DE4313085A1 - Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives - Google Patents
Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivativesInfo
- Publication number
- DE4313085A1 DE4313085A1 DE4313085A DE4313085A DE4313085A1 DE 4313085 A1 DE4313085 A1 DE 4313085A1 DE 4313085 A DE4313085 A DE 4313085A DE 4313085 A DE4313085 A DE 4313085A DE 4313085 A1 DE4313085 A1 DE 4313085A1
- Authority
- DE
- Germany
- Prior art keywords
- water
- weight
- acid
- soluble
- oil
- 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.)
- Ceased
Links
- 239000006185 dispersion Substances 0.000 title claims description 50
- 150000002462 imidazolines Chemical class 0.000 title claims description 10
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 title claims description 10
- 150000003856 quaternary ammonium compounds Chemical class 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- 125000002091 cationic group Chemical group 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- -1 cyclic Amidine compounds Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920006037 cross link polymer Polymers 0.000 claims description 7
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- BNZKJJKMNCBHIQ-UHFFFAOYSA-N 2-[(prop-2-enoylamino)methyl]butanoic acid Chemical compound CCC(C(O)=O)CNC(=O)C=C BNZKJJKMNCBHIQ-UHFFFAOYSA-N 0.000 claims description 3
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000012688 inverse emulsion polymerization Methods 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000004533 oil dispersion Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 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 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NCHJGQKLPRTMAO-XWVZOOPGSA-N [(2R)-2-[(2R,3R,4S)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NCHJGQKLPRTMAO-XWVZOOPGSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- LIHYMVNKAJDKBR-UHFFFAOYSA-N N'-ethyl-2-methylidenepentanehydrazide Chemical compound CCCC(=C)C(=O)NNCC LIHYMVNKAJDKBR-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- LUNQZVCDZKODKF-PFVVTREHSA-L copper acetic acid (2S)-6-amino-2-[[(2S)-2-[(2-aminoacetyl)amino]-3-(1H-imidazol-5-yl)propanoyl]amino]hexanoate (2S)-6-amino-2-[[(2S)-2-[(2-amino-1-oxidoethylidene)amino]-3-(1H-imidazol-5-yl)propanoyl]amino]hexanoate hydron Chemical compound [Cu+2].CC(O)=O.CC(O)=O.NCCCC[C@@H](C([O-])=O)NC(=O)[C@@H](NC(=O)CN)CC1=CN=CN1.NCCCC[C@@H](C([O-])=O)NC(=O)[C@@H](NC(=O)CN)CC1=CN=CN1 LUNQZVCDZKODKF-PFVVTREHSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 1
- 108010038983 glycyl-histidyl-lysine Proteins 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RRPJQNOJVXGCKC-UHFFFAOYSA-M methyl-tris(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(CC=C)CC=C RRPJQNOJVXGCKC-UHFFFAOYSA-M 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
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- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
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Description
Die Erfindung betrifft wäßrige Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Derivaten, die durch Wasser-in-Öl-Dispersionen kationischer, vernetzter, wasserquellbarer Polymerisate stabilisiert werden.The invention relates to aqueous dispersions of quaternary ammonium compounds and Imidazoline derivatives, which are water-in-oil dispersions of cationic, cross-linked, water-swellable Polymers are stabilized.
Quartäre Ammonium- bzw. cyclische Amidinverbindungen aus fettchemischen Rohstoffen, die beispielsweise als Wirkstoffkomponenten in Textil- und Wäscheweichspüler-Formulierungen eingesetzt werden, besitzen oftmals nur eine begrenzte Wasserlöslichkeit und neigen daher bei Einbringung in Wasser und Überschreitung der Löslichkeitsgrenze zu Abscheidungen. Dies führt nicht nur zu Schwierigkeiten bei der Lagerhaltung, sondern auch zu ungenauen bzw. fehlerhaften Dosierungen bei der Anwendung. Es hat daher nicht an Versuchen gefehlt, Mittel zu finden, mit denen lagerstabile gießfähige bzw. pastöse Dispersionen herstellbar sind. So beschreibt die WO 91/12364 wäßrige Zubereitungen, die gut lagerfähig sind und eine Wirkstoffkombination auf der Basis von Kondensationsprodukten aus Carbonsäuren oder Carbonsäure-Derivaten mit Hydroxyalkylpolyaminen und quartären Ammoniumverbindungen enthalten. Es gehört ebenfalls zum Stand der Technik, den bei Raumtemperatur festen, kationischen Ammonium- bzw. cyclischen Amidinverbindungen niedrigviskose, wasserlösliche Alkohole, wie Methanol, Ethanol oder Isopropanol zuzusetzen. Auch Ethylenglykol, Propandiol-1,2 und die homologen, höhermolekularen Polyalkylenglykolether finden wegen ihres höheren Flammpunktes Verwendung. Als nachteilig bewertet werden, daß diese Lösemittel nicht nur in hohem Maße brennbar sind und gegenüber Kunststoffverpackungsmaterialien migrationsfähig sein können, sondern auch bei weiterer Verdünnung mit Wasser destabilisierend auf die Dispersion wirken. Wünschenswert ist daher ein Stabilisator für wäßrige, kationische Dispersionen, dessen Flammpunkt über 100°C liegt und dessen Eigenschaften jede Kunststoffverpackung zulassen.Quaternary ammonium or cyclic amidine compounds from oleochemical raw materials, for example as active ingredient components in fabric and fabric softener formulations are often only of limited water solubility and therefore tend to be introduced into water and the solubility limit is exceeded Deposits. This not only leads to storage difficulties, but also also to inaccurate or incorrect dosages during use. It therefore has there was no lack of attempts to find means with which storage-stable pourable or pasty dispersions can be produced. Thus WO 91/12364 describes aqueous preparations which can be stored well and an active ingredient combination based on condensation products from carboxylic acids or carboxylic acid derivatives with hydroxyalkyl polyamines and contain quaternary ammonium compounds. It also belongs to the State of the art, the cationic ammonium or cyclic amidine compounds, low-viscosity, water-soluble alcohols, such as methanol, Add ethanol or isopropanol. Also ethylene glycol, propanediol-1,2 and the homologous, High molecular weight polyalkylene glycol ethers find because of their higher flash point Use. To be considered a disadvantage that these solvents are not are highly flammable and compared to plastic packaging materials may be capable of migration, but also destabilizing when diluted further with water act on the dispersion. A stabilizer for is therefore desirable aqueous, cationic dispersions whose flash point is above 100 ° C and whose Properties allow any plastic packaging.
Aufgabe der Erfindung ist es daher, die bekannten Stabilisierungszusätze in ihrer Wirkung weiter zu verbessern.The object of the invention is therefore the effect of the known stabilizing additives continue to improve.
Diese Aufgabe wird erfindungsgemäß gelöst mit schwach vernetzten, wasserquellbaren Copolymerisaten auf Basis von kationischen monoethylenisch ungesättigten Carbonsäurederivaten. This object is achieved with weakly cross-linked, water-swellable Copolymers based on cationic monoethylenically unsaturated carboxylic acid derivatives.
Polymere, die durch das Vorhandensein von wasserquellbaren Partikeln in Wasser oder wäßrigen Lösungen eine Viskositätserhöhung bewirken, werden in vielen Bereichen der Technik, Kosmetik und Pharmazie verwendet. Natürlich vorkommende Stoffe wie Alginate, Guarmehl und Stärke in unveränderter oder chemisch modifizierter Art werden in zunehmendem Maße durch synthetische Polymere ersetzt, wobei unter anderem Polymere von Acrylverbindungen zum Einsatz kommen.Polymers caused by the presence of water-swellable particles in water or aqueous solutions cause an increase in viscosity, are in many areas of Technology, cosmetics and pharmacy used. Naturally occurring substances such as alginates, Guar flour and starch, unchanged or chemically modified, are used in increasingly replaced by synthetic polymers, including polymers of acrylic compounds are used.
Hierbei werden durch Verwendung mehrfunktioneller Verbindungen in geringer Menge dreidimensionale Netzwerke geschaffen, so daß die Produkte große Mengen Wasser aufnehmen können, ohne vollständig in den Lösungszustand überzugehen. Sie sind nur noch wasserquellbar, obwohl sie im allgemeinen noch wasserlösliche Anteile enthalten.Here, by using multifunctional compounds in small quantities three-dimensional networks created so that the products have large amounts of water can record without going completely into the solution state. They are only still water-swellable, although they generally still contain water-soluble components.
Insbesondere Wasser-in-Öl-Emulsionspolymerisate dieser Acrylverbindungen, hergestellt durch inverse Emulsionspolymerisation, bieten wegen ihrer leichten Einbringbarkeit in Wasser oder wäßrige Medien Vorteile. Die Herstellung von wasserlöslichen Polymeren dieser Substanzklasse durch Emulsionspolymerisation wird in der US-PS 32 84 393 und in der DE-OS 22 26 143 beschrieben. Da diese Produkte Wasser-in-Öl-Dispersionen darstellen, die das Polymer in den emulgierten "Wassertröpfchen" enthalten, muß zur Auflösung in Wasser ein Umkehremulgator zur Dispergierung der äußeren Ölphase gemäß DE-OS 22 26 143 zugesetzt werden. Der Emulsionstyp kehrt sich nach Öl-in-Wasser um. Nach DE-OS 24 31 794 kann das Netzmittel bereits in der Dispersion enthalten sein, wodurch diese selbstinvertierend wird. Vernetzte, wasserunlösliche bzw. wasserquellbare Polymere von nichtionogenen bzw. anionischen Monomeren aus der Acrylreihe werden z. B. in den Patentschriften GB 20 07 238 und US 4 554 018 beschrieben.In particular, water-in-oil emulsion polymers of these acrylic compounds are produced through inverse emulsion polymerization, because of their ease of incorporation into Water or aqueous media benefits. The production of water-soluble polymers this class of substances by emulsion polymerization is in US-PS 32 84 393 and described in DE-OS 22 26 143. Because these products water-in-oil dispersions represent that contain the polymer in the emulsified "water droplets" must Dissolution in water according to a reverse emulsifier to disperse the outer oil phase DE-OS 22 26 143 can be added. The emulsion type changes to oil-in-water around. According to DE-OS 24 31 794, the wetting agent can already be contained in the dispersion which makes it self-inverting. Cross-linked, water-insoluble or water-swellable Polymers of non-ionic or anionic monomers from the acrylic series z. B. in the patents GB 20 07 238 and US 4 554 018.
Wasserlösliche, nicht vernetzte, inverse Emulsionspolymerisate aus der Acrylreihe mit kationischen Monomeren werden in der DE-OS 27 56 697 beschrieben, deren Herstellung und Anwendungsweise jedoch auf ihren speziellen Einsatzzweck als Flockungsmittel zugeschnitten sind. Als Verdicker für nichtwäßrige Lösungen werden in der EP- Anmeldung 0196 162 schwach vernetzte, inverse Emulsionspolymerisate mit kationischen (Meth)acrylsäureestern erwähnt. Entsprechende Wasser-in-Öl-Dispersionen von wasserquellbaren, schwach vernetzten, kationischen Polymeren werden in DE 37 30 781 C2 zur Herstellung von Druckpasten für den Textildruck vorgeschlagen. Weiter werden N- substituierte (Meth)acrylsäureaminoalkylamide wegen der stärkeren Hydrophilie der Amidgruppe gegenüber der Esterfunktion und somit wegen der besseren Wasserquellbarkeit als besonders geeignet angesehen. Gleichzeitig besitzen diese Amide eine bessere Hydrolysestabilität, was für Langzeitanwendungen in wäßriger Lösung wichig ist.Water-soluble, non-cross-linked, inverse emulsion polymers from the acrylic range Cationic monomers are described in DE-OS 27 56 697, their preparation and application, however, on their special purpose as a flocculant are tailored. As thickeners for non-aqueous solutions, the EP Application 0196 162 weakly cross-linked, inverse emulsion polymers with cationic (Meth) acrylic acid esters mentioned. Corresponding water-in-oil dispersions of water-swellable, weakly crosslinked, cationic polymers are described in DE 37 30 781 C2 proposed for the production of printing pastes for textile printing. Further N- substituted (meth) acrylic acid aminoalkylamides because of the greater hydrophilicity of the Amide group compared to the ester function and therefore because of the better water swellability regarded as particularly suitable. At the same time, these amides have a better one Hydrolysis stability, which is important for long-term use in aqueous solution.
Da die Viskosität ionischer Polymerisate duch Elektrolytzusatz erheblich abfällt, wird in EP 0 186 361 berichtet, daß die Verdickungswirkung von teilweise ionischen, bevorzugt anionischen schwach vernetzten Polymeren in elektrolythaltigen Medien durch Zusätze von ionischen Tensiden, wenn diese in der Ölphase der Wasser-in-Öl-Dispersionen in einem größeren Ausmaß löslich sind als in der Wasserphase, verbessert werden kann. Während dort anionische Polymere und anionische Tenside ausführlich und detailliert behandelt werden, finden kationische Produkte lediglich Berücksichtigung bei Nennung der Anwendungsmöglichkeiten, ohne Bezug auf experimentelle Befunde.Since the viscosity of ionic polymers drops considerably due to the addition of electrolytes, in EP 0 186 361 reports that the thickening effect of partially ionic is preferred anionic weakly cross-linked polymers in electrolyte-containing media through additives of ionic surfactants, if these in the oil phase of the water-in-oil dispersions in are soluble to a greater extent than in the water phase, can be improved. While there anionic polymers and anionic surfactants are detailed and detailed are treated, cationic products are only taken into account when mentioned the possible uses, without reference to experimental findings.
Gegenstand der Erfindung ist daher die Anwendung von Wasser-in-Öl-Dispersionen wasserquellbarer, überwiegend kationischer, vernetzter Polymerer zur Stabilisierung von wäßrigen Dispersionen von quatären Ammoniumverbindungen und Imidazolin-Derivaten, wie sie z. B. als sogenannte Textil- und Wäscheweichspüler Verwendung finden. Solche wäßrigen Dispersionen enthalten als gebräuchliche Wirkstoffe beispielsweise N,N- Distearyl-N,N-dimethylammoniumchlorid (DSDMAC), Imidazolin-Derivate (s. u. a. US-PS 4 762 685, EP-A 0199 383), quaternierte Fettsäureester des Triethanolamins (sog. Esterquats, s. u. a. US-PS 4 830 771) oder 2,3-Dihydroxypropyl-1-trimethyl-ammoniumsalz- Derivate (DE-OS 27 28 841).The invention therefore relates to the use of water-in-oil dispersions which are water-swellable, predominantly cationic, crosslinked polymer for the stabilization of aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives, as they e.g. B. find use as a so-called fabric and fabric softener. Such aqueous dispersions contain, for example, N, N Distearyl-N, N-dimethylammonium chloride (DSDMAC), imidazoline derivatives (see, inter alia, U.S. Pat 4,762,685, EP-A 0199 383), quaternized fatty acid esters of triethanolamine (so-called. Esterquats, s. u. a. U.S. Patent 4,830,771) or 2,3-dihydroxypropyl-1-trimethyl-ammonium salt Derivatives (DE-OS 27 28 841).
Allgemein werden Ammoniumverbindungen der Formel [R₁R₂R₃R₄N]⁺X⁻ verwendet,
wobei:
R₁ = eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, insbesondere Methyl,
R₂ = eine Alkyl- oder Alkenylgruppe mit 1 bis 22 Kohlenstoffatomen ist, oder eine
Hydroxyalkylgruppe mit 2 bis 4 Kohlenstoffatomen,
R₃ = eine Alkyl- oder Alkenylgruppe mit 1 bis 22 Kohlenstoffatomen, eine Acyloxyalkylgruppe,
deren Acylrest sich von gesättigten oder ungesättigten, linearen oder
verzweigten Fettsäuren mit 10 bis 22 Kohlenstoffatomen ableitet und deren
Oxyalkylgruppe die Oxyethyl- oder Oxypropyl- oder Oxyisopropylgruppe ist,
R₄ = R₃ oder R₂ und
X⁻ = ein Anion bedeuten.Ammonium compounds of the formula [R₁R₂R₃R₄N] ⁺X⁻ are generally used, where:
R₁ = an alkyl group with 1 to 4 carbon atoms, especially methyl,
R₂ = an alkyl or alkenyl group with 1 to 22 carbon atoms, or a hydroxyalkyl group with 2 to 4 carbon atoms,
R₃ = an alkyl or alkenyl group with 1 to 22 carbon atoms, an acyloxyalkyl group whose acyl radical is derived from saturated or unsaturated, linear or branched fatty acids with 10 to 22 carbon atoms and whose oxyalkyl group is the oxyethyl or oxypropyl or oxyisopropyl group,
R₄ = R₃ or R₂ and
X⁻ = represent an anion.
Die im allgemeinen bei instabilen Suspensionen während der Lagerung eintretenden Aufrahmungen bzw./oder Bodensatzbildungen, werden durch Viskositätserhöhungen zwar verlangsamt, aber nicht beseitigt. Bei Einsatz der erfindungsgemäßen Stabilisatoren wird der Dispersionszustand so verbessert, daß die Homogenität bei der Lagerung und Handhabung gewährleistet ist.The creams that generally occur in the case of unstable suspensions during storage or / or sediment formation are slowed down by viscosity increases, but not eliminated. When using the stabilizers of the invention Dispersion condition improved so that the homogeneity in storage and handling is guaranteed.
Die zur Stabilisierung verwendeten Wasser-in-Öl-Dispersionen bestehen aus:The water-in-oil dispersions used for stabilization consist of:
- A) 30 bis 70 Gew.-% kationisch wirksamen Homo- oder Copolymer,A) 30 to 70% by weight of cationically active homopolymer or copolymer,
- B) 20 bis 50 Gew.-% hydrophober, organischer Flüssigkeit,B) 20 to 50% by weight of hydrophobic organic liquid,
- C) 0 bis 10 Gew.-% Wasser-in-Öl-Emulgator,C) 0 to 10% by weight water-in-oil emulsifier,
- D) ggf. 0,5 bis 10 Gew.-% eines Netzmittels undD) optionally 0.5 to 10% by weight of a wetting agent and
- E) einer Restmenge Wasser.E) a residual amount of water.
Die Summe der Komponenten A) - E) ergibt 100 Gew.-%.The sum of components A) - E) is 100% by weight.
Die Herstellung der Homo- oder Copolymeren erfolgt durch Polymerisation einer Monomeren-Mischung vonThe homopolymers or copolymers are prepared by polymerizing one Monomer mixture of
-
a) mind. 50 Gew.-% eines oder mehrerer kationischer Monomeren der allgemeinen
Formel:
[CH₂=C(R₁)-CO-X-(CH₂)n-C(R₂R₃)-CH₂-N(R₄R₅R₆)]⁺A⁻,in der
R₁ = Wasserstoff oder Methyl-,
R₂, R₃ = Wasserstoff oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4 C-Atomen,
R₄, R₅, R₆ = gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen,
n = 0 oder 1,
X = -O- oder -NH- und
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten,a) at least 50 wt .-% of one or more cationic monomers of the general formula: [CH₂ = C (R₁) -CO-X- (CH₂) n -C (R₂R₃) -CH₂-N (R₄R₅R₆)] ⁺A⁻ ,in the
R₁ = hydrogen or methyl,
R₂, R₃ = hydrogen or identical or different alkyl radicals with 1 to 4 carbon atoms,
R₄, R₅, R₆ = identical or different alkyl radicals with 1 to 4 carbon atoms,
n = 0 or 1,
X = -O- or -NH- and
A = anion of an organic or inorganic acid, preferably hydrochloric acid or methylsulfuric acid, - b) 0 bis 40 Gew.-% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyethylmethacrylat,b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate,
- c) 0 bis 40 Gew.-% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und/oder deren Salze,c) 0 to 40% by weight of one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or its salts,
- d) 0,001-5,0 Gew.-% eines polyfunktionellen Monomeren.d) 0.001-5.0% by weight of a polyfunctional monomer.
Als kationische Monomeren werden quaterniertes Dimethylaminoethyl(meth)acrylat, quaterniertes Dimethylaminopropyl(meth)acrylamid, quaterniertes Dimethylamino-2,2- dimethylpropyl(meth)acrylamid, Diallyldimethylammoniumchlorid, Diallyldi-ethylammoniumchlorid und deren Mischungen untereinander verwendet. Die Quaternierung wird bevorzugt mit Methylchlorid, Natriumchloracetat, Dimethylsulfat und Dimethylcarbonat durchgeführt.Quaternized dimethylaminoethyl (meth) acrylate, quaternized dimethylaminopropyl (meth) acrylamide, quaternized dimethylamino-2,2- dimethylpropyl (meth) acrylamide, diallyldimethylammonium chloride, diallyldiethylammonium chloride and their mixtures used with each other. The quaternization will preferably with methyl chloride, sodium chloroacetate, dimethyl sulfate and dimethyl carbonate carried out.
Als hydrophobe, organische Flüssigkeiten sind einsetzbar: aromatische und aliphatische lineare, verzweigte und cyclische Kohlenwasserstoffe, deren Siedepunkte bei einem Druck von 1013 hPa im Bereich von 110 bis 380°C liegen. Hierzu zählen n- und iso- Paraffine, Destillate aus paraffinischen, naphthenbasischen und aromatischen Erdölen sowie Toluol, Xylol und Mesitylen. Weiterhin können auch lineare und verzweigte flüssige Ester natürlichen und synthetischen Ursprungs als Ölphase verwendet werden.The following can be used as hydrophobic, organic liquids: aromatic and aliphatic linear, branched and cyclic hydrocarbons, whose boiling points at one Pressure of 1013 hPa in the range of 110 to 380 ° C. These include n- and iso- Paraffins, distillates from paraffinic, naphthenic and aromatic petroleum as well as toluene, xylene and mesitylene. Furthermore, linear and branched liquid Esters of natural and synthetic origin can be used as an oil phase.
Zur Zubereitung der Polymerisation und Herstellung der monomerhaltigen Wasser-in- Öl-Emulsion werden bekannte öllösliche Emulgatoren mit niedrigem HLB-Wert benutzt, wie Teilester von Glycerin, Di- und Polyglycerin, Sorbit, Sorbitan und Additionsprodukte von Alylenoxiden, wie Ethylenoxid und Propylenoxid an höhere lineare und verzweigte Alkohole, Fettsäuren bzw. Nonylphenol. Es können auch die sogenannten polymeren Emulgatoren allein oder im Gemisch verwendet werden, wie es unter anderem in US-PS 4 786 681 beschrieben wird.For the preparation of the polymerization and preparation of the monomer-containing water-in Known oil-soluble emulsifiers with a low HLB value are used such as partial esters of glycerol, di- and polyglycerol, sorbitol, sorbitan and addition products from allene oxides such as ethylene oxide and propylene oxide to higher linear and branched ones Alcohols, fatty acids or nonylphenol. It can also be the so-called polymer Emulsifiers can be used alone or in a mixture, as described in U.S. Patent 4,786,681.
Als vernetzende Monomere werden mehrfach ungesättigte Vinyl-, Acryl- oder Allylverbindungen sowie Verbindungen mit mehreren Epoxygruppen verwendet. Geeignete Verbindungen sind beispielsweise Methylenbis-acrylamid sowie quaterniertes Triallylamin, insbesondere Tetraallyl- bzw. Triallylmethylammoniumchlorid. Die Vernetzung kann während der Polymerisation oder auch danach erfolgen. Für eine Nachvernetzung sind wasserlösliche Epoxiverbindungen, die sich von mehrwertigen Alkoholen ableiten, besonders geeignet.Polyunsaturated vinyl, acrylic or allyl compounds are used as crosslinking monomers as well as compounds with multiple epoxy groups. Suitable connections are, for example, methylenebisacrylamide and quaternized triallylamine, in particular tetraallyl or triallylmethylammonium chloride. Networking can take place during the polymerization or afterwards. For post-networking water-soluble epoxy compounds derived from polyhydric alcohols in particular suitable.
Die Technik der Polymerisation mit Emulsionsbildung, Homogenisierung der Mischung und Initiierung der Polymerisation ist bekannt. Sie erfolgt vorzugsweise adiabatisch, kann aber auch isotherm bei vorgewählter Temperatur erfolgen. Nach Beendigung der Polymerisation kann die Wasser-in-Öl-Dispersion direkt in die wäßrige, kationische Dispersion der quartären Ammonium- bzw. cyclischen Amidinverbindungen eingebracht werden. The technique of polymerization with emulsion formation, homogenization of the mixture and initiation of the polymerization is known. It is preferably adiabatic, can but also take place isothermally at a preselected temperature. After the end of the polymerization can the water-in-oil dispersion directly into the aqueous, cationic dispersion the quaternary ammonium or cyclic amidine compounds are introduced.
Die Wasser-in-Öl-Dispersionen sind verwendbar zur Stabilisierung von wäßrigen Dispersionen begrenzt wasserlöslicher, quartärer Ammoniumsalze, wie Dimethyldistearylammoniumchlorid, Dimethyldilaurylammoniumchlorid und quartäre Ester, z. B. N-Methyl-N,N-bis[2-(acyloxy)ethyl]-N-2-hydroxy-ethyl-ammonium-methos-ulfat oder N,N,N-Trimethyl-N-[1,2-di(acyl-oxy)propyl]-ammoniumchlorid bzw. Imidazolin- Derivate auf der Basis von Fettsäure, z. B. 1-[(Fettacyloxy)ethyl]-2-alkylimidazolin.The water-in-oil dispersions can be used to stabilize aqueous ones Dispersions of limited water-soluble quaternary ammonium salts, such as dimethyldistearylammonium chloride, dimethyldilaurylammonium chloride and quaternary esters, e.g. B. N-methyl-N, N-bis [2- (acyloxy) ethyl] -N-2-hydroxyethyl-ammonium methosulfate or N, N, N-trimethyl-N- [1,2-di (acyloxy) propyl] ammonium chloride or imidazoline Derivatives based on fatty acids, e.g. B. 1 - [(Fatty acyloxy) ethyl] -2-alkylimidazoline.
Die begrenzt wasserlöslichen, quartären Ammoniumsalze bzw. Imidazolin-Derivate liegen üblicherweise als wäßrige Aufschlämmungen/Dispersionen vor, z. B. mit Feststoffgehalten von 5 Gew.-%. Der Feststoffgehalt ist im übrigen nicht kritisch.The limited water-soluble quaternary ammonium salts or imidazoline derivatives are usually in the form of aqueous slurries / dispersions, e.g. B. with solids contents of 5% by weight. The solids content is otherwise not critical.
Die Anwendungskonzentrationen bewegen sich zwischen 0,01 und 10 Gew.-%, vorzugsweise zwischen 0,1 und 5 Gew.-%, insbesondere zwischen 0,2 und 2 Gew.-%, je nach gewünschter Stabilisierung der Dispersion. Zusätzlich können weiterhin viskositätserhöhende nichtionische bzw. kationische Substanzen benutzt werden.The application concentrations are between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight, in particular between 0.2 and 2% by weight, each after the desired stabilization of the dispersion. In addition, viscosity increases can continue nonionic or cationic substances are used.
Überraschenderweise hat sich gezeigt, daß die Stabilität von wäßrigen, kationischen Dispersionen, insbesondere von begrenzt wasserlöslichen quartären Ammoniumsalzen, mit Hilfe von Wasser-in-Öl-Dispersionen kationischer vernetzter wasserquellbarer Polymere deutlich erhöht wird.Surprisingly, it has been shown that the stability of aqueous, cationic Dispersions, in particular of limited water-soluble quaternary ammonium salts, with the help of water-in-oil dispersions of cationic crosslinked water-swellable polymers is significantly increased.
Die Erfindung wird durch die folgenden Beispiele näher erläutert:The invention is illustrated by the following examples:
In der Beschreibung der nachfolgenden Beispiele werden die Abkürzungen mit folgender Bedeutung benutzt:In the description of the following examples, the abbreviations are as follows Meaning used:
DMAEA = Dimethylªminoethylªcrylat
DMAEMA = Dimethylªminoethylmethªcrylat
DIMAPA = Dimethylªminopropylªcrylamid
TEMAPA = N,N,N,2,2-Tetramethylªminopropylªcrylamid
AMPS = 2-Acrylamido-2-methyl-propansulfonsäure
TAMAC = Triªllylmethylªmmoniumchlorid
ABAH = Azo-bis-(2-ªmidinopropan-hydrochlorid)
AIBN = Azoisobuttersäuredinitril
EDTA = Ethylendiamintetrªessigsäure
TBHP = tert.-Butylhydroperoxid
EO = Ethylenoxid
KWST = isoparaffinischer Kohlenwasserstoff mit einem Siedebereich von 210-250°C
und einer Dichte von 0,79 g/cm³DMAEA = D i m ethylªmino e thylªcrylat
DMAEMA = D i m ethylªmino e thyl m ethªcrylate
DIMAPA = Dim ethylªmino p ropylªcrylamid
TEMAPA = N, N, N, 2,2-Te tra m ethylªmino p ropylªcrylamid
AMPS = 2-A crylamido-2- m ethyl p ropan s ulfonsäure
TAMAC = T riªllyl m ethylªmmonium c hlorid
ABAH = A zo- b is- (2-idinmidinopropane h ydrochloride)
AIBN = A zo i so b uttersäuredi n itril
EDTA = E Thylen d iamin t etrªessigsäure
TBHP = t ert.- B utyl h ydro p eroxid
EO = E o Thylen dioxide
Ohlen KWST isoparaffinic = K w ater st off with a boiling range of 210-250 ° C and a density of 0.79 g / cm³
Alle %-Angaben bedeuten Gew.-%.All% data mean% by weight.
a) Herstellung der Dispersion eines Polymeren aus 80% DMAEA-CH₃Cl und 20% Acrylamid mit 40% wirksamer Substanz (wS).a) Preparation of the dispersion of a polymer from 80% DMAEA-CH₃Cl and 20% Acrylamide with 40% active substance (wS).
Man löst 160 g DMAEA-CH₃Cl und 40 g Acrylamid in 165 g Wasser. Sodann wird der pH-Wert mit Phosphorsäure auf 4,5 eingestellt und 0,4 g EDTA zugesetzt. Nach vollständiger Auflösung des Komplexbildners gießt man die Lösung unter Rühren in eine Mischung von 120 g KWST, 10 g Sorbitanmonoisostearat und 0,62 g TAMAC und homogenisiert mit einem haushaltsüblichen Mixstab (Viskosität der Emulsion 4200 mPa*s, Brookfield RVT, MK II/20 bei 20°C). Der gelöste Sauerstoff wird bei gleichzeitigem Erhitzen der Emulsion auf 60°C durch Einblasen von Stickstoff ausgetrieben. Man leitet ca. 30 Minuten lang weiter Stickstoff ein und startet anschließend die Polymerisation durch Zusatz von 0,11 g AIBN, gelöst in 4 g KWST. Durch die adiabatisch geführte, exotherme Reaktion steigt die Temperatur auf ca. 102°C. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9-EO-Nonylphenol.160 g of DMAEA-CH₃Cl and 40 g of acrylamide are dissolved in 165 g of water. The pH is then adjusted to 4.5 with phosphoric acid and 0.4 g of EDTA is added. After the complexing agent has completely dissolved, the solution is poured into a mixture of 120 g KWST, 10 g sorbitan monoisostearate and 0.62 g TAMAC with stirring and homogenized with a household mixing stick (emulsion viscosity 4200 mPa * s, Brookfield RVT, MK II / 20 at 20 ° C). The dissolved oxygen is expelled by blowing in nitrogen while heating the emulsion to 60 ° C. Nitrogen is passed in for about 30 minutes and then the polymerization is started by adding 0.11 g of AIBN, dissolved in 4 g of KWST. The temperature rises to approx. 102 ° C due to the adiabatic exothermic reaction. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) Mit Hilfe eines schnellaufenden Rührers werden 5 g dieser Dispersion in 1 l einer 5%igen Aufschlämmung von methylquaterniertem Ditalgfettsäuretriethanolaminester eingebracht, wobei eine lagerstabile Dispersion, die über einen Zeitraum von 6 Wochen keine Veränderung zeigt, entsteht.b) With the help of a high-speed stirrer, 5 g of this dispersion in 1 l of a 5% Slurry of methyl-quaternized ditallow fatty acid triethanolamine ester introduced, with a storage-stable dispersion that over a period of 6 weeks shows no change, arises.
a) Herstellung einer Dispersion eines Polymeren aus 80% DIMAPA-CH₃Cl und 20% Acrylamid mit 40% wS.a) Preparation of a dispersion of a polymer from 80% DIMAPA-CH₃Cl and 20% Acrylamide with 40% wh.
Man löst 160 g DIMAPA-CH₃Cl und 40 g Acrylamid in 170 g Wasser. Sodann wird mit konz. Salzsäure der pH-Wert auf 4,5 eingestellt und 0,4 g EDTA zugesetzt. Nach vollständiger Auflösung des Komplexbildners gießt man die Lösung unter Rühren in eine Mischung von 115 g KWST, 10 g Glycerinmonooleat und 0,62 g TAMAC und homogenisiert (Viskosität der Emulsion: 4500 mPa*s, Brookfield RVT, MK II/20 bei 20°C). Nach Beseitigung des gelösten Sauerstoffs mit Stickstoff wird die Polymerisation bei 60°C durch Zusatz von 0,11 g AIBN, gelöst in 4 g KWST, gestartet. Es erfolgt ein Temperaturanstieg auf ca. 102°C. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9- EO-Nonylphenol.160 g of DIMAPA-CH₃Cl and 40 g of acrylamide are dissolved in 170 g of water. Then with conc. Hydrochloric acid adjusted the pH to 4.5 and added 0.4 g EDTA. After the complexing agent has completely dissolved, the solution is poured with stirring into a mixture of 115 g KWST, 10 g glycerol monooleate and 0.62 g TAMAC and homogenized (viscosity of the emulsion: 4500 mPa * s, Brookfield RVT, MK II / 20 at 20 ° C). After removing the dissolved oxygen with nitrogen, the polymerization is started at 60 ° C. by adding 0.11 g of AIBN, dissolved in 4 g of KWST. The temperature rises to approx. 102 ° C. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) Durch Einrühren von 5 g dieser Dispersion in 1 l einer 5%igen Aufschlämmung von Distearyldimethylammoniumchlorid in Wasser entsteht eine lagerstabile Dispersion, deren Zustand sich über einen Zeitraum von 6 Wochen nicht ändert.b) By stirring 5 g of this dispersion in 1 l of a 5% slurry of Distearyldimethylammonium chloride in water creates a storage-stable dispersion, the Condition does not change over a period of 6 weeks.
a) Herstellung einer Dispersion eines Polymeren aus 75% DIMAPA-CH₃Cl, 12,5% Acrylamid und 12,5% Acrylsäure mit 40% wS.a) Preparation of a dispersion of a polymer from 75% DIMAPA-CH₃Cl, 12.5% Acrylamide and 12.5% acrylic acid with 40% wS.
150 g DIMAPA-CH₃Cl, 25 g Acrylamid und 0,4 g EDTA werden in 170 g Wasser gelöst und 25 g Acrylsäure zugesetzt. Danach stellt man die Lösung mit Natronlauge auf einen pH-Wert von ca. 4,5 ein und gießt sie unter Rühren in eine Mischung von 115 g KWST, 10 g Sorbitanmonoisostearat und 0,62 g TAMAC. Es wird mit einem Mixstab homogenisiert, mit Stickstoff gespült und anschließend die Polymerisation mit 0,0275 g AIBN, gelöst in 4 g KWST, gestartet.150 g of DIMAPA-CH₃Cl, 25 g of acrylamide and 0.4 g of EDTA are dissolved in 170 g of water and 25 g of acrylic acid added. Then the solution is made up with sodium hydroxide solution a pH of approx. 4.5 and poured into a mixture of 115 g while stirring KWST, 10 g sorbitan monoisostearate and 0.62 g TAMAC. It comes with a mixing stick homogenized, flushed with nitrogen and then the polymerization with 0.0275 g AIBN, dissolved in 4 g KWST, started.
b) Nach Abschluß der Polymerisation werden 5 g dieser Dispersion in 1 l einer 5%igen Aufschlämmung von methylquaternierten Ditalgfettsäuretriethanolaminester eingebracht, wobei eine lagerstabile Dispersion entsteht, deren Zustand über 6 Wochen stabil bleibt.b) After completion of the polymerization, 5 g of this dispersion in 1 l of a 5% Slurry of methyl-quaternized ditallow fatty acid triethanolamine ester introduced, whereby a storage-stable dispersion is formed, the condition of which is stable over 6 weeks remains.
a) Herstellung einer Dispersion von 92% DMAEMA-CH₃Cl und 8% Acrylamid mit 50% wS.a) Preparation of a dispersion of 92% DMAEMA-CH₃Cl and 8% acrylamide with 50% wS.
Man löst 230 g DMAEMA-CH₃Cl und 20 g Acrylamid in 110 g Wasser und fügt 0,5 g EDTA und 0,6 g ABAH hinzu. Der pH-Wert wird mit konz. Salzsäure auf 0,6 eingestellt. Die Bildung der Emulsion erfolgt wie in Beispiel 1 mit 120 g KWST und 10 g Sorbitanmonoisostearat (Viskosität: 1400 mPa*s bei 20°C). Es wird mit 6 mg TBHP und 12 mg Schwefeldioxid bei 20°C katalysiert, wobei innerhalb von 150 Minuten eine Spitzentemperatur von 72°C erreicht wird. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9-EO-Nonylphenol.230 g of DMAEMA-CH₃Cl and 20 g of acrylamide are dissolved in 110 g of water and 0.5 g of EDTA and 0.6 g of ABAH are added. The pH value is with conc. Hydrochloric acid set to 0.6. The emulsion is formed as in Example 1 with 120 g KWST and 10 g sorbitan monoisostearate (viscosity: 1400 mPa * s at 20 ° C). It is catalyzed with 6 mg TBHP and 12 mg sulfur dioxide at 20 ° C, with a peak temperature of 72 ° C being reached within 150 minutes. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) 5 g der Dispersion ergeben in 1 l einer 5%igen Aufschlämmung von Distearyldimethylammoniumchlorid bei 20°C eine lagerstabile Suspension, ohne Neigung zur Bodensatzbildung bzw. Aufrahmung.b) 5 g of the dispersion in 1 l of a 5% slurry of distearyldimethylammonium chloride at 20 ° C a storage stable suspension, without tendency to sediment formation or creaming.
a) Herstellung einer Dispersion von 60% DMAEA-CH₃Cl, 37% Acrylamid und 3% AMPS mit 46% wS.a) Preparation of a dispersion of 60% DMAEA-CH₃Cl, 37% acrylamide and 3% AMPS with 46% wS.
160 g DMAEA-CH₃Cl, 36 g Acrylamid, 19 g AMPS werden in 114 g Wasser gelöst und nach Einstellen des pH-Wertes mit Salzsäure auf 4,5 unter Rühren in 100 g KWST, 10 g Diglycerinsesquioleat, 0,8 g TAMAC und 0,2 g EDTA gegossen. Es wird homogenisiert, mit Stickstoff gespült und die Polymerisation mit 1 g AIBN gestartet.160 g DMAEA-CH₃Cl, 36 g acrylamide, 19 g AMPS are dissolved in 114 g water and after adjusting the pH to 4.5 with hydrochloric acid while stirring in 100 g KWST, 10 g diglycerol sesquioleate, 0.8 g TAMAC and 0.2 g EDTA poured. It is homogenized purged with nitrogen and the polymerization started with 1 g of AIBN.
b) 5 g dieser Dispersion ergeben in 1 l einer 5%igen Aufschlämmung von Distearyldimethylammoniumchlorid eine lagerstabile Suspension ohne Tendenz zur Inhomogenität. b) 5 g of this dispersion in 1 l of a 5% slurry of distearyldimethylammonium chloride a storage stable suspension with no tendency to inhomogeneity.
a) Die Herstellung der Dispersionen entspricht der Verfahrensweise der vorstehenden Beschreibungen. Die Polymerisationen wurden bei Raumtemperatur gestartet.a) The preparation of the dispersions corresponds to the procedure of the above Descriptions. The polymerizations were started at room temperature.
Alle in der Tabelle aufgeführten Dispersionen ergeben mit einem Zusatz von 5 g zu 5%igen Aufschlämmungen von N-Methyl-N,N-bis[2-(C16/18-acyloxy)-ethyl]-N-(2- hydroxyethyl)-ammoniummethosulfat lagerstabile Suspensionen ohne Neigung zu Bodensatzbildung oder Aufrahmungen.All the dispersions listed in the table add 5% to 5% when added Slurries of N-methyl-N, N-bis [2- (C16 / 18-acyloxy) ethyl] -N- (2- hydroxyethyl) ammonium methosulfate suspensions stable in storage without inclination to Sedimentation or creaming.
Claims (12)
- A) 30 bis 70 Gew.-% eines kationisch wirksamen Homo- oder Copolymeren,
- B) 20 bis 50 Gew.-% einer hydrophoben, organischen Flüssigkeit,
- C) 0,5 bis 10 Gew.-% eines Wasser-in-Öl-Emulgators,
- D) 0 bis 10 Gew.-% eines Netzmittels und
- E) einer Restmenge Wasser
- A) 30 to 70% by weight of a cationically active homopolymer or copolymer,
- B) 20 to 50% by weight of a hydrophobic, organic liquid,
- C) 0.5 to 10% by weight of a water-in-oil emulsifier,
- D) 0 to 10% by weight of a wetting agent and
- E) a residual amount of water
- a) 50 bis 100 Gew.-% eines Monomeren der allgemeinen Formel
[CH₂=C(R₁)-CO-X-(CH₂)n-C(R₂R₃)-CH₂-N(R₄R₅R₆)]⁺A⁻,in der
R₁ = Wasserstoff oder Methyl-,
R₂, R₃ = Wasserstoff oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4 C-Atomen,
R₄, R₅, R₆ = gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen,
n = 0 oder 1,
X = -O- oder -NH- und
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten, - b) 0 bis 40 Gew.-% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyethylmethacrylat,
- c) 0 bis 40 Gew.-% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und/oder deren Salze,
- d) 0,001-5,0 Gew.-% eines polyfunktionellen vernetzenden Monomeren
- a) 50 to 100 wt .-% of a monomer of the general formula [CH₂ = C (R₁) -CO-X- (CH₂) n -C (R₂R₃) -CH₂-N (R₄R₅R₆)] ⁺A⁻, in which
R₁ = hydrogen or methyl,
R₂, R₃ = hydrogen or identical or different alkyl radicals with 1 to 4 carbon atoms,
R₄, R₅, R₆ = identical or different alkyl radicals with 1 to 4 carbon atoms,
n = 0 or 1,
X = -O- or -NH- and
A = anion of an organic or inorganic acid, preferably hydrochloric acid or methylsulfuric acid, - b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate,
- c) 0 to 40% by weight of one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or their salts,
- d) 0.001-5.0% by weight of a polyfunctional crosslinking monomer
- A) 30 bis 70 Gew.-% eines kationisch wirksamen Homo- oder Copolymeren,
- B) 20 bis 50 Gew.-% einer hydrophoben, organischen Flüssigkeit,
- C) 0,5 bis 10 Gew.-% eines Wasser-in-Öl-Emulgators,
- D) 0 bis 10 Gew.-% eines Netzmittels und
- E) einer Restmenge Wasser
- A) 30 to 70% by weight of a cationically active homopolymer or copolymer,
- B) 20 to 50% by weight of a hydrophobic, organic liquid,
- C) 0.5 to 10% by weight of a water-in-oil emulsifier,
- D) 0 to 10% by weight of a wetting agent and
- E) a residual amount of water
- a) 50 bis 100 Gew.-% eines Monomeren der allgemeinen Formel
[CH₂=C(R₁)-CO-X-(CH₂)n-C(R₂R₃)-CH₂-N(R₄R₅R₆)]⁺A⁻,in der
R₁ = Wasserstoff oder Methyl-,
R₂, R₃ = Wasserstoff oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4 C-Atomen,
R₄, R₅, R₆ = gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen,
n = 0 oder 1,
X = -O- oder -NH- und
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten, - b) 0 bis 40 Gew.-% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyethylmethacrylat,
- c) 0 bis 40 Gew.-% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und/oder deren Salze,
- d) 0,001-5,0 Gew.-% eines polyfunktionellen vernetzenden Monomeren
- a) 50 to 100 wt .-% of a monomer of the general formula [CH₂ = C (R₁) -CO-X- (CH₂) n -C (R₂R₃) -CH₂-N (R₄R₅R₆)] ⁺A⁻, in which
R₁ = hydrogen or methyl,
R₂, R₃ = hydrogen or identical or different alkyl radicals with 1 to 4 carbon atoms,
R₄, R₅, R₆ = identical or different alkyl radicals with 1 to 4 carbon atoms,
n = 0 or 1,
X = -O- or -NH- and
A = anion of an organic or inorganic acid, preferably hydrochloric acid or methylsulfuric acid, - b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate,
- c) 0 to 40% by weight of one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or their salts,
- d) 0.001-5.0% by weight of a polyfunctional crosslinking monomer
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4313085A DE4313085A1 (en) | 1993-04-21 | 1993-04-21 | Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives |
| PCT/EP1994/001198 WO1994024255A1 (en) | 1993-04-21 | 1994-04-18 | Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivates |
| EP94914400A EP0701598A1 (en) | 1993-04-21 | 1994-04-18 | Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivates |
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| DE4313085A DE4313085A1 (en) | 1993-04-21 | 1993-04-21 | Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives |
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| DE (1) | DE4313085A1 (en) |
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| AU634493B2 (en) * | 1989-04-21 | 1993-02-25 | Colgate-Palmolive Company, The | A stable medium viscosity fabric softening composition comprising cationic softener, fatty alcohol and cationic polymer |
| FR2671352B1 (en) * | 1991-01-09 | 1993-04-23 | Hoechst Francaise Ste | NEW CATIONIC COPOLYMERS, NEW EMULSIONS AND THEIR APPLICATION. |
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1993
- 1993-04-21 DE DE4313085A patent/DE4313085A1/en not_active Ceased
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1994
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- 1994-04-18 WO PCT/EP1994/001198 patent/WO1994024255A1/en not_active Ceased
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997005220A1 (en) * | 1995-08-02 | 1997-02-13 | Jeyes Group Plc | Compositions |
| US6402976B1 (en) * | 1996-08-16 | 2002-06-11 | Henkel Kommanditgesellschaft Auf Aktien | Textile finishing agent |
| WO1998023714A1 (en) * | 1996-11-28 | 1998-06-04 | Henkel Kommanditgesellschaft Auf Aktien | Soil-releasing polymers for cotton textiles |
| WO2001010212A1 (en) * | 1999-08-05 | 2001-02-15 | Goldschmidt Ag | Composition containing an active substance, production and use thereof |
| US6329324B1 (en) | 1999-08-05 | 2001-12-11 | Stockhausen Gmbh & Co. Kg | Active substance-containing composition, its production and its use |
| DE10041393A1 (en) * | 2000-08-23 | 2002-03-07 | Stockhausen Chem Fab Gmbh | Water-in-oil polymer dispersions with improved environmental compatibility |
| US6861469B2 (en) | 2000-08-23 | 2005-03-01 | Stockhausen Gmbh & Co. Kg | Water-in-oil polymer dispersions with improved environmental compatibility |
| US7585832B2 (en) | 2000-12-27 | 2009-09-08 | Colgate-Palmolive Company | Thickened fabric conditioners |
| US6864223B2 (en) * | 2000-12-27 | 2005-03-08 | Colgate-Palmolive Company | Thickened fabric conditioners |
| US7687451B2 (en) | 2002-06-04 | 2010-03-30 | Ciba Specialty Chemicals Corporation | Aqueous polymer formulations |
| US7452854B2 (en) | 2002-06-04 | 2008-11-18 | Ciba Specialty Chemicals Corporation | Aqueous fabric softener formulations comprising copolymers of cationic acrylates and N-alkyl acrylamides |
| US6949500B2 (en) * | 2002-12-16 | 2005-09-27 | Colgate-Palmolive Company | Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers |
| AU2003300863B2 (en) * | 2002-12-16 | 2010-06-03 | Colgate-Palmolive Company | Fabric softener compositions containing a mixture of cationic polymers as rheology modifiers |
| US7304026B2 (en) | 2004-04-15 | 2007-12-04 | Colgate-Palmolive Company | Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient |
| US8022029B2 (en) * | 2007-05-31 | 2011-09-20 | Colgate-Palmolive Company | Fabric softening compositions comprising polymeric materials |
| US8026205B2 (en) * | 2007-05-31 | 2011-09-27 | Colgate-Palmolive | Fabric softening compositions comprising polymeric materials |
| US8093201B2 (en) | 2007-05-31 | 2012-01-10 | Colgate-Palmolive Company | Fabric softening compositions comprising polymeric materials |
| US8470762B2 (en) | 2007-05-31 | 2013-06-25 | Colgate-Palmolive Company | Fabric softening compositions comprising polymeric materials |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994024255A1 (en) | 1994-10-27 |
| EP0701598A1 (en) | 1996-03-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| OP8 | Request for examination as to paragraph 44 patent law | ||
| 8127 | New person/name/address of the applicant |
Owner name: STOCKHAUSEN GMBH & CO. KG, 47805 KREFELD, DE |
|
| 8131 | Rejection |