provided. The porous materials should, compared to the prior art, have improved thermal conductivity at low pressures. In particular, however, the porous materials should have a low thermal 10 conductivity in the ventilated state, i.e. at atmospheric pressure. Furthermore, the porous material should at the same time have a high porosity, a low density and a sufficiently high mechanical stability. Finally, mixing defects and thus the heterogeneities in the structure and the materials 15 properties of the porous materials formed in the reaction of the isocyanates with the amines should be avoided. We have accordingly found the process of the invention and the porous materials which can be obtained in this way. The porous materials of the present invention are 20 preferably aerogels or xerogels, in particular aerogels. The process of the invention for producing a porous material comprises reacting the following components: 25 (al) from 25 to 94.9% by weight of at least one polyfunctional isocyanate, and (a2) from 0.1 to 30% by weight of at least one polyfunctional aromatic amine having the general formula I Q2 Q 3 R2 30 where R 1 and R 2 can be identical or different and are each selected independently from among hydrogen and linear or branched alkyl groups having from 1 to 6 carbon atoms and all substituents Q1 to Q 5 and Q 1 ' to Q' are identical or different and are each 35 selected independently from among hydrogen, a primary amino group and a linear or branched alkyl group having from 1 to 12 carbon atoms, where the alkyl group can bear further functional groups, with the proviso that the compound having the general formula I comprises at least two primary amino groups, where at least one of Q1, Q 3 3 and Q 5 is a primary amino group and at least one of Q 1 ', Q 3 ' and Q 5 ' is a primary amino group, (a3) from 0 to 15% by weight of water, and 5 (a4) from 5 to 30% by weight of at least one catalyst, in each case based on the total weight of the components (al) to (a4), where the % by weight of the components (al) to (a4) add up to 100% by weight and the reaction is carried out in the presence of a solvent (C) which is removed after the reaction. 10 Preferred embodiments may be found in the claims and the description. Combinations of preferred embodiments do not go outside the scope of the present invention. Preferred embodiments of the components used are described below. 15 The polyfunctional isocyanates (al) will hereinafter be referred to collectively as component (al). Analogously, the polyfunctional amines (a2) will hereinafter be referred to collectively as component (a2). It will be obvious to a person skilled in the art that the monomer components mentioned are present in reacted form in the porous material. 20 For the purposes of the present invention, the functionality of a compound is the number of reactive groups per molecule. In the case of the monomer component (al), the functionality is the number of isocyanate groups per molecule. In the case of the amino groups of the monomer component (a2), the functionality is the number of 25 reactive amino groups per molecule. A polyfunctional compound has a functionality of at least 2. If mixtures of compounds having different functionalities are used as component (al) or (a2), the functionality of the components is in each case given by the number average 30 of the functionality of the individual compounds. A polyfunctional compound comprises at least two of the abovementioned functional groups per molecule. For the purposes of the present invention, a xerogel is a porous material which has been produced by a sol-gel process in which the liquid phase has been removed from 35 the gel by drying below the critical temperature and below the critical pressure of the liquid phase subcriticalal conditions"). An aerogel is a porous material which has been produced by a sol-gel process in which the liquid phase has been removed from the gel under supercritical conditions. 40 The reaction is preferably carried out using from 35 to 93.8% by weight, in particular from 40 to 92.6% by weight, of component (a1), from 0.2 to 25% by weight, in particular from 0.4 to 23% by weight, of component (a2), from 0 to 10% by weight, in particular from 0 to 9% by weight, of water and from 6 to 30% by weight, in particular from 7 to 4 28% by weight, of component (a4), in each case based on the total weight of the components (al) to (a4), where the % by weight of the components (al) to (a4) add up to 100% by weight. 5 The reaction is particularly preferably carried out using from 50 to 92.5% by weight, in particular from 57 to 91.3% by weight, of component (al), from 0.5 to 18% by weight, in particular from 0.7 to 16% by weight, of component (a2), from 0 to 8% by weight, in particular from 0 to 6% by weight, of water and from 7 to 24% by weight, in particular from 8 to 21% by weight, of component (a4), in each case based on the total weight of 10 the components (al) to (a4), where the % by weight of the components (al) to (a4) add up to 100% by weight. Within the abovementioned preferred ranges, the resulting gels are particularly stable and do not shrink or shrink only slightly in the subsequent drying step. 15 Component (al) In the process of the invention, at least one polyfunctional isocyanate is reacted as component (al). 20 Preferably the amount of component (al) used is at least 35, in particular at least 40, particularly preferably at least 45% by weight, especially at least 57% by weight. Preferably the amount of component (al) used is at most 93.8% by weight, in particular at most 92.6% by weight, particularly preferably at most 92.5% by weight, especially at 25 most 91.3% by weight, in each case based on the total weight of the components (al) to (a4). Possible polyfunctional isocyanates are aromatic, aliphatic, cycloaliphatic and/or araliphatic isocyanates. Such polyfunctional isocyanates are known per se or can be 30 prepared by methods known per se. The polyfunctional isocyanates can also be used, in particular, as mixtures, so that the component (al) in this case comprises various polyfunctional isocyanates. Polyfunctional isocyanates which are possible as monomer building blocks (al) have two (hereinafter referred to as diisocyanates) or more than two isocyanate groups per molecule of the monomer component. 35 Particularly suitable polyfunctional isocyanates are diphenylmethane 2,2'-, 2,4'- and/or 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), tolylene 2,4- and/or 2,6 diisocyanate (TDI), 3,3'-dimethylbiphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or p-phenylene diisocyanate (PPDI), trimethylene, tetramethylene, 40 pentamethylene, hexamethylene, heptamethylene and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isocyanato-3,3,5 trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 5 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4- and/or 2,6-diisocyanate and dicyclohexylmethane 4,4'-, 2,4' and/or 2,2'-diisocyanate. 5 As polyfunctional isocyanates (a1), preference is given to aromatic isocyanates. Particularly preferred polyfunctional isocyanates of the component (al) are the following embodiments: i) polyfunctional isocyanates based on tolylene diisocyanate (TDI), in particular 2,4 10 TDI or 2,6-TDI or mixtures of 2,4- and 2,6-TDI; ii) polyfunctional isocyanates based on diphenylmethane diisocyanate (MDI), in particular 2,2'-MDI or 2,4'-MDI or 4,4'-MDI or oligomeric MDI, also referred to as polyphenylpolymethylene isocyanate, or mixtures of two or three of the abovementioned diphenylmethane diisocyanates or crude MDI which is obtained 15 in the production of MDI or mixtures of at least one oligomer of MDI and at least one of the abovementioned low molecular weight MDI derivatives; iii) mixtures of at least one aromatic isocyanate according to embodiment i) and at least one aromatic isocyanate according to embodiment ii). 20 Oligomeric diphenylmethane diisocyanate is particularly preferred as polyfunctional isocyanate. Oligomeric diphenylmethane diisocyanate (hereinafter referred to as oligomeric MDI) is an oligomeric condensation product or a mixture of a plurality of oligomeric condensation products and thus a derivative/derivatives of diphenylmethane diisocyanate (MDI). The polyfunctional isocyanates can preferably also be made up of 25 mixtures of monomeric aromatic diisocyanates and oligomeric MDI. Oligomeric MDI comprises one or more condensation products of MDI which have a plurality of rings and a functionality of more than 2, in particular 3 or 4 or 5. Oligomeric MDI is known and is frequently referred to as polyphenylpolymethylene isocyanate or 30 as polymeric MDI. Oligomeric MDI is usually made up of a mixture of MDI-based isocyanates having various functionalities. Oligomeric MDI is usually used in admixture with monomeric MDI. The (average) functionality of an isocyanate comprising oligomeric MDI can vary in the 35 range from about 2.2 to about 5, in particular from 2.4 to 3.5, in particular from 2.5 to 3. Such a mixture of MDI-based polyfunctional isocyanates having various functionalities is, in particular, crude MDI which is obtained in the production of MDI. Polyfunctional isocyanates or mixtures of a plurality of polyfunctional isocyanates 40 based on MDI are known and are marketed, for example, by BASF Polyurethanes GmbH under the name Lupranat@.
6 The functionality of the component (al) is preferably at least two, in particular at least 2.2 and particularly preferably at least 2.5. The functionality of the component (al) is preferably from 2.2 to 4 and particularly preferably from 2.5 to 3. 5 The content of isocyanate groups in the component (al) is preferably from 5 to 10 mmol/g, in particular from 6 to 9 mmol/g, particularly preferably from 7 to 8.5 mmol/g. A person skilled in the art will know that the content of isocyanate groups in mmol/g and the equivalent weight in g/equivalent have a reciprocal relationship. The content of isocyanate groups in mmol/g can be derived from the content in % by weight 10 in accordance with ASTM D-5155-96 A. In a preferred embodiment, the component (al) comprises at least one polyfunctional isocyanate selected from among diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate and oligomeric diphenylmethane 15 diisocyanate. In this preferred embodiment, the component (al) particularly preferably comprises oligomeric diphenylmethane diisocyanate and has a functionality of at least 2.5. The viscosity of the component (al) used can vary within a wide range. The 20 component (al) preferably has a viscosity of from 100 to 3000 mPa.s, particularly preferably from 200 to 2500 mPa.s. Component (a2) 25 According to the invention, at least one polyfunctional substituted aromatic amine (a2) having the general formula I Q2 Q 3 Q3' Q 2 R2 41 / \" | / \ Q4 Q" QS Q (I), 30 where R 1 and R 2 can be identical or different and are each selected independently from among hydrogen and linear or branched alkyl groups having from I to 6 carbon atoms and all substituents Q 1 to Q 5 and Q 1 ' to Q 5 ' are identical or different and are each selected independently from among hydrogen, a primary amino group and a linear or branched alkyl group having from 1 to 12 carbon atoms, where the alkyl group can 35 bear further functional groups, with the proviso that the compound having the general formula I comprises at least two primary amino groups, where at least one of Q 1 , Q 3 and Q 5 is a primary amino group and at least one of Q 1 ', Q 3 ' and Q 5 ' is a primary amino group, is/are reacted as component (a2) in the presence of a solvent (C).
7 In a preferred embodiment, Q 2 , Q 4 , Q 2 ' and Q 4 ' are selected so that the compound having the general formula I has at least one linear or branched alkyl group, which can bear further functional groups, having from 1 to 12 carbon atoms in the a position 5 relative to at least one primary amino group bound to the aromatic ring. Component (a2) in this case comprises polyfunctional aromatic amines (a2-s). For the purposes of the present invention, polyfunctional amines are amines which have at least two amino groups which are reactive toward isocyanates per molecule. 10 Here, primary and secondary amino groups are reactive toward isocyanates, with the reactivity of primary amino groups generally being significantly higher than that of secondary amino groups. The amount of component (a2) used is preferably at least 0.2, in particular at least 0.4, 15 particularly preferably at least 0.7% by weight, especially at least 1 % by weight. The amount of component (a2) used is preferably at most 25% by weight, in particular at most 23% by weight, particularly preferably at most 20% by weight, especially at most 18% by weight, in each case based on the total weight of the components (al) to (a4). In a very particularly preferred embodiment, the amount of component (a2) used is at 20 least 5 and at most 20% by weight, based on the total weight of the components (al) to (a4). According to the invention, R 1 and R 2 in the general formula I are identical or different and are each selected independently from among hydrogen, a primary amino group 25 and a linear or branched alkyl group having from 1 to 6 carbon atoms. R 1 and R 2 are preferably selected from among hydrogen and methyl. Particular preference is given to R1 = R2 = H. In a particularly preferred embodiment Q 2 , Q 4 , Q 2 ' and Q 4 ' are selected so that the 30 substituted aromatic amine (a2-s) comprises at least two primary amino groups, where in each case one or two linear or branched alkyl groups having from I to 12 carbon atoms are located in the a position relative to the primary amino groups bound to the aromatic ring, where the alkyl groups may optionally bear further functional groups. If one or more of Q 2 , Q 4 , Q 2 ' and Q 4 ' are selected so that they correspond to linear or 35 branched alkyl groups which have from 1 to 12 carbon atoms and bear further functional groups, preference is given to amino groups and/or hydroxy groups and/or halogen atoms as such functional groups. The reduced reactivity brought about by the abovementioned alkyl groups in the a 40 position leads, in combination with the use of the component (a4) described in more detail below, to particularly stable gels having particularly good thermal conductivities in the ventilated state.
8 The alkyl groups as substituents Q in the general formula I are preferably selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. The amines (a2-s) are preferably selected from the group consisting of 3,3',5,5' 5 tetraalkyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraalkyl-2,2'-diaminodiphenyl methane and 3,3',5,5'-tetraalkyl-2,4'-diaminodiphenylmethane, where the alkyl groups in the 3,3',5 and 5' positions can be identical or different and are each selected independently from among linear or branched alkyl groups which have from 1 to 12 carbon atoms and can bear further functional groups. The abovementioned alkyl 10 groups are preferably methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl or t-butyl (in each case unsubstituted). In one embodiment, one, more than one or all hydrogen atoms of one or more alkyl groups of the substituents Q can have been replaced by halogen atoms, in particular 15 chlorine. As an alternative, one, more than one or all hydrogen atoms of one or more alkyl groups of the substituents Q can have been replaced by NH 2 or OH. However, the alkyl groups in the general formula I are preferably made up of carbon and hydrogen. In a particularly preferred embodiment, component (a2) comprises 3,3',5,5'-tetraalkyl 20 4,4'-diaminodiphenylmethane, where the alkyl groups can be identical or different and are each selected independently from among linear or branched alkyl groups which have from 1 to 12 carbon atoms and can optionally bear functional groups. The abovementioned alkyl groups are preferably selected from among unsubstituted alkyl groups, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl, 25 particularly preferably methyl and ethyl. Very particular preference is given to 3,3',5,5' tetraethyl-4,4'-diaminodiphenylmethane and/or 3,3',5,5'-tetramethyl-4,4' diaminodiphenylmethane. The abovementioned polyfunctional amines of the type (a2-s) are known per se to 30 those skilled in the art or can be prepared by known methods. One of the known methods is the reaction of aniline or derivatives of aniline with formaldehyde in the presence of an acid catalyst, in particular the reaction of 2,4- or 2,6-dialkylaniline. The component (a2) can optionally also comprise polyfunctional aromatic amines (a2 35 u) which differ from the amines of the structure (a2-s). The aromatic amines (a2-u) preferably have exclusively aromatically bound amino groups, but can also have both (cyclo)aliphatically and aromatically bound reactive amino groups. Suitable polyfunctional aromatic amines (a2-u) are, in particular, isomers and 40 derivatives of diaminodiphenylmethane. Isomers and derivatives of diaminodiphenylmethane which are preferred as constituents of component (a2) are, in particular, 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2' diaminodiphenylmethane and oligomeric diaminodiphenylmethane.
9 Further suitable polyfunctional aromatic amines (a2-u) are, in particular, isomers and derivatives of toluenediamine. Isomers and derivatives of toluenediamine which are preferred as constituents of component (a2) are, in particular, toluene-2,4-diamine 5 and/or toluene-2,6-diamine and diethyltoluenediamines, in particular 3,5-diethyltoluene 2,4-diamine and/or 3,5-diethyltoluene-2,6-diamine. In a first, particularly preferred embodiment, component (a2) consists exclusively of polyfunctional aromatic amines of the type (a2-s). In a second preferred embodiment, 10 component (a2) comprises polyfunctional aromatic amines of the types (a2-s) and (a2-u). In the latter, second preferred embodiment, the component (a2) preferably comprises at least one polyfunctional aromatic amine (a2-u), of which at least one is selected from among isomers and derivatives of diaminodiphenyl methane (MDA). 15 In the second preferred embodiment, component (a2) correspondingly particularly preferably comprises at least one polyfunctional aromatic amine (a2-u) selected from among 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2' diaminodiphenylmethane and oligomeric diaminodiphenylmethane. 20 Oligomeric diaminodiphenylmethane comprises one or more methylene-bridged condensation products of aniline and formaldehyde having a plurality of rings. Oligomeric MDA comprises at least one oligomer, but in general a plurality of oligomers, of MDA having a functionality of more than 2, in particular 3 or 4 or 5. Oligomeric MDA is known or can be prepared by methods known per se. Oligomeric 25 MDA is usually used in the form of mixtures with monomeric MDA. The (average) functionality of a polyfunctional amine (a2-u) comprising oligomeric MDA can vary in the range from about 2.3 to about 5, in particular from 2.3 to 3.5 and in particular from 2.3 to 3. One such mixture of MDA-based polyfunctional amines having 30 differing functionalities is, in particular, crude MDA which is formed, in particular, as intermediate in the condensation of aniline with formaldehyde, usually catalyzed by hydrochloric acid, in the production of crude MDI. In the abovementioned preferred second embodiment, particular preference is given to 35 the component (a2) comprising oligomeric diaminodiphenylmethane as compound (a2-u) and having an overall functionality of at least 2.1. The proportion of amines of type (a2-s) having the general formula I based on the total weight of all polyfunctional amines of the component (a2), which thus add up to a total 40 of 100% by weight, is preferably from 10 to 100% by weight, in particular from 30 to 100% by weight, very particularly preferably from 50 to 100% by weight, in particular from 80 to 100% by weight.
10 The proportion of polyfunctional aromatic amines (a2-u) which differ from the amines of type (a2-s) based on the total weight of all polyfunctional amines of the component (a2) is preferably from 0 to 90% by weight, in particular from 0 to 70% by weight, particularly preferably from 0 to 50% by weight, in particular from 0 to 20% by weight. 5 Component a3 Component (a3) is water. If water is used, the preferred amount of water used is at least 0.01% by weight, in particular at least 0.1% by weight, particularly preferably at 10 least 0.5% by weight, in particular at least 1 % by weight. If water is used, the preferred amount of water used is at most 15% by weight, in particular at most 13% by weight, particularly preferably at most 11 % by weight, in particular at most 10% by weight, very particularly preferably at most 9% by weight, in particular at most 8% by weight, in each case based on the total weight of the components (al) to (a4), which is 100% by 15 weight. A calculated content of amino groups can be derived from the water content and the content of reactive isocyanate groups of the component (al) by assuming complete reaction of the water with the isocyanate groups of the component (al) to form a 20 corresponding number of amino groups and adding this content to the content resulting from component (a2) (total namine). The resulting use ratio of the calculated remaining NCO groups nNCO to the amino groups calculated to have been formed and used will hereinafter be referred to as calculated use ratio nNcO/namine and is an equivalence ratio, i.e. a molar ratio of the respective functional groups. 25 Water reacts with the isocyanate groups to form amino groups and liberate CO 2 . Polyfunctional amines are therefore partially produced as intermediate (in situ). In the further course of the reaction, they are reacted with isocyanate groups to form urea linkages. The production of amines as intermediate leads to porous materials having 30 particularly high mechanical stability and low thermal conductivity. However, the CO 2 formed must not disrupt gelling to such an extent that the structure of the resulting porous material is influenced in an undesirable way. This gives the abovementioned preferred upper limits for the water content based on the total weight of the components (al) to (a4). 35 In this case, the calculated use ratio (equivalence ratio) nNCO/namine is preferably from 1.01 to 5. The equivalence ratio mentioned is particularly preferably from 1.1 to 3, in particular from 1.1 to 2. An excess of nNCO over namine leads, in this embodiment, to lower shrinkage of the porous material, in particular xerogel, in the removal of the 40 solvent and as a result of synergistic interaction with the catalyst (a4) to an improved network structure and to improved final properties of the resulting porous material.
11 The components (al) to (a4) will hereinafter be referred to collectively as organic gel precursor (A). It will be obvious to a person skilled in the art that the partial reaction of the component (al) to (a4) leads to the actual gel precursor (A) which is subsequently converted into a gel. 5 Catalyst (a4) The amount of component (a4) used is preferably at least 6% by weight, in particular at least 7% by weight, particularly preferably at least 8% by weight, in particular at least 10 9% by weight. The amount of component (a4) used is preferably at most 30% by weight, in particular at most 28% by weight, particularly preferably at most 24% by weight, in particular at most 21% by weight, in each case based on the total weight of the components (al) to (a4). 15 Possible catalysts are in principle all catalysts known to those skilled in the art which accelerate the trimerization of isocyanates (known as trimerization catalysts) and/or the reaction of isocyanates with amino groups (known as gelling catalysts) and/or the reaction of isocyanates with water (known as blowing catalysts). 20 The corresponding catalysts are known per se and have different relative activities in respect of the abovementioned three reactions. Depending on the relative activity, they can thus be assigned to one or more of the abovementioned types. Furthermore, it will be known to a person skilled in the art that reactions other than those mentioned above can also occur. 25 Corresponding catalysts can be characterized, inter alia, according to their gelling to blowing ratio, as is known, for example, from Polyurethane, 3rd edition, G. Oertel, Hanser Verlag, Munich, 1993. 30 Preferred catalysts (a4) have a balanced gelling to blowing ratio, so that the reaction of the component (al) with water is not too strongly accelerated, leading to an adverse effect on the network structure, and at the same time results in a short gelling time so that the demolding time is advantageously short. Preferred catalysts at the same time have a significant activity in respect of trimerization. This favorably influences the 35 homogeneity of the network structure, resulting in particularly advantageous mechanical properties. The catalysts can be able to be incorporated as a monomer building block (incorporatable catalyst) or not be able to be incorporated. 40 Catalysts suitable as component (a4) are in particular selected from the group consisting of primary, secondary and tertiary amines, triazine derivatives, organic metal compounds, metal chelates, organophosphorus compounds, in particular oxides of 12 phospholenes, quaternary ammonium salts, ammonium hydroxides, alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal alkoxides and ammonium and metal salts of carboxylic acids. 5 Suitable organophosphorus compounds, in particular oxides of phospholenes, are, for example, 1-methylphospholene oxide, 3-methyl-1-phenylphospholene oxide, 1 -phenylphospholene oxide, 3-methyl-1 -benzylphospholene oxide. The suitable catalysts are preferably trimerization catalysts. Suitable trimerization 10 catalysts are in particular strong bases, for example quaternary ammonium hydroxides such as tetraalkylammonium hydroxides having from 1 to 4 carbon atoms in the alkyl radical and benzyltrimethylammonium hydroxide, alkali metal hydroxides such as potassium or sodium hydroxide and alkali metal alkoxides such as sodium methoxide, potassium and sodium ethoxide and potassium isopropoxide. 15 Further suitable trimerization catalysts are, in particular, the ammonium and metal salts of carboxylic acids described further below and N-hydroxyalkyl quaternary ammonium carboxylates, e.g. trimethylhydroxypropylammonium formate. 20 Tertiary amines are also known per se to those skilled in the art as trimerization catalysts. Tertiary amines, i.e. compounds having at least one tertiary amino group, are particularly preferred as catalysts (a4). Suitable tertiary amines having distinct properties as trimerization catalysts are, in particular, N,N',N"-tris(dialkylaminoalkyl)-s hexahydrotriazines, such as N,N',N"-tris(dimethylaminopropyl)-s-hexahydrotriazine, 25 tris(dimethylaminomethyl)phenol. Metal-organic compounds are known per se as gel catalysts to a person skilled in the art. Tin-organic compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate are particularly preferred. 30 Tertiary amines are also known per se as gel catalysts to a person skilled in the art. As mentioned above, tertiary amines are particularly preferred as catalysts (a4). Suitable tertiary amines having good properties as gel catalysts are, in particular, N,N-dimethyl benzylamine, N,N'-dimethylpiperazine and N,N-dimethylcyclohexylamine and also 35 dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, N,N,N,N,N-pentamethyl diethylenetriamine, methylimidazole, dimethylimidazole, aminopropylimidazole, dimethylbenzylamine, 1,6-diazabicyclo[5.4.0]undec-7-ene, triethylamine, triethylenediamine (1,4-diazabicyclo[2.2.2]octane), dimethylaminoethanolamine, dimethylaminopropylamine, N,N-dimethylaminoethoxyethanol, N,N,N-trimethylamino 40 ethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine and butyldiethanolamine.
13 Catalysts which are particularly preferred as component (a4) are selected from the group consisting of dimethylcyclohexylamine, dimethylpiperazine, bis(2 dimethylaminoethyl) ether, N,N,N,N,N-pentamethyldiethylenetriamine, methylimidazole, dimethylimidazole, aminopropylimidazole, dimethylbenzylamine, 1,6-diazabicyclo 5 [5.4.0]undec-7-ene, trisdimethylaminopropylhexahydrotriazine, triethylamine, tris(dimethylaminomethyl)phenol, triethylenediamine (diazabicyclo[2.2.2]octane), dimethylaminoethanolamine, dimethylaminopropylamine, N,N-dimethylaminoethoxy ethanol, N,N,N-trimethylaminoethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, diisopropanolamine, methyldiethanolamine, butyldiethanolamine, 10 metal acetylacetonates, ammonium ethylhexanoates and metal ethylhexanoates. Very particular preference is given to dimethylcyclohexylamine, dimethylpiperazine, methylimidazole, dimethylimidazole, dimethylbenzylamine, 1,6-diazabicyclo[5.4.0] undec-7-ene, trisdimethylaminopropylhexahydrotriazine, triethylarnmine, tris(dimethylaminomethyl)phenol, triethylenediamine (diazabicyclo[2.2.2]octane), 15 dimethylaminoethanolamine, dimethylaminopropylamine, N,N,N-trimethylaminoethyl ethanolamine, triethanolamine, diethanolamine, methyldiethanolamine, butyldiethanolamine, ammonium ethylhexanoates and metal ethylhexanoates. In addition, very particular preference is given to using carboxylates as catalyst. 20 Preferred carboxylates have an alkali metal, alkaline earth metal or ammonium ion as cation, i.e. they are corresponding salts of carboxylic acids. Preferred carboxylates are formates, acetates, 2-ethylhexanoates, trifluoroacetates, adipates, benzoates and saturated or unsaturated long-chain fatty acid salts which have from 10 to 20 carbon atoms and optionally have OH groups on the side group. 25 Very particularly preferred catalysts are selected from among potassium formate, sodium acetate, potassium acetate, cesium acetate, potassium 2-ethylhexanoate, potassium trifluoroacetate, potassium adipate, sodium benzoate and alkali metal salts of saturated or unsaturated long-chain fatty acid salts which have from 10 to 20 carbon 30 atoms and optionally have OH groups on the side group. According to the present invention, the reaction takes place in the presence of a solvent (C). 35 For the purposes of the present invention, the term solvent (C) comprises liquid diluents, i.e. both solvents in the narrower sense and also dispersion media. The mixture can, in particular, be a true solution, a colloidal solution or a dispersion, e.g. an emulsion or suspension. The mixture is preferably a true solution. The solvent (C) is a compound which is liquid under the conditions of step (a), preferably an organic 40 solvent. The solvent (C) can in principle be an organic compound or a mixture of a plurality of compounds, with the solvent (C) being liquid under the temperature and pressure 14 conditions under which the mixture is provided in step (a) (dissolution conditions for short). The composition of the solvent (C) is selected so that it is able to dissolve or disperse, preferably dissolve, the organic gel precursor. Preferred solvents (C) are those which are a solvent for the organic gel precursor (A), i.e. ones which dissolve the 5 organic gel precursor (A) completely under the reaction conditions. The reaction product of the reaction in the presence of the solvent (C) is initially a gel, i.e. a viscoelastic chemical network which is swollen by the solvent (C). A solvent (C) which is a good swelling agent for the network formed in step (b) generally leads to a 10 network having fine pores and a small average pore diameter, while a solvent (C) which is a poor swelling agent for the gel resulting from step (b) generally leads to a coarse-pored network having a large average pore diameter. The choice of the solvent (C) thus influences the desired pore size distribution and the 15 desired porosity. The choice of the solvent (C) is also generally made in such a way that precipitation or flocculation due to formation of a precipitated reaction product does not occur to a significant extent during or after step (b) of the process of the invention. When a suitable solvent (C) is chosen, the proportion of precipitated reaction product is 20 usually less than I % by weight, based on the total weight of the mixture. The amount of precipitated product formed in a particular solvent (C) can be determined gravimetrically by filtering the reaction mixture through a suitable filter before the gelling point. 25 Possible solvents (C) are the solvents known from the prior art for isocyanate-based polymers. Preferred solvents are those which are a solvent for the components (al) to (a4), i.e. solvents which dissolve the constituents of the components (al) to (a4) virtually completely under the reaction conditions. The solvent (C) is preferably inert, i.e. unreactive, toward component (al). 30 Possible solvents (C) are, for example, ketones, aldehydes, alkyl alkanoates, amides such as formamide and N-methylpyrollidone, sulfoxides such as dimethyl sulfoxide, aliphatic and cycloaliphatic halogenated hydrocarbons, halogenated aromatic compounds and fluorine-containing ethers. Mixtures of two or more of the 35 abovementioned compounds are likewise possible. Further possibilities as solvent (C) are acetals, in particular diethoxymethane, dimethoxymethane and 1,3-dioxolane. 40 Dialkyl ethers and cyclic ethers are likewise suitable as solvents (C). Preferred dialkyl ethers are, in particular, those having from 2 to 6 carbon atoms, in particular methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, propyl ethyl ether, ethyl isopropyl ether, dipropyl ether, propyl isopropyl ether, diisopropyl ether, methyl 15 butyl ether, methyl isobutyl ether, methyl t-butyl ether, ethyl n-butyl ether, ethyl isobutyl ether and ethyl t-butyl ether. Preferred cyclic ethers are, in particular, tetrahydrofuran, dioxane and tetrahydropyran. 5 Aldehydes and/or ketones are particularly preferred as solvents (C). Aldehydes or ketones suitable as solvents (C) are, in particular, those corresponding to the general formula R 2 -(CO)-R1, where R 1 and R 2 are each hydrogen or an alkyl group having 1, 2, 3 or 4 carbon atoms. Suitable aldehydes or ketones are, in particular, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, 10 valeraldehyde, isopentaldehyde, 2-methylpentaldehyde, 2-ethyihexaldehyde, acrolein, methacrolein, crotonaldehyde, furfural, acrolein dimer, methacrolein dimer, 1,2,3,6 tetrahydrobenzaldehyde, 6-methyl-3-cyclohexenaldehyde, cyanoacetaldehyde, ethyl glyoxylate, benzaldehyde, acetone, methyl isobutyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, ethyl isopropyl ketone, 15 2-acetylfuran, 2-methoxy-4-methylpentan-2-one, cyclohexanone and acetophenone. The abovementioned aldehydes and ketones can also be used in the form of mixtures. Ketones and aldehydes having alkyl groups having up to 3 carbon atoms per substituent are preferred as solvents (C). Particular preference is given to methyl ethyl ketone. 20 Further preferred solvents are alkyl alkanoates, in particular methyl formate, methyl acetate, ethyl formate, butyl acetate, ethyl acetate and ethyl acetoacetate. Ethyl acetate is particularly preferred. Preferred halogenated solvents are described in WO 00/24799, page 4, line 12 to page 5, line 4. 25 In many cases, particularly suitable solvents (C) are obtained by using two or more completely miscible compounds selected from the abovementioned solvents in the form of a mixture. 30 To obtain a sufficiently stable gel which does not shrink too much during drying in step (c) in step (b), the proportion of the components (al) to (a4) based on the total weight of the components (al) to (a4) and the solvent (C), which is 100% by weight, must generally be not less than 5% by weight. The proportion of the components (al) to (a4) based on the total weight of the components (al) to (a4) and the solvent (C), which is 35 100% by weight, is preferably at least 6% by weight, particularly preferably at least 8% by weight, in particular at least 10% by weight. On the other hand, the concentration of the components (al) to (a4) in the mixture provided must not be too high since otherwise no porous material having favorable 40 properties is obtained. In general, the proportion of the components (al) to (a4) based on the total weight of the components (al) to (a4) and the solvent (C), which is 100% by weight, is not more than 40% by weight. The proportion of the components (al) to (a4) based on the total weight of the components (al) to (a4) and the solvent (C), 16 which is 100% by weight, is preferably not more than 35% by weight, particularly preferably not more than 25% by weight, in particular not more than 20% by weight. The total proportion by weight of the components (al) to (a4) based on the total weight 5 of the components (al) to (a4) and the solvent (S), which is 100% by weight, is preferably from 8 to 25% by weight, in particular from 10 to 20% by weight, particularly preferably from 12 to 18% by weight. Adherence to the amount of the starting materials in the range mentioned leads to porous materials having a particularly advantageous pore structure, low thermal conductivity and low shrinking during drying. 10 Before the reaction, it is necessary to mix the components used, in particular to mix them homogeneously. The rate of mixing should be high relative to the rate of the reaction in order to avoid mixing defects. Appropriate mixing methods are known per se to those skilled in the art. 15 Preferred process for producing the porous materials In a preferred embodiment, the process of the invention comprises at least the following steps: 20 (a) provision of the components (al) to (a4) and the solvent (C) as described above, (b) reaction of the components (al) to (a4) in the presence of the solvent (C) to form a gel and (c) drying of the gel obtained in the preceding step. 25 Preferred embodiments of steps (a) to (c) will be described in detail below. Step (a) 30 According to the invention, the components (al) to (a4) and the solvent (C) are provided in step (a). The components (al) and (a2) are preferably provided separately from one another, each in a suitable partial amount of the solvent (C). The separate provision makes it 35 possible for the gelling reaction to be optimally monitored or controlled before and during mixing. Component (a3) and (a4) is particularly preferably provided as a mixture with component (a2), i.e. separately from component (al). This avoids the reaction of water 40 or of the component (a4) with component (al) to form networks without the presence of component (a2). The prior mixing of water with component (al) otherwise leads to less favorable properties in respect of the homogeneity of the pore structure and the thermal conductivity of the resulting materials.
17 The mixture or mixtures provided in step (a) can also comprise customary auxiliaries known to those skilled in the art as further constituents. Mention may be made by way of example of surface-active substances, flame retardants, nucleating agents, oxidation 5 stabilizers, lubricants and mold release agents, dyes and pigments, stabilizers, e.g. against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, IR opacifiers, reinforcing materials and biocides. Further information regarding the abovementioned auxiliaries and additives may be 10 found in the specialist literature, e.g. in Plastics Additive Handbook, 5th edition, H. Zweifel, ed. Hanser Publishers, Munich, 2001. Step (b) 15 According to the invention, the reaction of the components (al) to (a4) takes place in the presence of the solvent (C) to form a gel in step (b). To carry out the reaction, a homogeneous mixture of the components provided in step (a) firstly has to be produced. 20 The provision of the components provided in step (a) can be carried out in a conventional way. A stirrer or another mixing device is preferably used here in order to achieve good and rapid mixing. The time required for producing the homogeneous mixture should be short in relation to the time during which the gelling reaction leads to at least partial formation of a gel, in order to avoid mixing defects. The other mixing 25 conditions are generally not critical; for example, mixing can be carried out at from 0 to 1000C and from 0.1 to 10 bar (absolute), in particular at, for example, room temperature and atmospheric pressure. After a homogeneous mixture has been produced, the mixing apparatus is preferably switched off. 30 The gelling reaction is a polyaddition reaction, in particular a polyaddition of isocyanate groups and amino groups. For the purposes of the present invention, a gel is a crosslinked system based on a polymer which is present in contact with a liquid (known as Solvogel or Lyogel, or with 35 water as liquid: aquagel or hydrogel). Here, the polymer phase forms a continuous three-dimensional network. In step (b) of the process of the invention, the gel is usually formed by allowing to rest, e.g. by simply allowing the container, reaction vessel or reactor in which the mixture is 40 present (hereinafter referred to as gelling apparatus) to stand. The mixture is preferably no longer stirred or mixed during gelling (gel formation) because this could hinder formation of the gel. It has been found to be advantageous to cover the mixture during gelling or to close the gelling apparatus.
18 Gelling is known per se to a person skilled in the art and is described, for example, in WO-2009/027310 on page 21, line 19 to page 23, line 13, the contents of which are hereby fully incorporated by reference. 5 Step (c) According to the invention, the gel obtained in the previous step is dried in step (c). 10 In a preferred embodiment, drying is carried out under supercritical conditions, preferably after replacement of the solvent by C02 or other solvents suitable for the purposes of supercritical drying. Such drying is known per se to a person skilled in the art. Supercritical conditions characterize a temperature and a pressure at which the fluid phase to be removed is present in the supercritical state. In this way, shrinkage of 15 the gel body on removal of the solvent can be reduced. The supercritical drying of the gel is preferably carried out in an autoclave. Here, supercritical C02 is particularly preferred, i.e. drying is preferably effected by extraction of the solvent by means of supercritical C02. The autoclave is preferably firstly filled 20 with an organic solvent to such an extent that the gel is completely covered, whereupon the autoclave is closed. This makes it possible to prevent shrinkage of the gel occurring as a result of evaporation of the organic solvent before the gel comes into contact with supercritical C02. 25 In an alternative embodiment, the drying of the gel obtained is carried out by converting the solvent (C) into the gaseous state at a temperature and a pressure below the critical temperature and the critical pressure of the solvent (C). Accordingly, drying is preferably carried out by removing the solvent (C) which was present in the reaction without prior replacement by a further solvent. 30 Such methods are likewise known to those skilled in the art and are described in WO 2009/027310 on page 26, line 22 to page 28, line 36, the contents of which are hereby fully incorporated by reference. 35 Properties of the porous materials and use The present invention further provides the porous materials which can be obtained by the process of the invention. Aerogels are preferred as porous materials for the purposes of the present invention, i.e. the porous material which can be obtained 40 according to the invention is preferably an aerogel.
19 The average pore diameter is determined by scanning electron microscopy and subsequent image analysis using a statistically significant number of pores. Corresponding methods are known to those skilled in the art. 5 The volume average pore diameter of the porous material is preferably not more than 4 microns. The volume average pore diameter of the porous material is particularly preferably not more than 3 microns, very particularly preferably not more than 2 microns and in particular not more than 1 micron. 10 Although a very small pore size combined with a high porosity is desirable from the point of view of a low thermal conductivity, from the point of view of production and to obtain a sufficiently mechanically stable porous material, there is a practical lower limit to the volume average pore diameter. In general, the volume average pore diameter is at least 50 nm, preferably at least 100 nm. 15 The porous material which can be obtained according to the invention preferably has a porosity of at least 70% by volume, in particular from 70 to 99% by volume, particularly preferably at least 80% by volume, very particularly preferably at least 85% by volume, in particular from 85 to 95% by volume. The porosity in % by volume means that the 20 specified proportion of the total volume of the porous material comprises pores. Although a very high porosity is usually desirable from the point of view of a minimal thermal conductivity, an upper limit is imposed on the porosity by the mechanical properties and the processability of the porous material. 25 The components (al) to (a3) and optionally (a4), as long as the catalyst can be incorporated, are present in reactive (polymer) form in the porous material which can be obtained according to the invention. Owing to the composition according to the invention, the monomer building blocks (al) and (a2) are predominantly bound via urea linkages and/or via isocyanurate linkages in the porous material, with the isocyanurate 30 groups being formed by trimerization of isocyanate groups of the monomer building blocks (al). If the porous material comprises further components, further possible linkages are, for example, urethane groups formed by reaction of isocyanate groups with alcohols or phenols. 35 The determination of the mol% of the linkages of the monomer building blocks in the porous material is carried out by means of NMR spectroscopy (nuclear magnetic resonance) in the solid or in the swollen state. Suitable methods of determination are known to those skilled in the art. 40 The density of the porous material which can be obtained according to the invention is usually from 20 to 600 g/l, preferably from 50 to 500 g/I and particularly preferably from 70 to 200 g/l.
20 The process of the invention gives a coherent porous material and not only a polymer powder or particles. Here, the three-dimensional shape of the resulting porous material is determined by the shape of the gel which is in turn determined by the shape of the gelling apparatus. Thus, for example, a cylindrical gelling vessel usually gives an 5 approximately cylindrical gel which can then be dried to give a porous material having a cylindrical shape. The porous materials which can be obtained according to the invention have advantageous thermal properties and also advantageous materials properties such as 10 simple processability and high mechanical stability, for example low brittleness. The porous materials have a low density and in addition have a small average pore size. The combination of the abovementioned properties allows the materials to be used according to the invention as insulation material for thermal insulation, in particular for applications in vacuum insulation panels and as building materials; the good thermal 15 insulation effect in the ventilated state is particularly advantageous in the field of building materials. Examples 20 The thermal conductivity X was determined in accordance with DIN EN 12667 using a plate instrument from Hesto (Lambda Control A50). The following compounds were used: 25 Component al: Oligomeric MDI (Lupranat@ M200) having an NCO content of 30.9 g per 100 g in accordance with ASTM D-5155-96 A, a functionality in the region of three and a viscosity of 2100 mPa.s at 25 0 C in accordance with DIN 53018 (hereinafter "compound 30 M200"). Component a2: 3,3',5,5'-Tetraethyl-4,4'-diaminodiphenylmethane (hereinafter "MDEA"). 35 Catalysts a4: Triethanolamine, triethylenediamine (IUPAC: 1,4-diazabicyclo[2.2.2]octane) and methyldiethanolamine. 40 Example 1 21 80 g of the compound M200 were dissolved while stirring at 200C in 220 g of 2-butanone in a glass beaker. 4 g of the compound MDEA and 12 g of triethanolamine were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was 5 allowed to stand at room temperature for 24 hours to effect curing. The gel was subsequently taken from the glass beaker and dried by solvent extraction as described below using supercritical C02 in an autoclave. The gel monolith was taken from the glass beaker and transferred to a 250 ml 10 autoclave. The autoclave was filled with acetone having a purity of >99% so that the monolith was completely covered by acetone and subsequently closed. The monolith was dried in a stream of C02 for 24 hours. The pressure (in the drying system) was in the range from 115 to 120 bar; the temperature was 40*C. At the end, the pressure in the system was reduced in a controlled manner to atmospheric pressure over a period 15 of about 45 minutes at a temperature of 400C. The autoclave was opened and the dried monolith was taken out. The porous material obtained had a density of 168 g/l. the thermal conductivity was 22.3 mW/m*K at 10C. 20 Example 2 80 g of the compound M200 were dissolved while stirring at 20*C in 250 g of ethyl acetate in a glass beaker. 4 g of the compound MDEA and 12 g of methyl 25 diethanolamine were dissolved in 250 g of ethyl acetate in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. In a manner corresponding to example 1, the gel was subsequently taken from the glass beaker and dried by solvent extraction with supercritical C02 in an autoclave. 30 The porous material obtained had a density of 165 g/l. The thermal conductivity was 20.9 mW/m*K at 100C. Example 3 35 80 g of the compound M200 were dissolved while stirring at 200C in 220 g of 2-butanone in a glass beaker. 4 g of the compound MDEA and 8 g of triethylenediamine were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. 40 The mixture was allowed to stand at room temperature for 24 hours to effect curing. In a manner corresponding to example 1, the gel was subsequently taken from the glass beaker and dried by solvent extraction with supercritical C02 in an autoclave.
22 The porous material obtained had a density of 155 g/Il. The thermal conductivity was 20.6 mW/m*K at 10*C. Example 4 5 48 g of the compound M200 were dissolved while stirring at 20 0 C in 220 g of 2-butanone in a glass beaker. 8 g of the compound MDEA and 8 g of methyl diethanolamine and also 1 g of water were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, 10 low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. In a manner corresponding to example 1, the gel was subsequently taken from the glass beaker and dried by solvent extraction with supercritical C02 in an autoclave. 15 The porous material obtained had a density of 130 g/l. The thermal conductivity was 19.5 mW/m*K at 10*C. Example 5C 20 80 g of the compound M200 were dissolved while stirring at 20*C in 220 g of 2-butanone in a glass beaker. 4 g of the compound MDEA and 1 g of triethanolamine were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a 25 slurry-like consistency and could not be demolded. Example 6C 80 g of the compound M200 were dissolved while stirring at 20 0 C in 220 g of 30 2-butanone in a glass beaker. 4 g of the compound MDEA and 3 g of triethanolamine were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a slurry-like consistency and could not be demolded. 35 Example 7C 80 g of the compound M200 were dissolved while stirring at 20*C in 250 g of ethyl acetate in a glass beaker. 4 g of the compound MDEA and 1 g of methyl 40 diethanolamine were dissolved in 250 g of ethyl acetate in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a slurry-like consistency and could not be demolded.
23 Example 8C 80 g of the compound M200 were dissolved while stirring at 200C in 250 g of ethyl 5 acetate in a glass beaker. 4 g of the compound MDEA and 2 g of methyl diethanolamine were dissolved in 250 g of ethyl acetate in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a slurry-like consistency and could not be demolded. 10 Example 9C 80 g of the compound M200 were dissolved while stirring at 200C in 220 g of 2-butanone in a glass beaker. 4 g of the compound MDEA and 1 g of triethylene 15 diamine were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a slurry-like consistency and could not be demolded. 20 Example 10C 48 g of the compound M200 were dissolved while stirring at 200C in 220 g of 2-butanone in a glass beaker. 8 g of the compound MDEA and 1 g of methyl diethanolamine and also 1 g of water were dissolved in 220 g of 2-butanone in a 25 second glass beaker. The two solutions from step (a) were mixed. This gave a clear, low-viscosity mixture. The mixture was allowed to stand at room temperature for 24 hours to effect curing. The gel had a slurry-like consistency and could not be demolded.
Claims (20)
1. A process for producing a porous material, which comprises reacting the following components: 5 (al) from 25 to 94.9% by weight of at least one polyfunctional isocyanate, and (a2) from 0.1 to 30% by weight of at least one polyfunctional aromatic amine having the general formula I 10 Q 2 Q 3 Qs' Q 2 R2 where R 1 and R 2 can be identical or different and are each selected independently from among hydrogen and linear or branched alkyl groups 15 having from 1 to 6 carbon atoms and all substituents Q 1 to Q 5 and Q 1 ' to Q5' are identical or different and are each selected independently from among hydrogen, a primary amino group and a linear or branched alkyl group having from I to 12 carbon atoms, where the alkyl group can bear further functional groups, with the proviso that the compound having the general 20 formula I comprises at least two primary amino groups, where at least one of Q 1 , Q 3 and Q 5 is a primary amino group and at least one of Q 1 ', Q 3 ' and Q 5 ' is a primary amino group, (a3) from 0 to 15% by weight of water, and 25 (a4) from 5 to 30% by weight of at least one catalyst, in each case based on the total weight of the components (al) to (a4), where the % by weight of the components (al) to (a4) add up to 100% by weight and the reaction is carried out in the presence of a solvent (C) which is removed after the 30 reaction.
2. The process according to claim 1 which comprises reacting from 35 to 93.8% by weight of component (a1), from 0.2 to 25% by weight of component (a2), from 0 to 10% by weight of water and from 6 to 30% by weight of component (a4), in 35 each case based on the total weight of the components (al) to (a4), where the % by weight of the components (a1) to (a4) add up to 100% by weight. 25
3. The process according to claim I or 2, wherein at least 5 and at the most 20% by weight of component (a2) are used, based on the total weight of the components (al) to (a4). 5
4. The process according to claim 1 or 2 which comprises reacting 52 to 92.5% by weight of component (al), from 0.5 to 18% by weight of component (a2), from 0 to 6% by weight of water and from 7 to 24% by weight of component (a4), in each case based on the total weight of the components (al) to (a4), where the % by weight of the components (a1) to (a4) add up to 100% by weight. 10
5. The process according to one or more of claims 1 to 4, wherein Q 2 , Q 4 , Q 2 ' and Q 4 ' are selected so that the aromatic amine (a2) having the general formula I comprises at least two primary amino groups which each have a linear or branched alkyl group which can bear further functional groups, having from 1 to 15 12 carbon atoms, in the a position relative to at least one primary amino group bound to the aromatic ring.
6. The process according to one or more of claims 1 to 5, wherein the amine component (a2) comprises at least one compound selected from the group 20 consisting of 3,3',5,5'-tetraalkyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraalkyl 2,2'-diaminodiphenylmethane and 3,3',5,5'-tetraalkyl-2,4'-diaminodiphenyl methane, where the alkyl groups in the 3,3',5 and 5' positions can be identical or different and are selected independently from among linear or branched alkyl groups which have from 1 to 12 carbon atoms and can bear further functional 25 groups.
7. The process according to one or more of claims 1 to 6, wherein the alkyl groups of the polyfunctional aromatic amines (a2) having the general formula I are selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert 30 butyl.
8. The process according to one or more of claims 1 to 7, wherein the polyfunctional aromatic amines (a2) having the general formula I are 3,3',5,5' tetraalkyl-4,4'-diaminodiphenylmethanes, preferably 3,3',5,5'-tetraethyl-4,4' 35 diaminodiphenylmethane and/or 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl methane.
9. The process according to one or more of claims 1 to 8, wherein component (a4) is selected from the group consisting of primary, secondary and tertiary amines, 40 triazine derivatives, metal-organic compounds, metal chelates, oxides of phospholenes, quaternary ammonium salts, ammonium hydroxides and alkali metal and alkaline earth metal hydroxides, alkoxides and carboxylates. 26
10. The process according to one or more of claims 1 to 9,wherein component (a4) is selected from the group consisting of dimethylcyclohexylamine, bis(2 dimethylaminoethyl) ether, N,N,N,N,N-pentamethyldiethylenetriamine, methylimidazole, dimethylimidazole, aminopropylimidazole, dimethylbenzyl 5 amine, 1,6-diazabicyclo[5.4.0]undec-7-ene, trisdimethylaminopropylhexa hydrotriazine, triethylamine, tris(dimethylaminomethyl)phenol, triethylenediamine (diazabicyclo[2.2.2]octane), dimethylaminoethanolamine, dimethylaminopropyl amine, N,N-dimethylaminoethoxyethanol, N,N,N-trimethylaminoethyl ethanolamine, triethanolamine, diethanolamine, triisopropanolamine, 10 diisopropanolamine, methyldiethanolamine, butyldiethanolamine, metal acetylacetonates, ammonium ethylhexanoates and metal ethylhexanoates.
11. The process according to one or more of claims 1 to 8, wherein component (a4) is selected from the group consisting of alkali metal carboxylates, alkaline earth 15 metal carboxylates and ammonium carboxylates.
12. The process according to one or more of claims I to 11, wherein component (a4) comprises potassium 2-ethylhexanoate. 20
13. The process according to one or more of claims I to 12, wherein no water is used.
14. The process according to one or more of claims 1 to 12, wherein at least 0.1% by weight of water is added. 25
15. The process according to one or more of claims 1 to 14, which comprises: a) provision of the components (al), (a2), (a4) and optionally (a3) and the solvent (C) defined in claims 1 to 11, 30 b) reaction of the components (al) to (a4) in the presence of the solvent (C) to form a gel and c) drying of the gel obtained in the preceding step.
16. The process according to claim 15, wherein the components (al) and (a2) to (a4) 35 are provided separately, in each case in a partial amount of the solvent (C).
17. The process according to either claim 15 or 16, wherein the drying of the gel obtained is carried out by converting the liquid comprised in the gel into the gaseous state at a temperature and a pressure below the critical temperature 40 and the critical pressure of the liquid comprised in the gel.
18. The process according to either claim 15 or 16, wherein the drying of the gel obtained is carried out under supercritical conditions. 27
19. A porous material which can be obtained by the process according to one or more of claims 1 to 18. 5
20. The use of porous materials according to claim 19 as insulation material or for vacuum insulation panels.
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KR102425703B1 (en) | 2014-09-25 | 2022-07-28 | 바스프 에스이 | Method for manufacturing a composite element for vacuum insulation elements |
CN107810218B (en) | 2015-04-27 | 2020-09-22 | 亨茨曼国际有限公司 | Functionalized porous materials based on isocyanates |
EP3405508A1 (en) * | 2016-01-18 | 2018-11-28 | Basf Se | Process for producing porous materials |
WO2017198658A1 (en) * | 2016-05-19 | 2017-11-23 | Henkel Ag & Co. Kgaa | Hybrid aerogels based on clays |
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US5478867A (en) * | 1993-07-07 | 1995-12-26 | The Dow Chemical Company | Microporous isocyanate-based polymer compositions and method of preparation |
AU5862099A (en) | 1998-10-22 | 2000-05-15 | Huntsman Ici Chemicals Llc | Insulated bodies |
WO2008138978A1 (en) * | 2007-05-16 | 2008-11-20 | Basf Se | Xerogels made from aromatic polyureas |
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CN105524247A (en) * | 2009-06-29 | 2016-04-27 | 巴斯夫欧洲公司 | Porous gels based on aromatic polyurea |
EP2510026B1 (en) | 2009-12-11 | 2014-02-26 | Basf Se | Improved porous materials based on aromatic amines |
EP2399945A1 (en) * | 2010-06-28 | 2011-12-28 | Basf Se | Method for producing porous materials on the basis of polyuric material |
EP2635616B1 (en) * | 2010-11-04 | 2017-08-02 | Basf Se | Process for producing aerogels or xerogels |
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RU2015115556A (en) | 2016-11-20 |
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MX2015004047A (en) | 2015-07-06 |
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