EP1313532B1 - Polymer dispersions for preventing and controlling fires with improved environmental compatibility - Google Patents
Polymer dispersions for preventing and controlling fires with improved environmental compatibility Download PDFInfo
- Publication number
- EP1313532B1 EP1313532B1 EP01958055A EP01958055A EP1313532B1 EP 1313532 B1 EP1313532 B1 EP 1313532B1 EP 01958055 A EP01958055 A EP 01958055A EP 01958055 A EP01958055 A EP 01958055A EP 1313532 B1 EP1313532 B1 EP 1313532B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- polymer
- oil
- polymer dispersions
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims description 57
- 239000006185 dispersion Substances 0.000 title claims description 45
- 230000007613 environmental effect Effects 0.000 title description 7
- 239000000178 monomer Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000004815 dispersion polymer Substances 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- -1 fatty acid ester Chemical class 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 5
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- RRPJQNOJVXGCKC-UHFFFAOYSA-M methyl-tris(prop-2-enyl)azanium;chloride Chemical group [Cl-].C=CC[N+](C)(CC=C)CC=C RRPJQNOJVXGCKC-UHFFFAOYSA-M 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004291 sulphur dioxide Substances 0.000 claims 2
- 239000004133 Sodium thiosulphate Substances 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- LDTLADDKFLAYJA-UHFFFAOYSA-L sodium metabisulphite Chemical compound [Na+].[Na+].[O-]S(=O)OS([O-])=O LDTLADDKFLAYJA-UHFFFAOYSA-L 0.000 claims 1
- UNHKSXOTUHOTAB-UHFFFAOYSA-N sodium;sulfane Chemical compound [Na].S UNHKSXOTUHOTAB-UHFFFAOYSA-N 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 239000003921 oil Substances 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 241000238578 Daphnia Species 0.000 description 8
- 229940048053 acrylate Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 241000195493 Cryptophyta Species 0.000 description 7
- 231100000419 toxicity Toxicity 0.000 description 7
- 230000001988 toxicity Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 4
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000007046 ethoxylation reaction Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 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 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- SRBSSROHORQGBO-UHFFFAOYSA-N 11-methyldodecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCCCCCCCCC(C)C SRBSSROHORQGBO-UHFFFAOYSA-N 0.000 description 2
- PRAMZQXXPOLCIY-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethanesulfonic acid Chemical compound CC(=C)C(=O)OCCS(O)(=O)=O PRAMZQXXPOLCIY-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- BANXPJUEBPWEOT-UHFFFAOYSA-N 2-methyl-Pentadecane Chemical compound CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 description 2
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 2
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- NYUTUWAFOUJLKI-UHFFFAOYSA-N 3-prop-2-enoyloxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOC(=O)C=C NYUTUWAFOUJLKI-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- AOHAPDDBNAPPIN-UHFFFAOYSA-N myristicinic acid Natural products COC1=CC(C(O)=O)=CC2=C1OCO2 AOHAPDDBNAPPIN-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- GKWCCSUCDFFLBP-UHFFFAOYSA-N oxirane Chemical compound C1CO1.C1CO1 GKWCCSUCDFFLBP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/005—Dispersions; Emulsions
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C99/00—Subject matter not provided for in other groups of this subclass
- A62C99/0009—Methods of extinguishing or preventing the spread of fire by cooling down or suffocating the flames
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Fireproofing Substances (AREA)
Description
Die vorliegende Erfindung betrifft Wasser-in-Öl-Polymerdispersionen, bestehend aus einer kontinuierlichen organischen Phase und darin fein verteilten vernetzten, wasserquellbaren Polymerisaten, wobei diese einen Restmonomerengehalt von kleiner 1.000 ppm aufweisen. Die vorliegende Erfindung betrifft desweiteren ein Verfahren zur Herstellung der erfindungsgemäßen Polymerdispersionen. Außerdem betrifft die vorliegende Erfindung Vorrichtungen zur Feuerverhütung und - bekämpfung und die Verwendung der erfindungsgemäßen Polymerdispersionen.The present invention relates to water-in-oil polymer dispersions consisting of a continuous organic phase and finely divided crosslinked, water-swellable polymers, these having a residual monomer content of less than 1,000 ppm. The present invention further relates to a method for producing the polymer dispersions according to the invention. In addition, the present invention relates to devices for fire prevention and control and the use of the polymer dispersions according to the invention.
Zur effektiven Verhütung und Bekämpfung von Feuern werden zur Erhöhung der Viskosität des Feuerlöschwassers Zusätze mit verdickenden Eigenschaften eingesetzt, um eine im Vergleich zu Wasser verbesserte Haftung des Feuerlöschmittels an Oberflächen, insbesondere an geneigten Oberflächen, zu erreichen. Die meisten der bekannten Feuerlöschwasserzusätze bestehen aus wasserquellbaren Polymeren, die jedoch aufgrund ihrer festen, körnigen Morphologie in der Anwendbarkeit eingeschränkt sind.To effectively prevent and fight fires, additives with thickening properties are used to increase the viscosity of the fire extinguishing water in order to achieve better adhesion of the fire extinguishing agent to surfaces, in particular to inclined surfaces, than water. Most of the known fire extinguishing water additives consist of water-swellable polymers, but their applicability is restricted due to their solid, granular morphology.
Um diesen Nachteil zu überwinden, werden in jüngster Zeit Polymerdispersionen in Form von Wasser-in-Öl-Emulsionen verwendet, wie sie in der EP 0 774 279 B1 beschrieben sind. Diese Emulsionen bestehen aus einer kontinuierlichen Ölphase, in der Teilchen eines vernetzten, wasserquellbaren Polymers dispergiert sind. Die Polymerteilchen haben Partikelgrößen von kleiner 2 µm, wodurch extrem kurze Quellzeiten von weniger als 3 Sekunden resultieren. Neben ihrer hohen Wasseraufnahmekapazität weisen die Wasser-in-Öl-Emulsionen die Eigenschaften eines Verdickungsmittel auf, so daß nach der Vermischung mit Wasser ein hochviskoses Feuerlöschmittel bzw. Feuerverhütungsmittel erhalten wird, das an jeglicher Art von Oberflächen, insbesondere an geneigten Oberflächen, gut haftet.In order to overcome this disadvantage, polymer dispersions in the form of water-in-oil emulsions have recently been used, as described in EP 0 774 279 B1. These emulsions consist of a continuous oil phase in which particles of a crosslinked, water-swellable polymer are dispersed. The polymer particles have particle sizes of less than 2 µm, which results in extremely short swelling times of less than 3 seconds. In addition to their high water absorption capacity, the water-in-oil emulsions have the properties of a thickener, so that after mixing with water a highly viscous fire extinguishing agent or fire prevention agent is obtained which adheres well to any type of surface, in particular to inclined surfaces.
Nachteilig an allen Zusätzen zu Feuerlöschwassern ist deren vergleichsweise geringe Umweltverträglichkeit, insbesondere deren toxische Wirkung gegenüber Mikroorganismen, wie z.B. Algen, und Daphnien. Als Maß für die Toxizität einer Substanz gegenüber Algen werden EC50-Werte verwendet, die nach der OECD Richtlinie 201 bestimmt werden und als Maß für die Toxizität gegenüber Daphnien werden entsprechende EC50-Werte verwendet, die nach der OECD Richtlinie 202 bestimmt werden. Aufgrund ihrer Toxizität gegenüber Algen bzw. Daphnien sind die bekannten Feuerlöschwasserzusätze nach europäischem Recht als "umweltgefährlich" eingestuft und müssen mit dem Gefahrensymbol "N" gekennzeichnet werden. Die Verwendung der Feuerlöschwasserzusätze gemäß dem Stand der Technik ist unter ökologischen Gesichtspunkten daher vor allem dann bedenklich, wenn sie in der freien Natur, also abseits von Plätzen, die mit einer Kanalisation oder Wasserrückhaltebecken ausgestattet sind, eingesetzt werden, wie beispielsweise bei Wald- oder Buschbränden.A disadvantage of all additives to fire extinguishing water is their comparatively low environmental compatibility, in particular their toxic effect Microorganisms such as algae and daphnia. As a measure of the toxicity of a substance to algae, EC 50 values are used, which are determined according to the OECD guideline 201 and as a measure of the toxicity to daphnia, corresponding EC 50 values are used, which are determined according to the OECD guideline 202. Due to their toxicity to algae and daphnia, the known fire extinguishing water additives are classified as "environmentally hazardous" according to European law and must be labeled with the hazard symbol "N". The use of fire extinguishing water additives according to the state of the art is therefore of particular concern from an ecological point of view if they are used in the wild, i.e. away from places that are equipped with a sewage system or water retention basin, such as in forest or bush fires ,
Aufgabe der vorliegenden Erfindung ist es daher, umweltverträglichere Polymerdispersionen zur Verfügung zu stellen, die als Zusatz zu Feuerlöschwassern eingesetzt werden können.The object of the present invention is therefore to provide more environmentally compatible polymer dispersions which can be used as an additive to fire-fighting water.
Die Aufgabe wird erfindungsgemäß durch die Bereitstellung von Wasser-in-Öl-Polymerdispersionen gelöst, die aus einer kontinuierlichen, mit Wasser praktisch nicht mischbaren organischen Phase und darin fein verteilten, vernetzten, wasserquellbaren Polymerisaten und gegebenenfalls Hilfsstoffen bestehen, wobei die Wasser-in-Öl-Polymerdispersionen einen Restmonomerengehalt von kleiner 1.000 ppm aufweisen.The object is achieved according to the invention by the provision of water-in-oil polymer dispersions which consist of a continuous organic phase which is practically immiscible with water and finely divided, crosslinked, water-swellable polymers and, if appropriate, auxiliaries, the water-in-oil Polymer dispersions have a residual monomer content of less than 1,000 ppm.
Eine Wasser-in-Öl-Polymerdispersion umfaßt sowohl eine Polymeremulsion als auch eine Polymersuspension, wie sie z.B. in Ullmann's Encyclopedia of Industrial Chemistry, 1988, Vol. A11, Seite 254 beschrieben sind, die hiermit als Referenz eingeführt wird und somit als Teil der Offenbarung gilt.A water-in-oil polymer dispersion comprises both a polymer emulsion and a polymer suspension, e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 1988, Vol. A11, page 254, which is hereby introduced as a reference and is therefore considered part of the disclosure.
Als Restmonomere im Sinne der vorliegenden Erfindung werden die in eine Polymerisationsreaktion eingesetzten und während der Polymerisation nicht umgesetzten Monomere verstanden, die somit nach der Polymerisation in der Polymerdispersion chemisch unverändert enthalten sind.For the purposes of the present invention, residual monomers are understood to be the monomers used in a polymerization reaction and not converted during the polymerization, which monomers are thus contained in the polymer dispersion in a chemically unchanged manner after the polymerization.
Bei den in den erfindungsgemäßen Wasser-in-Öl-Polymerdispersionen enthaltenen Polymerisaten handelt es sich um eine Klasse von Produkten, die vorzugsweise durch Umkehrphasen-Emulsionspolymerisation hergestellt werden. Dabei erzeugt man in einer kontinuierlichen, mit Wasser praktisch nicht mischbaren organischen Phase fein verteilte vernetzte, wasserquellbare Polymerisate unter Zusatz von Wasser-in-Öl-Emulgatoren.The polymers contained in the water-in-oil polymer dispersions according to the invention are a class of products which are preferably prepared by reverse-phase emulsion polymerization. This produces finely divided, crosslinked, water-swellable polymers in a continuous organic phase which is practically immiscible with water with the addition of water-in-oil emulsifiers.
Zur Herstellung der Polymerisate werden die Monomere der organischen Phase als Monomerenlösung, bestehend aus geeigneten Monomeren und vorzugsweise mindestens einem bifunktionellen Vernetzungsmittel, zugesetzt. Erfindungsgemäß enthält die Monomerenlösung wenigstens ein polymerisierbares, hydrophiles Monomer. Diese kann aber auch aus einer Mischung von zwei oder mehreren Monomeren aus der Gruppe der hydrophilen Monomere bestehen.To prepare the polymers, the monomers are added to the organic phase as a monomer solution consisting of suitable monomers and preferably at least one bifunctional crosslinking agent. According to the invention, the monomer solution contains at least one polymerizable, hydrophilic monomer. However, this can also consist of a mixture of two or more monomers from the group of the hydrophilic monomers.
Hydrophile Monomere sind beispielsweise Substanzen, die
- aus olefinisch ungesättigten Carbonsäuren und Carbonsäureanhydriden, insbesondere Acrylsäure, Methacrylsäure, Itaconsäure, Crotonsäure, Glutaconsäure, Maleinsäure und Maleinsäureanhydrid und deren wasserlöslichen Salzen,
- aus olefinisch ungesättigten Sulfonsäuren, insbesondere aliphatischen oder aromatischen Vinylsulfonsäuren, wie etwa Vinylsulfonsäure, Allylsulfonsäure, Styrolsulfonsäure, insbesondere Acryl- und Methacrylsulfonsäuren, wie etwa Sulfoethylacrylat, Sulfoethylmethacrylat, Sulfopropylacrylat, Sulfopropylmethacrylat, 2-Hydroxy-3-methacryloxypropylsulfonsäure und 2-Acrylamido-2-methylpropansulfonsäure (AMPS) und deren wasserlöslichen Salzen, und
- aus wasserlöslichen beziehungsweise wasserdisperbaren Derivaten der Acryl- und Methacrylsäuren, insbesondere Acrylamid, Methacrylamid, n-alkylsubstituierte Acrylamide, 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, Hydroxypropylacrylat, Hydroxypropylmethacrylat, einem C1-C4-Alkyl(meth)acrylat und Vinylacetat,
- from olefinically unsaturated carboxylic acids and carboxylic anhydrides, in particular acrylic acid, methacrylic acid, itaconic acid, crotonic acid, glutaconic acid, maleic acid and maleic anhydride and their water-soluble salts,
- from olefinically unsaturated sulfonic acids, in particular aliphatic or aromatic vinylsulfonic acids, such as vinylsulfonic acid, allylsulfonic acid, styrene sulfonic acid, in particular acrylic and methacrylicsulfonic acids, such as sulfoethylacrylate, sulfoethyl methacrylate, sulfopropylacrylate, sulfopropyl methacrylate, 2-hydroxy-3-methanoic acid 2-methacryloyloxamethyl-2-methacrylic-2-methacrylic-2-methacrylic-2-methacryloyl-2-methacrylic-2-methacrylic-2-methacrylic-2-methacrylic-2-methacrylic-2-methacryloyl-2-methacrylic-2-methacryloyl-2-and-2-methoxyl-2-methacrylate (AMPS) and their water-soluble salts, and
- from water-soluble or water-dispersible derivatives of acrylic and methacrylic acids, in particular acrylamide, methacrylamide, n-alkyl-substituted acrylamides, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, a C 1 -C 4 alkyl (meth) acrylate and vinyl acetate,
Bevorzugt enthält die Monomerenlösung als Monomere Acrylsäure und/oder ein Acrylsäurederivat, besonders bevorzugt wenigstens ein Salz der Acrylsäure und Acrylamid und ganz besonders bevorzugt eine Mischung aus Acrylsäure, Acrylamid und einem Salz der 2-Acrylamido-2-methylpropansulfonsäure.The monomer solution preferably contains, as monomers, acrylic acid and / or an acrylic acid derivative, particularly preferably at least one salt of acrylic acid and acrylamide and very particularly preferably a mixture of acrylic acid, acrylamide and a salt of 2-acrylamido-2-methylpropanesulfonic acid.
Neben einem oder mehreren hydrophilen Monomeren enthält die Monomerenlösung vorzugsweise zusätzlich 0,1 bis 1 Gew.% eines bifunktionellen Vernetzungsmittels. Der Vernetzungsgrad des Polymers beeinflußt ganz wesentlich die Viskosität und somit die Hafteigenschaften des resultierenden Polymers. Vorzugsweise werden als Vernetzer Methylenbisacrylamid, Allyl(meth)acrylat, Diallylphthalat, Polyethylenglycoldi(meth)acrylat, Tetraethylenglycoldi(meth)acrylat, Triethylenglycoldi(meth)acrylat, Diethylenglycoldi(meth)acrylat, Glycerindi(meth)acrylat, Hydroxypropyl(meth)acrylat oder Trimethylolpropantri(meth)acrylat verwendet. Besonders bevorzugt wird als Vernetzungsmittel Triallylmethylammoniumchlorid eingesetzt.In addition to one or more hydrophilic monomers, the monomer solution preferably additionally contains 0.1 to 1% by weight of a bifunctional crosslinking agent. The degree of crosslinking of the polymer significantly influences the viscosity and thus the adhesive properties of the resulting polymer. Preferred crosslinkers are methylene bisacrylamide, allyl (meth) acrylate, diallyl phthalate, polyethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, hydroxypropyl (meth) acrylate Trimethylolpropane tri (meth) acrylate used. Triallylmethylammonium chloride is particularly preferably used as the crosslinking agent.
Zur Vorbereitung der Polymerisation und Herstellung der monomerenhaltigen Wasser-in-Öl-Dispersion wird die Monomerenlösung einer organischen Phase zugesetzt, die einen Wasser-in-Öl-Emulgator enthält.To prepare for the polymerization and preparation of the monomer-containing water-in-oil dispersion, the monomer solution is added to an organic phase which contains a water-in-oil emulsifier.
Als organische Phase können prinzipiell alle dem Fachmann für eine Umkehr-Emulsionspolymerisation bekannten Substanzen verwendet werden.In principle, all substances known to the person skilled in the art for a reverse emulsion polymerization can be used as the organic phase.
In einer bevorzugten Ausführungsform dieser Erfindung werden als organische Phase Fettsäureester verwendet. Besonders bevorzugt werden Ester von linearen gesättigten bzw. ungesättigten Fettsäuren, insbesondere Fettsäuren mit einer Alkylkettenlänge von mehr als 11 Kohlenstoffatomen, besonders bevorzugt Laurin-, Myristin-, Palmitin-, Stearin- und Ölsäure, mit Alkoholen verwendet. Als Alkoholkomponente werden vorzugsweise kurzkettige Alkohole, bevorzugt C1-C4-Alkohole, verwendet. Ebenfalls bevorzugt werden höhere, einmal verzweigte Alkohole eingesetzt, die vorzugsweise durch eine Guerbetsynthese hergestellt werden. Durch Verwendung dieser Substanzen werden Wasser-in-Öl-Polymerdispersionen erhalten, die eine sehr geringe Daphnientoxizität, gemessen nach der OECD Richtlinie 202, aufweisen. Insbesondere werden durch Verwendung der bevorzugten organischen Phasen Wasser-in-Öl-Polymerdispersionen erhalten, die einen EC50-Wert, bestimmt nach OECD Richtlinie 202, von mehr als 10 mg/l aufweisen.In a preferred embodiment of this invention, fatty acid esters are used as the organic phase. Esters of linear saturated or unsaturated fatty acids, in particular fatty acids with an alkyl chain length of more than 11 carbon atoms, particularly preferably lauric, myristic, palmitic, stearic and oleic acid, with alcohols are particularly preferably used. Short-chain alcohols, preferably C 1 -C 4 alcohols, are preferably used as the alcohol component. Higher, once branched alcohols are also preferably used, which are preferably produced by Guerbet synthesis. By using these substances, water-in-oil polymer dispersions received, which have a very low daphnia toxicity, measured according to the OECD Guideline 202. In particular, by using the preferred organic phases, water-in-oil polymer dispersions are obtained which have an EC 50 value, determined according to OECD Guideline 202, of more than 10 mg / l.
Die Fettsäureester werden alleine oder bevorzugt in Mischung mit einem Kohlenwasserstoff oder einem Gemisch aus Kohlenwasserstoffen eingesetzt, wobei der Kohlenwasserstoff oder das Gemisch aus Kohlenwasserstoffen einen Siedepunkt von weniger als 200°C aufweisen. Ganz besonders bevorzugt werden zu diesem Zweck sogenannte Weißöle aus der Erdöldestillation oder Ligroin mit einem Siedebereich von 150-200°C verwendet.The fatty acid esters are used alone or preferably in a mixture with a hydrocarbon or a mixture of hydrocarbons, the hydrocarbon or the mixture of hydrocarbons having a boiling point of less than 200 ° C. So-called white oils from petroleum distillation or ligroin with a boiling range of 150-200 ° C. are very particularly preferably used for this purpose.
Vorzugsweise wird die organische Phase in einer Menge von 20 bis 80 Gew.%, bezogen auf die Menge der Dispersion, eingesetzt.The organic phase is preferably used in an amount of 20 to 80% by weight, based on the amount of the dispersion.
Als Emulgator werden der organischen Phase 0,5 bis 10 Gew.%, bezogen auf die Menge der Dispersion, eines öllöslichen Emulgators zugegeben. Vorzugsweise werden Emulgatoren aus der Gruppe der Tenside verwendet. Besonders bevorzugt werden Sorbitanester, Phthalsäureester, Fettsäureglyceride und ethoxylierte Derivate derselben eingesetzt. Ganz besonders bevorzugt werden polymere Emulgatoren mit dem Handelsnamen Hypermer® (von ICI, London, England) verwendet.As an emulsifier, 0.5 to 10% by weight, based on the amount of dispersion, of an oil-soluble emulsifier is added to the organic phase. Emulsifiers from the group of the surfactants are preferably used. Sorbitan esters, phthalic acid esters, fatty acid glycerides and ethoxylated derivatives thereof are particularly preferably used. Polymeric emulsifiers with the trade name Hypermer® (from ICI, London, England) are very particularly preferably used.
Nach Abschluß der Polymerisation wird der Polymerdispersion vorzugsweise ein Restmonomerenvernichter zugesetzt. Der Zusatz wird so bemessen, daß der Gehalt an Restmonomeren in der resultierenden Wasser-in-Öl-Polymerdispersion kleiner als 1.000 ppm ist.After the polymerization has ended, a residual monomer killer is preferably added to the polymer dispersion. The addition is such that the content of residual monomers in the resulting water-in-oil polymer dispersion is less than 1,000 ppm.
Restmonomerenvernichter im Sinne der vorliegenden Erfindung sind Substanzen, die polymerisierbare Monomere durch eine chemische Reaktion derart modifizieren, daß sie nicht mehr polymerisierbar sind, so daß sie im Sinne der vorliegenden Erfindung keine Monomere mehr sind. Zu diesem Zweck können Substanzen verwendet werden, die mit der in den Monomeren enthaltenen Doppelbindung reagieren und/oder Substanzen, die eine weitergehende Polymerisation einleiten können.Residual monomer destroyers in the sense of the present invention are substances which modify polymerizable monomers by a chemical reaction in such a way that they are no longer polymerizable, so that they are no longer monomers in the sense of the present invention. For this purpose, substances are used which react with the double bond contained in the monomers and / or substances which can initiate further polymerization.
Als Restmonomerenvemichter, die mit der Doppelbindung reagieren, können z.B. Reduktionsmittel verwendet werden, vorzugsweise
- Substanzen aus der Gruppe der sauren und neutralen Salze der vom Schwefel abgeleiteten Säuren mit einer Oxidationszahl kleiner als VI, bevorzugt Natriumdithionit, Natriumthiosulfat, Natriumsulfit oder Natriumdisulfit, und/oder
- Substanzen mit einer Schwefelwasserstoffgruppe, vorzugsweise Natriumhydrogensulfid oder Verbindungen aus der Gruppe der Thiole, bevorzugt Merkaptoethanol, Dodecylmerkaptan, Thiopropionsäure oder Salze der Thiopropionsäure oder Thiopropansulfonsäure oder Salze der Thiopropansulfonsäure, und/oder
- Substanzen aus der Gruppe der Amine, bevorzugt aus der Gruppe der Amine mit niederer Flüchtigkeit, vorzugsweise Diisopropanolamin oder Aminoethylethanolamin, und/oder
- Substanzen aus der Gruppe, die aus Buntesalzen, Formamidinsulfinsäure, Schwefeldioxid, wäßrigen und organischen Lösungen von Schwefeldioxid oder Thioharnstoff.
- Substances from the group of the acidic and neutral salts of the sulfur-derived acids with an oxidation number less than VI, preferably sodium dithionite, sodium thiosulfate, sodium sulfite or sodium disulfite, and / or
- Substances with a hydrogen sulfide group, preferably sodium hydrogen sulfide or compounds from the group of the thiols, preferably mercaptoethanol, dodecyl mercaptan, thiopropionic acid or salts of thiopropionic acid or thiopropanesulfonic acid or salts of thiopropanesulfonic acid, and / or
- Substances from the group of amines, preferably from the group of amines with low volatility, preferably diisopropanolamine or aminoethylethanolamine, and / or
- Substances from the group consisting of colored salts, formamidine sulfinic acid, sulfur dioxide, aqueous and organic solutions of sulfur dioxide or thiourea.
Der Fachmann erkennt, daß auch eine Mischung von mindestens zwei Restmonomerenvernichtern aus einer oder mehreren Gruppen eingesetzt werden können.Those skilled in the art will recognize that a mixture of at least two residual monomer destroyers from one or more groups can also be used.
Zur Reduzierung des Restmonomerengehaltes durch eine erneut eingeleitete Polymerisation können die oben genannten Reduktionsmittel in Kombination mit Oxidationsmitteln, vorzugsweise Substanzen aus der Gruppe der Peroxodisulfate oder Hydroperoxide, bevorzugt Wasserstoffperoxid, verwendet werden. Desweiteren eignen sich zur Reduzierung des Restmonomerengehaltes Verbindungen, die bei erhöhter Temperatur in Radikale zerfallen, wie vorzugsweise Substanzen aus der Gruppe der Azoverbindungen, Peroxide oder Peroxodisulfate.To reduce the residual monomer content by means of a renewed polymerization, the abovementioned reducing agents can be used in combination with oxidizing agents, preferably substances from the group of the peroxodisulfates or hydroperoxides, preferably hydrogen peroxide. Also suitable for reducing the residual monomer content are compounds which decompose into radicals at elevated temperature, such as preferably substances from the group of azo compounds, peroxides or peroxodisulfates.
Vorzugsweise werden 100 bis 20.000 ppm, bevorzugt 200 bis 5.000 ppm und besonders bevorzugt 500 bis 3.000 ppm, bezogen auf die Dispersion, an Restmonomerenvernichtern zugesetzt.Preferably 100 to 20,000 ppm, more preferably 200 to 5,000 ppm and particularly preferably 500 to 3,000 ppm, based on the dispersion, of residual monomer destroyers are added.
Abschließend wird der Wasser-in-Öl-Polymerdispersion ein auch als Aktivator oder Inverter bezeichneter Öl-in-Wasser-Emulgator in einer Menge von 0,5 bis 10 Gew.%, bezogen auf die Menge der Emulsion zugegeben. Vorzugsweise werden als Inverter ethoxylierte Fettalkohole eingesetzt, bevorzugt ethoxylierte Fettalkohole, die aus linearen und/oder verzweigten Fettalkoholen mit einer Alkylkettenlänge von mehr als 11 Kohlenstoffatomen hergestellt werden. Ebenfalls bevorzugt werden Ethoxylierungsprodukte von hochverzweigten Alkoholen, die durch Oxosynthese zugänglich sind, wie vorzugsweise Isotridecylalkohol, eingesetzt. Besonders bevorzugt wird als Invertor ein Ethoxylierungsprodukt von höheren, einmal verzweigten Alkoholen verwendet, die durch Guerbetsynthese zugänglich sind.Finally, the water-in-oil polymer dispersion is added an oil-in-water emulsifier, also referred to as an activator or inverter, in an amount of 0.5 to 10% by weight, based on the amount of the emulsion. Ethoxylated fatty alcohols are preferably used as inverters, preferably ethoxylated fatty alcohols which are produced from linear and / or branched fatty alcohols with an alkyl chain length of more than 11 carbon atoms. Ethoxylation products of highly branched alcohols, which are accessible by oxosynthesis, such as preferably isotridecyl alcohol, are likewise preferably used. An ethoxylation product of higher, once branched alcohols, which are accessible by Guerbet synthesis, is particularly preferably used as the inverter.
Die erfindungsgemäße Wasser-in-Öl-Polymerdispersion enthält vorzugsweise 10 bis 70 Gew.%, besonders bevorzugt 20 bis 50 Gew.% und ganz besonders bevorzugt 25 bis 35 Gew.%, an vernetzten, wasserquellbaren Polymerteilchen.The water-in-oil polymer dispersion according to the invention preferably contains 10 to 70% by weight, particularly preferably 20 to 50% by weight and very particularly preferably 25 to 35% by weight, of crosslinked, water-swellable polymer particles.
Die Polymerteilchen weisen vorzugsweise eine Partikelgröße von weniger als 2 µm, und besonders bevorzugt eine Partikelgröße von weniger als 1 µm auf. Vorzugsweise beträgt die Quellzeit der Polymerteilchen weniger als 3 sec.The polymer particles preferably have a particle size of less than 2 μm, and particularly preferably a particle size of less than 1 μm. The swelling time of the polymer particles is preferably less than 3 seconds.
Die erfindungsgemäßen, als Wasserzusatz zur Feuerverhütung und -bekämpfung einsetzbaren, Wasser-in-Öl-Polymerdispersionen zeichnen sich gegenüber den bisher bekannten Feuerlöschwasserzusätzen durch eine verbesserte Umweltverträglichkeit, insbesondere durch eine geringere Toxizität gegenüber Mikroorganismen aus. Insbesondere weisen sie einen nach dem Algentest gemäß der OECD Richtlinie 201 bestimmten EC50-Wert von über 10 mg/l auf. Teilweise werden auch im Daphnientest gemäß der OECD Richtlinie 202 EC50-Werte von über 10 mg/l erhalten, so daß die erfindungsgemäßen Dispersionen nach europäischen Recht lediglich als "schädlich für Wasserorganismen" eingestuft werden. Eine Kennzeichnungspflicht mit dem Gefahrensymbol "N" entfällt.The water-in-oil polymer dispersions according to the invention, which can be used as water additives for fire prevention and fighting, are distinguished from the previously known fire-fighting water additives by an improved environmental compatibility, in particular by a lower toxicity to microorganisms. In particular, they have an EC 50 value of over 10 mg / l, determined according to the algae test in accordance with OECD Guideline 201. In some cases 202 EC 50 values of over 10 mg / l are also obtained in the daphnia test according to the OECD guideline, so that the dispersions according to the invention comply with European Can only be classified as "harmful to aquatic organisms". A labeling requirement with the danger symbol "N" does not apply.
Durch diese verbesserte Umweltverträglichkeit sind die erfindungsgemäßen Feuerlöschwasserzusätze gegenüber den Feuerlöschwasserzusätzen nach dem Stand der Technik bei der Feuerverhütung und -bekämpfung aus ökologischen Gesichtspunkten vor allem in der freien Natur, vorzugsweise bei Wald- oder Buschbränden, bevorzugt einzusetzen.As a result of this improved environmental compatibility, the fire extinguishing water additives according to the invention are to be used with preference over fire extinguishing water additives according to the state of the art in fire prevention and control from an ecological point of view, especially in the wild, preferably in forest or bush fires.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Wasser-in-Öl-Polymerdispersionen vorzugsweise durch Phasenumkehr-Emulsionspolymerisation, wobei der Polymerdispersion nach der Polymerisation ein Restmonomerenvernichter zugesetzt wird.The present invention further provides a process for the preparation of the water-in-oil polymer dispersions according to the invention, preferably by phase reversal emulsion polymerization, with a residual monomer destroyer being added to the polymer dispersion after the polymerization.
Zur Herstellung der Reaktionslösung werden die Monomere der organischen Phase als Monomerenlösung, bestehend aus geeigneten Monomeren, Wasser und vorzugsweise mindestens einem bifunktionellen Vernetzungsmittel, zugesetzt.To prepare the reaction solution, the monomers are added to the organic phase as a monomer solution consisting of suitable monomers, water and preferably at least one bifunctional crosslinking agent.
Die Polymerisationsreaktion wird durch Zugabe der dem Fachmann bekannten Polymerisationsinitiatoren gestartet. Vorzugsweise werden hierzu Azoverbindungen, Peroxidverbindungen oder Redoxkatalysatoren, jeweils alleine oder in Mischung miteinander, in einer Menge von 0,001 bis 5 Gew.%, bezogen auf die Menge an Monomerenlösung, verwendet.The polymerization reaction is started by adding the polymerization initiators known to the person skilled in the art. For this purpose, azo compounds, peroxide compounds or redox catalysts, in each case alone or as a mixture with one another, are preferably used in an amount of 0.001 to 5% by weight, based on the amount of monomer solution.
Die Polymerisation wird adiabatisch, isotherm oder als Kombination eines adiabatischen und isothermen Verfahrens durchgeführt.The polymerization is carried out adiabatically, isothermally or as a combination of an adiabatic and isothermal process.
Bei der isothermen Prozeßführung nach der EP 0 228 397 B1 wird die Polymerisation bei einer bestimmten Temperatur unter vermindertem Druck gestartet. Der verminderte Druck wird dabei so eingestellt, daß durch die entstehende Polymerisationswärme flüchtige Stoffe, wie Wasser und Bestandteile der organischen Phase, abdestillieren und die Temperatur bis auf einige Grade konstant gehalten werden kann. Das Ende der Polymerisation ist dadurch charakterisiert, daß kein Destillat mehr übergeht. Nach der Polymerisation werden erfindungsgemäß der Polymerdispersion die o.g. Restmonomerenvemichter zugesetzt. Da die Dispersion nach dem Ende der Reaktion sauerstofffrei ist, verläuft die Reduzierung der Menge an Restmonomeren nach Zusatz der Restmonomerenvernichter bei diesem Verfahren besonders effektiv. Vorzugsweise werden 100 bis 20.000 ppm, bevorzugt 200 bis 5.000 ppm und besonders bevorzugt 500 bis 3.000 ppm, bezogen auf die Dispersion, an Restmonomerenvernichter eingesetzt.In the isothermal process control according to EP 0 228 397 B1, the polymerization is started at a certain temperature under reduced pressure. The reduced pressure is adjusted so that The resulting heat of polymerization distills off volatile substances such as water and constituents of the organic phase and the temperature can be kept constant to a few degrees. The end of the polymerization is characterized in that no more distillate passes over. After the polymerization, according to the invention, the abovementioned residual monomer eliminators are added to the polymer dispersion. Since the dispersion is oxygen-free after the end of the reaction, the reduction in the amount of residual monomers after the addition of the residual monomer destroyers is particularly effective in this process. 100 to 20,000 ppm, preferably 200 to 5,000 ppm and particularly preferably 500 to 3,000 ppm, based on the dispersion, of residual monomer destroyers are preferably used.
Analog zu dem isothermen Verfahren wird der adiabatische Prozeß bei einer bestimmten Temperatur gestartet. Die Polymerisation wird jedoch bei Atmosphärendruck ohne äußere Wärmezufuhr durchgeführt, bis durch die Polymerisationswärme eine von dem Gehalt an polymerisierbarer Substanz abhängige Endtemperatur erreicht wird. Nach dem Ende der Polymerisation erfolgt eine Abkühlung der Reaktionsmischung, in deren Verlauf der Restmonomerenvernichter zugesetzt wird. Da bei dieser Prozeßführung keine sauerstofffreie Dispersionen erhalten werden, müssen größere Mengen an Restmonomerenvernichter eingesetzt werden. Vorzugsweise werden bei dieser Prozeßführung 100 bis 20.000 ppm, bevorzugt 500 bis 5.000 ppm, an Restmonomerenvernichter eingesetzt.Analogous to the isothermal process, the adiabatic process is started at a certain temperature. However, the polymerization is carried out at atmospheric pressure without external heat supply, until a final temperature which is dependent on the content of polymerizable substance is reached by the heat of polymerization. After the end of the polymerization, the reaction mixture is cooled, in the course of which the residual monomer destroyer is added. Since no oxygen-free dispersions are obtained in this process, larger amounts of residual monomer destroyers must be used. Preferably 100 to 20,000 ppm, preferably 500 to 5,000 ppm, of residual monomer destroyers are used in this process.
Die Polymerisation kann desweiteren als Kombination eines isothermen und adiabatischen Prozesses durchgeführt werden. Ein solcher Prozeß wird vorzugsweise zunächst isotherm geführt. Zu einem vorher bestimmten Zeitpunkt wird die Apparatur mit Inertgas belüftet und die Polymerisation bis zu einer bestimmten Endtemperatur adiabatisch weitergeführt. Daran anschließend wird der Ansatz durch erneutes Anlegen von Vakuum und Destillation bis auf eine vorgewählte Temperatur abgekühlt. Durch diese Verfahrensführung wird eine sauerstofffreie Polymerdispersion erhalten, so daß die Reduzierung der Menge an Restmonomeren nach Zusatz der Restmonomerenvernichter besonders effektiv verläuft. Vorzugsweise werden 100 bis 20.000 ppm, bevorzugt 200 bis 5.000 ppm und besonders bevorzugt 500 bis 3.000 ppm an Restmonomerenvernichter, bezogen auf die Dispersion, eingesetzt.The polymerization can also be carried out as a combination of an isothermal and adiabatic process. Such a process is preferably carried out isothermally at first. At a predetermined time, the apparatus is aerated with inert gas and the polymerization is continued adiabatically up to a certain final temperature. The batch is then cooled to a preselected temperature by applying a new vacuum and distillation. This procedure results in an oxygen-free polymer dispersion, so that the reduction in the amount of residual monomers runs particularly effectively after adding the residual monomer destroyer. Preferably 100 to 20,000 ppm, preferably 200 to 5,000 ppm and particularly preferably 500 to 3,000 ppm of residual monomer destroyer, based on the dispersion, are used.
Abschließend wird der Dispersion ein auch als Aktivator oder Inverter bezeichneter Ö/W-Emulgator in einer Menge von 0,5 bis 10 Gew.%, bezogen auf die Menge der Dispersion, zugegeben. Als Inverter werden vorzugsweise ethoxylierte Fettalkohole eingesetzt, bevorzugt ethoxylierte Fettalkohole, die aus linearen und/oder verzweigten Fettalkoholen mit einer Alkylkettenlänge von mehr als 11 Kohlenstoffatomen hergestellt werden. Ebenfalls bevorzugt werden Ethoxylierungsprodukte von hochverzweigten Alkoholen, die durch Oxosynthese zugänglich sind, wie vorzugsweise Isotridecylalkohol, eingesetzt. Besonders bevorzugt wird als Invertor ein Ethoxylierungsprodukt von höheren, einmal verzweigten Alkoholen verwendet, die durch Guerbetsynthese zugänglich sind.Finally, an O / W emulsifier, also referred to as an activator or inverter, is added to the dispersion in an amount of 0.5 to 10% by weight, based on the amount of the dispersion. Ethoxylated fatty alcohols are preferably used as inverters, preferably ethoxylated fatty alcohols which are produced from linear and / or branched fatty alcohols with an alkyl chain length of more than 11 carbon atoms. Ethoxylation products of highly branched alcohols, which are accessible by oxosynthesis, such as preferably isotridecyl alcohol, are likewise preferably used. An ethoxylation product of higher, once branched alcohols, which are accessible by Guerbet synthesis, is particularly preferably used as the inverter.
Mit dem erfindungsgemäßen Verfahren können im Vergleich zu den Verfahren nach dem Stand der Technik umweltverträglichere Polymerdispersionen hergestellt werden, die als Zusatz zu Feuerlöschwassern eingesetzt werden können. Durch das erfindungsgemäße Verfahren werden Polymerdispersionen erhalten, die EC50-Werte nach dem Algentest gemäß der OECD Richtlinie 201 von über 10 mg/l aufweisen. Teilweise werden auch im Daphnientest gemäß der OECD Richtlinie 202 EC50-Werte von über 10 mg/l erhalten, so daß die erfindungsgemäßen Polymerdispersionen nach europäischen Recht lediglich als "schädlich für Wasserorganismen" eingestuft werden und eine Kennzeichnungspflicht mit dem Gefahrensymbol "N" entfällt.In comparison with the methods according to the prior art, the method according to the invention can be used to produce more environmentally compatible polymer dispersions, which can be used as an additive to fire-fighting water. The process according to the invention gives polymer dispersions which have EC 50 values according to the algae test in accordance with OECD Guideline 201 of over 10 mg / l. In some cases 202 EC 50 values of over 10 mg / l are obtained in the daphnia test in accordance with the OECD guideline, so that the polymer dispersions according to the invention are only classified as “harmful to aquatic organisms” under European law and there is no obligation to label them with the hazard symbol “N”.
Die vorliegende Erfindung betrifft desweiteren die Verwendung der erfindungsgemäßen Polymerdispersionen als Feuerlöschmittel, bei der die Polymerdispersion mit Wasser versetzt wird.The present invention further relates to the use of the polymer dispersions according to the invention as fire extinguishing agents, in which water is added to the polymer dispersion.
Feuerlöschmittel im Sinne der vorliegenden Erfindung sind Mittel, die geeignet sind, Oberflächen vor Feuer zu schützen und/oder Feuer zu bekämpfen.Fire extinguishing agents in the sense of the present invention are agents which are suitable for protecting surfaces against fire and / or for fighting fire.
Die Vermischung der erfindungsgemäßen Wasser-in-Öl-Polymerdispersionen mit Wasser kann mit allen zu diesem Zweck üblichen Vorrichtungen erfolgen, wie sie beispielsweise in der EP 0 774 279 B1 und in der DE 299 04 848 U1 beschrieben sind. Diese Schriften werden hiermit als Referenz eingeführt und gelten somit als Teil der Offenbarung.The water-in-oil polymer dispersions according to the invention can be mixed with water using all the devices customary for this purpose, as described, for example, in EP 0 774 279 B1 and in DE 299 04 848 U1. These writings are hereby introduced as a reference and are therefore considered part of the disclosure.
Vorzugsweise wird die Polymerdispersion dem Wasser in einer Konzentration von 0,01 bis 50 Vol.% zugesetzt. Besonders bevorzugt werden zur Mischung mit Wasser 0,02 bis 10 Vol.% und ganz besonders bevorzugt 1 bis 2 Vol.% an Wasser-in-Öl-Polymerdispersion verwendet.The polymer dispersion is preferably added to the water in a concentration of 0.01 to 50% by volume. 0.02 to 10% by volume and very particularly preferably 1 to 2% by volume of water-in-oil polymer dispersion are particularly preferably used for mixing with water.
Um eine gute Haftung des Feuerlöschmittels an Oberflächen zu erreichen, weist die Mischung aus Wasser und Polymerdispersion vorzugsweise eine Viskosität von über 100 mPa·s, besonders bevorzugt eine Viskosität im Bereich von 500 bis 50.000 mPa·s auf.In order to achieve good adhesion of the fire extinguishing agent to surfaces, the mixture of water and polymer dispersion preferably has a viscosity of over 100 mPa · s, particularly preferably a viscosity in the range from 500 to 50,000 mPa · s.
Die Verwendung der erfindungsgemäßen Wasser-in-Öl-Polymerdispersionen zeichnet sich gegenüber der Verwendung der bekannten Feuerlöschmittel durch eine höhere Umweltverträglichkeit, insbesondere durch eine geringere Toxizität gegenüber Mikroorganismen, aus.The use of the water-in-oil polymer dispersions according to the invention is distinguished from the use of the known fire extinguishing agents by a higher environmental compatibility, in particular by a lower toxicity to microorganisms.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Aufbringen der erfindungsgemäßen Wasser-in-Öl-Polymerdispersion auf eine Oberfläche zur Verhütung und/oder Bekämpfung von Bränden, wobei Wasser mit der Polymerdispersion in einer Menge versetzt wird, die ausreicht, um die Viskosität der resultierenden Wasser/Polymerdispersion-Mischung auf über 100 mPa·s anzuheben, und diese Mischung auf die Oberfläche aufgebracht wird.Another object of the present invention is a method for applying the water-in-oil polymer dispersion according to the invention to a surface for preventing and / or fighting fires, water being added to the polymer dispersion in an amount sufficient to adjust the viscosity of the the resulting water / polymer dispersion mixture to above 100 mPa · s, and this mixture is applied to the surface.
Um diese Viskosität zu erreichen, wird die Polymerdispersion mit Wasser oder wäßrigen Löschmitteln, vorzugsweise in einer Konzentration von 0,01 bis 50 Vol.%, besonders bevorzugt von 0,02 bis 10 Vol.% und ganz besonders bevorzugt von 1 bis 2 Vol.% vermischt.To achieve this viscosity, the polymer dispersion is mixed with water or aqueous extinguishing agents, preferably in a concentration of 0.01 to 50% by volume. particularly preferably from 0.02 to 10% by volume and very particularly preferably from 1 to 2% by volume.
Das Feuerlöschmittel gemäß dieser Erfindung kann mit jedem üblichen Brandbekämpfungsgerät auf die von Feuer betroffenen Oberflächen aufgebracht werden. Solche Geräte sind beispielsweise in der EP 0 774 279 B1 und in der DE 299 04 848 U1 beschrieben.The fire extinguishing agent according to this invention can be applied to the surfaces affected by fire with any conventional fire-fighting device. Such devices are described for example in EP 0 774 279 B1 and in DE 299 04 848 U1.
Die Vermischung der Polymerdispersion mit dem Wasser kann vorzugsweise kontinuierlich oder batchweise erfolgen.The polymer dispersion can preferably be mixed with the water continuously or in batches.
Das erfindungsgemäße Verfahren zeichnet sich durch eine gegenüber den bekannten Verfahren durch eine verbesserte Umweltverträglichkeit aus. Besonders geeignet ist das Verfahren daher in der freien Natur, also abseits von Plätzen, die mit einer Kanalisation oder Wasserrückhaltebecken ausgestattet sind, einzusetzen, wie beispielsweise bei Wald- oder Buschbränden.The method according to the invention is distinguished by an improved environmental compatibility compared to the known methods. The method is therefore particularly suitable for use in the wild, i.e. away from places that are equipped with a sewage system or water retention basin, such as in forest or bush fires.
Ein weiterer Gegenstand der vorliegenden Erfindung ist eine Vorrichtung zur Feuerverhütung und zum Feuerlöschen, die aus einem druckfesten Behälter zur Aufnahme eines aus Wasser und der erfindungsgemäßen Polymerdispersion bestehenden Feuerlöschmittels besteht.Another object of the present invention is a device for fire prevention and fire extinguishing, which consists of a pressure-resistant container for holding a fire extinguishing agent consisting of water and the polymer dispersion according to the invention.
Das Feuerlöschmittel kann in dem druckfesten Behälter als Mischung aus der erfindungsgemäßen Polymerdispersion und Wasser enthalten sein und durch übliche Auslaßvorrichtungen auf den Brandherd aufgebracht werden. Die beiden Komponenten, nämlich die Polymerdispersion und das Wasser, sind jedoch vorzugsweise zunächst getrennt voneinander, in verschiedenen, abgetrennten Abschnitten des Behälters untergebracht und werden durch Betätigen eines hierzu bekannten Auslösemechanismus miteinander vermischt.The fire-extinguishing agent can be contained in the pressure-resistant container as a mixture of the polymer dispersion according to the invention and water and can be applied to the source of the fire through conventional outlet devices. However, the two components, namely the polymer dispersion and the water, are preferably initially separated from one another and are accommodated in different, separate sections of the container and are mixed together by actuating a trigger mechanism known for this purpose.
Die Vorrichtung ist vorzugsweise ein Handfeuerlöscher oder ein Feuerlöschzug, wie sie in dem Stand der Technik, vorzugsweise in der EP 0 774 279 B1 und in der DE 299 04 848 U1, beschrieben sind.The device is preferably a hand-held fire extinguisher or a fire-fighting train as described in the prior art, preferably in EP 0 774 279 B1 and in DE 299 04 848 U1.
Die erfindungsgemäßen Vorrichtungen zeichnen sich durch eine erhöhte Umweltverträglichkeit des darin enthaltenen Feuerlöschmittels aus.The devices according to the invention are distinguished by an increased environmental compatibility of the fire extinguishing agent contained therein.
Die Ermittlung der Toxizität gegenüber Mikroorganismen wurde entsprechend den OECD "Guidelines for Testing of Chemicals" durchgeführt.The toxicity to microorganisms was determined in accordance with the OECD "Guidelines for Testing of Chemicals".
Im einzelnen sind dies die OECD Richtlinie 201, "Alga, Growth Inhibition Test", und die OECD Richtlinie 202, "Daphnia sp., Acute Immobilisation Test and Reproduction Test" Part 1.Specifically, these are the OECD Guideline 201, "Alga, Growth Inhibition Test", and the OECD Guideline 202, "Daphnia sp., Acute Immobilization Test and Reproduction Test" Part 1.
Im folgenden wird die Erfindung anhand von Beispielen erläutert. Diese Erläuterungen sind lediglich beispielhaft und schränken den allgemeinen Erfindungsgedanken nicht ein.In the following the invention is explained with the aid of examples. These explanations are only examples and do not limit the general inventive concept.
Dabei werden folgende Abkürzungen verwendet:
- ABAH
- 2,2'-Azo-bis-amidinopropan-dihydrochlorid
- AIBN
- 2,2'-Azo-bis-2-methylpropionitril
- AMPS
- 2-Acrylamido-2-methylpropansulfonsäure
- BO
- 2-Butyl-octanol
- EO
- Ethylenoxid (1,2-Epoxiethan)
- IHD
- Isohexadecan
- ITDA
- Isotridecylalkohol
- ITS
- Isotridecylstearat
- ÖFSBOE
- Ölfettsäurebutyloctylester
- RÖFSME
- Rübölfettsäuremethylester
- TAMAC
- Triallylmethylammoniumchlorid
- ABAH
- 2,2'-azo-bis-amidinopropane dihydrochloride
- AIBN
- 2,2'-azo-bis-2-methylpropionitrile
- AMPS
- 2-acrylamido-2-methylpropane
- BO
- 2-butyl-octanol
- EO
- Ethylene oxide (1,2-epoxyethane)
- IHD
- Isohexadecan
- ITDA
- isotridecylalcohol
- ITS
- isotridecylstearate
- ÖFSBOE
- Ölfettsäurebutyloctylester
- RÖFSME
- Rübölfettsäuremethylester
- TAMAC
- triallylmethylammonium
Das Vergleichsbeispiel wurde mit Firesorb® MF, einer Wasser-in-Öl-Polymerdispersion eines wasserquellbaren, vernetzten Polymerisats auf der Basis von Natriumacrylat, Acrylamid und eines 2-Acrylamido-2-methylpropansulfonsäure-Natirumsalzes durchgeführt. Firesorb® MF ist ein Produkt der Stockhausen GmbH & Co. KG, Bäkerpfad 25, D-47805 Krefeld.The comparative example was carried out using Firesorb® MF, a water-in-oil polymer dispersion of a water-swellable, crosslinked polymer based on sodium acrylate, acrylamide and a 2-acrylamido-2-methylpropanesulfonic acid sodium salt. Firesorb® MF is a product of Stockhausen GmbH & Co. KG, Bäkerpfad 25, D-47805 Krefeld.
Die Ergebnisse der Toxizitätstests gegenüber Daphnien- und Algen sind in der Tabelle 1 aufgeführt.The results of the toxicity tests against daphnia and algae are shown in Table 1.
In diesen Beispielen werden Wasser-in-Öl-Polymerdispersionen nach den in der Tabelle 1 angegebenen Polymerisationsverfahren ("Fahrweise") hergestellt, wobei "i" isotherm und "a" adiabatisch bedeutet. Für die adiabatischen bzw. isothermen Polymerisationsverfahren werden die im folgenden beschriebenen Ansätze verwendet.In these examples, water-in-oil polymer dispersions are prepared by the polymerization processes ("procedure") given in Table 1, where "i" isothermal and "a" means adiabatic. The approaches described below are used for the adiabatic or isothermal polymerization processes.
Allgemeiner Ansatz für die adiabatische Polymerisation (Fahrweise "a")General approach for adiabatic polymerization (mode of operation "a")
Zunächst wird eine wäßrige Monomerenlösung aus folgenden Komponenten hergestellt:
Danach werden 30 g Hypermer® 1083 in 480 g organischer Phase gelöst und die wäßrige Monomerenlösung unter Rühren zugefügt. Nach Ausbildung der Emulsion wird diese mit einem schnellaufenden Haushaltsmixer homogenisiert und durch Ausblasen mit Stickstoff von gelöstem Sauerstoff befreit. Die Polymerisation wird bei 20°C durch Zugabe von 2 ml einer 0,2 %igen tert.-Butylhydroperoxidlösung und 2,4 ml Schwefeldioxidgas gestartet, wobei der Ansatz durch die entstehende Polymerisationswärme bis auf etwa 100°C aufgewärmt wird. Nach Erreichen der Spitzentemperatur wird die Polymerdispersion durch Vakuumdestillation bis auf etwa 40°C heruntergekühlt.Then 30 g of Hypermer® 1083 are dissolved in 480 g of organic phase and the aqueous monomer solution is added with stirring. After the emulsion has been formed, it is homogenized with a high-speed household mixer and freed of dissolved oxygen by blowing out with nitrogen. The polymerization is started at 20 ° C. by adding 2 ml of a 0.2% tert-butyl hydroperoxide solution and 2.4 ml of sulfur dioxide gas, the batch being warmed up to about 100 ° C. by the heat of polymerization that arises. After the peak temperature has been reached, the polymer dispersion is cooled down to about 40 ° C. by vacuum distillation.
Im Falle der erfindungsgemäßen Beispiele werden noch unter Vakuum 40 g Nachsatz (SO2 in Exxsol 100 oder Na2SO3-Lösung) zur Restmonomerenverringerung eingesaugt und nach dem endgültigen Abkühlen 4 % Aktivator eingerührt.In the case of the examples according to the invention, 40 g of make-up (SO 2 in Exxsol 100 or Na 2 SO 3 solution) are sucked in under reduced pressure to reduce the residual monomers and, after the final cooling, 4% activator is stirred in.
Zunächst wird eine wäßrige Monomerenlösung aus folgenden Komponenten hergestellt:
Danach werden 40 g Hypermer® 1083 in 440 g organische Phase gelöst und die wäßrige Monomerenlösung unter Rühren zugefügt. Nach Ausbildung der Emulsion wird diese mit einem schnellaufenden Haushaltsmixer homogenisiert und auf 60°C aufgeheizt. Danach werden 0,3 g AIBN zugesetzt und Vakuum angelegt. Es wird solange Wasser abdestilliert, bis der Ansatz sauerstofffrei ist und die Polymerisation startet. Durch die Vakuumdestillation bleibt die Reaktionstemperatur in einem Bereich von 60 - 65°C konstant. Nachdem etwa 90 ml Wasser destilliert wurden, schließt man die Verbindung zur Vakuumpumpe und belüftet die Apparatur solange mit Stickstoff, bis Normaldruck erreicht wird. Durch die restliche Polymerisationswärme wird der Ansatz dann bis auf etwa 90°C aufgehetzt.Then 40 g of Hypermer® 1083 are dissolved in 440 g of organic phase and the aqueous monomer solution is added with stirring. After the emulsion has been formed, it is homogenized with a high-speed household mixer and heated to 60 ° C. Then 0.3 g of AIBN are added and a vacuum is applied. Water is distilled off until the batch is oxygen-free and the polymerization starts. Due to the vacuum distillation, the reaction temperature remains constant in a range of 60 - 65 ° C. After about 90 ml of water have been distilled, the connection to the vacuum pump is closed and the apparatus is aerated with nitrogen until normal pressure is reached. The batch is then heated up to about 90 ° C. by the remaining heat of polymerization.
Nach Erreichen der Spitzentemperatur wird die Dispersion durch erneute Vakuumdestillation auf etwa 40°C heruntergekühlt.After the peak temperature has been reached, the dispersion is cooled down to about 40 ° C. again by vacuum distillation.
Im Falle der erfindungsgemäßen Beispiele werden noch unter Vakuum 40 g Nachsatz (SO2 in Exxsol 100 oder Na2SO3-Lösung) zur Restmonomerenverringerung eingesaugt und nach dem endgültigen Abkühlen 4 % Aktivator eingerührt.In the case of the examples according to the invention, 40 g of make-up (SO 2 in Exxsol 100 or Na 2 SO 3 solution) are sucked in under reduced pressure to reduce the residual monomers and, after the final cooling, 4% activator is stirred in.
Die einzelnen Substanzen für die organische Phase, den Aktivator und den Nachsatz sowie die Ergebnisse der Toxizitätstests gegenüber Daphnien- und Algen sind in der Tabelle 1 aufgeführt.
Claims (23)
- Water-in-oil polymer dispersions consisting of a continuous virtually water-immiscible organic phase and crosslinked water-soluble polymers finely distributed therein and optionally auxiliaries, characterized in that they have a residual monomer content of less than 1 000 ppm.
- Water-in-oil polymer dispersions according to Claim 1, characterized in that they consist of:A) 10 to 70% by weight, preferably 20 to 50% by weight, particularly preferably 25 to 35% by weight, of a polymer,B) 20 to 80% by weight of an organic phase,C) 0.5 to 10% by weight of a water-in-oil emulsifier,D) 0.1 to 2% by weight of a residual monomer destroyer,E) 0.5 to 10% by weight of an inverter, andF) remainder to 100% by weight of water.
- Water-in-oil polymer dispersions according to Claim 1 or 2, characterized in that the organic phase is a fatty acid ester, preferably an ester of linear saturated and unsaturated fatty acids, having an alkyl chain length of more than 11 carbon atoms and of C1-C4-alcohols or higher mono-branched alcohols, or a mixture of at least two of these esters.
- Water-in-oil polymer dispersions according to Claim 3, characterized in that the fatty acid ester or the fatty acid esters are in a mixture with a hydrocarbon or a hydrocarbon mixture, where the boiling point of the hydrocarbon or of the hydrocarbon mixture is less than 200°C.
- Water-in-oil polymer dispersions according to one of Claims 1 to 4, characterized in that the polymer is an addition polymer of acrylic acid and/or an acrylic acid derivative.
- Water-in-oil polymer dispersions according to one of Claims 1 to 4, characterized in that the polymer is at least an addition polymer of the salt of acrylic acid and acrylamide.
- Water-in-oil polymer dispersions according to one of Claims 1 to 4, characterized in that the polymer is a terpolymer of a salt of acrylic acid, acrylamide and a salt of 2-acrylamido-2-methylpropanesulphonic acid.
- Water-in-oil polymer dispersions according to one of Claims 1 to 7, characterized in that the crosslinker is triallylmethylammonium chloride.
- Water-in-oil polymer dispersions according to one of Claims 1 to 8, characterized in that the largest dimension of the polymer particles is less than 2 µm and preferably less than 1 µm.
- Water-in-oil polymer dispersions according to one of Claims 1 to 9, characterized in that the swell time of the polymer particles is not more than three seconds.
- Water-in-oil polymer dispersions according to one of Claims 1 to 10, characterized in that it has an EC50 value determined in accordance with the OECD Guideline 202 and/or the OECD Guideline 201 of more than 10 mg/l.
- Process for the preparation of water-in-oil polymer dispersions according to Claims 1 to 11 by polymerization of a polymer emulsion, characterized in that a residual monomer destroyer is added after the polymerization.
- Process according to Claim 12, characterized in that the residual monomer destroyers used are substances from the group of acidic and neutral salts of acids derived from sulphur having an oxidation number of less than VI, preferably sodium dithionite, sodium thiosulphate, sodium sulphite or sodium disulphite, and/or substances with a hydrogensulphide group, preferably sodium hydrogensulphide or compounds from the group of thiols, preferably mercaptoethanol, dodecyl mercaptan, thiopropionic acid or salts of thiopropionic acid or thiopropanesulphonic acid or salts of thiopropanesulphonic acid, and/or substances from the group of amines, preferably from the group of amines with low volatility, and/or substances from the group which consists of Bunte salts, formamidinesulphinic acid, sulphur dioxide, aqueous and organic solutions of sulphur dioxide or thiourea.
- Process according to Claim 12 or 13, characterized in that residual monomer destroyers are used in an amount from 100 to 20 000 ppm, preferably 200 to 5 000 ppm and particularly preferably 500 to 3 000 ppm, based on the dispersion.
- Use of water-in-oil polymer dispersions according to one of Claims 1 to 11 as fire-extinguishing media, characterized in that the water and/or a hydrous extinguishing medium is added to the polymer dispersion.
- Use according to Claim 15, characterized in that water is added to the polymer dispersion in a concentration of from 0.01 to 50% by volume, preferably 0.02 to 10% by volume and particularly preferably from 1 to 2% by volume.
- Use according to either Claim 15 or 16, characterized in that the water/polymer dispersion mixture has a viscosity of more than 100 mPa·s, preferably a viscosity of from 500 to 50 000 mPa·s.
- Method of applying a water-in-oil polymer dispersion according to one of Claims 1-11 to a surface for preventing and/or controlling fires, characterized in that the polymer dispersion is added to water in an amount sufficient to increase the viscosity of the resulting water/polymer dispersion mixture to more than 100 mPa·s, and this mixture is applied to the surface.
- Method according to Claim 18, characterized in that the concentration of the polymer dispersion is 0.01 to 50% by volume, preferably 0.02 to 10% by volume and particularly preferably 1 to 2% by volume.
- Method according to Claim 18 or 19, characterized in that the polymer dispersion is mixed with the water in a customary discharge device for controlling fire, and is applied to a surface using this device.
- Method according to Claim 18 or 19, characterized in that the polymer dispersion is mixed with the water batchwise before the mixture is applied to the surface using a discharge device.
- Device for preventing fire and for extinguishing fire, characterized in that it consists of a pressure-tight container in which water and the polymer dispersion according to one of Claims 1 to 11 are present separately from one another.
- Device according to Claim 22, characterized in that it is a hand-held fire extinguisher or a fire engine.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10041395A DE10041395A1 (en) | 2000-08-23 | 2000-08-23 | Polymer dispersions for fire prevention and fire fighting with improved environmental compatibility |
DE10041395 | 2000-08-23 | ||
PCT/EP2001/009057 WO2002015982A1 (en) | 2000-08-23 | 2001-08-06 | Polymer dispersions for preventing and controlling fires with improved environmental compatibility |
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EP1313532A1 EP1313532A1 (en) | 2003-05-28 |
EP1313532B1 true EP1313532B1 (en) | 2004-04-28 |
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EP (1) | EP1313532B1 (en) |
AR (1) | AR030474A1 (en) |
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TR (1) | TR200401706T4 (en) |
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10041395A1 (en) | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Polymer dispersions for fire prevention and fire fighting with improved environmental compatibility |
DE10041394A1 (en) * | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Use of water-in-water polymer dispersions for fire prevention and fighting |
DE10118020A1 (en) * | 2001-04-10 | 2002-10-17 | Stockhausen Chem Fab Gmbh | Use of water-swellable polymers based on unsaturated sulfonic acid monomers as additives for increasing the viscosity of saline water used to prevent or fight fires |
DE102007050839A1 (en) | 2007-10-24 | 2009-04-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Carbohydrate-based additives with adhesive effect for aqueous fire and fire protection agents, their preparation and use |
US20100063180A1 (en) * | 2008-09-05 | 2010-03-11 | Seungkoo Kang | Fire protection and/or fire fighting additives, associated compositions, and associated methods |
CL2010000073A1 (en) * | 2009-01-29 | 2011-01-07 | Midwest Ind Supply Inc | Composition for chemical improvement of the soil comprising a synthetic fluid and a pour point reducer; composition comprising synthetic fluid, biodegradable material and synthetic fibers; composition comprising a base oil and polyisobutylene; composition comprising synthetic fluid and a binder; Application Method. |
US8177997B2 (en) | 2009-01-29 | 2012-05-15 | Midwest Industrial Supply, Inc. | Chemical method and composition for soil improvement |
US8210769B2 (en) | 2009-03-31 | 2012-07-03 | Midwest Industrial Supply, Inc. | Method and composition for modifying soil and dust control |
US8033750B2 (en) * | 2009-03-31 | 2011-10-11 | Midwest Industrial Supply, Inc. | Method and composition for modifying soil and dust control |
US8066448B2 (en) | 2009-03-31 | 2011-11-29 | Midwest Industrial Supply, Inc. | Dust suppression agent |
DE102009038065A1 (en) * | 2009-08-19 | 2011-02-24 | Li-Tec Battery Gmbh | Method and device for cooling an electrochemical energy store |
US8192653B2 (en) | 2009-09-30 | 2012-06-05 | EarthCleanCorporation | Fire suppression biodegradable suspension forming compositions |
US8961838B2 (en) | 2010-04-05 | 2015-02-24 | Earthclean Corporation | Non-aqueous fire suppressing liquid concentrate |
AP3224A (en) | 2010-05-07 | 2015-04-30 | Midwest Ind Suppy Ind | Method and composition for road construction and surfacing |
DE102010034826A1 (en) * | 2010-08-19 | 2012-02-23 | Li-Tec Battery Gmbh | Electrochemical energy storage with a plurality of electrochemical cells |
DE102010034825A1 (en) * | 2010-08-19 | 2012-02-23 | Li-Tec Battery Gmbh | Electrochemical energy storage |
US8702343B1 (en) | 2012-12-21 | 2014-04-22 | Midwest Industrial Supply, Inc. | Method and composition for road construction and surfacing |
US11673010B2 (en) | 2021-05-14 | 2023-06-13 | Tyco Fire Products Lp | Fire-fighting foam concentrate |
US11666791B2 (en) | 2021-05-14 | 2023-06-06 | Tyco Fire Products Lp | Fire-fighting foam composition |
CA3218803A1 (en) * | 2021-05-14 | 2022-11-17 | Joanna M. Monfils | Fire-fighting foam composition |
US11673011B2 (en) | 2021-05-14 | 2023-06-13 | Tyco Fire Products Lp | Firefighting foam composition |
US11497952B1 (en) | 2021-05-14 | 2022-11-15 | Tyco Fire Products Lp | Fire-fighting foam concentrate |
EP4337339A1 (en) | 2021-05-14 | 2024-03-20 | Tyco Fire Products LP | Fire-fighting foam composition with microfibrous cellulose |
Family Cites Families (126)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1077A (en) * | 1839-02-08 | Improvement in machines for making oakum | ||
US564302A (en) * | 1896-07-21 | Machine for drawing wire | ||
US362248A (en) * | 1887-05-03 | Breeching for harness | ||
US215983A (en) * | 1879-03-03 | 1879-05-27 | Improvement in horse-clothing | |
US649669A (en) * | 1899-12-22 | 1900-05-15 | Louis Myers | Cleaning attachment for type-writing machines. |
US670333A (en) * | 1900-03-09 | 1901-03-19 | Angelo Simonini | Self-lighting gas burner. |
US761701A (en) * | 1903-08-22 | 1904-06-07 | Railway And Stationary Refrigerating Company | Refrigerating apparatus. |
US2202505A (en) * | 1939-01-13 | 1940-05-28 | Baird Television Ltd | Electromagnetic focusing coil |
US2612846A (en) * | 1946-09-11 | 1952-10-07 | Megator Pumps & Compressors Lt | Venting and draining means for pumps |
US2647078A (en) * | 1949-12-17 | 1953-07-28 | Stone & Webster Eng Corp | Alcohol distillation process |
US2924663A (en) * | 1954-07-01 | 1960-02-09 | Itt | Party-line automatic telephone system |
US3354084A (en) * | 1964-06-24 | 1967-11-21 | Dow Chemical Co | Aqueous gel of water-swellable acrylic polymer and non-ionic filler |
DE1529199A1 (en) * | 1966-08-23 | 1969-12-04 | Philipp Kreis | Attachment for gas lights |
US3716304A (en) * | 1970-09-14 | 1973-02-13 | Mancole Co Ltd | Concrete pump |
US3758641A (en) | 1971-01-21 | 1973-09-11 | Dow Chemical Co | Adhesion of polymer gels to cellulose |
US3728258A (en) * | 1971-06-02 | 1973-04-17 | Factory Mutual Res Corp | Self-extinguishing flammable mixtures |
US3814751A (en) * | 1973-06-04 | 1974-06-04 | Du Pont | Process for preparing 6,6-difluoro-17alpha,21-dihydroxy 16alpha-methyl-4-pregnene-3,20-dione |
JPS51125468A (en) | 1975-03-27 | 1976-11-01 | Sanyo Chem Ind Ltd | Method of preparing resins of high water absorbency |
CA1074204A (en) | 1975-11-11 | 1980-03-25 | Byron C. Chambers | Composition and method for dispersing high molecular weight flocculant polymers in water |
US4272414A (en) * | 1978-05-26 | 1981-06-09 | Monsanto Company | Chemical retardants for forest fires |
JPS55721A (en) | 1978-06-19 | 1980-01-07 | Showa Denko Kk | Aqueous dispersion of water-soluble high polymer complex |
US4384988A (en) * | 1980-04-10 | 1983-05-24 | L.M.C. Inc. | Fire protection water barrier which is a gel composition of high water content and high viscosity |
US4447336A (en) * | 1981-12-18 | 1984-05-08 | Monsanto Company | Stabilized galactomannan gum compositions |
US4610311A (en) * | 1983-02-15 | 1986-09-09 | Sanitek Products, Inc. | Method for reducing the aerial drift of aqueous preparations |
DE3318218A1 (en) * | 1983-05-19 | 1984-11-22 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING WATER-IN-WATER SECONDARY DISPERSIONS OF WATER-SOLUBLE POLYMERISATES AND THE USE THEREOF AS A FLOCCANT |
US4624320A (en) | 1984-01-06 | 1986-11-25 | Romaine John W | Fire blanket |
DE3716304A1 (en) | 1987-05-15 | 1988-11-24 | Bluecher Hubert | EXTINGUISHING WATER ADDITION |
US5190110A (en) * | 1985-05-03 | 1993-03-02 | Bluecher Hubert | Use of an aqueous swollen macromolecule-containing system as water for fire fighting |
US4978460A (en) | 1985-05-03 | 1990-12-18 | Bluecher Hubert | Aqueous swollen macromolecule-containing system as water for firefighting |
DE3515865A1 (en) | 1985-05-03 | 1986-11-06 | Hasso von 4000 Düsseldorf Blücher | USE OF AN AQUEOUS, SWELLED MACROMOLECULE-CONTAINING SYSTEM AS FIREWATER |
DE3522419C1 (en) | 1985-06-22 | 1987-01-02 | Stockhausen Chem Fab Gmbh | Process for the preparation of concentrated emulsion polymers |
US4839065A (en) * | 1987-01-30 | 1989-06-13 | Monsanto Company | Fire retardant concentrates and methods for preparation thereof |
US4983326A (en) * | 1987-01-30 | 1991-01-08 | Monsanto Company | Fire retardant concentrates and methods for preparation thereof |
KR940002553B1 (en) * | 1987-04-30 | 1994-03-25 | 닛뽕쇼꾸 바이가가꾸고오교 가부시끼가이샤 | Method for production of hydrophilic polymer from hydrated gel polymer |
DE3724709A1 (en) * | 1987-07-25 | 1989-02-02 | Stockhausen Chem Fab Gmbh | METHOD FOR PRODUCING POLYMERISATES WITH LOW RESIDUAL MONOMER CONTENT |
US4942189A (en) * | 1987-11-02 | 1990-07-17 | Exxon Research And Engineering Company | Interfacial viscosification of aqueous solutions utilizing interpolymer complex |
US4799962A (en) * | 1987-12-24 | 1989-01-24 | Aqualon Company | Water-soluble polymer dispersion |
DE3814751C2 (en) | 1988-04-30 | 1997-05-22 | Hasso Von Bluecher | System to reduce the risk of fire spread |
CA2001397A1 (en) * | 1988-10-28 | 1990-04-28 | Tadao Shimomura | Method for production of acrylate and acrylate-containing polymer |
EP0384167B1 (en) * | 1989-01-31 | 1994-07-06 | Union Carbide Chemicals And Plastics Company, Inc. | Polysaccharides with alkaryl or aralkyl hydrophobes and latex compositions containing same |
US5001231A (en) * | 1989-06-07 | 1991-03-19 | Aqualon Company | Invert emulsion polysaccharide slurry |
US4990608A (en) * | 1989-06-07 | 1991-02-05 | Aqualon Company | Diaphragm wall construction gelatin composition |
DE3926169A1 (en) * | 1989-08-08 | 1991-02-14 | Basf Ag | METHOD FOR IMPROVING THE WATER CAPACITY OF CROSSLINKED, WATER-SWELLABLE POLYMERS |
WO1991003497A1 (en) * | 1989-09-04 | 1991-03-21 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method of preparing water-absorbent resin |
US5480480A (en) * | 1990-09-21 | 1996-01-02 | Multicolor Specialties, Inc. | Aqueous multicolor paint |
US5314535A (en) * | 1990-09-21 | 1994-05-24 | Multicolor Specialties, Inc. | Polyurethane-based water-in-water multicolor paint and method for making |
US5114485A (en) * | 1990-09-21 | 1992-05-19 | Multicolor Specialties, Inc. | Water-in-water multicolor paint and method |
US5318619A (en) * | 1990-09-21 | 1994-06-07 | Multicolor Specialties, Inc. | Polyurethane-based aqueous multicolor paint |
US5199980A (en) * | 1990-09-21 | 1993-04-06 | Multicolor Specialties, Inc. | Polyurethane-based water-in-water multicolor paint and method for making |
US5114484A (en) * | 1990-09-21 | 1992-05-19 | Multicolor Specialties, Inc. | Water-in-water multicolor paint and process for making same |
US5437719A (en) * | 1990-09-21 | 1995-08-01 | Multicolor Specialties, Inc. | Polyurethane-based aqueous multicolor paint |
ATE201063T1 (en) * | 1990-10-26 | 2001-05-15 | Twaron Products Bv | ARAMID YARN COATED WITH SUPERABSORBENS |
US5126390A (en) * | 1990-11-23 | 1992-06-30 | Xerox Corporation | Coating formulations for the preparation of transfer elements |
DE4138791A1 (en) * | 1991-08-21 | 1993-05-27 | Basf Ag | WATER-IN-OIL POLYMER EMULSIONS |
US5258069A (en) * | 1992-02-24 | 1993-11-02 | Aqualon Company | Process for preparing joint, spackling and texture compounds for gypsum dry walls |
FI923097A (en) * | 1992-03-31 | 1993-10-01 | Metsae Serla Chemicals Oy | STABILT CMC-SLAM |
EP0574260B1 (en) * | 1992-06-10 | 1999-03-03 | Nippon Shokubai Co., Ltd. | Method for production of hydrophilic resin |
US5362312A (en) * | 1992-10-14 | 1994-11-08 | Merck & Co., Inc. | Carrier fluid for the suspension and delivery of water soluble polymers |
DE69317636T2 (en) * | 1992-12-25 | 1998-11-12 | Nippon Catalytic Chem Ind | Absorber and method of making an absorbent resin |
US5629377A (en) * | 1993-03-10 | 1997-05-13 | The Dow Chemical Company | Water absorbent resin particles of crosslinked carboxyl containing polymers and method of preparation |
US5334243A (en) * | 1993-05-04 | 1994-08-02 | The Dow Chemical Company | Crack inhibitor for tape joint compositions |
DE4336319A1 (en) | 1993-10-25 | 1995-04-27 | Oeko Tec Umweltschutzsyst Gmbh | Extinguishing media and process for its manufacture |
DE4406624A1 (en) * | 1994-03-01 | 1995-09-07 | Roehm Gmbh | Crosslinked water-soluble polymer dispersions |
US5504123A (en) | 1994-12-20 | 1996-04-02 | Union Carbide Chemicals & Plastics Technology Corporation | Dual functional cellulosic additives for latex compositions |
US6214331B1 (en) * | 1995-06-06 | 2001-04-10 | C. R. Bard, Inc. | Process for the preparation of aqueous dispersions of particles of water-soluble polymers and the particles obtained |
US5849210A (en) | 1995-09-11 | 1998-12-15 | Pascente; Joseph E. | Method of preventing combustion by applying an aqueous superabsorbent polymer composition |
DK0861120T3 (en) * | 1995-10-11 | 2003-12-15 | Halliburton Energy Serv Inc | Oil-free, water-soluble, liquid hydroxyethyl cellulose polymer dispersion |
AU718417B2 (en) * | 1995-11-14 | 2000-04-13 | Stockhausen Gmbh & Co. Kg | Water additive and method for fire prevention and fire extinguishing |
US6100222A (en) * | 1996-01-16 | 2000-08-08 | Great Lakes Chemical Corporation | High density, viscosified, aqueous compositions having superior stability under stress conditions |
US5785747A (en) * | 1996-01-17 | 1998-07-28 | Great Lakes Chemical Corporation | Viscosification of high density brines |
JP3824695B2 (en) * | 1996-02-15 | 2006-09-20 | 出光興産株式会社 | Method for recovering cooling characteristics of water-soluble quenching agent and water-soluble quenching agent with improved cooling characteristics |
US5969012A (en) * | 1997-05-29 | 1999-10-19 | Rhodia Inc. | Non-aqueous slurries of water soluble polymers |
BR9709436A (en) * | 1996-06-07 | 1999-08-10 | Hercules Inc | Toothpaste composition containing carboxymethyl cellucose fluidized polymer suspensions |
GR1002790B (en) * | 1996-07-22 | 1997-10-17 | Methods and products for extinguishing fires. | |
US6750276B2 (en) * | 1996-08-05 | 2004-06-15 | Arch Chemicals, Inc. | Waterborne soft-feeling coating composition with high gloss |
JP3855311B2 (en) * | 1996-08-07 | 2006-12-06 | 住友化学株式会社 | Aerosol composition |
DE19637908C2 (en) * | 1996-09-18 | 1999-05-06 | Bundesrep Deutschland | Foam concentrate for the production of extinguishing foam and its use |
US5919854A (en) * | 1996-10-03 | 1999-07-06 | Cytec Technology Corp. | Process for preparing aqueous dispersions |
US5792366A (en) | 1996-10-03 | 1998-08-11 | Cytec Technology Corp. | Aqueous dispersions |
US6664326B1 (en) | 1996-10-03 | 2003-12-16 | Cytec Technology Corp. | Aqueous dispersions |
US6702946B1 (en) * | 1996-10-03 | 2004-03-09 | Cytec Technology Corp. | Aqueous dispersions |
US5843320A (en) | 1996-10-03 | 1998-12-01 | Cytec Technology Corp. | Aqueous dispersions |
US6608124B1 (en) * | 1996-10-03 | 2003-08-19 | Cytec Technology Corp. | Aqueous dispersions |
US5696228A (en) | 1996-10-03 | 1997-12-09 | Cytec Technology Corp. | Process for producing substantially dry polymer particles from aqueous dispersions |
MY118538A (en) | 1997-01-20 | 2004-12-31 | Ciba Spec Chem Water Treat Ltd | Polymeric compositions and their production and uses |
MY120719A (en) * | 1997-01-20 | 2005-11-30 | Ciba Spec Chem Water Treat Ltd | Polymeric compositions and their production and uses |
FR2758825A1 (en) * | 1997-01-24 | 1998-07-31 | Atochem Elf Sa | AQUEOUS DISPERSION BASED ON WATER-SOLUBLE POLYMERS |
US6080704A (en) * | 1997-03-11 | 2000-06-27 | Halliday; William S. | Glycols as gas hydrate inhibitors in drilling, drill-in, and completion fluids |
DE19741188A1 (en) * | 1997-09-18 | 1999-03-25 | Basf Ag | Reducing residual monomer content of e.g. acrylic polymer dispersions |
US6433056B1 (en) | 1997-10-17 | 2002-08-13 | Hercules Incorporated | Fluidized polymer suspension of hydrophobically modified poly(acetal- or ketal-polyether) polyurethane and polyacrylate |
FR2770526B1 (en) * | 1997-11-04 | 2000-01-14 | Atochem Elf Sa | STABLE AQUEOUS DISPERSIONS BASED ON WATER-SOLUBLE POLYMERS CONTAINING A CATIONIC DISPERSANT HAVING HYDROPHOBIC PATTERNS |
EP1032358B1 (en) * | 1997-11-19 | 2005-05-18 | Hercules Incorporated | Fluidized polymer suspensions of cationic polysaccharides in emollients and use thereof in preparing personal care compositions |
US6093769A (en) * | 1997-11-19 | 2000-07-25 | Hercules Incorporated | Fluidized polymer suspensions of cationic polysaccharides in polyols and use thereof in personal care compositions |
US5985992A (en) * | 1997-12-10 | 1999-11-16 | Cytec Technology Corp. | Anionic polymer products and processes |
US6262168B1 (en) * | 1998-03-11 | 2001-07-17 | Cytec Technology Corp. | Aqueous dispersions |
SE513735C2 (en) | 1998-05-06 | 2000-10-30 | Wirsbo Bruks Ab | Plastic media tubes, pipe systems, use of a liquid crystal polymer in media tubes and use of such a media tubing for hot water conduction |
DE19839199A1 (en) * | 1998-08-28 | 2000-03-02 | Basf Ag | Process for reducing the amount of residual monomers in aqueous polymer dispersions |
DE29904848U1 (en) | 1998-08-30 | 1999-06-17 | Hoermann Christina | Fire extinguishing device |
US6207796B1 (en) * | 1998-11-18 | 2001-03-27 | Nippon Shokubai Co., Ltd. | Production process for hydrophilic polymer |
DE19900187C1 (en) * | 1999-01-06 | 2000-06-15 | Stockhausen Chem Fab Gmbh | Filtration of flocculated water in a filter-press modified for hydrostatic filtration as a first stage to pressure dewatering |
US6489270B1 (en) * | 1999-01-07 | 2002-12-03 | Daniel P. Vollmer | Methods for enhancing wellbore treatment fluids |
US6635604B1 (en) * | 1999-02-11 | 2003-10-21 | Baker Hughes Incorporated | Low molecular weight water soluble organic compounds as crystallization point suppressants in brines |
US6818597B2 (en) | 2000-04-21 | 2004-11-16 | Benchmark Research & Technology, Inc. | Suspensions of water soluble polymers in surfactant free non-aqueous solvents |
DE10041393A1 (en) * | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Water-in-oil polymer dispersions with improved environmental compatibility |
DE10041395A1 (en) | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Polymer dispersions for fire prevention and fire fighting with improved environmental compatibility |
DE10041394A1 (en) | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Use of water-in-water polymer dispersions for fire prevention and fighting |
DE10044156A1 (en) * | 2000-09-06 | 2002-04-04 | Stockhausen Chem Fab Gmbh | Particle agglomeration method and apparatus |
DE10061483A1 (en) | 2000-12-08 | 2002-06-13 | Stockhausen Chem Fab Gmbh | Process for the preparation of water-in-water polymer dispersions |
US6964691B1 (en) | 2000-12-29 | 2005-11-15 | Nalco Company | Method of preparing a synthetic fuel from coal |
US6641624B1 (en) * | 2000-12-29 | 2003-11-04 | Ondeo Nalco Company | Method of preparing a synthetic fuel from coal |
DE10118020A1 (en) * | 2001-04-10 | 2002-10-17 | Stockhausen Chem Fab Gmbh | Use of water-swellable polymers based on unsaturated sulfonic acid monomers as additives for increasing the viscosity of saline water used to prevent or fight fires |
DE10119685A1 (en) * | 2001-04-20 | 2002-10-24 | Stockhausen Chem Fab Gmbh | Removing water-insolubles from aqueous metal solution, e.g. in production of aluminum oxide by the Bayer process, involves adding water-soluble cationic polyelectrolyte based on dimethylaminopropyl-acrylamide |
FR2824063B1 (en) | 2001-04-26 | 2004-03-05 | Atofina | PROCESS FOR THE MANUFACTURE OF 1,3-BIS ACRYLATE CHLORIDE (DIMETHYLBENZYLAMMONIUM) ISOPROPYL ALONE OR A MIXTURE OF OTHER MONOMERS AND (CO) POLYMERS THEREOF |
US6712897B2 (en) * | 2001-05-21 | 2004-03-30 | National Gypsum Properties, Llc. | Pre-blend composition, and method of making joint compound using same |
DE10129854A1 (en) | 2001-06-21 | 2003-01-02 | Bayer Ag | Aqueous secondary dispersions |
DE60223762T2 (en) * | 2001-08-10 | 2008-10-23 | Unilever N.V. | Composition containing dietary fibers |
GB0130518D0 (en) | 2001-12-21 | 2002-02-06 | Univ Gent | Pulsed bio-agent delivery systems based on degradable polymer solutions or hydrogels |
AU2003219046A1 (en) * | 2002-03-21 | 2003-10-08 | Basf Aktiengesellschaft | Cationic polymers and the use thereof in cosmetic formulations |
SE0201599D0 (en) * | 2002-03-21 | 2002-05-30 | Skyepharma Ab | microparticles |
EP1393718A1 (en) * | 2002-08-29 | 2004-03-03 | OctoPlus Sciences B.V. | Colloidal drug carrier system |
DE10240797A1 (en) | 2002-08-30 | 2004-03-11 | Stockhausen Gmbh & Co. Kg | Cationic polyelectrolytes with good environmental compatibility |
US20040225051A1 (en) * | 2002-11-15 | 2004-11-11 | Wynn Moy | Aqueous multicolor paint with improved solvent resistance |
US7129201B2 (en) * | 2003-08-18 | 2006-10-31 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Aqueous-aqueous emulsions comprising a dispersed phase and a continuous surfactant phase with rod-like surfactants |
FR2864776B1 (en) | 2004-01-05 | 2006-06-23 | Oreal | COSMETIC COMPOSITION OF WATER-IN-WATER EMULSION TYPE BASED ON SURFACTANTS AND CATIONIC POLYMERS |
DE102004013750A1 (en) | 2004-03-18 | 2005-11-03 | Stockhausen Gmbh | Anionic water-in-water polymer dispersions, process for their preparation and their use |
DE102004019179A1 (en) | 2004-04-16 | 2005-11-10 | Basf Ag | Process for the preparation of a water-in-water dispersion of polyvinyl lactam having a K value of> 120 |
-
2000
- 2000-08-23 DE DE10041395A patent/DE10041395A1/en not_active Withdrawn
-
2001
- 2001-08-06 DE DE50102155T patent/DE50102155D1/en not_active Expired - Lifetime
- 2001-08-06 AT AT01958055T patent/ATE265254T1/en active
- 2001-08-06 ES ES01958055T patent/ES2220791T3/en not_active Expired - Lifetime
- 2001-08-06 AU AU2001279805A patent/AU2001279805B2/en not_active Ceased
- 2001-08-06 EP EP01958055A patent/EP1313532B1/en not_active Expired - Lifetime
- 2001-08-06 AU AU7980501A patent/AU7980501A/en active Pending
- 2001-08-06 WO PCT/EP2001/009057 patent/WO2002015982A1/en active IP Right Grant
- 2001-08-06 PT PT01958055T patent/PT1313532E/en unknown
- 2001-08-06 TR TR2004/01706T patent/TR200401706T4/en unknown
- 2001-08-23 AR ARP010104027A patent/AR030474A1/en active IP Right Grant
-
2003
- 2003-02-27 US US10/377,980 patent/US20040006175A1/en not_active Abandoned
-
2008
- 2008-03-12 US US12/046,574 patent/US8475675B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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AU7980501A (en) | 2002-03-04 |
US20080185160A1 (en) | 2008-08-07 |
ATE265254T1 (en) | 2004-05-15 |
WO2002015982A1 (en) | 2002-02-28 |
EP1313532A1 (en) | 2003-05-28 |
AU2001279805B2 (en) | 2005-10-13 |
TR200401706T4 (en) | 2004-08-23 |
US20040006175A1 (en) | 2004-01-08 |
AR030474A1 (en) | 2003-08-20 |
DE10041395A1 (en) | 2002-03-07 |
DE50102155D1 (en) | 2004-06-03 |
US8475675B2 (en) | 2013-07-02 |
PT1313532E (en) | 2004-09-30 |
ES2220791T3 (en) | 2004-12-16 |
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