CA1219699A - Cationic polymer compositions - Google Patents
Cationic polymer compositionsInfo
- Publication number
- CA1219699A CA1219699A CA000420569A CA420569A CA1219699A CA 1219699 A CA1219699 A CA 1219699A CA 000420569 A CA000420569 A CA 000420569A CA 420569 A CA420569 A CA 420569A CA 1219699 A CA1219699 A CA 1219699A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- water
- oil
- composition according
- polymer
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229920006317 cationic polymer Polymers 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 16
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- 125000002091 cationic group Chemical group 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- -1 aliphatic fatty acid esters Chemical class 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 15
- 239000000194 fatty acid Substances 0.000 claims description 15
- 229930195729 fatty acid Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 229920001983 poloxamer Polymers 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000010802 sludge Substances 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002359 Tetronic® Polymers 0.000 claims description 2
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 150000003626 triacylglycerols Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims 1
- 230000016615 flocculation Effects 0.000 claims 1
- 238000005189 flocculation Methods 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000008394 flocculating agent Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 55
- 235000019198 oils Nutrition 0.000 description 53
- 239000000839 emulsion Substances 0.000 description 29
- 239000006185 dispersion Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 239000003995 emulsifying agent Substances 0.000 description 24
- 238000007792 addition Methods 0.000 description 23
- 239000004094 surface-active agent Substances 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 16
- 239000002480 mineral oil Substances 0.000 description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 12
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 235000010446 mineral oil Nutrition 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 229920000180 alkyd Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 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 7
- 239000003208 petroleum Substances 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 159000000007 calcium salts Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 108700028369 Alleles Proteins 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 4
- 208000003251 Pruritus Diseases 0.000 description 4
- 239000004133 Sodium thiosulphate Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HRKAMJBPFPHCSD-UHFFFAOYSA-N Tri-isobutylphosphate Chemical compound CC(C)COP(=O)(OCC(C)C)OCC(C)C HRKAMJBPFPHCSD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000004006 olive oil Substances 0.000 description 3
- 235000008390 olive oil Nutrition 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical class C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 208000037062 Polyps Diseases 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BGNTUSKZDOUZCZ-UHFFFAOYSA-N tris(1-butoxyethyl) phosphate Chemical compound CCCCOC(C)OP(=O)(OC(C)OCCCC)OC(C)OCCCC BGNTUSKZDOUZCZ-UHFFFAOYSA-N 0.000 description 2
- ZKIRNCACNZXACZ-VFQQELCFSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;propane-1,2,3-triol Chemical compound OCC(O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO ZKIRNCACNZXACZ-VFQQELCFSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000397426 Centroberyx lineatus Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera 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
- 241001315286 Damon Species 0.000 description 1
- 241001644893 Entandrophragma utile Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241001466538 Gymnogyps Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010034016 Paronychia Diseases 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 241000208422 Rhododendron Species 0.000 description 1
- 241001415849 Strigiformes Species 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- LUTSRLYCMSCGCS-BWOMAWGNSA-N [(3s,8r,9s,10r,13s)-10,13-dimethyl-17-oxo-1,2,3,4,7,8,9,11,12,16-decahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC=C3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 LUTSRLYCMSCGCS-BWOMAWGNSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000010727 cylinder oil Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000009963 fulling Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- RZSCFTDHFNHMOR-UHFFFAOYSA-N n-(2,4-difluorophenyl)-2-[3-(trifluoromethyl)phenoxy]pyridine-3-carboxamide;1,1-dimethyl-3-(4-propan-2-ylphenyl)urea Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1.FC1=CC(F)=CC=C1NC(=O)C1=CC=CN=C1OC1=CC=CC(C(F)(F)F)=C1 RZSCFTDHFNHMOR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- DWHGNUUWCJZQHO-ZVDZYBSKSA-M potassium;(2s,5r,6r)-6-[[(2r)-2-amino-2-(4-hydroxyphenyl)acetyl]amino]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;(2r,3z,5r)-3-(2-hydroxyethylidene)-7-oxo-4-oxa-1-azabicyclo[3.2.0]heptane-2-carboxylate Chemical compound [K+].[O-]C(=O)[C@H]1C(=C/CO)/O[C@@H]2CC(=O)N21.C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 DWHGNUUWCJZQHO-ZVDZYBSKSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/547—Tensides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/09—Sulfur-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paper (AREA)
- Colloid Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Detergent Compositions (AREA)
Abstract
IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS
Abstract of the Disclosure A cationic polymer composition suitable for use as a flocculating agent and as a retention aid in paper making consists of a mixture of a) a hydrophilic cationic polymer, b) an anionic surfactant, optionally c) a water-immiscible oil in which the polymer a) is insoluble, and, if c) is present, optionally d) a lipophilic non-ionic surfactant, optionally e) water and optionally f) an oil-miscible polar solvent.
The compositions may be prepared by water-in-oil emulsion polymerisation and are readily diluted with water.
Abstract of the Disclosure A cationic polymer composition suitable for use as a flocculating agent and as a retention aid in paper making consists of a mixture of a) a hydrophilic cationic polymer, b) an anionic surfactant, optionally c) a water-immiscible oil in which the polymer a) is insoluble, and, if c) is present, optionally d) a lipophilic non-ionic surfactant, optionally e) water and optionally f) an oil-miscible polar solvent.
The compositions may be prepared by water-in-oil emulsion polymerisation and are readily diluted with water.
Description
~2~g6~
- l -vase 150-4527 IMPROVEMENT IN OR RELATING TO ORGANIC COMPOUNDS
_ _ ____ _ _ ._ This invention relates to hydrophilic cat ionic polymers useful for example as flocculating agents. For slush uses, it is important that compositions containing the polymer can by rapidly dispersed or dissolved in water.
It has now been found that compositions containing an excess of a hydrophilic catlon;c polymer together with an anionic surfactant, which optionally forms a salt with the cat ionic polymer, can easily be dispersed or dissolved in water.
Accordingly, the present invention provides a water-miscible composition comprising a) a hydrophilic cat ionic polymer and b) an anionic surfactant, the molar quantity of b) being not greater Han the solar quantity 15 of the cat-ionic monomer units of a).
The polymer a is free of anionic monomer companionways, and is composed ether entirely of cat ionic monomer units or of both cat ionic and non-ionic ~ononler units. my the term cat ionic is meant that the monomer`ur,;t includes a group icily either carries a positive charge on or which has basic properties and can be prntonated under mild acid conditions. Preferably such groups asp amino or qua~ernary amlnonium groups. Suitable polymers a) include caticnic addition and condor.-
- l -vase 150-4527 IMPROVEMENT IN OR RELATING TO ORGANIC COMPOUNDS
_ _ ____ _ _ ._ This invention relates to hydrophilic cat ionic polymers useful for example as flocculating agents. For slush uses, it is important that compositions containing the polymer can by rapidly dispersed or dissolved in water.
It has now been found that compositions containing an excess of a hydrophilic catlon;c polymer together with an anionic surfactant, which optionally forms a salt with the cat ionic polymer, can easily be dispersed or dissolved in water.
Accordingly, the present invention provides a water-miscible composition comprising a) a hydrophilic cat ionic polymer and b) an anionic surfactant, the molar quantity of b) being not greater Han the solar quantity 15 of the cat-ionic monomer units of a).
The polymer a is free of anionic monomer companionways, and is composed ether entirely of cat ionic monomer units or of both cat ionic and non-ionic ~ononler units. my the term cat ionic is meant that the monomer`ur,;t includes a group icily either carries a positive charge on or which has basic properties and can be prntonated under mild acid conditions. Preferably such groups asp amino or qua~ernary amlnonium groups. Suitable polymers a) include caticnic addition and condor.-
- 2 - 150-4527 station polymers such as polyamideamines, polyethyleneimines and polyetheramines, as described for example in tJS Patents 3 210 308,
3 275 58S, 3 329 657, 3 632 55~, 3 ,53 931 and 4 ~56 510. Prefer-ably however polymer a) is at least partly composed of vinyl addition polymers of cat ionic and optionally non-ionic vinyl monomers. Preferably polymer a) comprises at least 70 Cub by weigh of such vinyl addition polymers, more preferably at least 90 ,b;
especially preferred polymers a) consist entirely Or such vinyl addition polymers.
lo Preferred vinelike monomers are water-soluble monomers based upon esters and asides of acrylic and methacrylic acid, vinyl-pardons, diallylamines, N-vinylpyrrolidones and vinyl ethers. Of the cat ionic monomers, preferred types include the clialkylaminoalkyl and dialkylaminohydroxyalkyl esters of acrylic and methacrylic acid, and the corresponding trialkylammoniunl compounds di~lkylaminoalkyl asides of acrylic and methacrylic acid, and the correspondit1g trialkylam~1onium compounds; dialkylsulpholliulnalkyl esters of acrylic and methacrylic acid; 2- and 4-vinylpyridine and the corresponding N-alkylpyridinium derivatives; and N-alkyl diallylamines and the corresponding N,N-dialkyldiallylammonium derivatives. In these compounds, the alkaline grollp forming the bridge between the N and O, O and S or N and N atoms preferably contains 2 to 4, more preferably 2 to 3 carbon atoms and the alkyd groups on nitrogen or Selfware contain preferably 1 to 4, more preferably 1 or 2 carton atoms and may be unsubstituted or substituted by phenol. Phenol-substituted alkyd is preferably bouncily; more preferably, however5the alkyd groups are unsuhstituted.
More preferred cat ionic monomers are those of formulae I-VlII
,~R2 SHEA C, CO Sheehan ITCH 2 up Sue SHUCKS C~2 CH--CH--N--R3 Aye 11 (SHEA = OH - Shea- N - R2 III
~/R2 (SHEA OH SHEA ^ N A IV
SCHICK SCHICK CH2=CH CH2=CH
A
Y VI VII VIII
In the above formulae, Al is H or methyl R2 is methyl or ethyl R3 us methyl or ethyl R4 is hydrogen, methyl or ethyl X is -0- or -NH-Y is H or -OH when X is -0-and H when X is -NH-n is 0 or 1, provided that when Y is -OH
n = 1- -and Assay an anion.
Preferably R2~ R3 and R4 are all methyl. may be any con-ventior;al anion, preferably a halide ion (particularly , Briar or an Reunion. In a preferred form of the invention, however, Axis Awry Aye is the anion of the anionic sur~actant I) .
. .
~3~39
especially preferred polymers a) consist entirely Or such vinyl addition polymers.
lo Preferred vinelike monomers are water-soluble monomers based upon esters and asides of acrylic and methacrylic acid, vinyl-pardons, diallylamines, N-vinylpyrrolidones and vinyl ethers. Of the cat ionic monomers, preferred types include the clialkylaminoalkyl and dialkylaminohydroxyalkyl esters of acrylic and methacrylic acid, and the corresponding trialkylammoniunl compounds di~lkylaminoalkyl asides of acrylic and methacrylic acid, and the correspondit1g trialkylam~1onium compounds; dialkylsulpholliulnalkyl esters of acrylic and methacrylic acid; 2- and 4-vinylpyridine and the corresponding N-alkylpyridinium derivatives; and N-alkyl diallylamines and the corresponding N,N-dialkyldiallylammonium derivatives. In these compounds, the alkaline grollp forming the bridge between the N and O, O and S or N and N atoms preferably contains 2 to 4, more preferably 2 to 3 carbon atoms and the alkyd groups on nitrogen or Selfware contain preferably 1 to 4, more preferably 1 or 2 carton atoms and may be unsubstituted or substituted by phenol. Phenol-substituted alkyd is preferably bouncily; more preferably, however5the alkyd groups are unsuhstituted.
More preferred cat ionic monomers are those of formulae I-VlII
,~R2 SHEA C, CO Sheehan ITCH 2 up Sue SHUCKS C~2 CH--CH--N--R3 Aye 11 (SHEA = OH - Shea- N - R2 III
~/R2 (SHEA OH SHEA ^ N A IV
SCHICK SCHICK CH2=CH CH2=CH
A
Y VI VII VIII
In the above formulae, Al is H or methyl R2 is methyl or ethyl R3 us methyl or ethyl R4 is hydrogen, methyl or ethyl X is -0- or -NH-Y is H or -OH when X is -0-and H when X is -NH-n is 0 or 1, provided that when Y is -OH
n = 1- -and Assay an anion.
Preferably R2~ R3 and R4 are all methyl. may be any con-ventior;al anion, preferably a halide ion (particularly , Briar or an Reunion. In a preferred form of the invention, however, Axis Awry Aye is the anion of the anionic sur~actant I) .
. .
~3~39
- 4 - 150-~527 Particularly preferred cat ionic monomers are those of formulae I and II especially Lucy in which Y is hydrogen and particularly those in which Y is hydrogen and X is -O-.
Preferred non-ionic monomers are acrylan1ide methacrylan1ide N-vinylpyrrolidone methyl vinyl ether ethyl vinyl ether and compounds of formula IX
SHEA - C - CON - C - SHEA CO - SHEA IX
Al SHEA
where Al is as defined above.
OF these acrylamide and methacrylamide particularly acry1amide are preferred.
in Preferred cat ionic polynlers a) are copolymers of cat ionic monon1ers of phenol I or II (Y = H X = -O-) with methacrylan1ide and/or acrylamide. In the kink polymers as the molar quantity of cat ionic monomer units is preferably at least I of the total more preferably 10-80 mow I particularly 10-40 mow %. It may be advantageous however to employ a mixture of two cat ionic polymers of differing cat ionic content for example a weekly kink polymer of eye. 5-20 mow YOU cat ionic units and a strongly cat ionic polymer Of e.g. 20-~0 mow preferably 30-60 mow % cat ionic units. Any desired cat ionic content within a defined range may then be obtained by mixing the two polymers in various proportions.
The molecular wiggly (weight average MY) of the polymer is preferably > 100 000 more preferably 500 000 particularly I' 1 000~000. The Lowe may be as high as desired for example up to 20 000 00C.
Ike preferred polymers may be structurally defined as random copolylners containing units of the following three types.
Preferred non-ionic monomers are acrylan1ide methacrylan1ide N-vinylpyrrolidone methyl vinyl ether ethyl vinyl ether and compounds of formula IX
SHEA - C - CON - C - SHEA CO - SHEA IX
Al SHEA
where Al is as defined above.
OF these acrylamide and methacrylamide particularly acry1amide are preferred.
in Preferred cat ionic polynlers a) are copolymers of cat ionic monon1ers of phenol I or II (Y = H X = -O-) with methacrylan1ide and/or acrylamide. In the kink polymers as the molar quantity of cat ionic monomer units is preferably at least I of the total more preferably 10-80 mow I particularly 10-40 mow %. It may be advantageous however to employ a mixture of two cat ionic polymers of differing cat ionic content for example a weekly kink polymer of eye. 5-20 mow YOU cat ionic units and a strongly cat ionic polymer Of e.g. 20-~0 mow preferably 30-60 mow % cat ionic units. Any desired cat ionic content within a defined range may then be obtained by mixing the two polymers in various proportions.
The molecular wiggly (weight average MY) of the polymer is preferably > 100 000 more preferably 500 000 particularly I' 1 000~000. The Lowe may be as high as desired for example up to 20 000 00C.
Ike preferred polymers may be structurally defined as random copolylners containing units of the following three types.
- 5 - 150-4527 I
- SHEA- C -- - OH -I C - SHEA C
1~3 Alp) JO Aye Z
(l) (2) (3) in which Al is as defined above, is a cat ionic residue preferably derived from a monomer of filial II, IV, IT or VIII, Alp is the annul of the surfactant b), Aye is a non-surfaciant anion such as halide or R405Q3~ and is a non-ionic residue, preferably of fornlula -COWAN, -nCH3, -OOZE or -CONHC(CH3)2CH2COC~3.
and a represent the molar proportions of units (l) (2) and (3) respectively, so that ~+~ = lo, (~) is preferably 5, more preferably Lowe, particularly Lowe and is preferably 5 lo, more preferably lo.
lo The anionic surfactant b) may be any conventional surfactant having at least one lipophilic hydrocarbon residue and at least one hydrophilic anionic group. Suitable surfactants are described for example in "Surfactant Science Series" (M. Decker In-, New York and Basic), vol. 7; and "Anionic Surfactants" (Ed. WOMB. Infield, 1g76), parts 1 and 2. The lipophilic residue is preferably aureole-phatic or aliphatic and contains at least 9 carbon atoms, prefer-ably 12-36 carbon assay. The anionic group may be any conventional acid group optionally in salt filial, for example carboxylate, phosphate, phosphona~e, sulfite and sulphonate, of which sulphonate is rnos~ preferred and phosphonate least preferred. The molecule may contain polyal~ylene glycol tiler groups, buy these are preferably .,. . ' , :
~L2~6~
- SHEA- C -- - OH -I C - SHEA C
1~3 Alp) JO Aye Z
(l) (2) (3) in which Al is as defined above, is a cat ionic residue preferably derived from a monomer of filial II, IV, IT or VIII, Alp is the annul of the surfactant b), Aye is a non-surfaciant anion such as halide or R405Q3~ and is a non-ionic residue, preferably of fornlula -COWAN, -nCH3, -OOZE or -CONHC(CH3)2CH2COC~3.
and a represent the molar proportions of units (l) (2) and (3) respectively, so that ~+~ = lo, (~) is preferably 5, more preferably Lowe, particularly Lowe and is preferably 5 lo, more preferably lo.
lo The anionic surfactant b) may be any conventional surfactant having at least one lipophilic hydrocarbon residue and at least one hydrophilic anionic group. Suitable surfactants are described for example in "Surfactant Science Series" (M. Decker In-, New York and Basic), vol. 7; and "Anionic Surfactants" (Ed. WOMB. Infield, 1g76), parts 1 and 2. The lipophilic residue is preferably aureole-phatic or aliphatic and contains at least 9 carbon atoms, prefer-ably 12-36 carbon assay. The anionic group may be any conventional acid group optionally in salt filial, for example carboxylate, phosphate, phosphona~e, sulfite and sulphonate, of which sulphonate is rnos~ preferred and phosphonate least preferred. The molecule may contain polyal~ylene glycol tiler groups, buy these are preferably .,. . ' , :
~L2~6~
- 6 - 'idea absent.
Preferred classes of anionic surfactallts are:
sulfite arty acid motto- dip all triglycerides, particularly sulpllated natural fats or oils end sulfated monoglyce~ri~les;
sulphatet~i fatty alcohols; sulpl~atecl foe acid all~ancla,llides;
sulp'ilonated nyclrocarbons, particularly alk.ylsulphonate~, olefin sulphonates and alkairyl sup foliates, especial lye petroleum sulk founts; sulphonated aliphatic carboxylic acids and esters, particularly ~-sulpihomonocarboYylic acids and esters an alkyd sulpi1osuccindtes; partial allele esters of phosphoric acid; elf-phatic carboxylic acids (soaps); and rarboxymethylation products of fatty alcohols, monoglycerides and Patty acid all~anolamides. Of the above, the slllphonates., particularly petroleum sulnhonat.es, are preferred.
It is preread that the anionic ~urfactant. is Grigirlally present at least partially in the Norm of a salt with a conventional cation, for example that of all allele metal, alkaline earth metal, ammonillnl or substituted alllmoniuln, Zn2~, Aye and Zr4~: Preferably it is in the form of a salt of a polyvalent inorganic cation, of Which Cay is particularly preferred. In the conlpositions of the inventions, however, after polymer a) is mixed with sur-factant b), the cation of the anionic surfactant may be wholly or partially replace by cat ionic units of tile polymer. Salts ox the surFactclnt with a polyvalent metal may be prepared in it by treating the sodium salt of the surfactant loath a water-soluble salt of the metal, for example Ike format or chloride. In the case of calcium, calcium chloride is preferred.
Tile anionic surFactal)t may have a greater or lesser degree of yore sealability or dispersibility. Preferred anionic surfactailJ!~s are lipophilie! an preferably are such that their sodium salts are oil-soluhle. Especially preread are those which in salt form (particularly the calcium salts) give no true solution on water, but act as Woo ~!ater-in-oil) enlulsifiers, particularly with the
Preferred classes of anionic surfactallts are:
sulfite arty acid motto- dip all triglycerides, particularly sulpllated natural fats or oils end sulfated monoglyce~ri~les;
sulphatet~i fatty alcohols; sulpl~atecl foe acid all~ancla,llides;
sulp'ilonated nyclrocarbons, particularly alk.ylsulphonate~, olefin sulphonates and alkairyl sup foliates, especial lye petroleum sulk founts; sulphonated aliphatic carboxylic acids and esters, particularly ~-sulpihomonocarboYylic acids and esters an alkyd sulpi1osuccindtes; partial allele esters of phosphoric acid; elf-phatic carboxylic acids (soaps); and rarboxymethylation products of fatty alcohols, monoglycerides and Patty acid all~anolamides. Of the above, the slllphonates., particularly petroleum sulnhonat.es, are preferred.
It is preread that the anionic ~urfactant. is Grigirlally present at least partially in the Norm of a salt with a conventional cation, for example that of all allele metal, alkaline earth metal, ammonillnl or substituted alllmoniuln, Zn2~, Aye and Zr4~: Preferably it is in the form of a salt of a polyvalent inorganic cation, of Which Cay is particularly preferred. In the conlpositions of the inventions, however, after polymer a) is mixed with sur-factant b), the cation of the anionic surfactant may be wholly or partially replace by cat ionic units of tile polymer. Salts ox the surFactclnt with a polyvalent metal may be prepared in it by treating the sodium salt of the surfactant loath a water-soluble salt of the metal, for example Ike format or chloride. In the case of calcium, calcium chloride is preferred.
Tile anionic surFactal)t may have a greater or lesser degree of yore sealability or dispersibility. Preferred anionic surfactailJ!~s are lipophilie! an preferably are such that their sodium salts are oil-soluhle. Especially preread are those which in salt form (particularly the calcium salts) give no true solution on water, but act as Woo ~!ater-in-oil) enlulsifiers, particularly with the
- 7 - 150-~527 oils defined Baylor under c).
The compositions of the invention preferably contain in addition to a) and b), c) a water-inlnliscible owl in which the polymer a) is insoluble.
isle compollellt c) is present, polymer a) is finely dispersed in the oil c).
Component c) may be a Sweeney oil or a mixture ox oils, all may be either natural or synthetic Suitable oils include oils from refining crude petrolel;nl, vital and animal oils, lo synthetic hydrocarbons, Modified paraffins and fatty acid esters.
examples of these types include the followillg:
1. Ho_ carbons 1.1. Hydrocarbons from petroleum refining, particularly 1.1.1. petroleum spirit, by 65-140C (de-aronlatised or arolnatic-containincl) 1.1.2. while spirits, paint thinllers etc., by 100 310C, preferably 140-300C especially those in Table I
Table I
,~, art attic content by C
aromatic-free 100-270 24-45 140-31~
~0-90 1~0-260 fully aromatic 160-310 1.1.3. Isoparaffins, by 110~260C
1.1.4. Paraffin oils (= mineral oils,e.g. diesel oil, spindle oil, on machine oil, cylinder oil liberating oil, medicinal paraffin oil) 1.1.5. petrolatuln (preferably mixed with n oil liquid at 20C) 1.2. Synthetic hydrocarbons, particularly from Fischer~lropsch synthesis or high pressure hydrogella~,;ion of carbon eye L96~
The compositions of the invention preferably contain in addition to a) and b), c) a water-inlnliscible owl in which the polymer a) is insoluble.
isle compollellt c) is present, polymer a) is finely dispersed in the oil c).
Component c) may be a Sweeney oil or a mixture ox oils, all may be either natural or synthetic Suitable oils include oils from refining crude petrolel;nl, vital and animal oils, lo synthetic hydrocarbons, Modified paraffins and fatty acid esters.
examples of these types include the followillg:
1. Ho_ carbons 1.1. Hydrocarbons from petroleum refining, particularly 1.1.1. petroleum spirit, by 65-140C (de-aronlatised or arolnatic-containincl) 1.1.2. while spirits, paint thinllers etc., by 100 310C, preferably 140-300C especially those in Table I
Table I
,~, art attic content by C
aromatic-free 100-270 24-45 140-31~
~0-90 1~0-260 fully aromatic 160-310 1.1.3. Isoparaffins, by 110~260C
1.1.4. Paraffin oils (= mineral oils,e.g. diesel oil, spindle oil, on machine oil, cylinder oil liberating oil, medicinal paraffin oil) 1.1.5. petrolatuln (preferably mixed with n oil liquid at 20C) 1.2. Synthetic hydrocarbons, particularly from Fischer~lropsch synthesis or high pressure hydrogella~,;ion of carbon eye L96~
- 8 - 1 50-4527 synthetic petrol (gasoline) by 65-170C
Kogasin by 190-230C
Cozen by Nikko synthetic paraffin oil by 300-450C.
1.3. Bunyan end al~;ylbenzenes e.g. Tulane, zillion, and methyl ethyl-, trim ethyl-, din~ethyletllyl-, tetralllethyl- and hither (C6 alkali benzenes 2. Natural vegetable or animal triglyce desk particularly olive oil, peanut oil, cottonseed oil, coconut fat, rape oil, sunflower oil, corn oil, castor oil and newts foot oil.
3. Fatty acid nlonoesters, primarily Of alkali esters of C12 24 preferably Clue 24 fatty acids, particularly methyl, bottle and isopropyl esters of Starkey, oleic, pallnitic and myristic acids and mixtures thereof.
Preferred oils are low-aroma~ic hydrocarbons and elf-phatic fatty acid esters, particularly hydrocarbons listed under 1.1.2., 1.1.3. and 1.1.4. above, especially aromatic-free and low-aromdtic white spirits, isoparaffin and paraffin, oils.
I on one particular embodinlent of the inversion componerlt c) comprises a mixture of at least two oils particularly of a mixture of an oil at) and an oil c2) chosen such that the oil/water required hydrofoil/ lipophile balance (0/l~-RHLB) value of Claus greater than that of the mixture of at) and c2).The GJl~-RHLB value of an oil is the optimum HLB-value Go a hypothetical surfactant which is sufficient to produce stable Owe emulsion of that oil and water;
see for example "Cosmetics, Science and Technology" Wiley, end edition, volume 3, i974, pup 602-7, or "Emulsion Sirius"
P. Sherman, Academic Press, 196~ pup 14~-7 or "Emulsion, Theory and Practice" P. Beaker, err. Chenille. Soc.~onc~raph series No. 162, end edition, 1965.
~2~96~
Kogasin by 190-230C
Cozen by Nikko synthetic paraffin oil by 300-450C.
1.3. Bunyan end al~;ylbenzenes e.g. Tulane, zillion, and methyl ethyl-, trim ethyl-, din~ethyletllyl-, tetralllethyl- and hither (C6 alkali benzenes 2. Natural vegetable or animal triglyce desk particularly olive oil, peanut oil, cottonseed oil, coconut fat, rape oil, sunflower oil, corn oil, castor oil and newts foot oil.
3. Fatty acid nlonoesters, primarily Of alkali esters of C12 24 preferably Clue 24 fatty acids, particularly methyl, bottle and isopropyl esters of Starkey, oleic, pallnitic and myristic acids and mixtures thereof.
Preferred oils are low-aroma~ic hydrocarbons and elf-phatic fatty acid esters, particularly hydrocarbons listed under 1.1.2., 1.1.3. and 1.1.4. above, especially aromatic-free and low-aromdtic white spirits, isoparaffin and paraffin, oils.
I on one particular embodinlent of the inversion componerlt c) comprises a mixture of at least two oils particularly of a mixture of an oil at) and an oil c2) chosen such that the oil/water required hydrofoil/ lipophile balance (0/l~-RHLB) value of Claus greater than that of the mixture of at) and c2).The GJl~-RHLB value of an oil is the optimum HLB-value Go a hypothetical surfactant which is sufficient to produce stable Owe emulsion of that oil and water;
see for example "Cosmetics, Science and Technology" Wiley, end edition, volume 3, i974, pup 602-7, or "Emulsion Sirius"
P. Sherman, Academic Press, 196~ pup 14~-7 or "Emulsion, Theory and Practice" P. Beaker, err. Chenille. Soc.~onc~raph series No. 162, end edition, 1965.
~2~96~
- 9 - l50-452~
( Preferably the 0/~,-RHLB value of c2) is less than that of at). Preferred oils at) haze I RHLB values in the range 10-15;
such oils include hydrocarbon oils fisted untie Lyle. 1 1.2.
1.1.3. and 1.3. above. Preferred oils c2) have 0/W-RHLB values in the range Lowe; such oils include those listed under I.1.4.
l.l.5 2. and 3. above.
Preferably the compositions accorciing to the invention contain in addition to a) b) and c) d) a lipophilic non-ionic surfactant.
lo Component d) is preferably oil-soluble end may be a jingle surfactant or a mixture. Component d) must function as a ~1/0 (water-in-oil) emulsifier that is it must be capable of forming a lo enlulsion with at least part of the oil c) in the presence of water. The surfactant d) is preferably insoluble in plater and has an LO value I more preferably in the range 3-8 part-ocularly in the range 4-7. If d) is a Metro, these values apply to the average HUB value of the mixture.
Component d) generally is one or more compounds Hun at lest one lipophilic hydrocarbon residue of at least 9 prefer-ably ~-24 carbon atoms and at least one non-icnic hydrophilic residue itch is preferably a moron or polyethylene glycol group optionally containing propylene glycol units or the residual o a polyol e.g. glycerol Manuel and surety . 0 her suitable types include hydrophobic.Pluron-,cs~Yan~ ~fetl^onics in ~ihic,l the high propylene oxide content can be regarded as the lipophilic residue.
Specs f i c types of non-ionic surfactants include:
Products obtainable by addition, of ethylene oxicic (En) Andre propylene oxide (Pi) (preferably cC alone) is aliphatic alcohols allele phenols fatty acids Patty acid a'lkanolamides partial fatty acid esters of polycls and vigil Go alp Sal fats or owls;
purl fatty acid esters of polyols; E0/P0 couplers with high Pi content (Pluronic type); EOJP0 addition products to ethylene Damon having a high Pi content (Tetronic type); Doris of Jo ~L219G~9 - lo - l~0-4527 moo- or polyethylene glycols with aliphatic alcohols and alkyd phenols; and divesters of moo- or polyethyle1le glycols with aliphatic Fatty acids.
The preferred nabber of ethylene oxide llnitS in addition prodl1cts of HO to fatty alcohols Alec alkyd phenols is 1-6 and in addition products to fatty acids and in ~1i-esters of polyalkylcne glycol tune nu1l1ber of I units is preferably lo These numbers are average values end need not be integral.
Fatty acid residuals may be saturated or unsaturated (if lo unsaturated preferably mor1oet1ylenically ut1saturate~) and are proofer azalea showpiece having 9-24 preferably l2-20 carbon attunes particularly residues of lyric myristicS Starkey and oleic acids.
If an allele group is the sole lipophilic group it has preferably 9-24 more preferably 9-l8 carton atoms arid may be stralg1lt chef or bra1lched. In a1kylar~vl grouts the alkyd group preferably has 4-12 carbon atoms anal may also be s~rai(1ht or branched.
Particularly preferred su)-factar1ts are those of formula X~XIII
I -I C~12C~12 t-t- OH X
Or ~-ocH2cH2-3-K~ OH XI
Rlo--co- I C~12C~2 -em Charlie XIII
in which R8 is Clue ~lkyl Rug is I l~alkyl or alkenyl Rl~CO is the assay residue of an aliphatic~Cl2 18 fatty acid Q is the monovalent residue of sorbitol glycerol or I- to tevra~ethylene yokel t is 2-3 r is l or 2 - lZ~96~9 k is 3-5 and m is 4-9.
The HAL values of non-ionic surfactants may be calculated by use of a standard Formula. In order to function as a I Emil-sifter on this system the calculated HUB value must be greater than 2.5.
When the owl c) is a mixture of oils at) and c2) then the oil mixture and the surfactant d) are preferably so chosen that the 0/W-RHLB value of the oil mixture is as close as possible to the HUB value of do, or at least is not less than this value.
Preferably the compositions according to the invention contain, in addition to components a), b), c) and preferably d), e) water.
lo The polymer a) and salts of the polymer with surfactant b) are hydrophilic and will take up water or form with water a gel or sol and in sufficient water will form a true or a colloidal solution. The quantity of water e) is chosen so that the polymer together with the water becomes finely dispersed in the oil. The dispersion may be in the form of a suspension of wet or water-swollen polymer or of an aqueous polymer gel in the oil, or an emulsion of an aqueous polymer sol or polymer solution in the oil.
In one particular aspect of the invention, the composition contains, in addition to components a) - c) preferably d) and optionally e) f) an oil-miscible polar solvent which is only slightly soluble in water, not self-dispersing in water, and which has no emulsifying properties of its own, but which reduces the water/oil interracial surface tension.
Suitable solvents f) are compounds which have extremely low HUB values but whose molecules are polar enough to orientate them-selves at the oillwater interface. Preferred solvents are C5 10 aliphatic alcohols phosphoric acid trimesters or Pluronics. Examples of suitable solvents include methyl isobutyl carbinol, 2-ethyl-I;
: `
.
Lo 1~36 - lo - l50-~527 hexanol, isononanol, isodecanol, 2,4,7,9-tetramethyl-5-decyn-Doyle, tributyl phosphate, tri-isobutyl phosphate, tri(butoxy-ethyl) phosphate and Pluronic Loll. The presence of f) is desirable when little or no water e) is present.
Compositions according to the invention may be prepared by mixing surfactant b) before, during or after the polymerization, with the polymer a) or the corresponding monomers, the polymer or monomers being present in Finely divided form. When a) is other than a vinyl addition polymer it is preferred to add the lo surfactant to the already formed polymer. The polymer should be in finely-divided form for example as an aqueous solution, a disk pension in oil, or, preferably as a W/0 emulsion of an aqueous solution of the polymer in oil; When polymer a) is a vinyl addition polymer, it is advantageous to carry out the polymerization in a lo W/0 emulsion system and to have at least part of the anionic sun-fact ant b) present before polymerization, or at least before addition of the cat ionic monomer. After polymerization water and/
or oil can if desired be removed by distillation, and optionally further additions of any of components a may be made.
Preferably the vinyl monomers are emulsified in the form of their aqueous solution in at least part of the oil c) in the presence of the anionic surfactant b) and preferably also in the presence of the lipophilic non-ionic surfactant d). This W/0 emulsion may be formed by adding the vinyl monomers to an already-formed W/0 emulsion, or the monomers may be added to an aqueous solution or dispersion of the anionic surfactant b), to which is then added the oil and optionally the non-ionic surfactant d), and polymerization is initiated by addition of a suitable catalyst.
The presence of the anionic surfactant in the monomer-containing W/0 emulsion before polymerization enables part of the cat ionic monomers, particularly in neutral to acid conditions, to form salts with the surfactants, which salts are less water-soluble and more lipophilic than the monomers themselves. These monomer-surFactant salts are novel and form part of the present invention. Preferred salts have the formula XIV
SHEA = C - Aye ZOO
where Al, and Awry as defined above.
Preferably is of formula XV
- CO - I SHEA OH- SHEA N \ R3 XV
where X, n, Y, R2, R3 and R4 are defined above, and Y is preferably H, and Assay the anion of a hydrocarbon sulphonate, particularly petroleum sulphonate.
An alternative method ox preparing compositions according to the present invention consists in forming a dispersion containing polymer a), water e) and lipophilic non-ionic surfactant d) in oil c) in the absence of anionic surfactant b), and then adding the anionic surfactant b) to this dispersion. For this process variant, it is preferred that the anionic surfactant is an oil-soluble, practically water-insoluble sulphonated hydrocarbon, and that the oil is a hydrocarbon oil of the type listed under 1.1. above, par-titularly white spirit. Preferably the dispersion is obtained by emulsion polymerization of the monomer solution in oil in the pro-since of surfactant d) as emulsifier, and optionally partial removal of water by distillation.
The emulsion polymerization, preferably in the presence of anionic surfactant b) may be carried out in conventional manner (see for example "High Polymers" vol. 9,1955 - "Emulsion Polyp merisation, Intrusions Publishers, NAY.). Conventional free radical initiators are used to catalyze the polymerization. Suitable initiator systems include peroxide compounds, e.g. t-butyl hyiroperoxide, in combination with redo systems, e.g. ferris salts plus sodium trio-sulfite. To sequester impurities, it is preferred to add a 3L2 Lo 39 completing agent such as salts of ethylenediaminetetraacetic acid (ETA). The aqueous phase may contain further additives; e.g. acids, bases or buffer systems to regulate pi and salts e.g. sodium sulfite and calcium chloride.
The air above the emulsion is normally replaced by an inert gas and polymerization is started by the addition of initiator.
The polymerization takes place for example at pi values between 2 and 8, preferably under acid conditions (pi 2.5-5, preferably 3-4). The water content of the W/O emulsion during polymerization is preferably 15-80 wt.%, more preferably 30-65 wt.% based on the total weight of the emulsion.
The polymerization is normally exothermic, and may be carried out under adiabatic or isothermal conditions, but preferably is carried out partially adiabatically, i.e. the temperature is allowed to increase within certain limits, e.g. up to 120C, underpricer if necessary. Preferred reaction temperatures are from 30-110C. If the reaction mixture contains hydrolyzable moo-mews, e.g. esters or primary asides, it is necessary to avoid reaction conditions under which significant amounts of hydrolysis would occur.
For the W/0 emulsion polymerization it is advantageous to use an oil c) comprising at least 50%, preferably at least 80% by wt.
hydrocarbons, which should preferably be as completely aliphatic as possible. The concentration of monomers in the emulsion is not critical, but for economic reasons it is advantageous to work with as high concentrations as is practicable. The concentration of surfactant used is adjusted to be sufficient to give a stable W/0 emulsion under the polymerization conditions.
After polymerization is complete the polymer-containing W/0 emulsion can be treated by addition of further quantities of components a) - f) or, if desired, the amount of components c) and/
or e) can be reduced by distillation. By such adjustments proper-~2~36~3 ties of the emulsion such as stability and ease of dilution with water can be influenced and improved. If in addition to vinyl addition polymer other cat ionic polymers a) are to be present, these are preferably added after the emulsion polymerization is complete.
If component f) is to be present, this is preferably added after the emulsion polymerization, more preferably after all other components have been added. It may be advantageous to mix f) with a little oil c) before addition.
If a mixture of oils c1) and c2) is to be used, the polyp merisation is preferably carried out either in the mixture or in at) alone or in a mixture of at) with less than all of the c2) The oil c2~, or that part of it not already present, may be added after the emulsion polymerization, optionally after some or all of the water has been distilled off.
The relative weights of the various components in the compositions according to the invention may be represented as follows: for every 100 parts by weight of the polymer a), the composition contains x parts by weight of b), y of c), z of d) u of e) and v of f). The figures 100 for a) and x for b) do not 20 take into account the salt formation between a) and b); that is, the weight of surfactant which forms a salt with the polymer is not counted as part of the polymer weight, but remains part of weight x.
The preferred ranges of x-v are set out in Table II below, the values for each component being independent of each other except where otherwise stated. For certain applications, the value of x may be as low as 0.5 Table II
(component a = 100) component value of preferred more preferred most preferred b x 1-30 1-15 1.5-10 c y 30-400 40-200 40-200 d z 0-80 1-80 2-30 e u 0-300 1-300 2-200 f v my 0-30 0-15 ( C Yo-yo ) ( Y/5 The water content (u) can vary within wisp limits and in theory it is possible to remove the water completely by distillation giving u = 0. In practice it is difficult to remove the last traces of water from the polymer; also it is possible to add water in the form of a further amount of W/0 emulsion or aqueous polymer solution; so that the water content of the composition can be high.
As it is not economically feasible to remove all the water, u can preferably be 5-300, more preferably 10-200.
Preferred compositions contain, for 100 parts by weight of a), 1-30 parts b), 30-400 parts c), 1-80 parts d), 0-300 parts e) and 0-30 parts f) where the weight of f) is less than 1/3 that of c).
Particularly preferred compositions are those in which the weight of each component present is within the range given in the "most preferred" column of Table II.
The oil-containing compositions according to the invention are dispersions which may show a wide range of viscosities. The Brook field rotation viscosity (measured in an LV-viscometer) may vary between 5 cup (spindle no. I and Lyon cup (spindle no. 4), preferably between 50 cup (spindle no. 2) and 5000 cup (spindle Noah).
The dispersions are stable and can be stored for long periods of time without change or, if separation into two layers occurs, can be restored to the original form by simple stirring. The combo-sessions of the invention, particularly those containing the oil) have particularly good dispersibility in water and can rapidly be diluted with water by stirring or by the use of conventional dilution apparatus.
In a preferred method of dilution, the dispersion is pumped through a nozzle into a stream of water which surrounds the nozzle. The water stream has a higher velocity than that of the stream of dispersion, and this velocity is sufficient to over-come at least partially the internal adhesive and cohesive forces in the dispersion, but not sufficient to reduce the size of the polymer molecules. The mixture of product and water is then alter-natively accelerated in narrow tubes and decelerated in wider mixing zones until the desired degree of mixing is obtained. No sieves or filters are used in this process from the time the Jo L~6~9 streams of water and of dispersion contact each other.
A mixing apparatus suitable for carrying out the above process comprises at least two cylindrical mixing chambers connect ted by rigid or flexible tubing of diameter not greater than half that of each mixing chamber. The first chamber is furnished with a coccal mounted tube for the inflow of a stream of water and a second tube, substantially at right angles to the first, ending in a jet situated between the axis and circumference of the first tube and just beyond the end of the first tube. Means are provided for pumping the dispersion through this second tube. Near the other end of the mixing chamber is an exit tube leading to the second mixing chamber. The second and any subsequent mixing chambers are each provided with an inlet and an exit tube, preferably set into the side walls one near each end of the chamber. Finally an exit tube from the last mixing chamber leads to the apparatus in which the dilute aqueous dispersion of the composition according to the invention is to be used.
A particularly preferred apparatus is illustrated by way of example in Figures 1 and 2. Figure 1 is a vertical elevation of a six-chamber mixing apparatus, the upper chamber 1 being shown in cross section. Figure 2 is a horizontal cross-section along XX' of Figure 1.
The chambers 1-6 are mounted alternately on opposite sides of a frame 7 and secured with clips 8. The chambers are constructed of cylindrical tubing 9 closed with screw caps 10 which can be removed for cleaning. In chamber 1 the tubing 9 is of transparent material to allow direct observation of the mixing process, in the other chambers it is of metal.
Chamber 1 is fitted with a coaxial water inlet tube 11, at right angles to which is mounted a dispersion inlet tube 12 which ends in a six-holed jet 13 postponed so as to be completely within the stream of water delivered by tube I In the cylindrical tubing 9, near the end remote from tube 11 is an opening 14 leading to Lo Lowe a flexible hose 15 which connects to a similar opening in the side wall of chamber 2. From a second opening in chamber 2 a further hose 16 leads to chamber 3. Chambers 2-6 are all identical in con-struction and are connected, each to the next, by hoses 16-19.
Finally, chamber 6 is provided with a flexible delivery hose 20.
In operation, a stream of water is led through tube 11 into chamber 1, and is allowed to run until all chambers are filled and the water is delivered from hose 20. The Reynolds number of the water flow at the exit of tube 11 is preferably between 25,000 and 75,000, and the pressure drop across the apparatus will for a medium size apparatus of total volume 1-100 lithe preferably be from 0.5 to 2.5 bar, more preferably from 0.6 to 1.5 bar.
The dispersion is then pumped through tube 12 at a rate sufficient to give the desired concentration of product. The dispersion passes through the jet 13, the size and number of whose holes may be varied according to the viscosity of the dispersion, and is rapidly mixed in the stream of water from tube 11. The mixture passes from chamber 1 through the narrow hose 15 in which its flow is accelerated, and then into the wide chamber 2 in which its flow is again slowed down. The alternating acceleration and slowing of the flow in the successive connecting hoses and mixing chambers provides a complete mixing of the dispersion in the water, and the water containing the product is delivered through hose 20 to the apparatus in which it is to be used.
The compositions according to the invention can be very rapidly diluted with water and thus are suitable for use in many large-scale continuous processes, in which cat ionic polymers are used. By the use of the mixer described above, fully diluted solutions or dispersions can be obtained without the use of any dwell tanks; the mixer may simply be connected up to the equipment in which the diluted product will be used.
The compositions may contain very high concentrations of cat ionic polymer, enabling the minimum handling of bulk liquids.
Jo ~2~g~
- 20 - 150-~527 Not only the concentrated compositions described above, but also partially diluted compositions containing at least 0.001% by weight of polymer a), more preferably at least 0.1% by weight of a) are included within the scope ox the present invention. The partially diluted compositions may be further diluted as required before use.
The compositions of the invention are useful as flocculating agents, particularly as retention and detouring agents in paper-making and as flocculating agents for aqueous sludge, particularly crude and treated sludge from sewage purification works. They may also be used in other processes where cat ionic polymers are employed, for example flotation of minerals or recovery of oil waste.
In paper making, the use of the compositions according to the invention can give a particularly homogeneous sheet formation.
The compositions also show Good biodegradability.
The following Examples illustrate the invention: ~11 parts and percentages are by weight unless otherwise stated.
Examples Emulsifiers used:
By sodium salt of petroleum monosulphonate, MY 440-470 (62% solution in mineral oil) By sodium salt of petroleum monosulphonate, MY 480 (60% solution in mineral oil) By sodium salt of secondary n-alkane sulphonate, obtained from sulphoxidation of paraffin. The alkyd group has the following average composition:
C13-15 58~, C16-17 39%, > C17 < 3%, < C13 < 1%
Do Cl2H25(ocH2cH2)2oH , HUB 6.5 Do Cl8H35(ocH2cH2)3oH~ HUB 6.5 Do sorbitol moonlit, HUB 4.0 .96~9 Do 1:1 molar mixture of moo- and dolts of ~I(OCH2CH2)6 50H , HUB 7.0 (average value) Oils used:
Of white spirit: aromatic-free, by 193-247C, mean MY 173 C2 white spirit: low-aromatic, by 190-250C
mean MY 180, aromatic content 0.5%
C3 mineral oil: partially unsaturated mineral oil with following properties: specific gravity (SO) 0.85-0.95 aniline point 70-80C, iodine number 20-30 I petrolatum: solidification point 50-85C
cone penetration 160-180 at 25C
C5 olive oil:
C6 isoparaffin: b.p.210-260C, aniline point 88C
isoparaffin content 80%, SO 0.78 C7 mixture of methyl esters ox C12 photo acids SO 0.87-0.90, acid number 1.12, saponification number 190-200, iodine number 100-110, hydroxy number 40-60 C8 mineral oil: SO 0.85-0.95, aniline point 95C, viscosity (20C) 30 cup Solvents used:
Fly triisobutyl phosphate (50% in isobutanol) F2 2 ethylhexanol F3 tri(butoxyethyl)phosphate F4 2,4,7,9-tetramethyl-6 decyn-4,7-diol F5 Pluronic L101 10:90 EO/PO copolymer, MY 3610 3L2 ~L~3~9 I
Example 1 43.5 Parts emulsifier By are mixed with 800 parts water, giving a fine opalescent emulsion. On addition of 8.2 parts calcium chloride, a precipitate of the water-insoluble calcium salt of By is formed. Finally 440 parts white spirit Of is added with stirring, giving a water-in-oil emulsion which is stabilized by addition of 99.5 parts emulsifier Do, To this emulsion is added in the following order 353 parts of 75% aqueous methacryloyloxyethyltrimethylammonium chloride, 454 parts acrylamide, 1.4 parts ETA sodium salt, 0.7 parts ferris sulfite and 0.7 parts t-butylhydroperoxide, after which the pi of the aqueous phase is 3.0, The emulsion is heated to 35C
under nitrogen, and an air-free solution of 2.7 parts sodium trio-sulfite in 50 parts water is added drops over 8 hours the temperature being kept at 35-40C by cooling.
Polymerization is complete when all the thiosulphate solution has been added. A stable, fine dispersion of polymer is obtained, of Brook field viscosity 1000 cup (spindle 3, 60 rum). The product is very easily diluted with water, the maximum viscosity of a 0.5%
aqueous dilution with cold water being reached after only 30-40 seconds. The viscosity of a freshly-prepared 1% aqueous dilution is approx. 500 cup (Brook field 3, 60 rum).
Example 2 454 Parts acrylamide, 353 parts of 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride, 1.4 parts disodium ETA, 0.7 parts ferris sulfite and 9.8 parts calcium chloride are added in the stated order to 600 parts water. The solution so obtained is then mixed with a solution of 52 parts emulsifierBl and 80 parts emulsifier D
in 600 parts white spirit Of, giving a water-in-oil emulsion whose aqueous phase has a pi of 3,0. Under a nitrogen atmosphere is added first 0.7 parts t-butylhydroperoxide and then an air-free solution of 1.1 parts sodium thiosulphate in 12 parts water. A strongly exothermic reaction sets in, giving a temperature rise of up to 90C
2 ~L~36~3~
even under light cooling. On cooling a fine dispersion of polymer is obtained which is easily diluted with water.
Example 3 _ _ _ _ 24 Parts emulsifier By is Maxwell with SO parts of Wesley S wiving a fine opalescent emulsion. To this is added I parts of 75~' aqueous methacryloyloxyethyltrililetilylalnllloniull chloride whereby the sul-actant salt of the catiollic monomer is frilled. The following compollerlts are then added in the stated order it stirring;
408.3 parts acrylalnide 1.43 parts dazedly EDDY 0.77 parts fork sulfite 480 parts white spirit Us on parts emulsifier Do 30 parts emulsifier Do 4.8 parts calci~nl~ chloride and 0.6 parts t-b~ty'lhydroperoxide.
The resolutely dispersings purged with nitrogell arid world to 30'~C then an air-free solutioll of' 2.97 parts sodium Thea sulfite in 42 parts water is added over 8 Halsey the temperature rising to 50C. A Fine clispersioll o-i-' polylller is obtained which is easily diluted with water.
example 4_ _ 500 parts of the product of Example l is stirred with lo parts white spirit Of and lo parts emulsifier By and then distilled ilk a Dean-Stclrke apparatus at 26 mar 40C until approx. 200 parts water has teen removed. A fine stable polynler dispersion, is obtained itch in spite of its lo water content is readily diluted with water.
Exan~pl The procedure of Example l is repeated and to the product is added owe of the total wow of the product of Example 3.1 of US 3 632 559 containing 20"~ wt. cat ionic poller and 80;'~ water.
A stable '1/0 emulsion is obtained.
~L23L~ 39 Example 6 i) Preparation of polymer dispersion without sl!rfactant p) 454 Parts acrylamide and 353 parts 75% aqueous methacryloyl-oxyethyltrimethylammonium chloride are dissolved in 800 parts water, and 1.43 parts disodium ETA and 0.72 parts ferris sulfite are added. The pi is adjusted to 3.0 with approx. 0.1 part 30% caustic soda, then a solution of 143 parts emulsifier Do in 440 parts white spirit C2 is added with vigorous stirring. A milky W/0 emulsion is formed, which is thoroughly de-aerated and stirred while bubbling a stream of nitrogen through the mixture.
After addition of 0.67 parts t-butyl hydroperoxide, the mixture is heated to 35C, and a solution of 2.7 parts sodium thiosulphate in 50 parts water is added drops over 5 hours, the temperature being held at 36-38C by cooling. After addition is complete, reaction is continued for 2 hours at 35C, and the product is then cooled to room temperature .
ii) Addition of surfactant b) A 20% aqueous emulsion of By (sodium petroleum sulphonate) is treated with excess Cook, and the precipitated calcium salt collected by filtration, dried under vacuum at 60-70C and taken up in mineral oil to give a 30% solution. 20 Parts of this solution and 20 parts white spirit C2 are added to 200 parts of the suspension prepared in i) above. A viscous product is obtained which in spite of its high viscosity may be rapidly diluted with water.
Example 7 - The calcium salt of emulsifier By is` prepared as described above for By, and 10 parts of this salt are dissolved in a mixture of 80 parts white spirit C2 and 30 parts mineral oil C3. 25 Parts of this solution are added to 200 parts of the suspension prepared in Example 6 i). The resulting mixture is readily diluted with water.
sample 8 To 200 parts Or the suspellsioll prepared in Example 6 i) are added 30 parts of a soluticil contclining 1~.3~' socliulll petroleunl sulphon~te By 57.~) % malarial oil I end 2~.6"~ of a 50~`~ solution 5 of triisobutyl phosphate in isobutallol (Ill. A viscous product is obtainer itch is readily diluted Oil addition to water.
_xalllple q To 221n parts of the polylller einulsion prepared in Exanlple 1 are added 330 parts mirleral nil C3 anal 330 parts petrolatulll I
end the mixture is evacuated to 26 mar under stirring end heated to 4nC oven cay 6 hours collecting S60 parts water in a Dean-Stalk trap any oil which distilled being returned to the distillation mixture A very fine stable slightly viscous (dispersion is obtainetl which may be diluted with water approximately as readily as eye lo product of Example 1.
Example 10 A dispersion containing 9G0 parts water 816.6 parts acryl-aside 1128 parts 75~ aqueous methacry'loyloxyethyltrilllet'nyla;n!nonium chloride 2.9 parts disodium Edits 1.5 parts ferris sulfite 2Q 9.1 parts closely chloride 48 parts emulsifier By 60 parts emulsifier Do 5G parts emulsifier Do and ~60 parts White spirit C1 is adjusted to pi I and 1.2 parts t~butylhydroperoxide are added.
Polymerisatic)n is carried out under nitrogen by adding 6.5 parts sodium thiosulphate in 20 parts water over hours the temperature rising to approx. 48C. in spite of cooling.
To the product are added 165.7 parts mineral oil C3 and 27.7 parts emulsifier Do and llg6 parts water is distilled off at 20-26 mar 5~C. The resulting fine mobile dispersion is mixed loath 157.5 parts olive oil C5 end 157.5 parts 2-ethy'lhexanol (F2). The product is practically instantaneously diluted in water.
~L2~L~6'~3 - 26 - l5n-4527 Examples 11-13 Example lug is repeated with F2 replaced by equal quanta-ties of Fly F3 end F4 respectively.
example I
43.5 Parts emulsifier By ale mixed with 83~ parts water to give a very fine opalescent emulsiotl. In orcIer to foreign the calcium salt of By $.2 parts calciulll chloride are added. Ike following components are theft added with stirring: 557 parts arylalnide 216 parts 75C~ aqueous methacryloyloxyethyltrilnethylalnMorlium chloride 1.4 parts disodiunl ETA and 0.7 parts ferris sulfite javelin a cloudy solution to which are added 400 parts isoparafFin C6 40 parts mineral oil C3~ 100 pyres emulsifier Do and 13 parts emulsifier By to give a I~I/0 emulsion which is polymerized under Newton by the addition of 0.7 parts t-butyl hydroperoxiie when 6 parts of a solution of I parts sodium i.hiosulpha~e in 50 parts water. The tempQratllre rises to 85C even it cooli1lg. Tile resultillg dispersion may be rapidly diluted with Atari Example 15 _ Example 14 is repeated with the following challges:
709 Parts water 183.3 parts acrylamide and 714 parts of the aqueous cat ionic monomer are used; the temperature rises to approx.
43C under adiabatic conditions; and after the polymerization 33 parts Pluronic L101 ~F5) and 165 parts Fatty acid esters C7 are added.
Example 16 Example 14 is repeated with the fullness changes:
160 Parts mineral oil C8 are used in place of 40 parts us and the temperature is kept between 35 and 40C.
eye 43.5 Parts emulsifier By are mixed with ~300 parts water and to the resulting emulsion are added 8.8 parts calcium chloride .
I
- 27 - 150-~527 363 parts acrylamide 124 parts dia11ylal1)ine 353 parts 75C~ aqueous methacryloyloxyetllyltrilllethylal~ ox lo chloride 131 parts 34~.
hydrochloric acid to adjust the pit to I 1.4 parts dazedly ETA
end 0.7 parts ferris. solute. holllngeneous nlonomer swallowtail i;
Formed to hill is added 400 parts White surety Of on pyrites mineral oil C3 Ann 100 parts elnulsifier [I A fine emulsion is fairyland which is polynlerised under nitrogen my tile atldition of 0.7 parts t butylhych~operoxide followed blue parts of a solution of 2.7 parts socliull1 tlliosulphate in 50 parts water. the temperatllre during polyllleiisati~l rises unideal adiabatic eon ions to 65~C.
_ ample 18 Example 2 is rel!eatecl with the felon Schloss:
29 rents emulsifier Al are usQcJ; anti the 80 pelts em iffy Do are replace by a mixture of I parts I and 65 parts Do.
Example_lg Example 17 is repeated with the fulling changes:
54 Parts acrylaMide replace 363 parts acrylamicle + 12~ pats diallylanrinc-; no CLUE is used; 54 Paris By replace 100 parts Do; 45 putts thios~llphate solution replaces 16 parts; and the tenlperature rises within 90 muons to 90~.
apple 20 43.5 Parts emulsifier By is mixed with 600 parts water. To this is added 8.2 parts calcium chloride 4~4 parts acrylamide 1.4 parts disdain ETA 0.7 parts ferris sulfite 400 parts white spirit Of 40 parts mineral oil C3 100 parts emulsifier Do and 13 parts emulsifier By. A water-in-oil emulsion is formed which is polymerized under Noreen us adding no parts t bottle hydra--peroxide and 1 part of a solution of 2.7 I-arts sodium thiosulphate in 50 parts water. the polymerization reaction is held at a temperature of 60C. liken the temperature begins id fall off a solution of 265 parts methacryloyloxyethyltrimethylalnnlon1um chloride in 288 parts water is added drools giving a further rise of temperature which is held at 55-60~C by coolillg. After the addition 3L2~36~9 is complete, the product is stirred 1 hour at 55C then cooled to room temperature.
Example 21 Example 15 is repeated with the following changes:
11 parts By are used in place of 43.5 parts; 25 parts Do are used in place of 100 parts; 3.25 parts By are used in place of 13 parts; and no F5 and C7 are added after polymerization.
Examele_22 Example 16 is repeated with the following changes:
21.75 parts By are used in place of 43.5 parts 50.00 parts Do are used in place of 100 parts 6.50 parts By are used in place of 13 parts.
Dilution Example A mixing apparatus as shown in Figure 1 is used, having 6 chambers each of inner diameter 11 cm and volume 2.5 1. The connecting hoses have an inner diameter of 15 mm and are each 40 cm long.
20~ Into the first chamber of the mixture is fed through a 15 mm dram jet a stream of water of 2000 l/hour, giving a speed of 3.2 m/sec. at the jet Reynolds number 47000). Into the water stream is fed, by means of a pump operating at a frequency of 50 Ho, 5 1/hr of the product of Example 1. The polymer jet has six holes of l mm diameter, and is equipped with a non-return valve.
The diluted product delivered from the mixer is a ready-to-use aqueous solution of the product suitable for use in paper making.
Application Example A
A 2% aqueous paper slurry of the following composition is prepared; 100 parts bleached sulfite pulp, 20 parts kaolin, I;`
3i6~
3 parts resin size, 2 parts alumlnium sulfite.
Four samples (250 ml) of this slurry are mixed with 5, 10, 15 and 20 ml respectively of a 0.0125% aqueous stock dilution of the product of Example 1 and 750 ml water. After stirring 5 sec. at 250 rum, each mixture is poured into 3 1 of water in the filling chamber of a Rapld-Kothen sheet wormer, and after a 20 sec. pause the suction valve is operated to form the sheet After drying and conditioning the paper sheet is incinerated and the ash content measured and calculated as a percentage of the weight ox filler which was used giving the % retention. The results are given in Table A.
Table A
amount of stock concentration of % ash % retention dilution added polymer emulsion (average of 2 measurements) based on dry paper weight (%) 0 - 8.51 51.1 0.0125 13.31 79.9 0.025 14.34 86.0 0.0375 14.66 88.0 0.05 14.73 88.4 Application Exhume B
200 Parts of a sewage suspension of 5% dry solids content are treated with W parts of a 0.23% aqueous stock dilution of the product of Example 1, stirred 10 sec. in a 'Briton' stirrer at lOOOrpm, then immediately filtered through a cloth filter. For each sample, the volume of filtrate after 30, 60, 90, 120 and 180 seconds is measured, and the mean value of these is calculated. The results are shown in Table B.
~L~196~9 - 30 - 150-~527 table 13 lo (parts by eight) Nina filtrate volt ( parts by vow l utile _.__ . _.~
O 1.5 13 15.3 ~0.4 17 ~9.1 the prodllcts no Examples 2--22 nay be used in analogous manlier to Application Example. I anal B.
. , .
( Preferably the 0/~,-RHLB value of c2) is less than that of at). Preferred oils at) haze I RHLB values in the range 10-15;
such oils include hydrocarbon oils fisted untie Lyle. 1 1.2.
1.1.3. and 1.3. above. Preferred oils c2) have 0/W-RHLB values in the range Lowe; such oils include those listed under I.1.4.
l.l.5 2. and 3. above.
Preferably the compositions accorciing to the invention contain in addition to a) b) and c) d) a lipophilic non-ionic surfactant.
lo Component d) is preferably oil-soluble end may be a jingle surfactant or a mixture. Component d) must function as a ~1/0 (water-in-oil) emulsifier that is it must be capable of forming a lo enlulsion with at least part of the oil c) in the presence of water. The surfactant d) is preferably insoluble in plater and has an LO value I more preferably in the range 3-8 part-ocularly in the range 4-7. If d) is a Metro, these values apply to the average HUB value of the mixture.
Component d) generally is one or more compounds Hun at lest one lipophilic hydrocarbon residue of at least 9 prefer-ably ~-24 carbon atoms and at least one non-icnic hydrophilic residue itch is preferably a moron or polyethylene glycol group optionally containing propylene glycol units or the residual o a polyol e.g. glycerol Manuel and surety . 0 her suitable types include hydrophobic.Pluron-,cs~Yan~ ~fetl^onics in ~ihic,l the high propylene oxide content can be regarded as the lipophilic residue.
Specs f i c types of non-ionic surfactants include:
Products obtainable by addition, of ethylene oxicic (En) Andre propylene oxide (Pi) (preferably cC alone) is aliphatic alcohols allele phenols fatty acids Patty acid a'lkanolamides partial fatty acid esters of polycls and vigil Go alp Sal fats or owls;
purl fatty acid esters of polyols; E0/P0 couplers with high Pi content (Pluronic type); EOJP0 addition products to ethylene Damon having a high Pi content (Tetronic type); Doris of Jo ~L219G~9 - lo - l~0-4527 moo- or polyethylene glycols with aliphatic alcohols and alkyd phenols; and divesters of moo- or polyethyle1le glycols with aliphatic Fatty acids.
The preferred nabber of ethylene oxide llnitS in addition prodl1cts of HO to fatty alcohols Alec alkyd phenols is 1-6 and in addition products to fatty acids and in ~1i-esters of polyalkylcne glycol tune nu1l1ber of I units is preferably lo These numbers are average values end need not be integral.
Fatty acid residuals may be saturated or unsaturated (if lo unsaturated preferably mor1oet1ylenically ut1saturate~) and are proofer azalea showpiece having 9-24 preferably l2-20 carbon attunes particularly residues of lyric myristicS Starkey and oleic acids.
If an allele group is the sole lipophilic group it has preferably 9-24 more preferably 9-l8 carton atoms arid may be stralg1lt chef or bra1lched. In a1kylar~vl grouts the alkyd group preferably has 4-12 carbon atoms anal may also be s~rai(1ht or branched.
Particularly preferred su)-factar1ts are those of formula X~XIII
I -I C~12C~12 t-t- OH X
Or ~-ocH2cH2-3-K~ OH XI
Rlo--co- I C~12C~2 -em Charlie XIII
in which R8 is Clue ~lkyl Rug is I l~alkyl or alkenyl Rl~CO is the assay residue of an aliphatic~Cl2 18 fatty acid Q is the monovalent residue of sorbitol glycerol or I- to tevra~ethylene yokel t is 2-3 r is l or 2 - lZ~96~9 k is 3-5 and m is 4-9.
The HAL values of non-ionic surfactants may be calculated by use of a standard Formula. In order to function as a I Emil-sifter on this system the calculated HUB value must be greater than 2.5.
When the owl c) is a mixture of oils at) and c2) then the oil mixture and the surfactant d) are preferably so chosen that the 0/W-RHLB value of the oil mixture is as close as possible to the HUB value of do, or at least is not less than this value.
Preferably the compositions according to the invention contain, in addition to components a), b), c) and preferably d), e) water.
lo The polymer a) and salts of the polymer with surfactant b) are hydrophilic and will take up water or form with water a gel or sol and in sufficient water will form a true or a colloidal solution. The quantity of water e) is chosen so that the polymer together with the water becomes finely dispersed in the oil. The dispersion may be in the form of a suspension of wet or water-swollen polymer or of an aqueous polymer gel in the oil, or an emulsion of an aqueous polymer sol or polymer solution in the oil.
In one particular aspect of the invention, the composition contains, in addition to components a) - c) preferably d) and optionally e) f) an oil-miscible polar solvent which is only slightly soluble in water, not self-dispersing in water, and which has no emulsifying properties of its own, but which reduces the water/oil interracial surface tension.
Suitable solvents f) are compounds which have extremely low HUB values but whose molecules are polar enough to orientate them-selves at the oillwater interface. Preferred solvents are C5 10 aliphatic alcohols phosphoric acid trimesters or Pluronics. Examples of suitable solvents include methyl isobutyl carbinol, 2-ethyl-I;
: `
.
Lo 1~36 - lo - l50-~527 hexanol, isononanol, isodecanol, 2,4,7,9-tetramethyl-5-decyn-Doyle, tributyl phosphate, tri-isobutyl phosphate, tri(butoxy-ethyl) phosphate and Pluronic Loll. The presence of f) is desirable when little or no water e) is present.
Compositions according to the invention may be prepared by mixing surfactant b) before, during or after the polymerization, with the polymer a) or the corresponding monomers, the polymer or monomers being present in Finely divided form. When a) is other than a vinyl addition polymer it is preferred to add the lo surfactant to the already formed polymer. The polymer should be in finely-divided form for example as an aqueous solution, a disk pension in oil, or, preferably as a W/0 emulsion of an aqueous solution of the polymer in oil; When polymer a) is a vinyl addition polymer, it is advantageous to carry out the polymerization in a lo W/0 emulsion system and to have at least part of the anionic sun-fact ant b) present before polymerization, or at least before addition of the cat ionic monomer. After polymerization water and/
or oil can if desired be removed by distillation, and optionally further additions of any of components a may be made.
Preferably the vinyl monomers are emulsified in the form of their aqueous solution in at least part of the oil c) in the presence of the anionic surfactant b) and preferably also in the presence of the lipophilic non-ionic surfactant d). This W/0 emulsion may be formed by adding the vinyl monomers to an already-formed W/0 emulsion, or the monomers may be added to an aqueous solution or dispersion of the anionic surfactant b), to which is then added the oil and optionally the non-ionic surfactant d), and polymerization is initiated by addition of a suitable catalyst.
The presence of the anionic surfactant in the monomer-containing W/0 emulsion before polymerization enables part of the cat ionic monomers, particularly in neutral to acid conditions, to form salts with the surfactants, which salts are less water-soluble and more lipophilic than the monomers themselves. These monomer-surFactant salts are novel and form part of the present invention. Preferred salts have the formula XIV
SHEA = C - Aye ZOO
where Al, and Awry as defined above.
Preferably is of formula XV
- CO - I SHEA OH- SHEA N \ R3 XV
where X, n, Y, R2, R3 and R4 are defined above, and Y is preferably H, and Assay the anion of a hydrocarbon sulphonate, particularly petroleum sulphonate.
An alternative method ox preparing compositions according to the present invention consists in forming a dispersion containing polymer a), water e) and lipophilic non-ionic surfactant d) in oil c) in the absence of anionic surfactant b), and then adding the anionic surfactant b) to this dispersion. For this process variant, it is preferred that the anionic surfactant is an oil-soluble, practically water-insoluble sulphonated hydrocarbon, and that the oil is a hydrocarbon oil of the type listed under 1.1. above, par-titularly white spirit. Preferably the dispersion is obtained by emulsion polymerization of the monomer solution in oil in the pro-since of surfactant d) as emulsifier, and optionally partial removal of water by distillation.
The emulsion polymerization, preferably in the presence of anionic surfactant b) may be carried out in conventional manner (see for example "High Polymers" vol. 9,1955 - "Emulsion Polyp merisation, Intrusions Publishers, NAY.). Conventional free radical initiators are used to catalyze the polymerization. Suitable initiator systems include peroxide compounds, e.g. t-butyl hyiroperoxide, in combination with redo systems, e.g. ferris salts plus sodium trio-sulfite. To sequester impurities, it is preferred to add a 3L2 Lo 39 completing agent such as salts of ethylenediaminetetraacetic acid (ETA). The aqueous phase may contain further additives; e.g. acids, bases or buffer systems to regulate pi and salts e.g. sodium sulfite and calcium chloride.
The air above the emulsion is normally replaced by an inert gas and polymerization is started by the addition of initiator.
The polymerization takes place for example at pi values between 2 and 8, preferably under acid conditions (pi 2.5-5, preferably 3-4). The water content of the W/O emulsion during polymerization is preferably 15-80 wt.%, more preferably 30-65 wt.% based on the total weight of the emulsion.
The polymerization is normally exothermic, and may be carried out under adiabatic or isothermal conditions, but preferably is carried out partially adiabatically, i.e. the temperature is allowed to increase within certain limits, e.g. up to 120C, underpricer if necessary. Preferred reaction temperatures are from 30-110C. If the reaction mixture contains hydrolyzable moo-mews, e.g. esters or primary asides, it is necessary to avoid reaction conditions under which significant amounts of hydrolysis would occur.
For the W/0 emulsion polymerization it is advantageous to use an oil c) comprising at least 50%, preferably at least 80% by wt.
hydrocarbons, which should preferably be as completely aliphatic as possible. The concentration of monomers in the emulsion is not critical, but for economic reasons it is advantageous to work with as high concentrations as is practicable. The concentration of surfactant used is adjusted to be sufficient to give a stable W/0 emulsion under the polymerization conditions.
After polymerization is complete the polymer-containing W/0 emulsion can be treated by addition of further quantities of components a) - f) or, if desired, the amount of components c) and/
or e) can be reduced by distillation. By such adjustments proper-~2~36~3 ties of the emulsion such as stability and ease of dilution with water can be influenced and improved. If in addition to vinyl addition polymer other cat ionic polymers a) are to be present, these are preferably added after the emulsion polymerization is complete.
If component f) is to be present, this is preferably added after the emulsion polymerization, more preferably after all other components have been added. It may be advantageous to mix f) with a little oil c) before addition.
If a mixture of oils c1) and c2) is to be used, the polyp merisation is preferably carried out either in the mixture or in at) alone or in a mixture of at) with less than all of the c2) The oil c2~, or that part of it not already present, may be added after the emulsion polymerization, optionally after some or all of the water has been distilled off.
The relative weights of the various components in the compositions according to the invention may be represented as follows: for every 100 parts by weight of the polymer a), the composition contains x parts by weight of b), y of c), z of d) u of e) and v of f). The figures 100 for a) and x for b) do not 20 take into account the salt formation between a) and b); that is, the weight of surfactant which forms a salt with the polymer is not counted as part of the polymer weight, but remains part of weight x.
The preferred ranges of x-v are set out in Table II below, the values for each component being independent of each other except where otherwise stated. For certain applications, the value of x may be as low as 0.5 Table II
(component a = 100) component value of preferred more preferred most preferred b x 1-30 1-15 1.5-10 c y 30-400 40-200 40-200 d z 0-80 1-80 2-30 e u 0-300 1-300 2-200 f v my 0-30 0-15 ( C Yo-yo ) ( Y/5 The water content (u) can vary within wisp limits and in theory it is possible to remove the water completely by distillation giving u = 0. In practice it is difficult to remove the last traces of water from the polymer; also it is possible to add water in the form of a further amount of W/0 emulsion or aqueous polymer solution; so that the water content of the composition can be high.
As it is not economically feasible to remove all the water, u can preferably be 5-300, more preferably 10-200.
Preferred compositions contain, for 100 parts by weight of a), 1-30 parts b), 30-400 parts c), 1-80 parts d), 0-300 parts e) and 0-30 parts f) where the weight of f) is less than 1/3 that of c).
Particularly preferred compositions are those in which the weight of each component present is within the range given in the "most preferred" column of Table II.
The oil-containing compositions according to the invention are dispersions which may show a wide range of viscosities. The Brook field rotation viscosity (measured in an LV-viscometer) may vary between 5 cup (spindle no. I and Lyon cup (spindle no. 4), preferably between 50 cup (spindle no. 2) and 5000 cup (spindle Noah).
The dispersions are stable and can be stored for long periods of time without change or, if separation into two layers occurs, can be restored to the original form by simple stirring. The combo-sessions of the invention, particularly those containing the oil) have particularly good dispersibility in water and can rapidly be diluted with water by stirring or by the use of conventional dilution apparatus.
In a preferred method of dilution, the dispersion is pumped through a nozzle into a stream of water which surrounds the nozzle. The water stream has a higher velocity than that of the stream of dispersion, and this velocity is sufficient to over-come at least partially the internal adhesive and cohesive forces in the dispersion, but not sufficient to reduce the size of the polymer molecules. The mixture of product and water is then alter-natively accelerated in narrow tubes and decelerated in wider mixing zones until the desired degree of mixing is obtained. No sieves or filters are used in this process from the time the Jo L~6~9 streams of water and of dispersion contact each other.
A mixing apparatus suitable for carrying out the above process comprises at least two cylindrical mixing chambers connect ted by rigid or flexible tubing of diameter not greater than half that of each mixing chamber. The first chamber is furnished with a coccal mounted tube for the inflow of a stream of water and a second tube, substantially at right angles to the first, ending in a jet situated between the axis and circumference of the first tube and just beyond the end of the first tube. Means are provided for pumping the dispersion through this second tube. Near the other end of the mixing chamber is an exit tube leading to the second mixing chamber. The second and any subsequent mixing chambers are each provided with an inlet and an exit tube, preferably set into the side walls one near each end of the chamber. Finally an exit tube from the last mixing chamber leads to the apparatus in which the dilute aqueous dispersion of the composition according to the invention is to be used.
A particularly preferred apparatus is illustrated by way of example in Figures 1 and 2. Figure 1 is a vertical elevation of a six-chamber mixing apparatus, the upper chamber 1 being shown in cross section. Figure 2 is a horizontal cross-section along XX' of Figure 1.
The chambers 1-6 are mounted alternately on opposite sides of a frame 7 and secured with clips 8. The chambers are constructed of cylindrical tubing 9 closed with screw caps 10 which can be removed for cleaning. In chamber 1 the tubing 9 is of transparent material to allow direct observation of the mixing process, in the other chambers it is of metal.
Chamber 1 is fitted with a coaxial water inlet tube 11, at right angles to which is mounted a dispersion inlet tube 12 which ends in a six-holed jet 13 postponed so as to be completely within the stream of water delivered by tube I In the cylindrical tubing 9, near the end remote from tube 11 is an opening 14 leading to Lo Lowe a flexible hose 15 which connects to a similar opening in the side wall of chamber 2. From a second opening in chamber 2 a further hose 16 leads to chamber 3. Chambers 2-6 are all identical in con-struction and are connected, each to the next, by hoses 16-19.
Finally, chamber 6 is provided with a flexible delivery hose 20.
In operation, a stream of water is led through tube 11 into chamber 1, and is allowed to run until all chambers are filled and the water is delivered from hose 20. The Reynolds number of the water flow at the exit of tube 11 is preferably between 25,000 and 75,000, and the pressure drop across the apparatus will for a medium size apparatus of total volume 1-100 lithe preferably be from 0.5 to 2.5 bar, more preferably from 0.6 to 1.5 bar.
The dispersion is then pumped through tube 12 at a rate sufficient to give the desired concentration of product. The dispersion passes through the jet 13, the size and number of whose holes may be varied according to the viscosity of the dispersion, and is rapidly mixed in the stream of water from tube 11. The mixture passes from chamber 1 through the narrow hose 15 in which its flow is accelerated, and then into the wide chamber 2 in which its flow is again slowed down. The alternating acceleration and slowing of the flow in the successive connecting hoses and mixing chambers provides a complete mixing of the dispersion in the water, and the water containing the product is delivered through hose 20 to the apparatus in which it is to be used.
The compositions according to the invention can be very rapidly diluted with water and thus are suitable for use in many large-scale continuous processes, in which cat ionic polymers are used. By the use of the mixer described above, fully diluted solutions or dispersions can be obtained without the use of any dwell tanks; the mixer may simply be connected up to the equipment in which the diluted product will be used.
The compositions may contain very high concentrations of cat ionic polymer, enabling the minimum handling of bulk liquids.
Jo ~2~g~
- 20 - 150-~527 Not only the concentrated compositions described above, but also partially diluted compositions containing at least 0.001% by weight of polymer a), more preferably at least 0.1% by weight of a) are included within the scope ox the present invention. The partially diluted compositions may be further diluted as required before use.
The compositions of the invention are useful as flocculating agents, particularly as retention and detouring agents in paper-making and as flocculating agents for aqueous sludge, particularly crude and treated sludge from sewage purification works. They may also be used in other processes where cat ionic polymers are employed, for example flotation of minerals or recovery of oil waste.
In paper making, the use of the compositions according to the invention can give a particularly homogeneous sheet formation.
The compositions also show Good biodegradability.
The following Examples illustrate the invention: ~11 parts and percentages are by weight unless otherwise stated.
Examples Emulsifiers used:
By sodium salt of petroleum monosulphonate, MY 440-470 (62% solution in mineral oil) By sodium salt of petroleum monosulphonate, MY 480 (60% solution in mineral oil) By sodium salt of secondary n-alkane sulphonate, obtained from sulphoxidation of paraffin. The alkyd group has the following average composition:
C13-15 58~, C16-17 39%, > C17 < 3%, < C13 < 1%
Do Cl2H25(ocH2cH2)2oH , HUB 6.5 Do Cl8H35(ocH2cH2)3oH~ HUB 6.5 Do sorbitol moonlit, HUB 4.0 .96~9 Do 1:1 molar mixture of moo- and dolts of ~I(OCH2CH2)6 50H , HUB 7.0 (average value) Oils used:
Of white spirit: aromatic-free, by 193-247C, mean MY 173 C2 white spirit: low-aromatic, by 190-250C
mean MY 180, aromatic content 0.5%
C3 mineral oil: partially unsaturated mineral oil with following properties: specific gravity (SO) 0.85-0.95 aniline point 70-80C, iodine number 20-30 I petrolatum: solidification point 50-85C
cone penetration 160-180 at 25C
C5 olive oil:
C6 isoparaffin: b.p.210-260C, aniline point 88C
isoparaffin content 80%, SO 0.78 C7 mixture of methyl esters ox C12 photo acids SO 0.87-0.90, acid number 1.12, saponification number 190-200, iodine number 100-110, hydroxy number 40-60 C8 mineral oil: SO 0.85-0.95, aniline point 95C, viscosity (20C) 30 cup Solvents used:
Fly triisobutyl phosphate (50% in isobutanol) F2 2 ethylhexanol F3 tri(butoxyethyl)phosphate F4 2,4,7,9-tetramethyl-6 decyn-4,7-diol F5 Pluronic L101 10:90 EO/PO copolymer, MY 3610 3L2 ~L~3~9 I
Example 1 43.5 Parts emulsifier By are mixed with 800 parts water, giving a fine opalescent emulsion. On addition of 8.2 parts calcium chloride, a precipitate of the water-insoluble calcium salt of By is formed. Finally 440 parts white spirit Of is added with stirring, giving a water-in-oil emulsion which is stabilized by addition of 99.5 parts emulsifier Do, To this emulsion is added in the following order 353 parts of 75% aqueous methacryloyloxyethyltrimethylammonium chloride, 454 parts acrylamide, 1.4 parts ETA sodium salt, 0.7 parts ferris sulfite and 0.7 parts t-butylhydroperoxide, after which the pi of the aqueous phase is 3.0, The emulsion is heated to 35C
under nitrogen, and an air-free solution of 2.7 parts sodium trio-sulfite in 50 parts water is added drops over 8 hours the temperature being kept at 35-40C by cooling.
Polymerization is complete when all the thiosulphate solution has been added. A stable, fine dispersion of polymer is obtained, of Brook field viscosity 1000 cup (spindle 3, 60 rum). The product is very easily diluted with water, the maximum viscosity of a 0.5%
aqueous dilution with cold water being reached after only 30-40 seconds. The viscosity of a freshly-prepared 1% aqueous dilution is approx. 500 cup (Brook field 3, 60 rum).
Example 2 454 Parts acrylamide, 353 parts of 75% aqueous methacryloyloxy-ethyltrimethylammonium chloride, 1.4 parts disodium ETA, 0.7 parts ferris sulfite and 9.8 parts calcium chloride are added in the stated order to 600 parts water. The solution so obtained is then mixed with a solution of 52 parts emulsifierBl and 80 parts emulsifier D
in 600 parts white spirit Of, giving a water-in-oil emulsion whose aqueous phase has a pi of 3,0. Under a nitrogen atmosphere is added first 0.7 parts t-butylhydroperoxide and then an air-free solution of 1.1 parts sodium thiosulphate in 12 parts water. A strongly exothermic reaction sets in, giving a temperature rise of up to 90C
2 ~L~36~3~
even under light cooling. On cooling a fine dispersion of polymer is obtained which is easily diluted with water.
Example 3 _ _ _ _ 24 Parts emulsifier By is Maxwell with SO parts of Wesley S wiving a fine opalescent emulsion. To this is added I parts of 75~' aqueous methacryloyloxyethyltrililetilylalnllloniull chloride whereby the sul-actant salt of the catiollic monomer is frilled. The following compollerlts are then added in the stated order it stirring;
408.3 parts acrylalnide 1.43 parts dazedly EDDY 0.77 parts fork sulfite 480 parts white spirit Us on parts emulsifier Do 30 parts emulsifier Do 4.8 parts calci~nl~ chloride and 0.6 parts t-b~ty'lhydroperoxide.
The resolutely dispersings purged with nitrogell arid world to 30'~C then an air-free solutioll of' 2.97 parts sodium Thea sulfite in 42 parts water is added over 8 Halsey the temperature rising to 50C. A Fine clispersioll o-i-' polylller is obtained which is easily diluted with water.
example 4_ _ 500 parts of the product of Example l is stirred with lo parts white spirit Of and lo parts emulsifier By and then distilled ilk a Dean-Stclrke apparatus at 26 mar 40C until approx. 200 parts water has teen removed. A fine stable polynler dispersion, is obtained itch in spite of its lo water content is readily diluted with water.
Exan~pl The procedure of Example l is repeated and to the product is added owe of the total wow of the product of Example 3.1 of US 3 632 559 containing 20"~ wt. cat ionic poller and 80;'~ water.
A stable '1/0 emulsion is obtained.
~L23L~ 39 Example 6 i) Preparation of polymer dispersion without sl!rfactant p) 454 Parts acrylamide and 353 parts 75% aqueous methacryloyl-oxyethyltrimethylammonium chloride are dissolved in 800 parts water, and 1.43 parts disodium ETA and 0.72 parts ferris sulfite are added. The pi is adjusted to 3.0 with approx. 0.1 part 30% caustic soda, then a solution of 143 parts emulsifier Do in 440 parts white spirit C2 is added with vigorous stirring. A milky W/0 emulsion is formed, which is thoroughly de-aerated and stirred while bubbling a stream of nitrogen through the mixture.
After addition of 0.67 parts t-butyl hydroperoxide, the mixture is heated to 35C, and a solution of 2.7 parts sodium thiosulphate in 50 parts water is added drops over 5 hours, the temperature being held at 36-38C by cooling. After addition is complete, reaction is continued for 2 hours at 35C, and the product is then cooled to room temperature .
ii) Addition of surfactant b) A 20% aqueous emulsion of By (sodium petroleum sulphonate) is treated with excess Cook, and the precipitated calcium salt collected by filtration, dried under vacuum at 60-70C and taken up in mineral oil to give a 30% solution. 20 Parts of this solution and 20 parts white spirit C2 are added to 200 parts of the suspension prepared in i) above. A viscous product is obtained which in spite of its high viscosity may be rapidly diluted with water.
Example 7 - The calcium salt of emulsifier By is` prepared as described above for By, and 10 parts of this salt are dissolved in a mixture of 80 parts white spirit C2 and 30 parts mineral oil C3. 25 Parts of this solution are added to 200 parts of the suspension prepared in Example 6 i). The resulting mixture is readily diluted with water.
sample 8 To 200 parts Or the suspellsioll prepared in Example 6 i) are added 30 parts of a soluticil contclining 1~.3~' socliulll petroleunl sulphon~te By 57.~) % malarial oil I end 2~.6"~ of a 50~`~ solution 5 of triisobutyl phosphate in isobutallol (Ill. A viscous product is obtainer itch is readily diluted Oil addition to water.
_xalllple q To 221n parts of the polylller einulsion prepared in Exanlple 1 are added 330 parts mirleral nil C3 anal 330 parts petrolatulll I
end the mixture is evacuated to 26 mar under stirring end heated to 4nC oven cay 6 hours collecting S60 parts water in a Dean-Stalk trap any oil which distilled being returned to the distillation mixture A very fine stable slightly viscous (dispersion is obtainetl which may be diluted with water approximately as readily as eye lo product of Example 1.
Example 10 A dispersion containing 9G0 parts water 816.6 parts acryl-aside 1128 parts 75~ aqueous methacry'loyloxyethyltrilllet'nyla;n!nonium chloride 2.9 parts disodium Edits 1.5 parts ferris sulfite 2Q 9.1 parts closely chloride 48 parts emulsifier By 60 parts emulsifier Do 5G parts emulsifier Do and ~60 parts White spirit C1 is adjusted to pi I and 1.2 parts t~butylhydroperoxide are added.
Polymerisatic)n is carried out under nitrogen by adding 6.5 parts sodium thiosulphate in 20 parts water over hours the temperature rising to approx. 48C. in spite of cooling.
To the product are added 165.7 parts mineral oil C3 and 27.7 parts emulsifier Do and llg6 parts water is distilled off at 20-26 mar 5~C. The resulting fine mobile dispersion is mixed loath 157.5 parts olive oil C5 end 157.5 parts 2-ethy'lhexanol (F2). The product is practically instantaneously diluted in water.
~L2~L~6'~3 - 26 - l5n-4527 Examples 11-13 Example lug is repeated with F2 replaced by equal quanta-ties of Fly F3 end F4 respectively.
example I
43.5 Parts emulsifier By ale mixed with 83~ parts water to give a very fine opalescent emulsiotl. In orcIer to foreign the calcium salt of By $.2 parts calciulll chloride are added. Ike following components are theft added with stirring: 557 parts arylalnide 216 parts 75C~ aqueous methacryloyloxyethyltrilnethylalnMorlium chloride 1.4 parts disodiunl ETA and 0.7 parts ferris sulfite javelin a cloudy solution to which are added 400 parts isoparafFin C6 40 parts mineral oil C3~ 100 pyres emulsifier Do and 13 parts emulsifier By to give a I~I/0 emulsion which is polymerized under Newton by the addition of 0.7 parts t-butyl hydroperoxiie when 6 parts of a solution of I parts sodium i.hiosulpha~e in 50 parts water. The tempQratllre rises to 85C even it cooli1lg. Tile resultillg dispersion may be rapidly diluted with Atari Example 15 _ Example 14 is repeated with the following challges:
709 Parts water 183.3 parts acrylamide and 714 parts of the aqueous cat ionic monomer are used; the temperature rises to approx.
43C under adiabatic conditions; and after the polymerization 33 parts Pluronic L101 ~F5) and 165 parts Fatty acid esters C7 are added.
Example 16 Example 14 is repeated with the fullness changes:
160 Parts mineral oil C8 are used in place of 40 parts us and the temperature is kept between 35 and 40C.
eye 43.5 Parts emulsifier By are mixed with ~300 parts water and to the resulting emulsion are added 8.8 parts calcium chloride .
I
- 27 - 150-~527 363 parts acrylamide 124 parts dia11ylal1)ine 353 parts 75C~ aqueous methacryloyloxyetllyltrilllethylal~ ox lo chloride 131 parts 34~.
hydrochloric acid to adjust the pit to I 1.4 parts dazedly ETA
end 0.7 parts ferris. solute. holllngeneous nlonomer swallowtail i;
Formed to hill is added 400 parts White surety Of on pyrites mineral oil C3 Ann 100 parts elnulsifier [I A fine emulsion is fairyland which is polynlerised under nitrogen my tile atldition of 0.7 parts t butylhych~operoxide followed blue parts of a solution of 2.7 parts socliull1 tlliosulphate in 50 parts water. the temperatllre during polyllleiisati~l rises unideal adiabatic eon ions to 65~C.
_ ample 18 Example 2 is rel!eatecl with the felon Schloss:
29 rents emulsifier Al are usQcJ; anti the 80 pelts em iffy Do are replace by a mixture of I parts I and 65 parts Do.
Example_lg Example 17 is repeated with the fulling changes:
54 Parts acrylaMide replace 363 parts acrylamicle + 12~ pats diallylanrinc-; no CLUE is used; 54 Paris By replace 100 parts Do; 45 putts thios~llphate solution replaces 16 parts; and the tenlperature rises within 90 muons to 90~.
apple 20 43.5 Parts emulsifier By is mixed with 600 parts water. To this is added 8.2 parts calcium chloride 4~4 parts acrylamide 1.4 parts disdain ETA 0.7 parts ferris sulfite 400 parts white spirit Of 40 parts mineral oil C3 100 parts emulsifier Do and 13 parts emulsifier By. A water-in-oil emulsion is formed which is polymerized under Noreen us adding no parts t bottle hydra--peroxide and 1 part of a solution of 2.7 I-arts sodium thiosulphate in 50 parts water. the polymerization reaction is held at a temperature of 60C. liken the temperature begins id fall off a solution of 265 parts methacryloyloxyethyltrimethylalnnlon1um chloride in 288 parts water is added drools giving a further rise of temperature which is held at 55-60~C by coolillg. After the addition 3L2~36~9 is complete, the product is stirred 1 hour at 55C then cooled to room temperature.
Example 21 Example 15 is repeated with the following changes:
11 parts By are used in place of 43.5 parts; 25 parts Do are used in place of 100 parts; 3.25 parts By are used in place of 13 parts; and no F5 and C7 are added after polymerization.
Examele_22 Example 16 is repeated with the following changes:
21.75 parts By are used in place of 43.5 parts 50.00 parts Do are used in place of 100 parts 6.50 parts By are used in place of 13 parts.
Dilution Example A mixing apparatus as shown in Figure 1 is used, having 6 chambers each of inner diameter 11 cm and volume 2.5 1. The connecting hoses have an inner diameter of 15 mm and are each 40 cm long.
20~ Into the first chamber of the mixture is fed through a 15 mm dram jet a stream of water of 2000 l/hour, giving a speed of 3.2 m/sec. at the jet Reynolds number 47000). Into the water stream is fed, by means of a pump operating at a frequency of 50 Ho, 5 1/hr of the product of Example 1. The polymer jet has six holes of l mm diameter, and is equipped with a non-return valve.
The diluted product delivered from the mixer is a ready-to-use aqueous solution of the product suitable for use in paper making.
Application Example A
A 2% aqueous paper slurry of the following composition is prepared; 100 parts bleached sulfite pulp, 20 parts kaolin, I;`
3i6~
3 parts resin size, 2 parts alumlnium sulfite.
Four samples (250 ml) of this slurry are mixed with 5, 10, 15 and 20 ml respectively of a 0.0125% aqueous stock dilution of the product of Example 1 and 750 ml water. After stirring 5 sec. at 250 rum, each mixture is poured into 3 1 of water in the filling chamber of a Rapld-Kothen sheet wormer, and after a 20 sec. pause the suction valve is operated to form the sheet After drying and conditioning the paper sheet is incinerated and the ash content measured and calculated as a percentage of the weight ox filler which was used giving the % retention. The results are given in Table A.
Table A
amount of stock concentration of % ash % retention dilution added polymer emulsion (average of 2 measurements) based on dry paper weight (%) 0 - 8.51 51.1 0.0125 13.31 79.9 0.025 14.34 86.0 0.0375 14.66 88.0 0.05 14.73 88.4 Application Exhume B
200 Parts of a sewage suspension of 5% dry solids content are treated with W parts of a 0.23% aqueous stock dilution of the product of Example 1, stirred 10 sec. in a 'Briton' stirrer at lOOOrpm, then immediately filtered through a cloth filter. For each sample, the volume of filtrate after 30, 60, 90, 120 and 180 seconds is measured, and the mean value of these is calculated. The results are shown in Table B.
~L~196~9 - 30 - 150-~527 table 13 lo (parts by eight) Nina filtrate volt ( parts by vow l utile _.__ . _.~
O 1.5 13 15.3 ~0.4 17 ~9.1 the prodllcts no Examples 2--22 nay be used in analogous manlier to Application Example. I anal B.
. , .
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS: -
1. A water-miscible composition comprising a) a hydrophilic cationic polymer and b) an anionic surfactant, the molar quantity of b) being not greater than the molar quantity of the cationic monomer units of a).
2. A composition according to Claim 1 in which component a) comprises at least 70 % by weight of vinyl addition polymers of cationic and optionally non-ionic vinyl monomers.
3. A composition according to Claim 1 in which component b) is selected from sulphated fatty acid mono-, di- and tri-glycerides; sulphated fatty alcohols; sulphated fatty alkanol-amides; sulphonated hydrocarbons; sulphonated aliphatic carboxylic acids and esters; partial alkyl esters of phosphoric acid; aliphatic carboxylic acids; and carboxymethylation pro-ducts of fatty alcohols, monoglycerides and fatty acid alkalnol-amides.
4. A composition according to Claim 1 containing in addition to a) and b) c) a water-immiscible oil in which the polymer a) is insoluble.
5. A composition according to Claim 4 in which the oil c) is selected from low-aromatic hydrocarbons and aliphatic fatty acid esters.
6. A composition according to Claim 4 comprising, in addition to a), b) and c) d) a lipophilic non-ionic surfactant
7. A composition according to Claim 6 in which d) is either i) one or more compounds having at least one lipophilic hydrocarbon residue of at least 9 carbon atoms and at least one non-ionic hydrophilic residue, which is either a mono- or poly-ethylene glycol group, optionally containing propylene glycol units, or the residue or a polyol or ii) one or more hydro-phobic Pluronics and Tetronics having a high propylene oxide content.
8. A composition according to Claim 4 containing, in addition to components a), b) and c) e) water.
9. A composition according to Claim 4 containing, in addition to components a), b) and c), f) an oil-miscible polar solvent which is only slightly soluble in water, not self-dispersing in water, and which has no emulsifying properties of its own, but which reduces the water/oil interfacial surface tension.
10. A composition according to Claim 9, in which component f) is selected from C5-10 aliphatic alcohols, phosphoric acid triesters and Pluronics.
11. A partially diluted composition according to Claim 1 containing at least 0.001 % by weight of component a).
12. A salt of a cationic vinyl monomer and an anionic surfactant.
13. A salt of a cationic polymer in which at least part of the cationic groups are associated with the anions of an anionic surfactant.
14. A water-in-oil emulsion containing a salt according to Claim 12.
15. A water-in-oil emulsion containing a salt according to Claim 13.
16. A process for flocculation of an aqueous sludge comprising the step of adding to the sludge an effective amount of a composition according to Claim 1.
17. A process for the manufacture of paper comprising the addition of a composition according to Claim 1 to the papermaking slurry.
18. A composition according to Claim 6 containing per 100 parts by weight of a) 1-30 parts b), 30-400 parts c) and 1-80 parts d).
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3203267.6 | 1982-02-01 | ||
DE3203267 | 1982-02-01 | ||
DEP3215491.7 | 1982-04-26 | ||
DE3215491 | 1982-04-26 | ||
DEP3239412.8 | 1982-10-25 | ||
DE3239412 | 1982-10-25 |
Publications (1)
Publication Number | Publication Date |
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CA1219699A true CA1219699A (en) | 1987-03-24 |
Family
ID=27189876
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000420569A Expired CA1219699A (en) | 1982-02-01 | 1983-01-31 | Cationic polymer compositions |
Country Status (11)
Country | Link |
---|---|
AT (1) | AT397215B (en) |
CA (1) | CA1219699A (en) |
CH (1) | CH660015A5 (en) |
DE (1) | DE3302069C3 (en) |
ES (1) | ES519408A0 (en) |
FR (1) | FR2530239B1 (en) |
GB (1) | GB2115829B (en) |
HK (1) | HK10786A (en) |
IT (1) | IT1219777B (en) |
NL (1) | NL8300326A (en) |
SE (1) | SE458526B (en) |
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CA1235141A (en) * | 1984-03-28 | 1988-04-12 | Laurence G. Dammann | High charge density, cationic methacrylamide based monomers and their polymers |
DE3426197A1 (en) * | 1984-07-17 | 1986-01-23 | Agfa-Gevaert Ag, 5090 Leverkusen | IONICALLY DESIGNED CONNECTIONS, METHOD FOR THEIR PRODUCTION AND USE OF THE NEW CONNECTIONS |
DE3524950C2 (en) * | 1985-07-12 | 1994-08-25 | Roehm Gmbh | Flocculant organosols |
FR2585712B1 (en) * | 1985-07-31 | 1989-11-24 | Sandoz Sa | MIXTURES OF VINYL ADDITION POLYMERS FOR USE AS FLOCCULATION AND DEHYDRATION AGENTS |
DE3624795A1 (en) * | 1985-07-31 | 1987-02-26 | Sandoz Ag | Vinyl addition polymers, and the use thereof |
DE3630666A1 (en) * | 1986-09-09 | 1988-03-17 | Nalco Chemical Co | METHOD FOR THE DRAINAGE OF CLEANING SLUDGE, IN PARTICULAR ON CHAMBER FILTER PRESSES |
GB2205591B (en) * | 1987-05-01 | 1990-03-07 | Grace W R & Co | Pitch control aid |
DE4111334A1 (en) * | 1990-11-14 | 1992-05-21 | Henkel Kgaa | NEW WATER-IN-OIL EMULSIONS |
RU2034788C1 (en) * | 1990-12-28 | 1995-05-10 | Совместное советско-западногерманское предприятие "Аква Ремонт" | Method of water treatment from organic compounds |
DE4138791A1 (en) * | 1991-08-21 | 1993-05-27 | Basf Ag | WATER-IN-OIL POLYMER EMULSIONS |
DE19731186C2 (en) * | 1997-07-10 | 2000-08-03 | Atotech Deutschland Gmbh | Solids-free pretreatment solution for electrically non-conductive surfaces as well as processes for the preparation of the solution and its use |
US6299622B1 (en) | 1999-08-19 | 2001-10-09 | Fox Hollow Technologies, Inc. | Atherectomy catheter with aligned imager |
US7708749B2 (en) | 2000-12-20 | 2010-05-04 | Fox Hollow Technologies, Inc. | Debulking catheters and methods |
US8328829B2 (en) | 1999-08-19 | 2012-12-11 | Covidien Lp | High capacity debulking catheter with razor edge cutting window |
US7713279B2 (en) | 2000-12-20 | 2010-05-11 | Fox Hollow Technologies, Inc. | Method and devices for cutting tissue |
DE10027016A1 (en) | 2000-05-31 | 2001-12-20 | Cht R Beitlich Gmbh | Polymer dispersion with improved biodegradability |
JP4080874B2 (en) | 2000-12-20 | 2008-04-23 | フォックス ハロウ テクノロジーズ,インコーポレイティド | Bulking catheter |
US6723207B2 (en) * | 2002-08-05 | 2004-04-20 | Johnsondiversey, Inc. | Method of treating paper making rolls |
US8246640B2 (en) | 2003-04-22 | 2012-08-21 | Tyco Healthcare Group Lp | Methods and devices for cutting tissue at a vascular location |
JP4025735B2 (en) * | 2003-08-21 | 2007-12-26 | ローム アンド ハース カンパニー | Method for treating aqueous systems |
US7658819B2 (en) | 2004-12-30 | 2010-02-09 | Akzo Nobel N.V. | Composition |
KR100919463B1 (en) * | 2004-12-30 | 2009-09-28 | 악조 노벨 엔.브이. | Composition and its use in papermaking |
US20070276419A1 (en) | 2006-05-26 | 2007-11-29 | Fox Hollow Technologies, Inc. | Methods and devices for rotating an active element and an energy emitter on a catheter |
US8784440B2 (en) | 2008-02-25 | 2014-07-22 | Covidien Lp | Methods and devices for cutting tissue |
EP2358282B1 (en) | 2008-10-13 | 2017-12-06 | Covidien LP | Devices for manipulating a catheter shaft |
US9687266B2 (en) | 2009-04-29 | 2017-06-27 | Covidien Lp | Methods and devices for cutting and abrading tissue |
KR101323514B1 (en) | 2009-05-14 | 2013-10-29 | 코비디엔 엘피 | Easily cleaned atherectomy catheters and methods of use |
JP5499180B2 (en) | 2009-12-02 | 2014-05-21 | コヴィディエン リミテッド パートナーシップ | Method and apparatus for cutting tissue |
RU2520801C2 (en) | 2009-12-11 | 2014-06-27 | ТАЙКО ХЕЛСКЕА ГРУП эЛПи | Device for material removal with improved capture efficiency and methods for using |
KR101493138B1 (en) | 2010-06-14 | 2015-02-12 | 코비디엔 엘피 | Material removal device |
EP2632352B1 (en) | 2010-10-28 | 2017-04-12 | Covidien LP | Material removal device |
JP5688160B2 (en) | 2010-11-11 | 2015-03-25 | コヴィディエン リミテッド パートナーシップ | Flexible weight loss catheter with imaging and methods of use and manufacture thereof |
EP2750862B1 (en) | 2011-09-01 | 2016-07-06 | Covidien LP | Catheter with helical drive shaft and methods of manufacture |
US9579157B2 (en) | 2012-09-13 | 2017-02-28 | Covidien Lp | Cleaning device for medical instrument and method of use |
US9943329B2 (en) | 2012-11-08 | 2018-04-17 | Covidien Lp | Tissue-removing catheter with rotatable cutter |
WO2015200702A1 (en) | 2014-06-27 | 2015-12-30 | Covidien Lp | Cleaning device for catheter and catheter including the same |
US10314667B2 (en) | 2015-03-25 | 2019-06-11 | Covidien Lp | Cleaning device for cleaning medical instrument |
US10292721B2 (en) | 2015-07-20 | 2019-05-21 | Covidien Lp | Tissue-removing catheter including movable distal tip |
US10314664B2 (en) | 2015-10-07 | 2019-06-11 | Covidien Lp | Tissue-removing catheter and tissue-removing element with depth stop |
CN117447034B (en) * | 2023-11-14 | 2024-04-05 | 中聚达新材料(廊坊)有限公司 | Sludge wrapping agent for recycling papermaking sludge and preparation method thereof |
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CH295647A (en) * | 1944-07-06 | 1954-01-15 | Basf Ag | Dispersants. |
GB790563A (en) * | 1955-06-20 | 1958-02-12 | Ici Ltd | Manufacture of polymeric quaternary ammonium compounds |
US3284393A (en) * | 1959-11-04 | 1966-11-08 | Dow Chemical Co | Water-in-oil emulsion polymerization process for polymerizing watersoluble monomers |
US3624019A (en) * | 1970-12-15 | 1971-11-30 | Nalco Chemical Co | Process for rapidly dissolving water-soluble polymers |
ZA723283B (en) * | 1971-07-12 | 1973-07-25 | Nalco Chemical Co | A water-in-oil emulsion having a polymer concentration |
GB1359932A (en) * | 1972-03-21 | 1974-07-17 | Lubrizol Corp | N-3-aminoalkyl amides polymers thereof and method for their prepa ration |
DE2333927C2 (en) * | 1973-07-04 | 1982-11-25 | Chemische Fabrik Stockhausen GmbH, 4150 Krefeld | Liquid or pumpable stable dispersions of the water-in-oil type and their use |
US4180643A (en) * | 1978-11-16 | 1979-12-25 | Texaco Development Corp. | Acrylamide or methacrylamide quaternary compounds |
DE3005446C2 (en) * | 1980-02-14 | 1984-08-30 | Chemische Fabrik Stockhausen GmbH, 4150 Krefeld | Gel based on water-soluble polymers, process for its preparation and its use |
-
1983
- 1983-01-20 CH CH321/83A patent/CH660015A5/en not_active IP Right Cessation
- 1983-01-22 DE DE3302069A patent/DE3302069C3/en not_active Expired - Fee Related
- 1983-01-28 GB GB08302375A patent/GB2115829B/en not_active Expired
- 1983-01-28 NL NL8300326A patent/NL8300326A/en not_active Application Discontinuation
- 1983-01-28 SE SE8300453A patent/SE458526B/en not_active IP Right Cessation
- 1983-01-31 AT AT0030483A patent/AT397215B/en not_active IP Right Cessation
- 1983-01-31 ES ES83519408A patent/ES519408A0/en active Granted
- 1983-01-31 IT IT1936583A patent/IT1219777B/en active
- 1983-01-31 CA CA000420569A patent/CA1219699A/en not_active Expired
- 1983-09-22 FR FR8315096A patent/FR2530239B1/fr not_active Expired
-
1986
- 1986-02-13 HK HK10786A patent/HK10786A/en unknown
Also Published As
Publication number | Publication date |
---|---|
DE3302069A1 (en) | 1983-08-04 |
FR2530239A1 (en) | 1984-01-20 |
GB2115829B (en) | 1985-10-09 |
FR2530239B1 (en) | 1987-10-02 |
HK10786A (en) | 1986-02-21 |
CH660015A5 (en) | 1987-03-13 |
DE3302069C3 (en) | 1996-11-21 |
IT1219777B (en) | 1990-05-24 |
ES8403327A1 (en) | 1984-03-16 |
DE3302069C2 (en) | 1990-03-29 |
GB2115829A (en) | 1983-09-14 |
IT8319365A0 (en) | 1983-01-31 |
AT397215B (en) | 1994-02-25 |
SE8300453D0 (en) | 1983-01-28 |
ES519408A0 (en) | 1984-03-16 |
NL8300326A (en) | 1983-09-01 |
SE8300453L (en) | 1983-08-02 |
SE458526B (en) | 1989-04-10 |
GB8302375D0 (en) | 1983-03-02 |
ATA30483A (en) | 1993-07-15 |
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