EP2296836B1 - Methansulfonsäurehaltige katalysatoren für das saürehärtungsverfahren - Google Patents
Methansulfonsäurehaltige katalysatoren für das saürehärtungsverfahren Download PDFInfo
- Publication number
- EP2296836B1 EP2296836B1 EP09749648.3A EP09749648A EP2296836B1 EP 2296836 B1 EP2296836 B1 EP 2296836B1 EP 09749648 A EP09749648 A EP 09749648A EP 2296836 B1 EP2296836 B1 EP 2296836B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- binder
- molding material
- mold
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002253 acid Substances 0.000 title claims description 85
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 41
- 229940098779 methanesulfonic acid Drugs 0.000 title claims description 24
- 239000003054 catalyst Substances 0.000 title description 41
- 239000011230 binding agent Substances 0.000 claims description 94
- 239000000203 mixture Substances 0.000 claims description 94
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 238000000465 moulding Methods 0.000 claims description 28
- 150000007524 organic acids Chemical class 0.000 claims description 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 4
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 230000009969 flowable effect Effects 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000012778 molding material Substances 0.000 description 88
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 78
- 238000005266 casting Methods 0.000 description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000004576 sand Substances 0.000 description 24
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
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- -1 aromatic sulfonic acids Chemical class 0.000 description 18
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- 150000002576 ketones Chemical class 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- 230000009257 reactivity Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000006004 Quartz sand Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
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- 239000007789 gas Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 239000004606 Fillers/Extenders Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 230000002028 premature Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
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- 238000004132 cross linking Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- LPCJHUPMQKSPDC-UHFFFAOYSA-N 3,5-diethylphenol Chemical compound CCC1=CC(O)=CC(CC)=C1 LPCJHUPMQKSPDC-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- RCNCKKACINZDOI-UHFFFAOYSA-N 4,5-dimethylbenzene-1,3-diol Chemical compound CC1=CC(O)=CC(O)=C1C RCNCKKACINZDOI-UHFFFAOYSA-N 0.000 description 2
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001896 cresols Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical class OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical class 0.000 description 1
- IYMSIPPWHNIMGE-UHFFFAOYSA-N silylurea Chemical class NC(=O)N[SiH3] IYMSIPPWHNIMGE-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/224—Furan polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
- B22C1/10—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives for influencing the hardening tendency of the mould material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/2246—Condensation polymers of aldehydes and ketones
- B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
Definitions
- the invention relates to a process for the production of cores and molds for the foundry industry and to a molding material mixture as used in the process.
- Molds for the production of metal bodies are composed of so-called cores and molds.
- the casting mold essentially represents a negative mold of the casting to be produced, wherein cores serve to form cavities in the interior of the casting, while the molds form the outer boundary.
- Different requirements are placed on the cores and molds.
- a relatively large surface area is available to dissipate gases that form during casting by the action of the hot metal.
- cores usually only a very small area is available, through which the gases can be derived. If there is too much gas, there is a risk that gas will transfer from the core into the liquid metal and there to form casting defects leads.
- the internal cavities are therefore imaged by cores solidified by cold-box binders, a polyurethane-based binder, while the outer contour of the casting is represented by lower cost forms, such as a green sand mold, a furan resin mold. or a phenol resin bound form or by a steel mold.
- Casting molds are made of a refractory material, such as quartz sand, whose grains are connected after molding of the mold by a suitable binder to ensure sufficient mechanical strength of the mold.
- a refractory molding material which is mixed with a suitable binder.
- the molding material mixture obtained from molding material and binder is preferably present in a free-flowing form, so that it can be filled into a suitable mold and compacted there.
- the binder produces a firm cohesion between the particles of the molding base material, so that the casting mold obtains the required mechanical stability.
- both organic and inorganic binders can be used, the curing of which can be effected by cold or hot processes.
- Cold processes are processes which are carried out essentially at room temperature without heating the molding material mixture.
- the curing is usually carried out by a chemical reaction, which can be triggered, for example, by passing a gaseous catalyst through the molding material mixture to be cured, or by adding a liquid catalyst to the molding material mixture.
- hot processes the molding material mixture is heated after molding to a sufficiently high temperature, for example, in the Drill binder contained solvents or to initiate a chemical reaction by which the binder is cured by crosslinking.
- organic binders e.g. Polyurethane, furan resin or epoxy-acrylate binders used in which the curing of the binder is carried out by adding a catalyst.
- binder depends on the shape and size of the casting to be produced, the conditions of production and the material used for the casting. For example, in the production of small castings that are produced in large numbers, polyurethane binders are often used because they allow fast cycle times and thus also a series production.
- Processes in which the curing of the molding material mixture by heat or by subsequent addition of a catalyst have the advantage that the processing of the molding material mixture is not subject to any special time restrictions.
- the molding material mixture can first be produced in larger quantities, which are then processed within a longer period of time, usually several hours.
- the curing of the molding material mixture takes place only after molding, with a rapid reaction is sought.
- the mold can be removed immediately after curing from the mold so that short cycle times can be realized. However, in order to obtain a good strength of the mold, the curing of the molding material mixture must be uniform within the mold. If the curing of the molding material mixture by subsequent addition of a catalyst, the mold is gassed after molding with the catalyst. For this purpose, the gaseous catalyst is passed through the casting mold.
- the molding material mixture hardens immediately after contact with the catalyst and can therefore be removed very quickly from the mold.
- the gassing times are prolonged, but can still arise sections in the mold, which are achieved very poorly or not at all by the gaseous catalyst.
- the amount of catalyst therefore increases sharply with increasing size of the mold.
- no-bake binders are used mostly.
- the refractory base molding material is first coated with a catalyst.
- the binder is added and distributed evenly by mixing on the already coated with the catalyst grains of the refractory base molding material.
- the molding material mixture can then be shaped into a shaped body. Since binder and catalyst are evenly distributed in the molding material mixture, the curing is largely uniform even with large moldings.
- the reaction rate can be influenced for a given amount of the binder and the refractory base molding material, for example, by the type and amount of the catalyst or by the addition of retarding components.
- the processing of the molding material mixture must be carried out under very controlled conditions, since the rate of curing is influenced, for example, by the temperature of the molding material mixture.
- the classic no-bake binders are based on furan resins and phenolic resins. They are offered as two-component systems, one component comprising a reactive furan resin and the other component an acid which acts as a catalyst for the curing of the reactive resin component.
- Furan and phenolic resins show very good disintegration properties during casting. Under the action of heat of the liquid metal, the furan or phenolic resin decomposes and the strength of the mold is lost. After casting, therefore, cores, possibly after prior shaking of the casting, pour out very well from cavities.
- furfuryl alcohol as an essential component.
- Furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol can react with itself under acid catalysis and form a polymer.
- furfuryl alcohol is generally not pure furfuryl alcohol used but added to the furfuryl alcohol further compounds which are polymerized into the resin. Examples of such compounds are aldehydes, such as formaldehyde or furfural, ketones, such as acetone, phenols, urea or even polyols, such as sugar alcohols or ethylene glycol.
- the resins may be added with other components that affect the properties of the resin, such as its elasticity. Melamine can be added, for example, to
- Furan no-bake binders are most often prepared by first producing furfuryl-containing precondensates from, for example, urea, formaldehyde, and furfuryl alcohol under acidic conditions. The reaction conditions are chosen so that only a slight polymerization of furfuryl alcohol occurs. These precondensates are then diluted with furfuryl alcohol.
- Resoles can also be used to prepare furan no-bake binders. Resoles are prepared by polymerization of mixtures of phenol and formaldehyde. These resoles are then diluted with furfuryl alcohol.
- the second component of the furan no-bake binder forms an acid.
- this acid neutralizes alkaline components which are contained in the refractory molding material and, on the other hand, catalyzes the crosslinking of the reactive furan resin.
- acids mostly aromatic sulfonic acids and in some special cases also phosphoric acid or sulfuric acid are used.
- Phosphoric acid is used in concentrated form, ie at concentrations greater than 75%.
- Sulfuric acid can be added as a relatively strong acid starter for the curing of furan resins to weaker acids.
- a smell typical of sulfur compounds develops.
- there is a risk that the casting material sulfur is absorbed, which affects its properties.
- aromatic sulfonic acids are used as catalysts. Because of their good availability and their high acidity especially toluene sulfonic acid, xylylene sulfonic acid and benzenesulfonic acid are used.
- the choice of catalyst has a great influence on the properties of the binder.
- the rate of curing can be influenced by the amount of acid and by the strength of the acid. Higher amounts of acid or stronger acids lead to an increase in the curing rate.
- the furan resin becomes brittle upon curing, which adversely affects the strength of the mold.
- the resin is not completely cured or the curing takes a long time which leads to a lower strength of the mold.
- Phenolic resins as the second large group of acid-catalyzed curable no-bake binders contain resoles as reactive resin components, ie phenolic resins which have been prepared with an excess of formaldehyde. Phenol resins show a significantly lower reactivity compared to furan resins and require strong sulfonic acids as catalysts. Phenolic resins show a relatively high viscosity, which is still with longer storage of the resin increases. Especially at temperatures below 20 ° C, the viscosity increases sharply, so that the sand must be heated in order to apply the binder evenly on the surface of the grains of sand can.
- the molding compound After the phenol no-bake binder has been applied to the refractory base molding material, the molding compound should be processed as promptly as possible so as not to suffer deterioration in the quality of the molding compound due to premature curing, resulting in deterioration of the strength of the molding compound mixture produced molds can lead.
- the flowability of the molding material mixture is usually poor. In the production of the mold, the molding material mixture must therefore be carefully compacted in order to achieve a high strength of the mold can.
- the preparation and processing of the molding material mixture should be carried out at temperatures in the range of 15 to 35 ° C. If the temperature is too low, the molding material mixture is difficult to process because of the high viscosity of the phenol no-bake resin. At temperatures of more than 35 ° C, the processing time is shortened by premature curing of the binder.
- molding mixtures based on phenol no-bake binders can also be worked up again, in which case mechanical or thermal or combined mechanical / thermal processes can also be used.
- the acid used as catalyst in the case of furan or phenol no-bake processes has a very great influence on the properties of the casting mold.
- the acid must have sufficient strength to ensure a sufficient rate of reaction in the curing of the mold.
- the curing must be well controllable, so that also sufficiently long processing times can be set. This is especially for the production of molds for very large Castings important, whose construction requires a longer period.
- the acid must not accumulate in the regeneration of the regeneration of old sands. If acid is introduced into the molding material mixture via the regenerate, this shortens the processing time and leads to a deterioration in the strength of the casting mold produced from the regenerate.
- the cured binder should decompose, so that the mold loses its strength.
- the aromatic sulfonic acids used as catalyst in particular p-toluenesulfonic acid, benzenesulfonic acid and xylenesulfonic acid, disintegrate under the influence of heat and the reducing atmosphere generated during casting and, in addition to sulfur dioxide, release aromatic pollutants such as benzene, toluene or xylene (BTX). Some of these decomposition products also remain in the used sand and can be released during reprocessing.
- the WO 97/31732 discloses furan-based binder for molding sands containing methanesulfonic acid as a hardener.
- the EP 1531018 A1 relates to acid hardeners for furan binders containing sulfuric acid, aliphatic carboxylic acid and arylsulphonic acid.
- the WO 97/31732 and the EP 1531013 A1 do not disclose the claimed manufacturing process.
- WO 97/31732 describes a self-hardening furan no-bake molding material mixture for the production of casting forums, which contains in addition to a furan-containing resin methanesulfonic acid as a catalytically active acid.
- the methanesulfonic acid may also be used in admixture with an organic sulfonic acid or an inorganic acid.
- organic sulfonic acids there are mentioned p-toluenesulfonic acid, benzenesulfonic acid and xylenesulfonic acid.
- sulfuric acid is mentioned.
- Methanesulfonic acid has a higher acid strength than, for example, p-toluenesulfonic acid. When using this acid, therefore, a faster curing of the furan no-bake binder is achieved or the curing can be achieved even at low temperatures, ie at temperatures below 25 ° C within acceptable periods.
- methanesulfonic acid is very problematic because of its high reactivity, especially in the production of very large casting molds, since it acts as a fast curing agent, thus allowing only relatively short processing periods.
- Another disadvantage is the use of methanesulfonic acid or methanesulfonic acid mixed with organic sulfonic acids for the emission of sulfur dioxide during casting.
- MAK maximum workplace concentration
- the invention was therefore based on the object to provide a method for the production of cores and molds for the foundry industry, which allows the production of molds, the casting a lower emission of pollutants show when this occurs with the use of currently conventional aromatic sulfonic acids.
- the emission of pollutants in particular the emission of sulfur dioxide and aromatic pollutants, such as benzene, toluene or xylene, can be drastically reduced during casting. As a result, the burden of used sand with these pollutants can be reduced.
- the acid used as a catalyst for the curing of the resin is a mixture of methanesulfonic acid and at least one further sulfur-free acid.
- refractory materials which are customary for the production of moldings for the foundry industry can be used as the refractory molding base material per se.
- suitable refractory mold bases are quartz sand, zircon sand, olivine sand, aluminum silicate sand and chrome ore sand or mixtures thereof.
- quartz sand is used.
- the refractory base molding material should have a sufficient particle size so that the molded article produced from the molding material mixture has a sufficiently high porosity to allow escape of volatile compounds during the casting process.
- at least 70 wt .-%, particularly preferably at least 80 wt .-% of the refractory molding base material has a particle size ⁇ 290 microns.
- the average particle size of the refractory base molding material should preferably be between 100 and 350 ⁇ m.
- the particle size can be determined, for example, by sieve analysis.
- the refractory base molding material should be present in free-flowing form, so that the catalyst or the acid-curable binder can be well applied, for example in a mixer to the grains of the refractory base molding material.
- Regenerated used sands are preferably used as refractory mold bases. From the used sand larger aggregates are removed and the used sand is separated into individual grains. After a mechanical or thermal treatment, the old sands are dedusted and can then be reused. Before reuse, the acid balance of the regenerated used sand is preferably tested. In particular, during thermal regeneration, by-products such as carbonates contained in the sand can be converted to the corresponding oxides, which then react alkaline and neutralize the acid added to the binder as a catalyst. Likewise, for example, in a mechanical regeneration, acid remain in the used sand, which should be considered in the preparation of the binder so as not to shorten the processing time of the molding material mixture.
- the refractory molding base should preferably be dry because the curing reaction is slowed by water.
- the refractory base molding material contains less than 1 wt .-% water.
- the refractory base molding material should not be too warm.
- the refractory base molding material should have a temperature in the range of 20 to 35 ° C. Possibly. the refractory molding material can be cooled or heated
- An acid is then applied to the free-flowing refractory to yield an acid-coated refractory molding base.
- the acid is applied by conventional methods to the refractory base molding material, for example, by spraying the acid onto the refractory base molding material.
- the Amount of acid is preferably selected in the range of 5 to 45 wt .-%, particularly preferably in the range of 20 to 30 wt .-%, based on the weight of the binder and calculated as the pure acid, ie without consideration of any solvent used , Unless the acid is already in liquid form and has a sufficiently low viscosity to be distributed in the form of a thin film on the grains of the refractory base molding material, the acid is dissolved in a suitable solvent.
- Exemplary solvents are water or alcohols or mixtures of water and alcohol.
- the solution is prepared as concentrated as possible in order to minimize the introduced into the binder or the molding material amount of water.
- the mixture of refractory base molding material and acid is well homogenized.
- An acid-curable binder is then applied to the acid-coated refractory base stock.
- the amount of the binder is preferably selected in the range of 0.25 to 5 wt .-%, particularly preferably in the range of 1 to 3 wt .-%, based on the refractory molding base material and calculated as the resin component.
- the acid-curable binder it is possible to use, as such, all acid-curable binders, especially those acid-curable binders which are already customary for the production of molding compounds for the foundry industry.
- the binder may also contain other customary components, for example solvents for adjusting the viscosity or extenders which replace part of the crosslinkable resin.
- the binder is applied to the acid coated refractory base stock and agitated by agitating the mixture onto the base
- Granules of refractory base molding material distributed in the form of a thin film.
- the amounts of binder and acid are chosen so that on the one hand sufficient strength of the casting mold and on the other hand a sufficient processing time of the molding material mixture is achieved.
- a processing time in the range of 5 to 45 minutes is suitable.
- the binder-coated refractory molding base stock is then formed into a shaped article by conventional methods.
- the molding material mixture can be introduced into a suitable mold and compacted there.
- the resulting molded body is then allowed to cure.
- the catalyst used is a mixture of methanesulfonic acid and at least one further sulfur-free acid.
- the use of the mixture can reduce both the emissions of aromatic pollutants, in particular BTX, produced during casting and the emissions of sulfur dioxide.
- BTX aromatic pollutants
- the proportion of methanesulfonic acid having high acid strength is reduced, sufficient reactivity is achieved to cure the binder within a time suitable for industrial applications.
- any acid can be used per se, as long as it does not comprise sulfur-containing groups. Both inorganic and organic acids can be used, with a good reactivity of the binder system being achieved even in the case of organic acids, although such organic acids usually have a relatively low acid strength.
- the proportion of methanesulfonic acid in the acid used as catalyst depends on the reactivity of the resin used in the binder, the at least one sulfur-free acid used in addition to the methanesulfonic acid and the amount of the acid used.
- the proportion of methanesulfonic acid in the acid used as catalyst is preferably less than 70% by weight, preferably less than 65% by weight, particularly preferably less chosen as 60 wt .-% and particularly preferably less than 55 wt .-%.
- the proportion of methanesulfonic acid in the acid used as the catalyst is preferably greater than 20 wt .-%, preferably greater than 30 wt .-%, more preferably greater than 35 wt .-% and particularly preferably greater than 40 wt .-% chosen.
- the proportion of the sulfur-free acid is preferably greater than 30 wt .-%, preferably greater than 35 wt .-%, more preferably greater than 40 wt .-%, and particularly preferably greater than 45 wt .-% selected.
- an aromatic sulfonic acid may also be present in a small proportion in the acid used as catalyst. This proportion is preferably less than 20% by weight, preferably less than 10% by weight and more preferably less than 5% by weight. Most preferably, no aromatic sulfonic acid is included in the acid used as a catalyst.
- Exemplary aromatic sulfonic acids are toluenesulfonic acid, benzenesulfonic acid and xylenesulfonic acid.
- the data refers to the anhydrous acids.
- any binder which can be cured by acid catalysis can be used per se in the process according to the invention.
- the acid-curable binder it is preferable to use a furan no-bake binder or a phenol no-bake binder.
- furan no-bake binder all furan resins can be used per se, as they are already used in furan no-bake binder systems.
- the furan resins used in technical furan no-bake binders are usually precondensates or mixtures of furfuryl alcohol with other monomers or precondensates.
- the precondensates contained in furan no-bake binders are prepared in a manner known per se.
- furfuryl alcohol is used in combination with urea and / or formaldehyde or urea / formaldehyde precondensates.
- Formaldehyde can be used both in monomeric form, for example in the form of a formalin solution, as well as in the form of its polymers, such as trioxane or paraformaldehyde.
- formaldehyde other aldehydes or ketones can be used.
- Suitable aldehydes are, for example, acetaldehyde, propionaldehyde, butyraldehyde, acrolein, crotonaldehyde, benzaldehyde, salicylaldehyde, cinnamaldehyde, glyoxal and mixtures of these aldehydes.
- Formaldehyde is preferred, this being preferably used in the form of paraformaldehyde.
- ketones As ketone component, all ketones can be used which have a sufficiently high reactivity. Exemplary ketones are methyl ethyl ketone, methyl propyl ketone and acetone, with acetone being preferred.
- the said aldehydes and ketones can be used as a single compound but also in admixture with each other.
- the molar ratio of aldehyde, in particular formaldehyde, or ketone to furfuryl alcohol can be selected within wide ranges.
- 0.4 to 4 moles of furfuryl alcohol, preferably 0.5 to 2 moles of furfuryl alcohol, may be used per mole of aldehyde.
- furfuryl alcohol, formaldehyde and urea can be heated to boiling, for example, after the pH has been adjusted to more than 4.5, water being continuously distilled off from the reaction mixture.
- the reaction time can be several hours, for example 2 hours. Under these reaction conditions occurs almost no polymerization of furfuryl alcohol. However, the furfuryl alcohol is condensed into a resin together with the formaldehyde and the urea.
- furfuryl alcohol, formaldehyde and urea are reacted at a pH of well below 4.5, for example at a pH of 2.0, in the heat, wherein the water formed in the condensation are distilled off under reduced pressure can.
- the reaction product has a relatively high viscosity and is diluted with furfuryl alcohol to produce the binder until the desired viscosity is achieved.
- phenol can be reacted under alkaline conditions, first with formaldehyde to a resole resin.
- This resol can then be treated with furfuryl alcohol or a furan group containing Resin reacted or mixed.
- furan group-containing resins can be obtained, for example, by the methods described above.
- phenols for example resorcinol, cresols or bisphenol A.
- the proportion of phenol or higher phenols to the binder is preferably in the range of up to 45 wt .-%, preferably up to 20 wt .-%, more preferably selected up to 10 wt .-%. According to one embodiment, the proportion of phenol or higher phenols can be greater than 2 wt .-%, according to a further embodiment greater than 4 wt .-% can be selected.
- condensates of aldehydes and ketones which are then mixed with furfuryl alcohol to produce the binder.
- Such condensates can be prepared by reacting aldehydes and ketones under alkaline conditions.
- the aldehyde used is preferably formaldehyde, in particular in the form of paraformaldehyde.
- the ketone used is preferably acetone.
- the relative molar ratio of aldehyde to ketone is preferably selected in the range of 7: 1 to 1: 1, preferably 1.2: 1 to 3.0: 1.
- the condensation is preferably carried out under alkaline conditions at pH values in the range of 8 to 11.5, preferably 9 to 11.
- a suitable base is, for example, sodium carbonate.
- the proportion of furfuryl alcohol on Binder in the range of 30 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 60 to 85 wt .-% selected.
- the proportion of urea and / or formaldehyde in the binder is preferably selected in the range of 2 to 70 wt .-%, preferably 5 to 45 wt .-%, particularly preferably 15 to 30 wt .-%.
- the proportions include both the unbound portions of these compounds contained in the binder and those bound in the resin.
- the proportion of these extenders in the binder is therefore preferably less than 25% by weight, preferably less than 15% by weight and more preferably less than 10% by weight. In order to achieve a cost saving without having to put an excessive influence on the strength of the mold, the proportion of extenders is chosen according to an embodiment greater than 5 wt .-%.
- the furan no-bake binders may further contain water.
- the proportion of water is preferably chosen as low as possible.
- the proportion of water in the binder is preferably less than 20% by weight, preferably less than 15% by weight. From an economic point of view, an amount of water of more than 5% by weight in the binder can be tolerated.
- Resoles are mixtures of hydroxymethylphenols which are linked via methylene and methylene ether bridges and by Reaction of aldehydes and phenols in a molar ratio of 1: ⁇ 1, optionally in the presence of a catalyst, for example a basic catalyst, are available. They have a molecular weight M w of ⁇ 10,000 g / mol.
- phenolic resins For the preparation of phenolic resins, all conventionally used phenols are suitable. In addition to unsubstituted phenol, substituted phenols or mixtures thereof can be used. The phenolic compounds are unsubstituted either in both ortho positions or in an ortho and in the para position to allow polymerization. The remaining ring carbon atoms may be substituted. The choice of the substituent is not particularly limited so long as the substituent does not adversely affect the polymerization of the phenol or the aldehyde. Examples of substituted phenols are alkyl-substituted phenols, alkoxy-substituted phenols and aryloxy-substituted phenols.
- the abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms.
- suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylene, 3,4-xylene, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-dibutylphenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.
- phenol itself.
- higher condensed phenols such as bisphenol A, are suitable.
- polyhydric phenols having more than one phenolic hydroxyl group are also suitable.
- Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups.
- suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, fluoroglycine, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol.
- Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.
- phenols of general formula I for the preparation of the phenolic resin component, wherein A, B and C independently of one another from a hydrogen atom, a branched or unbranched alkyl radical, which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms, an aryl or alkylaryl radical, such as, for example, bisphenyls.
- a branched or unbranched alkyl radical which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably having from 1 to 15 carbon atoms, a branched or unbranched alkenoxy radical which may, for example, have 1 to 26, preferably 1 to 15, carbon atoms,
- aldehydes for the production of the phenolic resin component are the same aldehydes as are used in the preparation of the furan resin component in furan no-bake binders.
- aldehydes of the formula: R-CHO wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
- Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde. It is particularly preferred to use formaldehyde, either in its aqueous form, as para-formaldehyde or trioxane.
- the molar ratio of aldehyde to phenol is preferably 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.
- Sodium hydroxide, ammonia, sodium carbonate, calcium, magnesium and barium hydroxide or also tertiary amines can be used as bases in the preparation of the resoles.
- the resoles can also be modified by further compounds, for example nitrogen-containing compounds, such as urea.
- the resoles are preferably mixed with furfuryl alcohol in the preparation of the binder.
- the binders may contain other customary additives, for example silanes as adhesion promoters.
- Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as ⁇ -hydroxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane.
- silane is added to the binder in a proportion of 0.1 to 3% by weight, preferably 0.1 to 1% by weight.
- the binders may also contain activators which accelerate the curing of the binder.
- activators are, for example, resorcinol, bisphenol A. It is also possible to use mixtures which remain in the bottom during the distillation of resorcinol or bisphenol A. These mixtures contain oligomers of resorcinol or bisphenol A, for example dimers, trimers or polymers.
- polyols may also be added to the binder, such as polyether polyols or polyester polyols.
- Polyester polyols can be prepared, for example, by reaction of a dicarboxylic acid or a dicarboxylic acid anhydride with a glycol. Suitable dicarboxylic acids are, for example, adipic acid or oxalic acid.
- Suitable glycols are, for example, ethylene glycol, propylene glycol or diethylene glycol. The molecular weight of these compounds is preferably in the range of 300 to 800.
- Polyether polyols are commercially available. They can be prepared by reaction of an alkylene oxide with a glycol. Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide or butylene oxide. Examples of suitable glycols are ethylene glycol, diethylene glycol and propylene glycol.
- solvents may also be present in the binder.
- a suitable solvent is, for example, water or alcohols, such as methanol or ethanol.
- the binder may also contain plasticizers, for example monoethylene glycol or diisobutyl phthalate.
- the molding material mixture may contain other customary constituents.
- Exemplary further constituents are iron oxide, ground fibrous fibers, wood flour granules, ground coal or clay.
- organic acids are preferably used.
- Organic acids can easily be removed during the regeneration of the used sand, so that they do not accumulate in the regenerated used sand.
- the organic acids decompose into harmless compounds, ultimately water and carbon dioxide, so that when using organic acids no special measures must be taken, for example, to clean the exhaust air during regeneration.
- Organic acids are compounds based on hydrocarbons which comprise at least one carboxyl group.
- the organic acids may also comprise further functional groups, for example hydroxy groups, aldehyde groups, or even double bonds.
- the organic acids preferably comprise 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.
- Saturated carboxylic acids are preferably used, since these are readily available and have a high stability, so that they can be stored for a long time without sacrificing quality.
- Sulfur-free acid used is preferably those organic acids which have a high acid strength.
- the organic acid preferably comprises, in addition to the at least one carboxyl group, at least one further electron-withdrawing group.
- the at least one further electron-withdrawing group is selected from the group of carboxyl group, hydroxy group, aldehyde group. Particular preference is given to using dicarboxylic acids, tricarboxylic acids or hydroxycarboxylic acids.
- the organic acid is selected from the group of citric acid, lactic acid, glycolic acid, glyoxylic acid, malic acid, oxalic acid.
- the acids can be used both individually and in admixture.
- the at least one further acid, in particular organic acid preferably has a pK s value of less than 4.5, preferably less than 4.0.
- the at least one further acid, in particular organic acid has a pK s value of more than 1.0, according to a further embodiment a pK s value of more than 2.
- the at least one further sulfur-free acid has a pK s value in the range from 3 to 4.
- the acid is preferably added in the form of a solution.
- a solution As the solvent, water is preferably used. Since water, as already explained, slows down the hardening of the molding material mixture, a concentrated solution of the acid is preferably used, the concentration of the acid in the solution preferably being chosen to be greater than 30% by weight.
- the temperature during the production and processing of the molding material mixture is preferably not too high.
- the curing of the molded body produced from the molding material should be as uniform as possible in order to achieve high strength.
- the curing of the shaped body is carried out at a temperature of less than 40 ° C, preferably in a temperature range of 15 to 30 ° C.
- a molding material mixture is used used, which is particularly suitable for the production of large molds, these molds show a reduced emission of defective compounds during casting, especially BTX and sulfur compounds.
- the invention relates to molds and cores, as obtained by the method according to the invention, as well as their use for metal casting, in particular iron and steel casting.
- the mold was filled with 4.3 kg of liquid iron (casting temperature: 1400 ° C), so that the weight ratio of mold and molten iron was about 1: 1.
- a defined partial flow was drawn off via a sampling probe and the substances contained in the partial flow were adsorbed on active carbon in accordance with the process according to DIN EN 14662-2.
- the qualitative and quantitative analysis of the adsorbed substances was carried out by gas chromatography.
- a partial flow was discharged from the exhaust gas and with a vacuum device in a Aspirated PE bag.
- the concentration of sulfur dioxide was determined by mass spectrometry.
- Table 2 Emissions of a casting mold during casting (Technikum scale) Molding material mixture 1 (not according to the invention) Molding material mixture 2 (according to the invention) Benzene [mg / m 3 ] 6095 560 Toluene [mg / m 3 ] 30000 300 Xylene [mg / m 3 ] 930 105.5 Sulfur dioxide [ppm by volume] 3600 1300
- Table 4 Emissions of a casting mold during casting (practical application) Molding material mixture 3 (not according to the invention) Molding material mixture 4 (according to the invention) Benzene [mg / m 3 ] 15.0 5.0 Toluene [mg / m 3 ] 18.0 6.0 Xylene [mg / m 3 ] ⁇ 0.5 ⁇ 0.5 Sulfur dioxide [ppm by volume] 22.5 19.1
- the molding material mixture is compacted in a mold, 100 mm in height and 100 mm in diameter, with a hand plate.
- the surface is checked at certain intervals with the surface hardness tester GF. If the test ball no longer penetrates into the core surface, the demolding time is given.
- the remaining remainder of the sand mixture after bending core production is assessed visually for its flowability and rolling behavior. If unrolling occurs like a scoop, the sand processing time is over.
- test bars were placed in a Georg Fischer strength tester equipped with a three-point bending device (DISA-Industrie AG, Schaffhausen, CH) and the force was measured, which resulted in the breakage of the test bars.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mold Materials And Core Materials (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL09749648T PL2296836T3 (pl) | 2008-05-23 | 2009-05-22 | Katalizatory zawierające kwas metanosulfonowy do sposobu utwardzania kwasami |
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DE102008024727A DE102008024727A1 (de) | 2008-05-23 | 2008-05-23 | Methansulfonsäurehaltige Katalysatoren für das Säurehärtungsverfahren |
PCT/EP2009/003643 WO2009141158A1 (de) | 2008-05-23 | 2009-05-22 | Methansulfonsäurehaltige katalysatoren für das saürehärtungsverfahren |
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EP2296836A1 EP2296836A1 (de) | 2011-03-23 |
EP2296836B1 true EP2296836B1 (de) | 2013-12-04 |
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EP09749648.3A Active EP2296836B1 (de) | 2008-05-23 | 2009-05-22 | Methansulfonsäurehaltige katalysatoren für das saürehärtungsverfahren |
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US (1) | US8919421B2 (zh) |
EP (1) | EP2296836B1 (zh) |
JP (1) | JP5557293B2 (zh) |
KR (1) | KR101643703B1 (zh) |
CN (1) | CN102076440A (zh) |
BR (1) | BRPI0912685B1 (zh) |
DE (1) | DE102008024727A1 (zh) |
EA (1) | EA021549B1 (zh) |
MX (1) | MX2010012742A (zh) |
PL (1) | PL2296836T3 (zh) |
UA (1) | UA101502C2 (zh) |
WO (1) | WO2009141158A1 (zh) |
ZA (1) | ZA201008061B (zh) |
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JP5486293B2 (ja) * | 2009-12-24 | 2014-05-07 | 花王株式会社 | 鋳型造型用粘結剤組成物 |
JP5913359B2 (ja) * | 2010-12-16 | 2016-04-27 | ヒユツテネス−アルベルトス ヘーミッシエ ヴエルケ ゲーエムベーハー | 鋳物工業用の低−放出性常温硬化性結合剤 |
JP5986457B2 (ja) * | 2011-08-31 | 2016-09-06 | 花王株式会社 | 自硬性鋳型造型用粘結剤組成物 |
DE102012201971B4 (de) * | 2012-02-09 | 2024-09-12 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Verwendung einer Mischung als Additiv für die Polyisocyanat-Komponente eines Zwei-Komponenten-Bindemittelsystems zur Herstellung eines Polyurethan-Harzes, Polyisocyanat enthaltende Lösung zur Verwendung als Komponente eines Formstoff-Bindemittelsystems, Zwei-Komponenten-Bindemittelsystem zur Herstellung eines Polyurethan-Harzes, Gemisch zur Herstellung eines Kerns oder einer Form für die Gießerei, Form oder Kern für die Gießerei und Verfahren zur Herstellung eines Kerns oder einer Form |
JP6069047B2 (ja) | 2012-04-27 | 2017-01-25 | 花王株式会社 | 鋳型造型用硬化剤組成物 |
JP5355805B1 (ja) | 2013-02-19 | 2013-11-27 | 伊藤忠セラテック株式会社 | 鋳型用耐火性粒子の改質方法及びそれによって得られた鋳型用耐火性粒子並びに鋳型の製造方法 |
JP6277545B2 (ja) * | 2014-02-13 | 2018-02-14 | 群栄化学工業株式会社 | 酸硬化性樹脂用硬化剤組成物 |
CN103822803A (zh) * | 2014-02-28 | 2014-05-28 | 湖北工业大学 | 一种砂型铸造尾气的采集装置和方法 |
US10174183B2 (en) | 2015-03-09 | 2019-01-08 | Technology Research Association For Future Additive Manufacturing | Organic binder, granular material, three-dimensional lamination-shaped mold manufacturing apparatus, and three-dimensional lamination-shaped mold manufacturing method |
CN107530765B (zh) * | 2016-04-20 | 2020-07-24 | 技术研究组合次世代3D积层造形技术总合开发机构 | 粒状材料、粒状材料的制造方法、三维层叠造型铸型的制造装置以及三维层叠造型铸型的制造方法 |
DE102017107658A1 (de) * | 2017-01-04 | 2018-07-05 | HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung | Schlichtezusammensetzung für die Gießereiindustrie, enthaltend partikuläres, amorphes Siliziumdioxid und Säure |
JP6892284B2 (ja) * | 2017-02-28 | 2021-06-23 | ダイハツ工業株式会社 | 砂型の製造方法および鋳物砂 |
DE102018100694A1 (de) * | 2018-01-12 | 2019-07-18 | Ask Chemicals Gmbh | Formaldehydreduziertes Phenolharzbindemittel |
JP7168337B2 (ja) * | 2018-03-29 | 2022-11-09 | 群栄化学工業株式会社 | 鋳型造型用粘結剤組成物、鋳型造型用砂組成物、及び鋳型の製造方法 |
JP7329388B2 (ja) * | 2018-09-11 | 2023-08-18 | 花王株式会社 | 鋳型造型用粘結剤組成物 |
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JPS5586642A (en) * | 1978-12-26 | 1980-06-30 | Dainippon Ink & Chem Inc | Composition for organic self-hardening mold |
JPS5772750A (en) * | 1980-10-27 | 1982-05-07 | Aisin Chem Co Ltd | Binder composition for mold |
US4478962A (en) * | 1982-02-25 | 1984-10-23 | Cl Industries, Inc. | Binder compositions comprising furfuryl ester and furfuryl ester-furuyl alcohol combinations |
US5248707A (en) * | 1990-08-02 | 1993-09-28 | Borden, Inc. | Accelerators for refractory magnesia |
US5491180A (en) * | 1994-08-17 | 1996-02-13 | Kao Corporation | Binder composition for mold making, binder/curing agent composition for mold making, sand composition for mold making, and process of making mold |
JPH09234540A (ja) | 1996-02-29 | 1997-09-09 | Elf Atochem Japan Kk | 鋳型用結合剤被覆砂粒 |
CN1251824C (zh) * | 2001-05-14 | 2006-04-19 | 山东莱芜润达化工有限公司 | 用于铸造覆膜砂的粘土/酚醛树脂纳米复合物、生产方法及用途 |
DE10352796A1 (de) | 2003-11-12 | 2005-06-23 | Backers Maschinenbau Gmbh | Siebaggregat und Siebstern |
ITMI20032217A1 (it) | 2003-11-14 | 2005-05-15 | Cavenaghi Spa | Sistema legante per fonderia a basso sviluppo di idrocarburi aromatici |
US7211137B2 (en) | 2004-10-15 | 2007-05-01 | Ashland Licensing And Intellectual Property Llc | Binder composition comprising condensed tannin and furfuryl alcohol and its uses |
-
2008
- 2008-05-23 DE DE102008024727A patent/DE102008024727A1/de not_active Withdrawn
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2009
- 2009-05-22 PL PL09749648T patent/PL2296836T3/pl unknown
- 2009-05-22 KR KR1020107028541A patent/KR101643703B1/ko active IP Right Grant
- 2009-05-22 MX MX2010012742A patent/MX2010012742A/es active IP Right Grant
- 2009-05-22 EP EP09749648.3A patent/EP2296836B1/de active Active
- 2009-05-22 EA EA201071344A patent/EA021549B1/ru not_active IP Right Cessation
- 2009-05-22 US US12/993,994 patent/US8919421B2/en not_active Expired - Fee Related
- 2009-05-22 UA UAA201015488A patent/UA101502C2/ru unknown
- 2009-05-22 WO PCT/EP2009/003643 patent/WO2009141158A1/de active Application Filing
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- 2009-05-22 CN CN2009801246237A patent/CN102076440A/zh active Pending
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CN102076440A (zh) | 2011-05-25 |
ZA201008061B (en) | 2011-09-28 |
EA201071344A1 (ru) | 2011-06-30 |
EP2296836A1 (de) | 2011-03-23 |
BRPI0912685A2 (pt) | 2016-01-26 |
JP2011520615A (ja) | 2011-07-21 |
KR101643703B1 (ko) | 2016-07-29 |
WO2009141158A1 (de) | 2009-11-26 |
MX2010012742A (es) | 2010-12-21 |
US8919421B2 (en) | 2014-12-30 |
JP5557293B2 (ja) | 2014-07-23 |
BRPI0912685B1 (pt) | 2018-01-16 |
EA021549B1 (ru) | 2015-07-30 |
US20110073269A1 (en) | 2011-03-31 |
DE102008024727A1 (de) | 2009-11-26 |
PL2296836T3 (pl) | 2014-05-30 |
KR20110010795A (ko) | 2011-02-07 |
UA101502C2 (ru) | 2013-04-10 |
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