NO315318B1 - Use of graft polymers of ketone aldehyde condensation products as hardening retardants for aqueous binder suspensions - Google Patents
Use of graft polymers of ketone aldehyde condensation products as hardening retardants for aqueous binder suspensions Download PDFInfo
- Publication number
- NO315318B1 NO315318B1 NO19952460A NO952460A NO315318B1 NO 315318 B1 NO315318 B1 NO 315318B1 NO 19952460 A NO19952460 A NO 19952460A NO 952460 A NO952460 A NO 952460A NO 315318 B1 NO315318 B1 NO 315318B1
- Authority
- NO
- Norway
- Prior art keywords
- weight
- use according
- condensation products
- ketone
- parts
- Prior art date
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- 239000007859 condensation product Substances 0.000 title claims description 42
- -1 ketone aldehyde Chemical class 0.000 title claims description 20
- 229920000578 graft copolymer Polymers 0.000 title claims description 13
- 239000011230 binding agent Substances 0.000 title claims description 8
- 239000000725 suspension Substances 0.000 title claims description 8
- 239000004568 cement Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 26
- 150000002576 ketones Chemical class 0.000 claims description 17
- 150000002736 metal compounds Chemical class 0.000 claims description 17
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000010440 gypsum Substances 0.000 claims description 10
- 229910052602 gypsum Inorganic materials 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052925 anhydrite Inorganic materials 0.000 claims description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000003077 lignite Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- 150000004950 naphthalene Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 56
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000007787 solid Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000035515 penetration Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 235000010265 sodium sulphite Nutrition 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000006418 Brown reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 229920001875 Ebonite Polymers 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000000546 pharmaceutical excipient Substances 0.000 description 3
- 239000011505 plaster Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 229960002449 glycine Drugs 0.000 description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 2
- 229960003868 paraldehyde Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ISRBGQYORQCISR-UHFFFAOYSA-N (4-methoxyfuran-2-yl)methanol Chemical compound COC1=COC(CO)=C1 ISRBGQYORQCISR-UHFFFAOYSA-N 0.000 description 1
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- YSEFYOVWKJXNCH-UHFFFAOYSA-N 2-methoxyacetaldehyde Chemical compound COCC=O YSEFYOVWKJXNCH-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- OXGJKCALURPRCN-UHFFFAOYSA-N 3-methoxypropanal Chemical compound COCCC=O OXGJKCALURPRCN-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000010755 BS 2869 Class G Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- KWKOTMDQAMKXQF-UHFFFAOYSA-N [2-methyl-2-(prop-2-enoylamino)propyl]phosphonic acid Chemical compound OP(=O)(O)CC(C)(C)NC(=O)C=C KWKOTMDQAMKXQF-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N alpha-isobutyric acid Natural products CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical class [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 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
- 238000011161 development Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HFTNNOZFRQLFQB-UHFFFAOYSA-N ethenoxy(trimethyl)silane Chemical compound C[Si](C)(C)OC=C HFTNNOZFRQLFQB-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
- 239000001530 fumaric acid Substances 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Gjenstanden for den foreliggende oppfinnelse er anvendelse av podepolymerer basert på keton-aldehyd-kondensasjonsprodukter eller -kokondensasjonsprodukter, og/eller énverdige eller flerverdige metallforbindelser av disse, som herdeforsinkere for vandige bindemiddelsuspensjoner basert på sement, gips eller anhydritt. The object of the present invention is the use of graft polymers based on ketone-aldehyde condensation products or co-condensation products, and/or monovalent or multivalent metal compounds thereof, as retarders for aqueous binder suspensions based on cement, gypsum or anhydrite.
Keton-aldehyd-kondensasjonsprodukter og kokondensasjonsprodukter har vært kjent lenge. Således beskrives som hjelpestoff i eksempelvis DE patent-søknad nr. 23 41 923 godt vannløselige kondensasjonsprodukter av sykloalkanoner og formaldehyd, med natriumsulfitt anvendt som syregrupper. En alvorlig ulempe med disse kondensasjonsprodukter er imidlertid Ketone-aldehyde condensation products and cocondensation products have been known for a long time. Thus, for example, DE patent application no. 23 41 923 describes as excipients highly water-soluble condensation products of cycloalkanones and formaldehyde, with sodium sulphite used as acid groups. A serious disadvantage of these condensation products is, however
deres dårlige termiske stabilitet, hvilket innskrenker anvendelsesområdet meget sterkt. their poor thermal stability, which narrows the field of application very much.
God termostabilitet oppviser de syregruppeholdige kondensasjonsprodukter av aldehyder og ketoner beskrevet i DE utlegningsskrift nr. 31 44 673, kokondensasjonsproduktene ifølge DE utlegningsskrift nr. 33 15 152, samt metallforbindelser av disse (ko)kondensasjonsprodukter ifølge DE utlegningsskrift nr. 34 29 068. Disse produkter kan riktignok anvendes som fortykningsmiddel, retensjonsmiddel, overflateaktivt middel, dispergeringsmiddel eller som flytgjørende middel for vandige systemer, men når det gjelder produktegenskaper så er disse for mange anvendelsesområder ikke optimale. Således har disse (ko)kondensasjonsprodukter bare svakt forsinkende egenskaper for sement-, gips- eller anhydritt-holdige bindemi ddelsuspensj on er. The acid group-containing condensation products of aldehydes and ketones described in DE specification no. 31 44 673, the cocondensation products according to DE specification no. 33 15 152, and metal compounds of these (co)condensation products according to DE specification no. 34 29 068 exhibit good thermostability. These products can although used as a thickener, retention agent, surface-active agent, dispersant or as a fluidizing agent for aqueous systems, but when it comes to product properties, these are not optimal for many application areas. Thus, these (co)condensation products only have slightly retarding properties for cement, gypsum or anhydrite-containing binder suspensions.
Målet med den foreliggende oppfinnelse er således å modifisere disse keton-aldehyd-kondensasjonsprodukter, eller -kokondensasjonsprodukter, eller metallforbindelser av disse, slik at de tilsvarende derivater får klart forbedrede anvendelsestekniske egenskaper. The aim of the present invention is thus to modify these ketone-aldehyde condensation products, or -cocondensation products, or metal compounds thereof, so that the corresponding derivatives have clearly improved application technical properties.
Disse mål oppfylles ifølge oppfinnelsen ved anvendelse av podepolymerer av henholdsvis keton-aldehyd-kondensasjonsprodukter og/eller keton-aldehyd-kokondensasjonsprodukter som inneholder syregrupper og/eller énverdige eller flerverdige metallforbindelser av syregruppeholdige keton-aldehyd-kondensasjonsprodukter og -kokondensasjonsprodukter, hvor kondensasjonsproduktet består av These goals are met according to the invention by using graft polymers of ketone-aldehyde condensation products and/or ketone-aldehyde co-condensation products, respectively, which contain acid groups and/or monovalent or polyvalent metal compounds of acid group-containing ketone-aldehyde condensation products and co-condensation products, where the condensation product consists of
a) symmetriske eller usymmetriske ketoner med alifatiske, aralifatiske, sykliske eller aromatiske hydrokarbonrester med a) symmetrical or unsymmetrical ketones with aliphatic, araliphatic, cyclic or aromatic hydrocarbon residues with
minst én ikke-aromatisk rest, at least one non-aromatic residue,
b) et aldehyd med formelen R-(CHO)nhvor n = 1 - 2 og R kan være hydrogen, en alifatisk, aralifatisk, aromatisk eller heterosyklisk b) an aldehyde of the formula R-(CHO)where n = 1 - 2 and R can be hydrogen, an aliphatic, araliphatic, aromatic or heterocyclic
rest, rest,
og på hvilket det er podet anioniske og/eller ikke-ioniske og/eller kationiske umettede monomerer, and on which anionic and/or non-ionic and/or cationic unsaturated monomers are grafted,
som herdeforsinkere for vandige bindemiddelsuspensjoner basert på sement, gips eller anhydritt. as setting retarders for aqueous binder suspensions based on cement, gypsum or anhydrite.
Foretrukne utførelsesformer er angitt i underkravene. Preferred embodiments are set forth in the subclaims.
Det har nemlig uventet vist seg at gjennom påpoding av de nevnte umettede monomerer på (ko)kondensasjonsproduktene, eller metallforbindelsene av disse, så lar de seg målrettet påvirke slik at de også oppviser forsinkende egenskaper. It has unexpectedly been shown that by grafting the aforementioned unsaturated monomers onto the (co)condensation products, or the metal compounds thereof, they can be purposefully influenced so that they also exhibit retarding properties.
Grunnmaterialet eller podegrunnlaget for podepolymerene anvendt ifølge oppfinnelsen består av keton-aldehyd-kondensasjonsprodukter og/eller syregruppeholdige keton-aldehyd-kokondensasjonsprodukter og/eller én- eller flereverdige metallforbindelser av disse syregruppeholdige keton-aldehyd-kondensasjonsprodukter eller -kokondensasjonsprodukter, slik som eksempelvis beskrevet i DE utlegnings-skrifter nr. 31 44 673, 33 15 152 eller 34 29 068. Som ketoner anvendes her symmetriske eller usymmetriske forbindelser med alifatiske, aralifatiske, sykliske eller aromatiske hydrokarbonrester med minst en ikke-aromatisk rest, hvor det totale antall karbon- og heteroatomer i ketonene fortrinnsvis er 3-12. Som alifatiske rester kan anvendes rettkjedede eller forgrenede, umettede og fortrinnsvis mettede alkylrester, som f.eks. metyl, etyl, propyl og isobutyl. Aralifatiske rester er f.eks. benzyl eller fenetyl, og aromatiske rester er f.eks. a- eller j3-naftyl, og fortrinnsvis fenyl. The base material or graft base for the graft polymers used according to the invention consists of ketone-aldehyde condensation products and/or acid group-containing ketone-aldehyde co-condensation products and/or monovalent or polyvalent metal compounds of these acid group-containing ketone-aldehyde condensation products or co-condensation products, as for example described in DE explanatory documents no. 31 44 673, 33 15 152 or 34 29 068. As ketones used here are symmetrical or unsymmetrical compounds with aliphatic, araliphatic, cyclic or aromatic hydrocarbon residues with at least one non-aromatic residue, where the total number of carbon and heteroatoms in the ketones is preferably 3-12. As aliphatic residues, straight-chain or branched, unsaturated and preferably saturated alkyl residues can be used, such as e.g. methyl, ethyl, propyl and isobutyl. Araliphatic residues are e.g. benzyl or phenethyl, and aromatic residues are e.g. α- or β-naphthyl, and preferably phenyl.
Ketonene kan også inneholde én eller flere substituenter, som f.eks. amino-, hydroksy-, alkoksy-, acetyl- eller alkoksykarbonylgrupper. Eksempler på ketoner med mettede alifatiske rester er aceton, metyletylketon og metylisobutylketon; eksempler på ketoner med substituerte alifatiske rester er metoksyaceton, diacetonalkohol og aceteddiksyreetylester; eksempler på ketoner med umettede alifatiske rester er metylvinylketon, mesityloksid og foron; eksempel på ketoner med aralifatiske rester er benzylaceton; eksempler på ketoner med sykliske rester er sykloheksanon og syklopentanon; eksempler på ketoner med aromatiske rester er acetofenon og 4-metoksy-acetofenon. The ketones can also contain one or more substituents, such as e.g. amino, hydroxy, alkoxy, acetyl or alkoxycarbonyl groups. Examples of ketones with saturated aliphatic residues are acetone, methyl ethyl ketone and methyl isobutyl ketone; examples of ketones with substituted aliphatic residues are methoxyacetone, diacetone alcohol and acetoacetic acid ethyl ester; examples of ketones with unsaturated aliphatic residues are methyl vinyl ketone, mesityl oxide and furon; examples of ketones with araliphatic residues are benzylacetone; examples of ketones with cyclic residues are cyclohexanone and cyclopentanone; examples of ketones with aromatic residues are acetophenone and 4-methoxy-acetophenone.
Som aldehyder med formelen R-(CHO)ner det aktuelt med slike forbindelser hvor n er 1 - 2 og R er hydrogen, en alifatisk, aralifatisk, aromatisk eller heterosyklisk rest, og hvor det totale antall karbon- og heteroatomer fortrinnsvis er 1-11. Alifatiske rester er særlig alkylrester, fortrinnsvis med 1 -6 karbonatomer, som f.eks. metyl, etyl, propyl, butyl, etc. De alifatiske rester kan også være forgrenede eller umettede (som f.eks vinyl). Aromatiske rester er f.eks. a- eller /3-naftyl eller fenyl, og heterosykliske rester er f.eks. furfuryl. As aldehydes with the formula R-(CHO) such compounds are applicable where n is 1-2 and R is hydrogen, an aliphatic, araliphatic, aromatic or heterocyclic residue, and where the total number of carbon and heteroatoms is preferably 1-11 . Aliphatic residues are particularly alkyl residues, preferably with 1-6 carbon atoms, such as e.g. methyl, ethyl, propyl, butyl, etc. The aliphatic residues can also be branched or unsaturated (such as vinyl). Aromatic residues are e.g. α- or β-naphthyl or phenyl, and heterocyclic residues are e.g. furfuryl.
Aldehydene kan også inneholde én eller flere substituenter, som f.eks. amino-, hydroksy-, alkoksy- eller alkoksykarbonyl-grupper og/eller eventuelt syregrupper inneholdt i kondensasjonsproduktene. Det kan også anvendes aldehyder med mer enn én aldehydgruppe, i særdeleshet dialdehyder. Det er også mulig å anvende de lavere mettede aldehyder, som formaldehyd eller acetaldehyd i sine polymere former (paraformaldehyd eller paraldehyd). Eksempler på aldehyder med mettede alifatiske rester er formaldehyd (eller paraformaldehyd), acetaldehyd (eller paraldehyd) og butyraldehyd. Eksempler på aldehyder med substituerte, mettede alifatiske rester er metoksyacetaldehyd, 3-metoksypropionaldehyd og acetaldol. Eksempler på aldehyder med umettede alifatiske rester er akrolein og krotonaldehyd. Eksempler på aldehyder med aralifatiske rester er fenylacetaldehyd og fenylpropion-aldehyd. Eksempler på aldehyder med aromatiske eller heterosykliske rester er benz-aldehyd, furfurol og 4-metoksyfurfurol. Som dialdehyd kan det eksempelvis anvendes glyoksal eller glutardialdehyd. Som særlig foretrukket aldehyd anvendes formaldehyd. The aldehydes can also contain one or more substituents, such as e.g. amino, hydroxy, alkoxy or alkoxycarbonyl groups and/or possibly acid groups contained in the condensation products. Aldehydes with more than one aldehyde group can also be used, in particular dialdehydes. It is also possible to use the lower saturated aldehydes, such as formaldehyde or acetaldehyde in their polymeric forms (paraformaldehyde or paraldehyde). Examples of aldehydes with saturated aliphatic residues are formaldehyde (or paraformaldehyde), acetaldehyde (or paraldehyde) and butyraldehyde. Examples of aldehydes with substituted, saturated aliphatic residues are methoxyacetaldehyde, 3-methoxypropionaldehyde and acetaldol. Examples of aldehydes with unsaturated aliphatic residues are acrolein and crotonaldehyde. Examples of aldehydes with araliphatic residues are phenylacetaldehyde and phenylpropionaldehyde. Examples of aldehydes with aromatic or heterocyclic residues are benzaldehyde, furfurol and 4-methoxyfurfurol. For example, glyoxal or glutardialdehyde can be used as dialdehyde. Formaldehyde is used as a particularly preferred aldehyde.
Til forskjell fra keton-aldehyd-kondensasjonsprodukter inneholder kokondensasjonsproduktene også syregrupper som fortrinnsvis utgjøres av karboksy-, sulfo-, sulfamido-, sulfoksy-, sulfoalkylamin- eller sulfoalkyloksy-grupper. En alkylgruppe i disse rester består fortrinnsvis av 1-5 karbonatomer og er i særdeleshet metyl eller etyl. Som syregruppe-innførende forbindelser anvendes fortrinnsvis uorganiske syrer, f.eks. amidosulfonsyre, eller salter av disse, f.eks. natriumsulfitt, natriumbisulfitt eller natriumpyrosulfitt, eller organiske syrer, særlig karboksylsyrer, f.eks. aminoeddiksyre. De aktuelle kokondensasjonsprodukter kan også inneholde to eller flere forskjellige syregrupper. In contrast to ketone-aldehyde condensation products, the cocondensation products also contain acid groups which preferably consist of carboxy, sulfo, sulfamido, sulfoxy, sulfoalkylamine or sulfoalkyloxy groups. An alkyl group in these residues preferably consists of 1-5 carbon atoms and is in particular methyl or ethyl. Inorganic acids are preferably used as acid group-introducing compounds, e.g. amidosulfonic acid, or salts thereof, e.g. sodium sulphite, sodium bisulphite or sodium pyrosulphite, or organic acids, especially carboxylic acids, e.g. aminoacetic acid. The relevant cocondensation products can also contain two or more different acid groups.
Molforholdet mellom ketoner og aldehyder kan varieres innen vide grenser, men er som regel fra 1:0,5 til 1:18. Kokondensasjonsproduktet, som eksempelvis er beskrevet i DE utlegningsskrift 3315152, inneholder keton, aldehyd og syregruppe i et foretrukket molforhold fra 1:0,5 til 18:0,1-3, samt 2-60 vekt%, fortrinnsvis 10-40 vekt%, av en ytterligere bestanddel valgt blant aminoplastdanner og/eller lignin og/eller ligninderivat. Som aminoplastdanner kan det her anvendes alle vanlige nitrogenholdige forbindelser, særlig de som er egnet til kondensasjon med formaldehyd, og spesielt urea, melamin, dicyandiamid eller et guanamin (fortrinnsvis acetoguanamin eller benzoguanamin). The molar ratio between ketones and aldehydes can be varied within wide limits, but is usually from 1:0.5 to 1:18. The cocondensation product, which is for example described in DE explanatory document 3315152, contains ketone, aldehyde and acid group in a preferred molar ratio from 1:0.5 to 18:0.1-3, as well as 2-60% by weight, preferably 10-40% by weight, of a further component selected from among aminoplast formers and/or lignin and/or lignin derivative. All common nitrogen-containing compounds can be used here as aminoplast formers, especially those suitable for condensation with formaldehyde, and especially urea, melamine, dicyandiamide or a guanamine (preferably acetoguanamine or benzoguanamine).
Som aromatiske forbindelser kan det fortrinnsvis anvendes fenoler som er egnet for dannelse av fenolharpikser, altså særlig fenol, kresoler eller xylenoler. Ved siden av kan det imidlertid også anvendes reaktive, substituerte og/eller flere-kjernige aromater, f.eks. naftalin og dets derivater. Aminoplastdannere eller aromatiske forbindelser kan også helt eller delvis være i form av forkondensater eller kondensasjonsprodukter av forskjellig kondensasjonsgrad. Likeså kan det anvendes aminoplastdannere og aromatiske forbindelser som inneholder syregrupper, f.eks. naftalinsulfonsyre. Som lignittforbindelser kan det anvendes rent lignitt, lignitt behandlet med alkali, og/eller sulfonert eller sulfoalkylert lignitt. Med ligninfor-bindelser forstås innen rammen for foreliggende oppfinnelse også svartlut som er dannet ved behandling av tre med natriumsulfitt (sulfitt-prosessen), men også ligninsulfonateter og deres formaldehydharpikser. Ligninene eller lignittene kan også anvendes i form av metallforbindelser (særlig jern og krom). As aromatic compounds, phenols which are suitable for the formation of phenolic resins, i.e. particularly phenol, cresols or xylenols, can preferably be used. In addition, however, reactive, substituted and/or polynuclear aromatics can also be used, e.g. naphthalene and its derivatives. Aminoplast formers or aromatic compounds can also be wholly or partly in the form of precondensates or condensation products of different degrees of condensation. Likewise, aminoplast formers and aromatic compounds containing acid groups can be used, e.g. naphthalene sulfonic acid. Pure lignite, lignite treated with alkali, and/or sulphonated or sulphoalkylated lignite can be used as lignite compounds. Within the scope of the present invention, lignin compounds are also understood to mean black liquor which is formed by treating wood with sodium sulphite (the sulphite process), but also lignin sulphonates and their formaldehyde resins. The lignins or lignites can also be used in the form of metal compounds (especially iron and chromium).
I stedet for de syregruppeholdige kokondensasjonsprodukter kan man også anvende én- eller flerverdige metallforbindelser av de syregruppeholdige keton-aldehyd-kondensasjonsprodukter eller -kokondensasjonsprodukter, som beskrevet i DE utlegningsskrift 3429068. Som metallforbindelser er fortrinnsvis forbindelser med metaller fra grupper II A til VIII A og/eller grupper IB til V B (ifølge definisjonen i Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Publishers New York-London-Sydney, 2. utg. 1965, vol. 8, sider 94-96) egnet, hvor særlig de én- eller flerverdige uorganiske eller organiske salter av disse metaller finner anvendelse. Instead of the acid-group-containing cocondensation products, one can also use monovalent or polyvalent metal compounds of the acid-group-containing ketone-aldehyde condensation products or -cocondensation products, as described in DE explanatory note 3429068. As metal compounds, preferably are compounds with metals from groups II A to VIII A and/ or groups IB to V B (according to the definition in Kirk-Othmer, Encyclopedia of Chemical Technology, Interscience Publishers New York-London-Sydney, 2nd ed. 1965, vol. 8, pages 94-96) suitable, where in particular the one- or polyvalent inorganic or organic salts of these metals are used.
Eksempler på metallforbindelser er to- eller fireverdige mangansalter, toverdige nikkelsalter, to- eller fireverdige blysalter, tre- eller seksverdige kromfor-bindelser, to- eller treverdige jernforbindelser, treverdige aluminiumforbindelser, Examples of metal compounds are divalent or tetravalent manganese salts, divalent nickel salts, divalent or tetravalent lead salts, trivalent or hexavalent chromium compounds, divalent or trivalent iron compounds, trivalent aluminum compounds,
en- og toverdige kobberforbindelser, toverdige magnesiumforbindelser, samt treverdige bismutforbindelser. Andelen metall i disse forbindelser ligger på < 70 vekt%, fortrinnsvis på 0,1-20 vekt%. Fremstillingen av disse metallforbindelser er beskrevet i DE utlegningsskrift 3429068. monovalent and divalent copper compounds, divalent magnesium compounds, as well as trivalent bismuth compounds. The proportion of metal in these compounds is < 70% by weight, preferably 0.1-20% by weight. The production of these metal compounds is described in DE layingningskrift 3429068.
Det er vesentlig for anvendelsen som herdeforsinkere at de aktuelle keton-aldehyd-kondensasjonsprodukter eller syregruppeholdige-kokondensasjonsprodukter eller metallforbindelsene av disse syregruppeholdige (kokondensasjonsprodukter, er podet med anioniske og/eller ikke-ioniske og/eller kationiske, umettede monomerer. It is essential for the application as curing retarders that the relevant ketone-aldehyde condensation products or acid group-containing co-condensation products or the metal compounds of these acid group-containing (co-condensation products) are grafted with anionic and/or non-ionic and/or cationic, unsaturated monomers.
Som anioniske umettede monomerer anvendes fortrinnsvis vinylforbindelser med karboksy-, sulfo- eller fosforsyregrupper. Eksempler på slike umettede forbindelser med karboksysyregrupper er akrylsyre, metakrylsyre, maleinsyre, fumar-syre og itakonsyre, og salter av disse. Eksempler på vinylforbindelser med sulfon-syregrupper er vinylsulfonsyre, allylsulfonsyre, meta-allylsulfonsyre, AMPS og styrensulfonsyre, og salter av disse. Eksempler på vinylforbindelser med fosforsyregrupper er vinylfosfonsyre, 2-akrylamido-2-metyl-propanfosfonsyre og metakryloksy-etylfosfat. Vinyl compounds with carboxy, sulfo or phosphoric acid groups are preferably used as anionic unsaturated monomers. Examples of such unsaturated compounds with carboxylic acid groups are acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, and salts thereof. Examples of vinyl compounds with sulfonic acid groups are vinylsulfonic acid, allylsulfonic acid, meta-allylsulfonic acid, AMPS and styrenesulfonic acid, and salts thereof. Examples of vinyl compounds with phosphoric acid groups are vinylphosphonic acid, 2-acrylamido-2-methylpropanephosphonic acid and methacryloxyethyl phosphate.
I stedet for de anioniske, umettede monomerforbindelser kan det også anvendes ikke-ioniske monomerer, hvor vinyl- eller akrylderivater er å anse som foretrukket. Her finner først og fremst N-vinylpyrrolidon, akrylamid, metakrylamid, N,N-di-metakrylamid, akrolein, mesityloksid, allylalkohol, akrylnitril og vinylacetat, samt styren, anvendelse. Instead of the anionic, unsaturated monomer compounds, non-ionic monomers can also be used, where vinyl or acrylic derivatives are to be considered preferred. Here primarily N-vinylpyrrolidone, acrylamide, methacrylamide, N,N-di-methacrylamide, acrolein, mesityl oxide, allyl alcohol, acrylonitrile and vinyl acetate, as well as styrene, are used.
Ytterligere eksempler på slike umettede forbindelser er esterne av de umettede syrer nevnt over. Further examples of such unsaturated compounds are the esters of the unsaturated acids mentioned above.
Endelig er det ved podingen også mulig å anvende kationiske umettede monomerer, som fortrinnsvis er kvaternære ammoniumforbindelser. Eksempler på slike kvaternære ammoniumforbindelser er metakroyloksyetyltrimetylammonium-klorid (MET AC), (met)akrylamidopropyltrimetylammoniumklorid (MAPTAC), trimetylallyloksyetylammoniumklorid (TAAC) og dimetyldiallylammoniumklorid Finally, during the grafting, it is also possible to use cationic unsaturated monomers, which are preferably quaternary ammonium compounds. Examples of such quaternary ammonium compounds are methacroyloxyethyltrimethylammonium chloride (MET AC), (meth)acrylamidopropyltrimethylammonium chloride (MAPTAC), trimethylallyloxyethylammonium chloride (TAAC) and dimethyldiallylammonium chloride
(DMDAAC). (DMDAAC).
Vektforholdet mellom keton-aldehyd-kondensasjonsproduktet eller -kokondensasjonsproduktet, og den umettede monomer kan varieres innen vide grenser, imidlertid har det vist seg særlig fordelaktig å anvende et forhold mellom 1:0,02 og 1:10. Gjennomføringen av podereaksjonen er forholdsvis ukritisk og kan gjennomføres etter vanlig kjente metoder. Fortrinnsvis gjennomføres podereaksjonen i vandig løsning ved en temperatur fra 0 til 100 °C, samt ved en pH-verdi fra 1 til 13, idet det benyttes vanlige radikalinitiatorer på basis av redokssystemer, som f.eks. H202 og jern(II)-salter (f.eks. jern(II)-sulfat-heptahydrat), peroksodisulfat/pyrosulfitt eller sulfitt, cerium(IV)-salter eller termiske initiatorer som AIBN, eller organiske eller uorganiske peroksider. The weight ratio between the ketone-aldehyde condensation product or co-condensation product and the unsaturated monomer can be varied within wide limits, however, it has proven particularly advantageous to use a ratio between 1:0.02 and 1:10. Carrying out the grafting reaction is relatively uncritical and can be carried out according to commonly known methods. The grafting reaction is preferably carried out in aqueous solution at a temperature from 0 to 100 °C, as well as at a pH value from 1 to 13, using common radical initiators based on redox systems, such as e.g. H 2 O 2 and iron(II) salts (eg iron(II) sulfate heptahydrate), peroxodisulfate/pyrosulfite or sulfite, cerium(IV) salts or thermal initiators such as AIBN, or organic or inorganic peroxides.
Etter gjennomføringen av podereaksjonen, som vanligvis er ferdig i løpet av noen få timer, blir reaksjonsløsningen fortrinnsvis nøytralisert med vanlige baser eller syrer. Den således dannede podepolymerisatløsning har vanligvis et faststoffinnhold mellom 5 og 50 vekt%. After completion of the grafting reaction, which is usually completed within a few hours, the reaction solution is preferably neutralized with common bases or acids. The graft polymer solution thus formed usually has a solids content of between 5 and 50% by weight.
De benyttede podepolymerer, eller fremstillingen av dem, er kjent fra The graft polymers used, or their preparation, are known from
tysk patentsøknad P 4322112.2. Disse podepolymerer, med en molekylvekt fra 500 til 2000000 og en viskositet som alt etter faststoffinnholdet fortrinnsvis er fra 10 til 5000 mPas, oppviser overraskende gode forsinkende egenskaper ved utherding av sement-, gips- eller anhydrid-holdige bindemiddelsuspensjoner. De forlenger på utmerket måte bearbeidbarheten av eksempelvis betong, mørtel, sementslam (eksempelvis også for borehullsementering), gips- og anhydrittslam, idet disse podepolymerer på grunn av god termostabilitet heller ikke mister effekten ved forholdsvise høye temperaturer. De aktuelle podepolymerer anvendes her fortrinnsvis i en mengde fra 0,01 til 5 vekt%, fortrinnsvis fra 0,3 til 1,0 vekt%, basert på vekten av det tilsvarende bindemiddel, for å oppnå den ønskede herdeforsinkelse. German patent application P 4322112.2. These graft polymers, with a molecular weight of from 500 to 2,000,000 and a viscosity which, depending on the solids content, is preferably from 10 to 5,000 mPas, exhibit surprisingly good retarding properties during curing of cement, gypsum or anhydride-containing binder suspensions. They excellently extend the workability of concrete, mortar, cement mud (for example also for borehole cementing), gypsum and anhydrite mud, as these graft polymers do not lose their effect at relatively high temperatures due to their good thermostability. The relevant graft polymers are preferably used here in an amount from 0.01 to 5% by weight, preferably from 0.3 to 1.0% by weight, based on the weight of the corresponding binder, in order to achieve the desired curing delay.
De etterfølgende eksempler vil belyse oppfinnelsen nærmere. I Tabell 1 gis en oversikt over utgangsproduktene anvendt i fremstillingseksemplene. The following examples will illustrate the invention in more detail. Table 1 gives an overview of the starting products used in the manufacturing examples.
A. Synteseeksempler A. Synthesis examples
Eksempel A. 1 Example A. 1
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i angitt rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in the specified order
129,1 vektdeler vann, 129.1 parts by weight water,
54.2 vektdeler natriumsulfitt og 54.2 parts by weight sodium sulphite and
39,9 vektdeler aceton 39.9 parts by weight of acetone
og varmet til 56 °C. and heated to 56 °C.
Så snart acetontilbakeløpet startet ble 258,2 vektdeler 30 %ig formalde-hydløsning tilsatt dråpevis innen 10 min. På grunn av den sterke eksoterme reaksjon ble den første tiendedel av formalinløsningen tilsatt langsomt og jevnt. Etter at reaksjonen hadde startet, hvilket viste seg gjennom begynnende gulfarging av innholdet og et forsterket acetontilbakeløp, ble resten av formalinet tilsatt, hvoretter temperaturen i satsen fikk stige til kokepunktet. Etter at formaldehydet var tilsatt ble det gjennomført en ytterligere 30 min lang termisk etterbehandling av den dyprøde sats ved 95 °C. Etter avkjøling til værelsestemperatur ble pH-verdien justert fra 9,8 til 4 med 42,4 vektdeler 96 %ig eddiksyre. As soon as the acetone reflux started, 258.2 parts by weight of 30% formaldehyde-hydrogen solution were added dropwise within 10 min. Because of the strong exothermic reaction, the first tenth of the formalin solution was added slowly and evenly. After the reaction had started, which was shown by the incipient yellowing of the contents and an increased acetone reflux, the rest of the formalin was added, after which the temperature in the batch was allowed to rise to the boiling point. After the formaldehyde had been added, a further 30-minute long thermal post-treatment of the deep red batch was carried out at 95 °C. After cooling to room temperature, the pH value was adjusted from 9.8 to 4 with 42.4 parts by weight of 96% acetic acid.
Til harpiksløsningen ble det tilsatt 68,6 vektdeler av en 40 %ig vandig jern(III)sulfat-løsning og satsen omrørt i 2 timer ved værelsestemperatur. For frem-stilling av jern-krom-forbindelsen ble det tilsatt til den brune løsning av jernfor-bindelse 50,0 vektdeler av en 45 %ig vandig løsning av natriumdikromat-dihydrat og omrørt på nytt i 2 timer ved værelsestemperatur. pH-verdien ble justert fra 3,5 til 2,0 med 27,3 vektdeler 50 %ig H2S04. Faststoffinnholdet i den lawiskøse løsning utgjorde 29 vekt%. 68.6 parts by weight of a 40% aqueous iron (III) sulphate solution were added to the resin solution and the mixture was stirred for 2 hours at room temperature. To prepare the iron-chromium compound, 50.0 parts by weight of a 45% aqueous solution of sodium dichromate dihydrate were added to the brown solution of the iron compound and stirred again for 2 hours at room temperature. The pH value was adjusted from 3.5 to 2.0 with 27.3 parts by weight of 50% H 2 SO 4 . The solids content in the viscous solution was 29% by weight.
Den brune løsning ble oppvarmet til 60 °C og luften i rørebeholderen fortrengt med en 30 min nitrogenstrøm. Med 30 min mellomrom ble det tilsatt The brown solution was heated to 60 °C and the air in the stirrer displaced with a 30 min stream of nitrogen. It was added at 30 min intervals
37,5 vektdeler jern(II)sulfatheptahydrat, 37.5 parts by weight of iron (II) sulfate heptahydrate,
193,0 vektdeler akrylsyre, og 193.0 parts by weight acrylic acid, and
15.3 vektdeler 30 %ig hydrogenperoksidløsning jevnt dosert i løpet av 2 min ved hjelp av en slangepumpe. Derved steg temperaturen til 90 °C, og løsningen ble høy-viskøs. Den brune reaksjonsløsning ble omrørt i 2 timer ved 60 °C, fortynnet med 200 vektdeler vann og etter avkjøling til værelsestemperatur nøytralisert med ca. 383 vektdeler 35 %ig natronlut. Podepolymerisatet hadde et faststoffinnhold på 30 vekt% og en viskositet på 146 mPas. 15.3 parts by weight of 30% hydrogen peroxide solution dosed evenly over the course of 2 minutes using a hose pump. Thereby the temperature rose to 90 °C, and the solution became highly viscous. The brown reaction solution was stirred for 2 hours at 60 °C, diluted with 200 parts by weight of water and, after cooling to room temperature, neutralized with approx. 383 parts by weight 35% caustic soda. The graft polymer had a solids content of 30% by weight and a viscosity of 146 mPas.
Eksempel A. 2 Example A. 2
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i angitt rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in the specified order
166,7 vektdeler vann, 166.7 parts by weight water,
52.1 vektdeler taurin, 52.1 parts by weight taurine,
16,7 vektdeler fast natriumhydroksid, samt 16.7 parts by weight solid sodium hydroxide, as well as
48.3 vektdeler aceton 48.3 parts by weight of acetone
og varmet til 56 °C. Så snart denne temperatur var nådd, ble det fra en lagerbeholder tilsatt totalt 250 vektdeler av en 30 %ig vandig glyoksal-løsning i løpet av 10 min, hvorpå temperatur steg til 65 °C. Etter aldehyd-tilsetningen ble det omrørt i ytterligere 6 timer ved 70 °C. For overføring til metall forbindelse ble den brune varme harpiks-løsning tilsatt 30,6 vektdeler av en 60 %ig løsning av kobber(II)sulfat-pentahydrat og omrørt i 2 timer ved 85 °C. and heated to 56 °C. As soon as this temperature was reached, a total of 250 parts by weight of a 30% aqueous glyoxal solution were added from a storage container over the course of 10 minutes, after which the temperature rose to 65 °C. After the aldehyde addition, it was stirred for a further 6 hours at 70 °C. For transfer to the metal compound, 30.6 parts by weight of a 60% strength solution of copper (II) sulfate pentahydrate was added to the brown hot resin solution and stirred for 2 hours at 85 °C.
Den avkjølte løsning hadde et faststoffinnhold på 22 vekt% og en pH-verdi på 2,1. Løsningen ble oppvarmet til 60 °C og luften fortrengt fra rørebeholderen med en 30 min nitrogenstrøm. The cooled solution had a solids content of 22% by weight and a pH value of 2.1. The solution was heated to 60 °C and the air displaced from the stirring vessel with a 30 min stream of nitrogen.
Med 30 min mellomrom ble det tilsatt It was added at 30 min intervals
19.2 vektdeler jern(II)sulfatheptahydrat, 19.2 parts by weight of iron (II) sulfate heptahydrate,
30.4 vektdeler akryl syre + 36,2 vektdeler vinylacetat, og 30.4 parts by weight acrylic acid + 36.2 parts by weight vinyl acetate, and
7,96 vektdeler 30 %ig hydrogenperoksid-løsningsmiddel ble med en slangepumpe dosert jevnt innen 2 min. 7.96 parts by weight of 30% hydrogen peroxide solvent were dosed evenly within 2 minutes with a hose pump.
Deretter ble den brune reaksjonsløsning omrørt i ytterligere 2 timer ved 60 °C og etter avkjøling til værelsestemperatur nøytralisert med ca. 108 vektdeler 35 %ig natronlut. The brown reaction solution was then stirred for a further 2 hours at 60 °C and, after cooling to room temperature, neutralized with approx. 108 parts by weight 35% caustic soda.
Løsningen hadde et faststoffinnhold på 27 vekt% og en Brookfield-viskositet på 10 mPas. The solution had a solids content of 27% by weight and a Brookfield viscosity of 10 mPas.
Eksempel A. 3 Example A. 3
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i angitt rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in the specified order
116,6 vektdeler vann, 116.6 parts by weight water,
62,4 vektdeler natriumsulfitt, samt 62.4 parts by weight of sodium sulphite, as well as
10,7 vektdeler sykloheksanon 10.7 parts by weight cyclohexanone
og denne suspensjon ble varmet til 90 °C. and this suspension was heated to 90 °C.
Fra en lagerbeholder lot man deretter totalt 275,1 vektdeler formaldehydløsning (30 %ig) langsomt tilflyte innholdet, hvorved temperaturen i reaksjonsløsningen kunne stige til 100 °C. Etter formalin-tilsetningen ble det gjennomført en ytterligere 10 min lang termisk etterbehandling av satsen ved 95-100 °C. A total of 275.1 parts by weight of formaldehyde solution (30%) was then allowed to slowly flow into the contents from a storage container, whereby the temperature in the reaction solution could rise to 100 °C. After the addition of formalin, a further 10-minute long thermal post-treatment of the batch was carried out at 95-100 °C.
Den således oppnådde rødbrune harpiksløsning ble tilsatt 88,3 vektdeler av en 40 %ig vandig jern(III)sulfat-løsning. Etter 2 timers omrøring ved 95 °C var dannelsen av metallforbindelsen ferdig. Satsen ble avkjølt til 60 °C, og med 17,2 vektdeler 50 %ig svovelsyre ble pH justert fra 3,3 til 2. Deretter ble luften fortrengt fra rørebeholderen med en 30 min nitrogenstrøm. The red-brown resin solution thus obtained was added to 88.3 parts by weight of a 40% aqueous iron (III) sulphate solution. After 2 hours of stirring at 95 °C, the formation of the metal compound was complete. The batch was cooled to 60 °C, and with 17.2 parts by weight of 50% sulfuric acid, the pH was adjusted from 3.3 to 2. The air was then displaced from the stirring vessel with a 30 min stream of nitrogen.
Med 30 min mellomrom ble det tilsatt It was added at 30 min intervals
70 vektdeler jern(II)sulfatheptahydrat, 70 parts by weight of iron (II) sulfate heptahydrate,
150 vektdeler metakrylsyre, og 150 parts by weight of methacrylic acid, and
57 vektdeler 30 %ig hydrogenperoksid-løsningsmiddel ble dosert jevnt innen 5 min med en slangepumpe. 57 parts by weight of 30% hydrogen peroxide solvent was dosed evenly within 5 min with a hose pump.
Deretter ble den rødbrune reaksjonsløsning omrørt i ytterligere 3 timer ved 60 °C, og etter avkjøling til værelsestemperatur ble det nøytralisert med 19,3 vektdeler 35 %ig natronlut av pH 1,0. The red-brown reaction solution was then stirred for a further 3 hours at 60 °C, and after cooling to room temperature it was neutralized with 19.3 parts by weight of 35% caustic soda of pH 1.0.
Den brune lavviskøse polymerisatløsning hadde et faststoffinnhold på 34 vekt% og en Brookfield-viskositet på 15 mPas. The brown low viscosity polymer solution had a solids content of 34% by weight and a Brookfield viscosity of 15 mPas.
Eksempel A. 4 Example A. 4
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i angitt rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in the specified order
119,2 vektdeler vann, 119.2 parts by weight water,
20,0 vektdeler natriumsulfitt, 20.0 parts by weight sodium sulphite,
7,2 vektdeler urea, samt 7.2 parts by weight urea, as well as
34,6 vektdeler diacetonalkohol 34.6 parts by weight of diacetone alcohol
og varmet til 60 °C. and heated to 60 °C.
Til dette gulaktige, klare innhold ble 119,1 vektdeler 30 %ig formaldehyd tilsatt jevnt, dråpevis i løpet av 10 min slik at temperaturen steg til 90 °C. Dette ble omrørt ved 90 °C i 2 timer og fortynnet med vann etter behov. Den dyprøde løsning hadde et faststoffinnhold på 10 vekt% og viskositet på 180 mPas. To this yellowish, clear content, 119.1 parts by weight of 30% formaldehyde were added evenly, drop by drop over the course of 10 minutes so that the temperature rose to 90 °C. This was stirred at 90 °C for 2 hours and diluted with water as needed. The deep red solution had a solids content of 10% by weight and a viscosity of 180 mPas.
Etter avkjøling til værelsestemperatur ble løsningen justert fra pH 12,7 til pH 2 med 23 vektdeler 50 %ig svovelsyre, og varmet til 60 °C. Luft ble fortrengt fra rørebeholderen med en 30 min nitrogenstrøm. After cooling to room temperature, the solution was adjusted from pH 12.7 to pH 2 with 23 parts by weight of 50% sulfuric acid, and heated to 60 °C. Air was displaced from the stirrer with a 30 min stream of nitrogen.
Etter 30 min ble det tilsatt After 30 min it was added
32,0 vektdeler jern(II)sulfatheptahydrat, 32.0 parts by weight of iron (II) sulfate heptahydrate,
200,0 vektdeler vann, 200.0 parts by weight water,
72,0 vektdeler akrylsyre, og 72.0 parts by weight acrylic acid, and
15,2 vektdeler 30 %ig hydrogenperoksidløsning 15.2 parts by weight 30% hydrogen peroxide solution
som ved hjelp av en slangepumpe ble jevnt tilført innen 1 min. which, with the help of a hose pump, was supplied evenly within 1 min.
Deretter ble reaksjonsløsningen omrørt i ytterligere 2 timer ved 60 °C og etter avkjøling til værelsestemperatur nøytralisert med ca. 131 vektdeler 35 %ig natronlut. Den høyviskøse, brune gel hadde et faststoffinnhold på 18 vekt% og en viskositet på 1800 mPas. The reaction solution was then stirred for a further 2 hours at 60 °C and, after cooling to room temperature, neutralized with approx. 131 parts by weight 35% caustic soda. The highly viscous, brown gel had a solids content of 18% by weight and a viscosity of 1800 mPas.
Eksempel A. 5 Example A. 5
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in sequence
161,3 vektdeler vann, 161.3 parts by weight water,
36,9 vektdeler fast natriumhydroksid, 36.9 parts by weight solid sodium hydroxide,
34,6 vektdeler aminoeddiksyre, 34.6 parts by weight of aminoacetic acid,
43,4 vektdeler fenol, samt 43.4 parts by weight phenol, as well as
26,8 vektdeler aceton, 26.8 parts by weight acetone,
og oppvarmet til begynnende acetontilbakeløp. and heated to incipient acetone reflux.
Til dette fargeløse, klare innhold ble det fra en lagerbeholder tilført totalt 138,3 vektdeler 30 %ig formaldehydløsning i løpet av 5 min, idet temperaturen ved slutten av formalin-tilsetningen kunne stige til 95 °C. Etter formalin-tilsetningen ble den gule, klare løsning holdt ved 95 °C i ytterligere 1 time, og ble etter avkjøling til værelsestemperatur justert fra pH 12 til pH 2 med 110 vektdeler 50 %ig svovelsyre. Den oransjerøde reaksjonsløsning (faststoffinnhold: 30 vekt%, viskositet: 10 mPas) ble varmet til 60 °C og luften i rørebeholderen fortrengt med en 30 min stadig nitrogenstrøm. To this colorless, clear content, a total of 138.3 parts by weight of 30% formaldehyde solution were added from a storage container over the course of 5 minutes, as the temperature at the end of the formalin addition could rise to 95 °C. After the formalin addition, the yellow, clear solution was kept at 95 °C for a further 1 hour, and after cooling to room temperature was adjusted from pH 12 to pH 2 with 110 parts by weight of 50% sulfuric acid. The orange-red reaction solution (solids content: 30% by weight, viscosity: 10 mPas) was heated to 60 °C and the air in the stirring vessel displaced with a 30 min constant stream of nitrogen.
Med 30 min mellomrom ble det tilsatt It was added at 30 min intervals
26,0 vektdeler jern(II)sulfatheptahydrat, 26.0 parts by weight of iron (II) sulfate heptahydrate,
60,0 vektdeler styrensulfonsyre (Aldrich), 60.0 parts by weight styrene sulfonic acid (Aldrich),
og etter ytterligere 30 min ble and after another 30 min was
11,0 vektdeler 30 %ig hydrogenperoksidløsning tilført innen 1 min ved hjelp av en slangepumpe. 11.0 parts by weight of 30% hydrogen peroxide solution added within 1 min using a hose pump.
Deretter ble den mørkebrune reaksjonsløsning omrørt i ytterligere 2 timer ved 60 °C og etter avkjøling til værelsestemperatur nøytralisert med 110 vektdeler 35 %ig natronlut. The dark brown reaction solution was then stirred for a further 2 hours at 60 °C and, after cooling to room temperature, neutralized with 110 parts by weight of 35% caustic soda.
Den mørkebrune lavviskøse podepolymeirsatløsning hadde et faststoffinnhold på 34 vekt% og en viskositet på 18 mPas. The dark brown low-viscosity graft polymer solution had a solids content of 34% by weight and a viscosity of 18 mPas.
Eksempel A. 6 Example A. 6
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det i angitt rekkefølge fylt In a mixing container with an internal thermometer and reflux cooler, it was filled in the specified order
39,8 vektdeler vann, 39.8 parts by weight water,
17,4 vektdeler natriumsulfitt, samt 17.4 parts by weight of sodium sulphite, as well as
15,2 vektdeler aceton 15.2 parts by weight of acetone
og suspensjonen ble oppvarmet til 56 °C. and the suspension was heated to 56 °C.
Så snart aceton-tilbakeløpet begynte ble totalt 82,9 vektdeler 30 %ig formaldehydløsning tilsatt dråpevis i løpet av 10 min. Etter formaldehyd-tilsetningen ble nok en 30 min lang termisk etterbehandling av den dyprøde sats gjennomført ved 95 °C. Til denne 95 °C varme harpiksløsning ble det tilsatt 26,1 vektdeler av en 40 %ig jern(III)sulfat-løsning og så varmet 2 timer ved koking. Den erholdte løsning av metallforbindelse hadde et faststoffinnhold på 27 vekt%. Brookfield-viskositeten etter avkjøling til værelsestemperatur var 15 mPas. As soon as the acetone reflux began, a total of 82.9 parts by weight of 30% formaldehyde solution was added dropwise over 10 min. After the formaldehyde addition, another 30-minute long thermal post-treatment of the deep red batch was carried out at 95 °C. To this 95 °C hot resin solution, 26.1 parts by weight of a 40% iron (III) sulphate solution were added and then heated for 2 hours by boiling. The obtained solution of metal compound had a solids content of 27% by weight. The Brookfield viscosity after cooling to room temperature was 15 mPas.
Reaksjonsløsningen ble varmet til 90 °C og tilsatt 181 vektdeler 40 %ig 95 °C varm vandig ligno-Cr-løsning, 13,7 vektdeler salisylsyre, samt 13,7 vektdeler paraformaldehyd. Reaksjonsblandingen ble omrørt i 6 timer ved 95 °C. Løsningen hadde et faststoffinnhold på 34 vekt% og en viskositet på 50 mPas. The reaction solution was heated to 90 °C and 181 parts by weight of 40% 95 °C hot aqueous ligno-Cr solution, 13.7 parts by weight of salicylic acid and 13.7 parts by weight of paraformaldehyde were added. The reaction mixture was stirred for 6 hours at 95 °C. The solution had a solids content of 34% by weight and a viscosity of 50 mPas.
Løsningens pH-verdi ble justert fra 3,7 til 3,2 med 10 vektdeler 50 %ig H2S04. Den rødbrune løsning ble varmet til 60 °C og luften i rørebeholderen fortrengt med en 30 min nitrogenstrøm. The solution's pH value was adjusted from 3.7 to 3.2 with 10 parts by weight of 50% H2SO4. The red-brown solution was heated to 60 °C and the air in the stirrer displaced with a 30 min stream of nitrogen.
Til innholdet ble det etter 30 min tilsatt After 30 min, it was added to the contents
55 vektdeler jern(II)sulfatheptahydrat, 55 parts by weight of iron (II) sulfate heptahydrate,
117 vektdeler maleinsyre, og 117 parts by weight of maleic acid, and
45 vektdeler 30 %ig hydrogenperoksidløsning, tilført jevnt innen 8 min ved hjelp av en slangepumpe. 45 parts by weight of 30% hydrogen peroxide solution, supplied evenly within 8 minutes using a hose pump.
Deretter ble reaksjonsløsningen omrørt i nok 3 timer ved 60 °C og etter avkjøling til værelsestemperatur justert fra pH 1,0 til nøytral med 288 vektdeler 35 %ig natronlut. Løsningen hadde et faststoffinnhold på 34 vekt% og en viskositet på 19 mPas. The reaction solution was then stirred for another 3 hours at 60 °C and, after cooling to room temperature, adjusted from pH 1.0 to neutral with 288 parts by weight of 35% caustic soda. The solution had a solids content of 34% by weight and a viscosity of 19 mPas.
Eksempel A. 7 Example A. 7
Et aldolkondensat uten syrefunksjon ble fremstilt analogt oppskriften til Houben-Weyl, bind 14/11 (1963), s. 422 eksempel 3(a). An aldol condensate without an acid function was prepared analogously to the recipe of Houben-Weyl, volume 14/11 (1963), p. 422 example 3(a).
I et begerglass ble det i den angitte rekkefølge fylt In a beaker, it was filled in the specified order
696 vektdeler aceton, 696 parts by weight acetone,
2178 vektdeler 30 %ig formaldehydløsning, 2178 parts by weight 30% formaldehyde solution,
20 vektdeler kaliumkarbonat løst i 20 parts by weight of potassium carbonate dissolved in
35 vektdeler vann. 35 parts by weight of water.
I den klare løsningen steg temperaturen til koking i løpet av 45 min. Løsningen fikk stå i 26 timer og ble deretter nøytralisert med ca. 5 vektdeler konsentrert saltsyre. Den fargeløse løsning ble deretter i en rotasjonsfordamper dampet inn fra 17 vekt% faststoffinnhold til ca. 40 vekt%, og ikke omsatt aceton og formaldehyd ble fjernet. Den således oppnådde, fullt vannløselige harpiksløsning var fargeløs og hadde en Brookfield-viskositet på 70 mPas ved et faststoffinnhold på 42,4 vekt%. In the clear solution, the temperature rose to boiling within 45 min. The solution was allowed to stand for 26 hours and was then neutralized with approx. 5 parts by weight concentrated hydrochloric acid. The colorless solution was then evaporated in a rotary evaporator from 17 wt% solids content to approx. 40% by weight, and unreacted acetone and formaldehyde were removed. The fully water-soluble resin solution thus obtained was colorless and had a Brookfield viscosity of 70 mPas at a solids content of 42.4% by weight.
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det fylt 500 vektdeler 20 %ig aldolkondensat-Iøsning som var fremstilt etter oppskriften over, justert fra pH 8,6 til 7 med 0,6 vektdeler 50 %ig svovelsyre og oppvarmet til 80 °C. Luften i rørebeholderen ble fortrengt med en 30 min stadig nitrogenstrøm. 500 parts by weight of 20% aldol condensate solution prepared according to the above recipe, adjusted from pH 8.6 to 7 with 0.6 parts by weight of 50% sulfuric acid and heated to 80 °C were filled in a stirring vessel with an internal thermometer and reflux cooler. The air in the mixing vessel was displaced with a 30-min constant stream of nitrogen.
Til innholdet ble det pumpet en løsning bestående av 2,9 vektdeler 2,2-azobis-(2-metyl-propionsyrenitril) (AIBN) og 100,0 vektdeler metakrylsyre innen 20 min. A solution consisting of 2.9 parts by weight of 2,2-azobis-(2-methyl-propionic acid nitrile) (AIBN) and 100.0 parts by weight of methacrylic acid was pumped into the contents within 20 min.
Den gulaktige løsning ble omrørt i 3 timer ved 80 °C og etter behov fortynnet med vann. The yellowish solution was stirred for 3 hours at 80 °C and diluted with water as needed.
Den gulaktige, høyviskøse polymerløsning hadde et faststoffinnhold på 34 vekt% og en viskositet på 2000 mPas. The yellowish, highly viscous polymer solution had a solids content of 34% by weight and a viscosity of 2000 mPas.
Eksempel A. 8 Example A. 8
Et aldolkondensat uten syrefunksjon ble fremstilt analogt oppskriften til Houben-Weyl, bind 14/11 (1963), s. 422 eksempel 3(a). An aldol condensate without an acid function was prepared analogously to the recipe of Houben-Weyl, volume 14/11 (1963), p. 422 example 3(a).
I et begerglass ble det i den angitte rekkefølge fylt In a beaker, it was filled in the specified order
696 vektdeler aceton, 696 parts by weight acetone,
2178 vektdeler 30 %ig formaldehydløsning, 2178 parts by weight 30% formaldehyde solution,
20 vektdeler kaliumkarbonat løst i 20 parts by weight of potassium carbonate dissolved in
35 vektdeler vann. 35 parts by weight of water.
I den klare løsningen steg temperaturen til koking i løpet av 45 min. Løsningen fikk stå i 26 timer og ble deretter nøytralisert med ca. 5 vektdeler konsentrert saltsyre. Den fargeløse løsning ble deretter dampet inn i en rotasjonsfordamper fra 17 vekt% faststoffinnhold til ca. 40 vekt%, og ikke omsatt aceton og formaldehyd ble fjernet. Den således oppnådde, fullt vannløselige harpiksløsning var fargeløs og hadde en Brookfield-viskositet på 70 mPas ved et faststoffinnhold på 42,4 vekt%. In the clear solution, the temperature rose to boiling within 45 min. The solution was allowed to stand for 26 hours and was then neutralized with approx. 5 parts by weight concentrated hydrochloric acid. The colorless solution was then evaporated into a rotary evaporator from 17 wt% solids content to approx. 40% by weight, and unreacted acetone and formaldehyde were removed. The fully water-soluble resin solution thus obtained was colorless and had a Brookfield viscosity of 70 mPas at a solids content of 42.4% by weight.
I en rørebeholder med innvendig termometer og tilbakeløpskjøler ble det fylt 500 vektdeler 20 %ig aldolkondensat-Iøsning som var fremstilt etter oppskriften over, oppvarmet til 60 °C, og luften i beholderen ble fortrengt med en 30 min stadig nitrogenstrøm. Til dette innhold ble det tilsatt 120 g Na-AMPS ("Lubrizol 2405") og 30 g N-vinylpyrrolidon, og omrørt i 2 min. Deretter ble 2,5 g 30 %ig hydrogenper-oksid tilsatt, og etter kort omrøring (ca. 1 min) ble reaksjonen startet gjennom tilsetning av 6,15 g jern(II)sulfatheptahydrat, og omrørt i 2 timer ved 60 °C. In a mixing vessel with an internal thermometer and reflux cooler, 500 parts by weight of a 20% aldol condensate solution prepared according to the recipe above were filled, heated to 60 °C, and the air in the vessel was displaced with a 30-min constant stream of nitrogen. To this content were added 120 g of Na-AMPS ("Lubrizol 2405") and 30 g of N-vinylpyrrolidone, and stirred for 2 min. Then 2.5 g of 30% hydrogen peroxide was added, and after short stirring (approx. 1 min) the reaction was started by adding 6.15 g of iron (II) sulphate heptahydrate, and stirred for 2 hours at 60 °C.
Den brune reaksjonsløsning ble justert fra pH 3,8 til nøytral med 32,4 vektdeler 5 %ig natronlut. Løsningen hadde et faststoffinnhold på 19,3 vekt% og en Brookfield-viskositet på 120 mPas. The brown reaction solution was adjusted from pH 3.8 to neutral with 32.4 parts by weight of 5% caustic soda. The solution had a solids content of 19.3% by weight and a Brookfield viscosity of 120 mPas.
B. Anvendelseseksempler B. Application examples
B. l Stivneforsinkelse av sementvelling med B. l Setting delay of cement slurry with
normstivhet ( DIN 1164) standard stiffness (DIN 1164)
Resept Prescription
500 g Portlandsement PZ35F 500 g Portland cement PZ35F
100-125 g vann 100-125 g of water
2,5 g hjelpestoff (0,5 vekt% basert på sementinnhold) 2.5 g auxiliary material (0.5% by weight based on cement content)
Utførelse Execution
I henhold til DIN 1164 ble det tilberedt en vann-sement-blanding som hadde en eksakt, definert normstivhet. I en blander ble det til denne tilsatt en vandig løsning av hjelpestoffer og 100-125 g vann, og 500 g sement ble tilsatt til dette. Blandingen ble blandet i 3 min og deretter støpt i en hårdgummiring. 5 min etter blandestart ble stiv- According to DIN 1164, a water-cement mixture was prepared which had an exact, defined standard stiffness. In a mixer, an aqueous solution of auxiliaries and 100-125 g of water was added to this, and 500 g of cement was added to this. The mixture was mixed for 3 min and then cast into a hard rubber ring. 5 min after the start of mixing became stiff
heten bestemt med et Vicat-apparat som var forsett med en inntrengningsstav. The temperature was determined with a Vicat device fitted with a penetration rod.
Sementen har normstivhet når inntrengningsstaven 30 s etter at den er frigjort befinner seg 5-7 mm over hårdgummiringens grunnflate. Den foreliggende vannmengde må varieres inntil normstivhet oppnås. Har sementvellingen normstivhet blir prøven så vel som hårdgummiringen anbragt i en kasse med vanndampmettet luft. The cement has standard stiffness when the penetration rod 30 s after it has been released is 5-7 mm above the base surface of the hard rubber ring. The amount of water present must be varied until standard stiffness is achieved. If the cement slurry has standard stiffness, the sample as well as the hard rubber ring are placed in a box with air saturated with water vapour.
For bestemmelse av stivnestarten ble inntrengningsstaven byttet med en nål med nøyaktig definerte dimensjoner, og sementens stivhet ble målt med 10 min intervaller. Som stivnestart gjelder det tidspunkt hvor nålen forblir 3 til 5 mm over grunnflaten. To determine the onset of setting, the penetration rod was replaced with a needle of precisely defined dimensions, and the stiffness of the cement was measured at 10 min intervals. The point at which the needle remains 3 to 5 mm above the ground surface applies as the start of hardening.
For bestemmelse av stivneslutten ble, etter at stivnestarten var bestemt, hårdgummiringen samt sementvellingkj eglen stilt på hodet og nålens inntrengning i den tidligere grunnflate målt med 10 min mellomrom. Stivneslutten er definert som det tidspunkt når nålen trenger høyst 1 mm inn i den stivnede sementvelling. To determine the end of setting, after the start of setting had been determined, the hard rubber ring and the cement rolling cone were placed on the head and the penetration of the needle into the previous base surface was measured at 10 minute intervals. The end of setting is defined as the time when the needle penetrates no more than 1 mm into the set cement slurry.
Resultater Results
B. 2 Forsinkelse av stivnestart hos gips med inntrengningskonus ifølge DIN 1168 B. 2 Delay in the start of setting in plaster with a penetration cone according to DIN 1168
Resept Prescription
700 g of-CaSC-4 x 1/2H20 700 g of -CaSC-4 x 1/2H 2 O
140-200 g vann 140-200 g of water
3,5 g hjelpestoff (0,5 vekt% basert på gipsinnholdet) 3.5 g excipient (0.5% by weight based on the gypsum content)
Utførelse Execution
I henhold til DIN 1168 ble det tilberedt en vann-gips-blanding som hadde en spredningsgrad på 16-17 cm. Til denne ble det tilsatt 140-200 g vann og den vandige løsning av hjelpestoffet med 700 g at-gips x 1/2 H20. Etter en svelletid på 1 min ble gipsblandingen blandet i en blander i 3 min og deretter ble spredningsgraden bestemt.Den foreliggende vannmengde ble variert inntil det ble oppnådd en spredningsgrad på 16 - 17 cm. According to DIN 1168, a water-gypsum mixture was prepared which had a spreading rate of 16-17 cm. To this was added 140-200 g of water and the aqueous solution of the auxiliary substance with 700 g of at-gypsum x 1/2 H20. After a swelling time of 1 min, the gypsum mixture was mixed in a mixer for 3 min and then the degree of spreading was determined. The amount of water present was varied until a spreading degree of 16 - 17 cm was achieved.
For å bestemme stivningsstarten ble det blandet en blanding med riktig spredningsgrad, og umiddelbart etter blanding fulgte måling med et Vicaapparat med inntrengningskonus. Som stivnestart er angitt tiden i minutter inntil inntrengnings-konusen ble stående 18 ± 2 mm over gipskjeglens grunnflate. Tiden regnes fra innblanding av gips begynner. In order to determine the start of hardening, a mixture with the correct degree of dispersion was mixed, and immediately after mixing, measurement followed with a Vica apparatus with a penetration cone. The start of setting is the time in minutes until the penetration cone stood 18 ± 2 mm above the base surface of the plaster cone. The time is calculated from the start of mixing the plaster.
Resultater Results
B. 3 Stivneforsinkelse av borehullsement B. 3 Setting delay of borehole cement
B. 3. 1 Test med atmosfærisk konsistometer B. 3. 1 Test with atmospheric consistometer
Resept Prescription
792 g "Dyckerhoff Class G" sement 792 g "Dyckerhoff Class G" cement
77 g NaCl 77 g NaCl
349 g vann 349 g of water
3,96 g hjelpestoff (0,5 vekt% basert på sementinnhold) 3.96 g auxiliary material (0.5% by weight based on cement content)
Utførelse Execution
Vann og hjelpestoff ble fremstilt som løsning og deretter rørt sammen med sement og NaCl i en "Waring Blendor". Sementvellingen ble deretter fylt i en celle i det atmosfæriske konsistometer og stivnetiden bestemt ved 87,8 °C (190 °F). Under stivningen av sementvellingen ble det tegnet opp en stadig stigende viskosi-tetskurve. Stivnetiden er definert som tidsintervallet mellom målestart og tidspunktet når det oppnås et dreiemoment på 70 Bc. Water and excipients were prepared as a solution and then mixed together with cement and NaCl in a "Waring Blendor". The cement slurry was then filled into a cell of the atmospheric consistometer and the setting time determined at 87.8°C (190°F). During the hardening of the cement slurry, a constantly rising viscosity curve was drawn. The setting time is defined as the time interval between the start of the measurement and the time when a torque of 70 Bc is achieved.
Resultater Results
B. 3. 2. Test med HTHP- konsistometer B. 3. 2. Test with HTHP consistometer
Resept Prescription
860 g "Lone Star Class H" sement 860 g "Lone Star Class H" cement
327 g vann 327 g of water
4,3 g hjelpestoff (0,5 vekt% basert på sementinnhold) 4.3 g auxiliary material (0.5% by weight based on cement content)
Utførelse Execution
Vann og hjelpestoff ble fylt i et "Waring"-blandebeger og sementen rørt inn med et "Waring-Blendor". Sementvellingen ble fylt i en HTHP-målecelle og stivnetiden målt etter måleprogram 6 g ifølge API-spesifikasjon 10 (utgave 1991). Water and auxiliary material were filled in a "Waring" mixing cup and the cement stirred in with a "Waring-Blendor". The cement slurry was filled into an HTHP measuring cell and the setting time measured according to measuring program 6 g according to API specification 10 (edition 1991).
Resultater Results
B. 4 Forsinkelse av trykkfasthetutviklingen hos betong B. 4 Delay in the development of compressive strength in concrete
Resept Prescription
6,3-6,4 kg sement "Kiefersfelden PZ 35 F" 6.3-6.4 kg cement "Kiefersfelden PZ 35 F"
v/s = 0,48 v/s = 0.48
17,2 kg sand 0/4 mm 17.2 kg of sand 0/4 mm
2,8 kg grus 4/8 mm 2.8 kg gravel 4/8 mm
8,5 kg grus 8/16 mm 8.5 kg gravel 8/16 mm
11,5 kg grus 16/32 mm 11.5 kg gravel 16/32 mm
Betongfremstilling Concrete production
Tilslagsmaterialet (sand, grus) og sementen ble forblandet i 1 min i en 301 syklon-tvangsblander, tilsatt vann og blandet i ytterligere 1 min. Deretter ble sementfor-sinkeren (A.2, A.7) tilsatt og det ble blandet i nok 1 min. Vannmengden ble under hensyntagen til sementforsinkerens vanninnhold (vandige løsninger) valgt slik at det for alle betongblandinger ble oppnådd et v/s-forhold på 0,48. The aggregate (sand, gravel) and cement were premixed for 1 min in a 301 cyclone forced mixer, water added and mixed for another 1 min. Then the cement for sinker (A.2, A.7) was added and it was mixed for another 1 min. Taking into account the water content of the cement retarder (aqueous solutions), the amount of water was chosen so that a w/s ratio of 0.48 was achieved for all concrete mixtures.
Betongblandingen ble deretter i et "Wicker-rystebord RTL" rystet med 9000 svingninger pr. min, og til slutt ble det støpt terningformede prøvelegemer med 15 cm kantlengde. Prøvelegemene ble lagret ved 20 °C og 65 % relativ luftfuktighet, og testet etter varierende tidsrom med hensyn på trykkfasthet. The concrete mixture was then shaken in a "Wicker shaking table RTL" with 9,000 oscillations per second. min, and finally cube-shaped specimens with an edge length of 15 cm were cast. The specimens were stored at 20 °C and 65% relative humidity, and tested after varying periods of time with regard to compressive strength.
Resultater Results
Claims (17)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4421715A DE4421715A1 (en) | 1994-06-21 | 1994-06-21 | Use of graft polymers based on ketone-aldehyde condensation or co-condensation products |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO952460D0 NO952460D0 (en) | 1995-06-20 |
| NO952460L NO952460L (en) | 1995-12-22 |
| NO315318B1 true NO315318B1 (en) | 2003-08-18 |
Family
ID=6521152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO19952460A NO315318B1 (en) | 1994-06-21 | 1995-06-20 | Use of graft polymers of ketone aldehyde condensation products as hardening retardants for aqueous binder suspensions |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0688744B1 (en) |
| CA (1) | CA2152197C (en) |
| DE (2) | DE4421715A1 (en) |
| NO (1) | NO315318B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19627531B4 (en) * | 1996-07-09 | 2006-11-02 | Construction Research & Technology Gmbh | Water-soluble formaldehyde-free polycondensation products based on amino-s-triazines |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD79580A (en) * | ||||
| DE2341923C3 (en) | 1973-08-18 | 1980-01-31 | Bayer Ag, 5090 Leverkusen | Inorganic binding agent mortar, method of making and using the same |
| DE3144673A1 (en) | 1981-11-10 | 1983-05-26 | Skw Trostberg Ag, 8223 Trostberg | ACID GROUPS CONTAINING THERMOSTABLE, HYDROPHILIC CONDENSATION PRODUCTS OF ALDEHYDES AND KETONES |
| DE3315152A1 (en) | 1983-04-27 | 1984-11-08 | Skw Trostberg Ag, 8223 Trostberg | CO-CONDENSATION PRODUCTS OF KETONE ALDEHYDE RESINS |
| DE3429068A1 (en) | 1984-08-07 | 1986-02-20 | Skw Trostberg Ag, 8223 Trostberg | METAL COMPOUNDS OF CONDENSATION PRODUCTS CONTAINING ACID GROUPS OR CO-CONDENSATION PRODUCTS OF KETONES AND ALDEHYDES |
| US5355955A (en) * | 1993-07-02 | 1994-10-18 | Halliburton Company | Cement set retarding additives, compositions and methods |
| DE4322112A1 (en) * | 1993-07-02 | 1995-01-12 | Sueddeutsche Kalkstickstoff | Graft polymers of ketone-aldehyde condensation or co-condensation products |
-
1994
- 1994-06-21 DE DE4421715A patent/DE4421715A1/en not_active Withdrawn
-
1995
- 1995-06-19 EP EP95109472A patent/EP0688744B1/en not_active Expired - Lifetime
- 1995-06-19 DE DE59504783T patent/DE59504783D1/en not_active Expired - Fee Related
- 1995-06-20 CA CA002152197A patent/CA2152197C/en not_active Expired - Fee Related
- 1995-06-20 NO NO19952460A patent/NO315318B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2152197C (en) | 2007-05-22 |
| DE59504783D1 (en) | 1999-02-25 |
| CA2152197A1 (en) | 1995-12-22 |
| EP0688744B1 (en) | 1999-01-13 |
| NO952460D0 (en) | 1995-06-20 |
| DE4421715A1 (en) | 1996-01-04 |
| NO952460L (en) | 1995-12-22 |
| EP0688744A1 (en) | 1995-12-27 |
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