WO2006127924A2 - Anionic and cationic saccharide-siloxane copolymers - Google Patents
Anionic and cationic saccharide-siloxane copolymers Download PDFInfo
- Publication number
- WO2006127924A2 WO2006127924A2 PCT/US2006/020292 US2006020292W WO2006127924A2 WO 2006127924 A2 WO2006127924 A2 WO 2006127924A2 US 2006020292 W US2006020292 W US 2006020292W WO 2006127924 A2 WO2006127924 A2 WO 2006127924A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- saccharide
- siloxane copolymer
- ionically
- anhydride
- copolymer according
- Prior art date
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 112
- 125000002091 cationic group Chemical group 0.000 title claims description 37
- 125000000129 anionic group Chemical group 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 47
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- -1 ethylenediamine Chemical group 0.000 claims description 54
- 125000005647 linker group Chemical group 0.000 claims description 41
- 150000001720 carbohydrates Chemical class 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 33
- 125000001424 substituent group Chemical group 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 150000008064 anhydrides Chemical class 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 150000002924 oxiranes Chemical class 0.000 claims description 17
- 150000003944 halohydrins Chemical class 0.000 claims description 16
- 125000005375 organosiloxane group Chemical group 0.000 claims description 15
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 150000007942 carboxylates Chemical class 0.000 claims description 12
- 235000012209 glucono delta-lactone Nutrition 0.000 claims description 12
- 229960003681 gluconolactone Drugs 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- 239000010452 phosphate Chemical group 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- FSICMNGKCHFHGP-AMTLMPIISA-N lactobiono-1,5-lactone Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(=O)[C@H](O)[C@H]1O FSICMNGKCHFHGP-AMTLMPIISA-N 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- 229940100198 alkylating agent Drugs 0.000 claims description 6
- 239000002168 alkylating agent Substances 0.000 claims description 6
- 150000003868 ammonium compounds Chemical group 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 238000007142 ring opening reaction Methods 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 150000003512 tertiary amines Chemical group 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 239000012682 cationic precursor Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- NCYNKWQXFADUOZ-UHFFFAOYSA-N 1,1-dioxo-2,1$l^{6}-benzoxathiol-3-one Chemical compound C1=CC=C2C(=O)OS(=O)(=O)C2=C1 NCYNKWQXFADUOZ-UHFFFAOYSA-N 0.000 claims description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 2
- WQMAANNAZKNUDL-UHFFFAOYSA-N 2-dimethylaminoethyl chloride Chemical compound CN(C)CCCl WQMAANNAZKNUDL-UHFFFAOYSA-N 0.000 claims description 2
- IHYAGCYJVNHXCT-UHFFFAOYSA-N 3,3,4,4,5,5-hexafluorooxane-2,6-dione Chemical class FC1(F)C(=O)OC(=O)C(F)(F)C1(F)F IHYAGCYJVNHXCT-UHFFFAOYSA-N 0.000 claims description 2
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 claims description 2
- OUJCFCNZIUTYBH-UHFFFAOYSA-N 3,4-diphenylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 OUJCFCNZIUTYBH-UHFFFAOYSA-N 0.000 claims description 2
- UOQHWNPVNXSDDO-UHFFFAOYSA-N 3-bromoimidazo[1,2-a]pyridine-6-carbonitrile Chemical compound C1=CC(C#N)=CN2C(Br)=CN=C21 UOQHWNPVNXSDDO-UHFFFAOYSA-N 0.000 claims description 2
- UYCICMIUKYEYEU-UHFFFAOYSA-N 3-dodec-2-enyloxolane-2,5-dione Chemical compound CCCCCCCCCC=CCC1CC(=O)OC1=O UYCICMIUKYEYEU-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- HDFKMLFDDYWABF-UHFFFAOYSA-N 3-phenyloxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1=CC=CC=C1 HDFKMLFDDYWABF-UHFFFAOYSA-N 0.000 claims description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 2
- JFHFMHPKOSJJTE-UHFFFAOYSA-N 4,5-dimethyl-2-benzofuran-1,3-dione Chemical compound CC1=CC=C2C(=O)OC(=O)C2=C1C JFHFMHPKOSJJTE-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- YDHWWBZFRZWVHO-UHFFFAOYSA-N [hydroxy(phosphonooxy)phosphoryl] phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(O)=O YDHWWBZFRZWVHO-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001241 acetals Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical class CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 claims description 2
- 229940008406 diethyl sulfate Drugs 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 229940099563 lactobionic acid Drugs 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000007764 o/w emulsion Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- VSFOXJWBPGONDR-UHFFFAOYSA-M potassium;3-prop-2-enoyloxypropane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)CCCOC(=O)C=C VSFOXJWBPGONDR-UHFFFAOYSA-M 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000003381 solubilizing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000009472 formulation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 235000014633 carbohydrates Nutrition 0.000 description 5
- 150000004676 glycans Chemical class 0.000 description 5
- 229960004592 isopropanol Drugs 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229950006191 gluconic acid Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- LFXGVNNHUHYULN-UHFFFAOYSA-N 2-(methoxymethyl)-2,4,4,6,6,8-hexamethyl-8-propyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CCC[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(COC)O1 LFXGVNNHUHYULN-UHFFFAOYSA-N 0.000 description 1
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- XGSXUSCKTLWSLU-UHFFFAOYSA-N 3-[dimethyl(trimethylsilyloxy)silyl]propan-1-ol Chemical compound C[Si](C)(C)O[Si](C)(C)CCCO XGSXUSCKTLWSLU-UHFFFAOYSA-N 0.000 description 1
- GSSWFBLVISCYBP-UHFFFAOYSA-N 3-chloropropyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)CCCCl GSSWFBLVISCYBP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000208199 Buxus sempervirens Species 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001153 anti-wrinkle effect Effects 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- AMNQQNTZDFYVGH-UHFFFAOYSA-N dimethyl-phenyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 AMNQQNTZDFYVGH-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JYTUSYBCFIZPBE-AMTLMPIISA-N lactobionic acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O JYTUSYBCFIZPBE-AMTLMPIISA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
Definitions
- This invention relates to anionic and cationic modified saccharide-siloxane copolymers and dispersions, including emulsions, prepared therefrom. Due to their unique hydrophilicity and substantivity, the novel ionic saccharide-siloxanes may be used to provide benefits to a wide variety of formulation based treatment and care compositions and products.
- compositions comprising covalently bonded saccharide siloxanes and dispersions and emulsions thereof are known in the chemical arts. Saccharide-siloxanes have been recently demonstrated to provide advantages to treatment formulations for personal care substrates, household care substrates, and industrial surface substrates, among others.
- cationic and anionic functional organic material are known in the art. Because of their charge, such ionic functional organics are useful in treating substrates that are similarly charged, such as textiles, certain hard surfaces, and personal care substrates.
- ionic functional organics are useful in treating substrates that are similarly charged, such as textiles, certain hard surfaces, and personal care substrates.
- cationic modification of polymers through addition or formation of quaternary ammonium functionality has provided the bases for the enhancement of many useful properties based on the ionic interactions.
- compositions comprising carbohydrates and siloxanes with one or both of them comprising ionic functionality are also known in the art.
- International Application No. WO9429322 describes cationic siloxanyl modified polyhydroxy hydrocarbons or carbohydrates for use as surfactants in formulations with particular application in the plant protection art.
- the cationic functionality disclosed is achieved by reacting a chloroacetoxy-functional siloxane or an epoxy-functional quaternary siloxane with a tertiary amine-functional polyhydroxy moiety.
- Multifunctional ionic siloxane copolymers are disclosed in International Application No. WO200078844 and described as being useful in modifying synthetic materials such as fabrics.
- the specific intended use is to modify synthetic materials for improved hydrophilicity, thermal regulative properties and softening.
- the anionic functionality is located on one substituted silicon atom while the nonionic saccharide functionality is located on another, rather than having both the ionic and saccharide functionalities occur on the same silicon atom.
- Japanese Patent No. J2002115802 describes a process for preparing cationic modified siloxane graft polysaccharide derivatives. The material is prepared by the reaction of carboxyl group functional polysaccharide derivatives with epoxy functional siloxanes and epoxy functional quaternary amines.
- cationic functionality and siloxane functionality are disclosed to be on differing carbohydrate hydroxyl atoms and there is no disclosure of a cationic functionality and saccharide functionality occurring on the same substituted silicon atom
- An anti-wrinkle silicone polysaccharide compound for use in laundry detergents is disclosed in International Patent No. WO200350144.
- the compound comprises siloxane and anionic units with the anionic functionality and siloxane functionality located on different carbohydrate hydroxyl atoms rather than on the same substituted silicon atom.
- an epoxy functional silicone is reacted with a secondary amine to form a tertiary amine functional silicone.
- This product is then reacted with an alkyl halide to yield a quaternary ammonium functional silicone.
- Methods wherein a tertiary amine salt is reacted with a pendant epoxy functional silicone are also known. More recently, U.S. Patent No. 6,482,969 to Helmrick et al., fully incorporated herein by reference, discloses silicon based quaternary ammonium functional compositions made by reacting a quaternary ammonium compound having an epoxide functional or halohydrin functional substituent with a carboxy or amino-functional organo-functional silicone or silane.
- Saccharide-siloxanes have been discovered to impart beneficial characteristics to a wide variety of household and personal care compositions. It is contemplated that they will have additional utility in arts wherein the unique attributes they confer to compositions comprising them enhance the intended functioning of the composition. However, there are applications in particular solvent environments where ionic character would be beneficial to the ionic stability and functioning of the composition. Hence, there is a need in the art for ionically functionalized saccharide siloxanes, and dispersions and compositions comprising them.
- the present invention is directed to novel saccharide-siloxanes that are ionically modified and are capable of imparting the combined desirable chacteristics of silocone, saccharide, and charged ingredients to formulation-based products such as personal care, household care, and industrial care compositions.
- the saccharide-siloxane copolymer has a saccharide component and an organosiloxane component which are linked by a linking group.
- the saccharide-siloxane copolymer that is modified according to embodiments of the present invention has the following formula:
- each R 1 can be the same or different and comprises hydrogen, C 1 - C 12 alkyl, an organic radical, or R 3 -Q,
- Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenedianiine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality
- m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3, y is an integer such that the copolymer has a molecular weight less than 1 million
- R 2 has the formula Z-(G ⁇ b -(G 2 ),;, and there is at least one R 2 per copolymer, wherein G 1 is a saccharide component comprising 5 to 12 carbons, b+c is 1-10, b or e can be O,
- G 2 is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals, Z is the linking group and is independently selected from the group consisting of: - R 3 -NHC(O)-R 4 - ;
- R 3 and R 4 are divalent spacer groups comprising (R 5 ) r (R 6 ) s (R 7 ) t , where at least one of r, s and t must be 1 , and
- R 5 and R 7 are either Ci-C 12 alkyl or ((Ci-Ci 2 )O) p where p is any integer 1- 50 and each (C 1 -Ci 2 )O may be the same or different, R 6 is -N(R 8 )-, where R 8 is H or Ci-Ci 2 alkyl, or is Z-X where Z is previously defined or R 3 , X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R 3 and R 4 must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.
- One embodiment is directed to a cationic saccharide-siloxane wherein the cationic character is provided by a quaternary ammonium compound comprising a substituent group.
- the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
- cationic character is provided by a tertiary ammonium compound comprising a substituent group, with the substituent group comprising epoxide, halohydrin, anhydride or acrylate functionality and wherein the tertiary ammonium compound is subsequently converted to a quaternary ammonium compound by alkylation.
- a further embodiment is directed to anionic saccharide-siloxanes wherein the anionic character is provided by a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group.
- the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
- a cyclic anhydride compound provides a carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond to the linker group of the saccharide-siloxane copolymer.
- the ionically functionalized saccharide siloxane is formed into a dispersion.
- the dispersion comprises a solution or an emulsion.
- Embodiments of the present invention also provide methods of making saccharide- siloxane based ionically functional compositions.
- the method comprises: reacting a quaternary ammonium compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above.
- the method comprises: reacting a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above.
- the method comprises reacting a cyclic anhydride compound comprising carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond, with a linker group of a saccharide-siloxane copolymer.
- the incorporation of the cationic or anionic monomers provides a lower cost route to hydrophilicity than prior mechanisms such as chain extension of the saccharide group.
- the increased substantivity or ionic stability are also benefits with utility in personal care and household care formulations, and other applications where such characteristics are desirable.
- Anionic and cationic modified saccharide siloxane copolymers in accordance with embodiments of the present invention when compared to unmodified saccharide siloxane copolymers, provide increased hydrophilicity and substantivity to formulations in which they are added.
- the ionic saccharide-siloxanes are prepared by reacting anionic or cationic monomers or oligomers to functional sites of the saccharide siloxanes. The reactive site forms a covalent bond with the saccharide siloxane via the linking group or unreacted Q moieties, as defined in the saccharide-siloxane backbone below.
- the saccharide-siloxane copolymer that reacts with a cationic or anionic monomer or oligomer to form the present inventive compounds has a saccharide component and an organosiloxane component which are linked by a linking group and has the following formula:
- each R 1 can be the same or different and comprises hydrogen, C 1 -
- Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality
- m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3, y is an integer such that the copolymer has a molecular weight less than 1 million
- R 2 has the formula Z-(G 1 ) b -(G 2 ) c , and there is at least one R 2 per copolymer, wherein G 1 is a saccharide component comprising 5 to 12 carbons, b+c is 1-10, b or c can be 0,
- G 2 is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals,
- Z is the linking group and is independently selected from the group consisting of:
- R 3 and R 4 are divalent spacer groups comprising (R 5 ) r (R 6 ) s (R 7 ) t , where at least one of r, s and t must be 1, and
- R 5 and R 7 are either Ci-Ci 2 alkyl or ((Ci-C 12 )O) p where p is any integer 1- 50 and each (Ci-Ci 2 )O may be the same or different, R 6 is -N(R 8 )-, where R 8 is H or Ci-Ci 2 alkyl, or is Z-X where Z is previously defined or R 3 ,
- X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R 3 and R 4 must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.
- the saccharide-siloxane copolymer is formed from hydroxyl-functional saccharides.
- the hydroxyl-functional saccharide comprises an aldonic acid or an oligoaldonic acid.
- the aldonic acid or the oligoaldonic acid comprises a lactone.
- Two exemplary lactones include gluconolactone (GL) and lactobionolactone (LBL). Both gluconolactone (GL) and lactobionolactone (LBL) are commercially available.
- Gluconic acid found naturally occurring in cells, is a polyhydroxy alpha-hydroxy aldonic acid and is typically contained in products in the gluconolactone form.
- Lactobionic acid (4-O-beta-D-galactopyranosyl- D-gluconic acid) is comprised of a galactose molecule attached to one molecule of gluconic acid via an ether-like linkage. While GL and LBL are readily commercially available saccharides, one of ordinary skill in the art will appreciate that other saccharides are suitable for forming the copolymers of the present invention.
- the organosiloxane polymer comprises a polydimethylsiloxane.
- the linking group comprises an amide, an amino, a urethane, a urea, an ester, an ether, a thioether, or an acetal functional linking group.
- the linking group comprises an amino functional linking group, and in very specific embodiments the amino functional linking group comprises aminopropyl or aminoethylarninoisobutyl functional groups.
- Aldonolactones are particularly suitable saccharides when the organosiloxane comprises amino-functionali ⁇ y and in very specific embodiments the saccharide-siloxane copolymer comprises the reaction product of an amino-functional organosiloxane and a lactone. Hence, in even more specific embodiments, the saccharide-siloxane copolymer comprises the reaction product of an amino-functional organosiloxane and an aldonolactone such as GL or LBL.
- the sites for covalent bonding to the ionic monomer or oligomer include the linking group, Z or a reactive group on the Q moiety.
- the reactive anionic or cationic molecules suitable for reacting with a saccharide siloxane to form the inventive ionic saccharide-siloxanes herein contain both an ionic component and a reactive site which forms the bond with the saccharide siloxane.
- the reactive component is selected from the group consisting of a ⁇ - halogenated alkyl, a 3-chloro-2-hydroxypropyl radical, 2,3-epoxypropyl group, anhydride, acrylate and methacrylate.
- the ionic component is selected from alkylammonium halide, sulfate, sulfonate, phosphate, carboxylic acid and the salts thereof.
- One embodiment is directed to a cationic saccharide-siloxane wherein the cationic character is provided by a quaternary ammonium compound comprising a substituent group.
- the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
- cationic character is provided by a tertiary ammonium compound comprising a substituent group, with the substituent group comprising epoxide, halohydrin, anhydride or acrylate functionality and wherein the tertiary ammonium compound is subsequently converted to a quaternary ammonium compound by alkylation.
- the quaternary ammonium compound has the following structural formula:
- Y is a divalent hydrocarbon group
- R 3 is a monovalent hydrocarbon group or hydrogen
- R 4 , R 5 and R 6 are independently monovalent hydrocarbon groups
- X " is a counter ion.
- a further embodiment is directed to anionic saccharide-siloxanes wherein the anionic character is provided by a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group.
- the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
- a cyclic anhydride compound provides a carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond to the linker group of the saccharide-siloxane copolymer.
- the ionic saccharide siloxanes may also be formed by reacting a molecule comprising a reactive component wherein the reactive component reacts with the linker functionality to impart the cationic or anionic functionality to the saccharide siloxane.
- a reactive component reacts with the linker functionality to impart the cationic or anionic functionality to the saccharide siloxane.
- Non-limiting examples of such molecules which impart cationic character include: 3- chloro-2-hydroxypropyltrimethylammonium chloride (chlorohydrin), 2,3- epoxypropyltrimethylammonium chloride (glycidyltrimethylammonium chloride); 2- )Acryloyloxy)ethyl]trimethylammonium chloride; chlorostyrene; and 3-chloro-2- hydrorxypropyl-alkyl-dimethylammonium chloride, wherein the alkyl is selected from dodecyl-, cocoalkyl, or stearyl. In the product of these reactions,
- Non-limiting examples of molecules that react with the linker functionality Z to impart anionic character include: 3-sulfopropyl acrylate potassium salt, chloroacetic acid, 2-carboxyethyl acrylate, poly(2-carboxyethyl) acrylate,maleic anhydride, substituted maleic anhydride, e.g.
- 4-sulfo-l,8- naphthalic anhydride potassium salt 4-amino-l,8-naphthalic anhydride, dimethylphthalic anhydride, succinic anhydride and its derivatives, e.g., (2-dodecen-l-yl)succinic anhydride, phenylsuccinic anhydride, 2-sulfobenzoic acid cyclic anhydride, itaconic anhydride, phosphoric acid, tetraphosphoric acid and phosphoric anhydride. In some instances it may be desirable to take a precursor route to synthesis of the cationic functional saccharide-siloxane.
- Certain molecules may react with, for example, the secondary amine on the linking group to yield a tertiary amine functional group.
- the tertiary amine functional group may then be converted to a quaternary ammonium group by reaction with a suitable alkylating agent.
- suitable alkylating agent examples include, but are not limited to, 2-(diethylamino)ethyl acrylate, 2-dimethylaminoethyl chloride, 2- diethylaminoethyl chloride, and N-(2,3-epoxy ⁇ ropyl) diethylamine.
- Suitable saccharide- siloxanes include those wherein the linker group comprises functionality such as a secondary amine or hydroxyl.
- Non-limiting examples of alkylating agents methyl chloride, dimethyl sulfate, diethyl sulfate, and benzyl chloride.
- 2-(diethylamino)ethyl acrylate is reacted with a saccharide siloxane comprising a linker functionality comprising a secondary amine to form a tertiary amine cationic precursor.
- the tertiary amine is reacted with an alkylating agent to form the quaternary ammonium cation.
- the aklylating agent comprises benzyl chloride.
- generally acceptable counter ions include halogen ions, such as chlorine and bromine, as well as others such as acetate and methyl sulfate.
- generally acceptable counter ions include, sodium, potassium, lithium, ammonium, and organic amines, e.g triethanolatnine or diethylamine. Counter ions are preferably non-reactive internally; that is, non-reactive with the corresponding saccharide-siloxane portion of the molecule as a whole or others like it.
- the ionic saccharide-siloxane copolymers of the present invention typically exist as gums, waxy solids or solids at ambient conditions.
- the ionic saccharide-siloxane copolymers may be formulated into in a substantially pure form, or as dispersions in the form of either solutions or emulsions.
- the ionic saccharide-siloxane copolymers may be formulated into oil in water, water in oil, water in silicone and silicone in water systems.
- the ionic saccharide-siloxane may be added directly to the formulation as a solid.
- the dispersion is in the form of a solution.
- the solvent may be substantially aqueous or substantially non-aqueous depending on the nature of the particular ionic saccharide-siloxane selected.
- the substantially nonaqueous solvent comprises a volatile or non-volatile solvent and in a very specific embodiment the substantially nonaqueous solvent comprises a volatile hydrocarbon or a silicone or mixtures thereof. In a more specific embodiment the substantially nonaqueous solvent comprises a silicone.
- the solubilized copolymer may be used to form a solution or emulsion for ready delivery into target compositions.
- the particular solvent blend is selected based upon the ionic properties of the saccharide-siloxane copolymer, and the suitability of that solvent for the intended application.
- the solvent blend comprises a mixture of paraffin and an alcohol.
- the alcohol comprises isopropyl alcohol.
- dispersion means a two-phase system where a first phase comprises finally divided particles distributed throughout a bulk second phase and the first phase constitutes an "internal” or dispersed phase while the second phase constitutes an "external” or continuous phase.
- solution as used herein is intended broadly to include mechanical dispersions, colloidal dispersions and true solutions, and should not be construed as limited to the latter.
- a solution is a dispersion comprising a uniformly dispersed mixture wherein a first phase constitutes the solute and a second phase constitutes the solvent.
- emulsion means a dispersion comprising a mixture of two immiscible liquids with the liquid constituting the first, dispersed internal phase being suspended in the second, continuous phase with the aid of an emulsifier.
- volatile means that the solvent exhibits a significant vapor pressure at ambient conditions.
- suitable volatile silicones include siloxanes such as phenyl pentamethyl disiloxane, phenylethylpenamethyl disiloxane, hexamethyldisiloxane, methoxy propylheptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and mixtures thereof.
- Particularly suitable silicones are the cyclomethicones.
- the volatile silicone comprises a cyclic siloxane.
- the ionic saccharide-siloxane copolymer may be delivered into compositions as a dispersion. Diluting or dispersing the copolymers makes them easier to process and suitably employable solvents include polydimethylsiloxanes, hydrocarbons, and alcohols. Particularly suitable solvents are cyclic siloxanes and hydrocarbon-alcohol mixtures and water.
- ionic saccharide-siloxane copolymer Due to the compatibility of the ionic saccharide-siloxane copolymer with hydrocarbons, silicones and alcohols, as well as with water, they may be incorporated into both aqueous and non-aqueous based compositions and products Various synthetic routes to saccharide siloxane copolymers are well known in the art and may be employed.
- suitable saccharide-siloxanes may be formed from a variety of synthetic means and that the saccharide may be covalently linked to the siloxane through a variety of linking bonds including esters, ethers, amides, urethanes, ureas, epoxides and the like.
- the ionic saccharide-siloxanes may be dispersed as emulsions.
- the emulsion is an oil in water emulsion comprising an internal phase comprising the ionic saccharide-siloxane and a continuous phase comprising water.
- the ionic saccharide-siloxane emulsion comprises at least one surfactant which maintains the dispersion of the internal phase due to its amphipathic character.
- the anionic or cationic functionality may provide additional emulsion stability by augmenting steric stabilization with electrostatic repulsion.
- the ionic saccharide-siloxane emulsions may be prepared either by: 1) emulsifying preformed saccharide-siloxane fluids and polymers or 2) by polymerizing saccharide-siloxane monomers into higher molecular weight fluids and polymers in each individual emulsion particle, e.g. via emulsion or suspension polymerization.
- a surfactant- water blend is added to a solubilized saccharide-siloxane copolymer first in order to establish the dispersion and fix the water phase.
- Optional additional portions of water are added as required by the desired property profile of the emulsion and/or its intended applications.
- Ionic saccharide-siloxane emulsions share similar constraints with other emulsions. That is, they are thermodynamically unstable, require a surfactant to maintain the dispersion, and need an input of energy to initiate emulsification. Simple agitation via mixing may be sufficient, or higher shear means including the employment of high shear devices may be required. In other instances, a polymer emulsification or inversion method is needed.
- a degree of agitation necessary to form the emulsion may require employment of mixing devices.
- Mixing devices typically provide the required energy input.
- Non-limiting examples of these mixing devices spanning the shear range include: 1) a vessel with an impeller, for example, propeller, pitched blade impeller, straight blade impeller, Rushton impeller, or Cowles blade; 2) kneading type mixers, for example, Baker-Perkins; 3) high shear devices which use positive displacement through an orifice to generate shear, for example, homogenizer, sonolater, or microfluidizer; 4) high shear devices using a rotor and stator configuration, for example, colloid mills, homomic line mills, IKA, or Bematek; 5) continuous compounders with single or dual screws; 6) change can mixers with internal impellers or rotor/stator devices, for example, Turello mixer; and 7) centrifugal mixers, for example, Hauschild speedmixers.
- Combinations of mixing devices can also provide benefits, for example a vessel with an impeller can be connected to a high shear device.
- the choice of mixing device is based on the type of internal phase to be emulsified. For example, low viscosity internal phases can be emulsified using high shear devices which use positive displacement through an orifice. However, in the case of high viscosity internal phases, a rotor/stator device, twin screw compounder or change can mixer are often better choices.
- internal phases that contain hydrophilic groups are often easier to emulsify and therefore a simple vessel configured with an impeller may be sufficient.
- the viscosity of the ionic saccharide-siloxane copolymers is dependent on such factors as the molecular weight of the siloxane portion, the number of saccharide units, the mole percent of saccharide units per siloxane, and the external conditions such as temperature and pressure.
- variable internal phase viscosities may be achieved by varying proportions in blends of saccharide-siloxane copolymers with solvents or solvent mixtures.
- a desirable order of addition for a thick-phase emulsification may be: (a) solubilize the saccharide-siloxane copolymer in a solvent or solvent blend to a desired viscosity; (b) blend in a surfactant; (c) add water in increments with shear until a thick phase emulsion forms; (d) dilute with water to desired concentration, with shear.
- a desirable order of addition for a "pre-mix" with high shear may be: (a) add all the water to a mixing vessel configured with an impeller; (b) blend at least one surfactant with the water; (c) slowly add the saccharide-siloxane copolymer phase to the water to make a rough emulsion; (d) convey the rough emulsion through a high shear device until a desired particle size is achieved.
- Nonionic surfactants are suitable for making the emulsions and include alkyl ethoxylates, alcohol ethoxylates, alkylphenol ethoxylates, and mixtures thereof. Cationic, amphoteric and /or anion surfactants are also suitable and are typically added in addition to a nonionic surfactant.
- the emulsion comprises at least one nonionic surfactant and in another specific embodiment the emulsion comprises at least one cationic surfactant and at least one nonionic surfactant.
- the present invention also provides methods of making compositions comprising ionically modified saccharide-siloxanes.
- the method comprises: reacting a quaternary ammonium compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above.
- the method comprises: reacting a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above.
- the reaction takes place between the functionalities of the substituent and the Z or Q functionality of the saccharide siloxane copolymer.
- the method comprises reacting a cyclic anhydride compound comprising carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond, with a linker group of a saccharide- siloxane copolymer as formulaically described above.
- any ranges disclosed should be construed to specifically disclose not only the endpoint(s) of the range, but all the values falling between the endpoints, individually, as well.
- a range of C1-C5 carbons would disclose C2, C3 and C4 carbons in addition to Cl and C5 carbons.
- a range of 1-10 would disclose, inter alia, 3.1, 5, 9.9 and so on.
- reaction product at 1 1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) is diluted to 50% copolymer in 2-propanol. 194g of this solution is loaded into a nitrogen purged, three-necked 500 mL round bottomed flask equipped with a condenser and temperature control and magnetic stirrer. 5.91g of (2,3-epoxypropyl)- trimethylammonium chloride (Fluka , Buchs, Switerland) is added with stirring. The reaction is maintained at 50° C for four hours. The resultant product was straw colored and opaque. A waxy solid material is recoverable after the solvent is removed using a rotary evaporator. (B ⁇ chi Labortechnik AG, Flawil, Switerland)
- Example 2 Preparation of a Cationic Sugar Siloxane Emulsion Using a Nonionic Surfactant
- Example 3 Preparation of a Cationic Sugar Siloxane Emulsion using a Cationic Surfactant 5Og of a solution prepared according to Example 1 were placed on a rotary evaporator and the solvent removed until an 80% solid solution remained. 4Og of this solution, 2.5g of 2- propanol, and 11.72g of Arquad 16-29 cationic surfactant (Akzo Nobel, Amersfoort, the Netherlands) were placed in a disposable cup and mixed on a centrifugal mixer (Hauschild Speedmixer, Landrum SC). 2g increments of water were added and mixed until a gel was formed. 4-5 g increments of water were added and mixed to dilute the resultant emulsion. The final emulsion contained 40% copolymer. The particle size was measured using a Nicomp 370(Particle Sizing Systems, Santa Barbara, CA). The volume weighted median particle size was 183 nanometers.
- the reaction product at 1:1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) was diluted to 50% copolymer in 2-propanol. 49g of this solution was loaded into a nitrogen purged, single-necked 100 mL round bottomed flask equipped with a condenser and magnetic stirrer. Ig of succinic anhydride (Sigma- Aldrich, St. Louis Mo.) was added with stirring. The reaction was maintained at reflux for three hours. The resultant product was straw colored and slightly hazy. A waxy solid material was recovered after the solvent was removed using a rotary evaporator. (B ⁇ chi Labortechnik AG, Flawil, Switzerland). An FT-IR spectrum was obtained using a Nicolet Nexus 670 FTIR. A carbonyl peak was observed at 1731 cm "1 .
- the reaction product at 1:1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) was diluted to 50% copolymer in 2-propanol. 5Og of this solution was loaded into a nitrogen purged, single-necked 100 mL round bottomed flask equipped with a condenser and magnetic stirrer. Ig of maleic anhydride (Sigma-Aldrich, St. Louis Mo.) was added with stirring. The reaction was maintained at reflux for three hours. The resultant product was straw colored and slightly hazy. A waxy solid material was recovered after the solvent was removed using a rotary evaporator. (B ⁇ chi Labortechnik AG, Flawil, Switerland). An FT-IR spectrum was obtained using a Nicolet Nexus 670 FTIR. A carbonyl peak was observed at 1715 cm "1 .
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Abstract
Ionically-modified saccharide siloxane copolymers that comprises a reaction product between an ionic monomer or oligomer and a saccharide-siloxane copolymer, wherein the saccharide-siloxane copolymer has a specified formula, are provided. Dispersions, including emulsions, comprising the ionic saccharide-siloxane copolymers, and methods for manufacturing these compositions, dispersions, and emulsions are also provided.
Description
ANIONIC AND CATIONIC SACCHARIDE-SILOXANE
This invention relates to anionic and cationic modified saccharide-siloxane copolymers and dispersions, including emulsions, prepared therefrom. Due to their unique hydrophilicity and substantivity, the novel ionic saccharide-siloxanes may be used to provide benefits to a wide variety of formulation based treatment and care compositions and products.
Compositions comprising covalently bonded saccharide siloxanes and dispersions and emulsions thereof are known in the chemical arts. Saccharide-siloxanes have been recently demonstrated to provide advantages to treatment formulations for personal care substrates, household care substrates, and industrial surface substrates, among others.
In addition, cationic and anionic functional organic material are known in the art. Because of their charge, such ionic functional organics are useful in treating substrates that are similarly charged, such as textiles, certain hard surfaces, and personal care substrates. In particular, cationic modification of polymers through addition or formation of quaternary ammonium functionality has provided the bases for the enhancement of many useful properties based on the ionic interactions.
Compositions comprising carbohydrates and siloxanes with one or both of them comprising ionic functionality are also known in the art. For example, International Application No. WO9429322 describes cationic siloxanyl modified polyhydroxy hydrocarbons or carbohydrates for use as surfactants in formulations with particular application in the plant protection art. The cationic functionality disclosed, however, is achieved by reacting a chloroacetoxy-functional siloxane or an epoxy-functional quaternary siloxane with a tertiary amine-functional polyhydroxy moiety.
Multifunctional ionic siloxane copolymers are disclosed in International Application No. WO200078844 and described as being useful in modifying synthetic materials such as fabrics. The specific intended use is to modify synthetic materials for improved hydrophilicity, thermal regulative properties and softening. The anionic functionality, however, is located on one substituted silicon atom while the nonionic saccharide functionality is located on another, rather than having both the ionic and saccharide functionalities occur on the same silicon atom.
Japanese Patent No. J2002115802 describes a process for preparing cationic modified siloxane graft polysaccharide derivatives. The material is prepared by the reaction of carboxyl group functional polysaccharide derivatives with epoxy functional siloxanes and epoxy functional quaternary amines. The intended use is for hair cosmetics to provide a bright and smooth feeling. Again, however, cationic functionality and siloxane functionality are disclosed to be on differing carbohydrate hydroxyl atoms and there is no disclosure of a cationic functionality and saccharide functionality occurring on the same substituted silicon atom
An anti-wrinkle silicone polysaccharide compound for use in laundry detergents is disclosed in International Patent No. WO200350144. The compound comprises siloxane and anionic units with the anionic functionality and siloxane functionality located on different carbohydrate hydroxyl atoms rather than on the same substituted silicon atom.
International Patent No. WO200424799 describes an organopolysiloxane modified polysaccharide obtained by esterification of an organopolysiloxane having a carboxylic anhydride residue with a polysaccharide having hydroxy groups. However, the resultant copolymer will not have cationic or anionic functionality unless it is already present on the polysaccharide. In this case the anionic or cationic functionality and siloxane functionality will be on different carbohydrate hydroxyl atoms, rather than the same silicon as the linking group. Quaternary ammonium functional silicones are well known in the art. For example, U.S. Patent No. 3,389,160 discloses such compounds and a two-step method for making them. In the first step, an epoxy functional silicone is reacted with a secondary amine to form a tertiary amine functional silicone. This product is then reacted with an alkyl halide to yield a quaternary ammonium functional silicone. Methods wherein a tertiary amine salt is reacted with a pendant epoxy functional silicone are also known. More recently, U.S. Patent No. 6,482,969 to Helmrick et al., fully incorporated herein by reference, discloses silicon based quaternary ammonium functional compositions made by reacting a quaternary ammonium compound having an epoxide functional or halohydrin functional substituent with a carboxy or amino-functional organo-functional silicone or silane.
Saccharide-siloxanes have been discovered to impart beneficial characteristics to a wide variety of household and personal care compositions. It is contemplated that they will have additional utility in arts wherein the unique attributes they confer to compositions comprising them enhance the intended functioning of the composition. However, there are applications in particular solvent environments where ionic character would be beneficial to the ionic stability and functioning of the composition. Hence, there is a need in the art for ionically functionalized saccharide siloxanes, and dispersions and compositions comprising them.
Accordingly, the present invention is directed to novel saccharide-siloxanes that are ionically modified and are capable of imparting the combined desirable chacteristics of silocone, saccharide, and charged ingredients to formulation-based products such as personal care, household care, and industrial care compositions.
It was surprisingly found that the modificaiton of saccharide-siloxane copolymers into ionic form provides copolymers that, when formulated directly or as dispersions into compositions adapted for various applications, provide increased hydrophilicity and substantivity compared to the formulations comprising unmodified saccharide-siloxanes.
The saccharide-siloxane copolymer has a saccharide component and an organosiloxane component which are linked by a linking group. The saccharide-siloxane copolymer that is modified according to embodiments of the present invention has the following formula:
wherein each R1 can be the same or different and comprises hydrogen, C1- C12 alkyl, an organic radical, or R3-Q,
Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenedianiine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality, m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3,
y is an integer such that the copolymer has a molecular weight less than 1 million,
R2 has the formula Z-(G^b-(G2),;, and there is at least one R2 per copolymer, wherein G1 is a saccharide component comprising 5 to 12 carbons, b+c is 1-10, b or e can be O,
G2 is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals, Z is the linking group and is independently selected from the group consisting of: - R3-NHC(O)-R4- ;
- R3-NHC(O)O- R4- ;
- R^NH-C(O)-NH-R4- ;
- R3-C(O)-O-R4-;
- R3-O-R4- ; - R3-CH(OH)-CH2-O-R4 - ;
- R3-S-R4
- R3-CH(OH)-CH2-NH-R4- ; and
- R3-N(R!)-R4 , and
R3 and R4 are divalent spacer groups comprising (R5)r(R6)s(R7)t, where at least one of r, s and t must be 1 , and
R5 and R7 are either Ci-C12 alkyl or ((Ci-Ci2)O)p where p is any integer 1- 50 and each (C1-Ci2)O may be the same or different, R6 is -N(R8)-, where R8 is H or Ci-Ci2 alkyl, or is Z-X where Z is previously defined or R3, X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R3 and R4 must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.
One embodiment is directed to a cationic saccharide-siloxane wherein the cationic character is provided by a quaternary ammonium compound comprising a substituent group. The substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality. In another embodiment, cationic character is provided by a tertiary ammonium compound comprising a substituent group, with the substituent group comprising epoxide, halohydrin, anhydride or acrylate functionality and wherein the tertiary ammonium compound is subsequently converted to a quaternary ammonium compound by alkylation.
A further embodiment is directed to anionic saccharide-siloxanes wherein the anionic character is provided by a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group. The substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality. In another embodiment a cyclic anhydride compound provides a carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond to the linker group of the saccharide-siloxane copolymer. In additional embodiments the ionically functionalized saccharide siloxane is formed into a dispersion. In specific embodiments the dispersion comprises a solution or an emulsion.
Embodiments of the present invention also provide methods of making saccharide- siloxane based ionically functional compositions. In a specific embodiment the method comprises: reacting a quaternary ammonium compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above. In another specific embodiment the method comprises: reacting a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above. In a further specific embodiment the method comprises reacting a cyclic anhydride compound comprising carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond, with a linker group of a saccharide-siloxane copolymer.
The incorporation of the cationic or anionic monomers provides a lower cost route to hydrophilicity than prior mechanisms such as chain extension of the saccharide group. The increased substantivity or ionic stability are also benefits with utility in personal care and household care formulations, and other applications where such characteristics are desirable.
Anionic and cationic modified saccharide siloxane copolymers in accordance with embodiments of the present invention, when compared to unmodified saccharide siloxane copolymers, provide increased hydrophilicity and substantivity to formulations in which they are added. Generally, the ionic saccharide-siloxanes are prepared by reacting anionic or cationic monomers or oligomers to functional sites of the saccharide siloxanes. The reactive site forms a covalent bond with the saccharide siloxane via the linking group or unreacted Q moieties, as defined in the saccharide-siloxane backbone below.
The saccharide-siloxane copolymer that reacts with a cationic or anionic monomer or oligomer to form the present inventive compounds has a saccharide component and an organosiloxane component which are linked by a linking group and has the following formula:
JTaRVa)SiO-IX SiR >2zτR, lO)m-( SiR'2O)n ]y-SiR (3-a) R
wherein each R1 can be the same or different and comprises hydrogen, C1-
C12 alkyl, an organic radical, or R3-Q,
Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality, m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3, y is an integer such that the copolymer has a molecular weight less than 1 million,
R2 has the formula Z-(G1)b-(G2)c, and there is at least one R2 per copolymer, wherein G1 is a saccharide component comprising 5 to 12 carbons,
b+c is 1-10, b or c can be 0,
G2 is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals,
Z is the linking group and is independently selected from the group consisting of:
- R3-NHC(O)-R4- ;
- R3-NHC(O)O- R4- ;
- R^NH-C(O)-NH-R4- ;
- R3-C(O)-O-R4-; - R3-O-R4- ;
- R3-CH(OH)-CH2-O-R4 - ;
- R3-S-R4
- R3-CH(OH)-CH2-NH-R4- ; and
- R'-NCR1)-!*4 , and R3 and R4 are divalent spacer groups comprising (R5)r(R6)s(R7)t, where at least one of r, s and t must be 1, and
R5 and R7 are either Ci-Ci2 alkyl or ((Ci-C12)O)p where p is any integer 1- 50 and each (Ci-Ci2)O may be the same or different, R6 is -N(R8)-, where R8 is H or Ci-Ci2 alkyl, or is Z-X where Z is previously defined or R3,
X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R3 and R4 must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.
The saccharide-siloxane copolymer is formed from hydroxyl-functional saccharides. In specific embodiments the hydroxyl-functional saccharide comprises an aldonic acid or an oligoaldonic acid. In a more specific embodiment the aldonic acid or
the oligoaldonic acid comprises a lactone. Two exemplary lactones include gluconolactone (GL) and lactobionolactone (LBL). Both gluconolactone (GL) and lactobionolactone (LBL) are commercially available. Gluconic acid, found naturally occurring in cells, is a polyhydroxy alpha-hydroxy aldonic acid and is typically contained in products in the gluconolactone form. Lactobionic acid (4-O-beta-D-galactopyranosyl- D-gluconic acid) is comprised of a galactose molecule attached to one molecule of gluconic acid via an ether-like linkage. While GL and LBL are readily commercially available saccharides, one of ordinary skill in the art will appreciate that other saccharides are suitable for forming the copolymers of the present invention. In one embodiment the organosiloxane polymer comprises a polydimethylsiloxane.
In specific embodiments the linking group comprises an amide, an amino, a urethane, a urea, an ester, an ether, a thioether, or an acetal functional linking group. In more specific embodiments the linking group comprises an amino functional linking group, and in very specific embodiments the amino functional linking group comprises aminopropyl or aminoethylarninoisobutyl functional groups.
Aldonolactones are particularly suitable saccharides when the organosiloxane comprises amino-functionaliτy and in very specific embodiments the saccharide-siloxane copolymer comprises the reaction product of an amino-functional organosiloxane and a lactone. Hence, in even more specific embodiments, the saccharide-siloxane copolymer comprises the reaction product of an amino-functional organosiloxane and an aldonolactone such as GL or LBL.
The sites for covalent bonding to the ionic monomer or oligomer include the linking group, Z or a reactive group on the Q moiety.
The reactive anionic or cationic molecules suitable for reacting with a saccharide siloxane to form the inventive ionic saccharide-siloxanes herein contain both an ionic component and a reactive site which forms the bond with the saccharide siloxane. In one specific embodiment the reactive component is selected from the group consisting of a β- halogenated alkyl, a 3-chloro-2-hydroxypropyl radical, 2,3-epoxypropyl group, anhydride, acrylate and methacrylate. In a further specific embodiment the ionic component is selected from alkylammonium halide, sulfate, sulfonate, phosphate, carboxylic acid and the salts thereof.
One embodiment is directed to a cationic saccharide-siloxane wherein the cationic character is provided by a quaternary ammonium compound comprising a substituent group. The substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality. In another embodiment cationic character is provided by a tertiary ammonium compound comprising a substituent group, with the substituent group comprising epoxide, halohydrin, anhydride or acrylate functionality and wherein the tertiary ammonium compound is subsequently converted to a quaternary ammonium compound by alkylation. In a specific embodiment the quaternary ammonium compound has the following structural formula:
-CH(R3)CH(OH)YN+(R4)(R5)(R6)X",
wherein Y is a divalent hydrocarbon group; R3 is a monovalent hydrocarbon group or hydrogen; R4, R5 and R6 are independently monovalent hydrocarbon groups; and X" is a counter ion.
It should be understood in construing the scope of the formula provided herein that an designated "R" may exhibit some variation allowed by the overall definition given, unless specifically stated otherwise.
A further embodiment is directed to anionic saccharide-siloxanes wherein the anionic character is provided by a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group. The substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality. In another embodiment a cyclic anhydride compound provides a carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond to the linker group of the saccharide-siloxane copolymer. The ionic saccharide siloxanes may also be formed by reacting a molecule comprising a reactive component wherein the reactive component reacts with the linker functionality to impart the cationic or anionic functionality to the saccharide siloxane. Non-limiting examples of such molecules which impart cationic character include: 3- chloro-2-hydroxypropyltrimethylammonium chloride (chlorohydrin), 2,3- epoxypropyltrimethylammonium chloride (glycidyltrimethylammonium chloride); 2- )Acryloyloxy)ethyl]trimethylammonium chloride; chlorostyrene; and 3-chloro-2-
hydrorxypropyl-alkyl-dimethylammonium chloride, wherein the alkyl is selected from dodecyl-, cocoalkyl, or stearyl. In the product of these reactions, a methyl group within the quaternary ammonium group is substituted by a long-chain alkyl group.
Non-limiting examples of molecules that react with the linker functionality Z to impart anionic character include: 3-sulfopropyl acrylate potassium salt, chloroacetic acid, 2-carboxyethyl acrylate, poly(2-carboxyethyl) acrylate,maleic anhydride, substituted maleic anhydride, e.g. poly(ethylene-co-butyl acrylate-co-maleic anhydride), poly(methyl vinyl ether-alt-maleic anhydride), dichloromaleic anhydride, dimethyhnaleic anhydride, diphenylmaleic anhydride, glutaric anhydride, substituted glutaric anhydride, e.g., hexafluoroglutaric anhydride, phthalic anhydride and derivatives e.g. 4-sulfo-l,8- naphthalic anhydride potassium salt, 4-amino-l,8-naphthalic anhydride, dimethylphthalic anhydride, succinic anhydride and its derivatives, e.g., (2-dodecen-l-yl)succinic anhydride, phenylsuccinic anhydride, 2-sulfobenzoic acid cyclic anhydride, itaconic anhydride, phosphoric acid, tetraphosphoric acid and phosphoric anhydride. In some instances it may be desirable to take a precursor route to synthesis of the cationic functional saccharide-siloxane. Certain molecules may react with, for example, the secondary amine on the linking group to yield a tertiary amine functional group. The tertiary amine functional group may then be converted to a quaternary ammonium group by reaction with a suitable alkylating agent. Examples of compounds with functionality that could react with the linker group to yield a cationic group precursor include, but are not limited to, 2-(diethylamino)ethyl acrylate, 2-dimethylaminoethyl chloride, 2- diethylaminoethyl chloride, and N-(2,3-epoxyρropyl) diethylamine. Suitable saccharide- siloxanes include those wherein the linker group comprises functionality such as a secondary amine or hydroxyl. Non-limiting examples of alkylating agents methyl chloride, dimethyl sulfate, diethyl sulfate, and benzyl chloride.
In a specific embodiment 2-(diethylamino)ethyl acrylate is reacted with a saccharide siloxane comprising a linker functionality comprising a secondary amine to form a tertiary amine cationic precursor. In a more specific embodiment the tertiary amine is reacted with an alkylating agent to form the quaternary ammonium cation. In a very
specific embodiment the aklylating agent comprises benzyl chloride. The two step procedure may have utility where it is desired to form the cationic group in-situ.
For the cationic compounds of the present invention, generally acceptable counter ions include halogen ions, such as chlorine and bromine, as well as others such as acetate and methyl sulfate. For the anionic compounds, generally acceptable counter ions include, sodium, potassium, lithium, ammonium, and organic amines, e.g triethanolatnine or diethylamine. Counter ions are preferably non-reactive internally; that is, non-reactive with the corresponding saccharide-siloxane portion of the molecule as a whole or others like it. The ionic saccharide-siloxane copolymers of the present invention typically exist as gums, waxy solids or solids at ambient conditions. It should be noted, however, that there is a small subset of the copolymer that does exist in a liquid form, and liquid dispersible forms may also be produced by manipulating conditions such as temperature. However, in order for most of the ionic saccharide-siloxane copolymers to achieve a viscosity range that permits ready formation of dispersions, for example solutions or emulsions, they must first be solubilized by being dissolved in a suitable solvent or solvent blend.
The ionic saccharide-siloxane copolymers may be formulated into in a substantially pure form, or as dispersions in the form of either solutions or emulsions. Depending on the form used, the ionic saccharide-siloxane copolymers may be formulated into oil in water, water in oil, water in silicone and silicone in water systems. In the case of some aqueous-based formulations the ionic saccharide-siloxane may be added directly to the formulation as a solid. In one embodiment the dispersion is in the form of a solution. The solvent may be substantially aqueous or substantially non-aqueous depending on the nature of the particular ionic saccharide-siloxane selected. In a specific embodiment the substantially nonaqueous solvent comprises a volatile or non-volatile solvent and in a very specific embodiment the substantially nonaqueous solvent comprises a volatile hydrocarbon or a silicone or mixtures thereof. In a more specific embodiment the substantially nonaqueous solvent comprises a silicone. The solubilized copolymer may be used to form a solution or emulsion for ready delivery into target compositions. The particular solvent blend is selected based upon the
ionic properties of the saccharide-siloxane copolymer, and the suitability of that solvent for the intended application. In one specific embodiment the solvent blend comprises a mixture of paraffin and an alcohol. In a very specific embodiment the alcohol comprises isopropyl alcohol. The term "dispersion" as used herein means a two-phase system where a first phase comprises finally divided particles distributed throughout a bulk second phase and the first phase constitutes an "internal" or dispersed phase while the second phase constitutes an "external" or continuous phase.
The term "solution" as used herein is intended broadly to include mechanical dispersions, colloidal dispersions and true solutions, and should not be construed as limited to the latter. A solution is a dispersion comprising a uniformly dispersed mixture wherein a first phase constitutes the solute and a second phase constitutes the solvent.
The term "emulsion" as used herein means a dispersion comprising a mixture of two immiscible liquids with the liquid constituting the first, dispersed internal phase being suspended in the second, continuous phase with the aid of an emulsifier.
The term "volatile" as used herein means that the solvent exhibits a significant vapor pressure at ambient conditions. Examples of suitable volatile silicones include siloxanes such as phenyl pentamethyl disiloxane, phenylethylpenamethyl disiloxane, hexamethyldisiloxane, methoxy propylheptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane and mixtures thereof. Particularly suitable silicones are the cyclomethicones. In a very specific embodiment the volatile silicone comprises a cyclic siloxane.
The ionic saccharide-siloxane copolymer may be delivered into compositions as a dispersion. Diluting or dispersing the copolymers makes them easier to process and suitably employable solvents include polydimethylsiloxanes, hydrocarbons, and alcohols. Particularly suitable solvents are cyclic siloxanes and hydrocarbon-alcohol mixtures and water.
Due to the compatibility of the ionic saccharide-siloxane copolymer with hydrocarbons, silicones and alcohols, as well as with water, they may be incorporated into both aqueous and non-aqueous based compositions and products
Various synthetic routes to saccharide siloxane copolymers are well known in the art and may be employed. One of ordinary skill in the art will appreciate that suitable saccharide-siloxanes may be formed from a variety of synthetic means and that the saccharide may be covalently linked to the siloxane through a variety of linking bonds including esters, ethers, amides, urethanes, ureas, epoxides and the like.
The ionic saccharide-siloxanes may be dispersed as emulsions. In one embodiment, the emulsion is an oil in water emulsion comprising an internal phase comprising the ionic saccharide-siloxane and a continuous phase comprising water. The ionic saccharide-siloxane emulsion comprises at least one surfactant which maintains the dispersion of the internal phase due to its amphipathic character. The anionic or cationic functionality may provide additional emulsion stability by augmenting steric stabilization with electrostatic repulsion.
Other embodiments provide methods for preparing the emulsions. The ionic saccharide-siloxane emulsions may be prepared either by: 1) emulsifying preformed saccharide-siloxane fluids and polymers or 2) by polymerizing saccharide-siloxane monomers into higher molecular weight fluids and polymers in each individual emulsion particle, e.g. via emulsion or suspension polymerization. In one embodiment, a surfactant- water blend is added to a solubilized saccharide-siloxane copolymer first in order to establish the dispersion and fix the water phase. Optional additional portions of water are added as required by the desired property profile of the emulsion and/or its intended applications.
It will be understood by one of ordinary skill in the art that there is a continuum for the ease with which a desired emulsion forms. Ionic saccharide-siloxane emulsions share similar constraints with other emulsions. That is, they are thermodynamically unstable, require a surfactant to maintain the dispersion, and need an input of energy to initiate emulsification. Simple agitation via mixing may be sufficient, or higher shear means including the employment of high shear devices may be required. In other instances, a polymer emulsification or inversion method is needed.
A degree of agitation necessary to form the emulsion may require employment of mixing devices. Mixing devices typically provide the required energy input. Non-limiting examples of these mixing devices spanning the shear range include: 1) a vessel with an
impeller, for example, propeller, pitched blade impeller, straight blade impeller, Rushton impeller, or Cowles blade; 2) kneading type mixers, for example, Baker-Perkins; 3) high shear devices which use positive displacement through an orifice to generate shear, for example, homogenizer, sonolater, or microfluidizer; 4) high shear devices using a rotor and stator configuration, for example, colloid mills, homomic line mills, IKA, or Bematek; 5) continuous compounders with single or dual screws; 6) change can mixers with internal impellers or rotor/stator devices, for example, Turello mixer; and 7) centrifugal mixers, for example, Hauschild speedmixers. Combinations of mixing devices can also provide benefits, for example a vessel with an impeller can be connected to a high shear device. The choice of mixing device is based on the type of internal phase to be emulsified. For example, low viscosity internal phases can be emulsified using high shear devices which use positive displacement through an orifice. However, in the case of high viscosity internal phases, a rotor/stator device, twin screw compounder or change can mixer are often better choices. In addition, internal phases that contain hydrophilic groups are often easier to emulsify and therefore a simple vessel configured with an impeller may be sufficient.
The viscosity of the ionic saccharide-siloxane copolymers is dependent on such factors as the molecular weight of the siloxane portion, the number of saccharide units, the mole percent of saccharide units per siloxane, and the external conditions such as temperature and pressure. One skilled in the art would recognize that variable internal phase viscosities may be achieved by varying proportions in blends of saccharide-siloxane copolymers with solvents or solvent mixtures.
The most desirable order of ingredient addition in the preparation of the emulsion is determined empirically. For example, a desirable order of addition for a thick-phase emulsification may be: (a) solubilize the saccharide-siloxane copolymer in a solvent or solvent blend to a desired viscosity; (b) blend in a surfactant; (c) add water in increments with shear until a thick phase emulsion forms; (d) dilute with water to desired concentration, with shear. A desirable order of addition for a "pre-mix" with high shear may be: (a) add all the water to a mixing vessel configured with an impeller; (b) blend at least one surfactant with the water; (c) slowly add the saccharide-siloxane copolymer
phase to the water to make a rough emulsion; (d) convey the rough emulsion through a high shear device until a desired particle size is achieved.
Nonionic surfactants are suitable for making the emulsions and include alkyl ethoxylates, alcohol ethoxylates, alkylphenol ethoxylates, and mixtures thereof. Cationic, amphoteric and /or anion surfactants are also suitable and are typically added in addition to a nonionic surfactant. In a specific embodiment the emulsion comprises at least one nonionic surfactant and in another specific embodiment the emulsion comprises at least one cationic surfactant and at least one nonionic surfactant.
The present invention also provides methods of making compositions comprising ionically modified saccharide-siloxanes. In one embodiment the method comprises: reacting a quaternary ammonium compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above. In another specific embodiment the method comprises: reacting a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with a saccharide-siloxane copolymer as formulaically described above. The reaction takes place between the functionalities of the substituent and the Z or Q functionality of the saccharide siloxane copolymer. In a further specific embodiment, the method comprises reacting a cyclic anhydride compound comprising carboxylate character wherein a ring opening yields a carboxylic acid group and an amide bond, with a linker group of a saccharide- siloxane copolymer as formulaically described above.
It should be understood that in the context of this disclosure any ranges disclosed should be construed to specifically disclose not only the endpoint(s) of the range, but all the values falling between the endpoints, individually, as well. For instance, a range of C1-C5 carbons would disclose C2, C3 and C4 carbons in addition to Cl and C5 carbons. Likewise, a range of 1-10 would disclose, inter alia, 3.1, 5, 9.9 and so on.
The following examples are provided for illustrative purposes only and should not be construed as limiting the scope of the invention.
EXAMPLES
Example 1 : Preparation of a Cationic Sugar Siloxane;
The reaction product at 1 : 1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) is diluted to 50% copolymer in 2-propanol. 194g of this solution is loaded into a nitrogen purged, three-necked 500 mL round bottomed flask equipped with a condenser and temperature control and magnetic stirrer. 5.91g of (2,3-epoxypropyl)- trimethylammonium chloride (Fluka , Buchs, Switerland) is added with stirring. The reaction is maintained at 50° C for four hours. The resultant product was straw colored and opaque. A waxy solid material is recoverable after the solvent is removed using a rotary evaporator. (Bϋchi Labortechnik AG, Flawil, Switerland)
Example 2: Preparation of a Cationic Sugar Siloxane Emulsion Using a Nonionic Surfactant
5Og of a solution prepared according to Example 1 is placed on a rotovap and the solvent is removed until an 80% solid solution remains. 22g of this solution, 0.9g of Tergitol 15-S- 3 and 2.6g of Tergitol 15-S-40 nonionic surfactants are placed in a disposable cup and mixed on a centrifugal mixer (Hauschild Speedmixer, Landrum SC). Ig increments of water are added and mixed until a gel forms. 4-1Og increments of water are added and mixed to dilute the resultant emulsion. The final emulsion prepared according to this example contained 24% copolymer. The particle size was measured using a Nicomp 370(Particle Sizing Systems, Santa Barbara, CA). The volume weighted median particle size was 135 nanometers.
Example 3: Preparation of a Cationic Sugar Siloxane Emulsion using a Cationic Surfactant
5Og of a solution prepared according to Example 1 were placed on a rotary evaporator and the solvent removed until an 80% solid solution remained. 4Og of this solution, 2.5g of 2- propanol, and 11.72g of Arquad 16-29 cationic surfactant (Akzo Nobel, Amersfoort, the Netherlands) were placed in a disposable cup and mixed on a centrifugal mixer (Hauschild Speedmixer, Landrum SC). 2g increments of water were added and mixed until a gel was formed. 4-5 g increments of water were added and mixed to dilute the resultant emulsion. The final emulsion contained 40% copolymer. The particle size was measured using a Nicomp 370(Particle Sizing Systems, Santa Barbara, CA). The volume weighted median particle size was 183 nanometers.
Example 4: Preparation of an Anionic Sugar Siloxane
The reaction product at 1:1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) was diluted to 50% copolymer in 2-propanol. 49g of this solution was loaded into a nitrogen purged, single-necked 100 mL round bottomed flask equipped with a condenser and magnetic stirrer. Ig of succinic anhydride (Sigma- Aldrich, St. Louis Mo.) was added with stirring. The reaction was maintained at reflux for three hours. The resultant product was straw colored and slightly hazy. A waxy solid material was recovered after the solvent was removed using a rotary evaporator. (Bϋchi Labortechnik AG, Flawil, Switzerland). An FT-IR spectrum was obtained using a Nicolet Nexus 670 FTIR. A carbonyl peak was observed at 1731 cm"1.
Example 5: Preparation of an Anionic Sugar Siloxane
The reaction product at 1:1 saccharide to amine functional group of Dow Corning ® 2- 8175 (Dow Corning Corp, Midland, Mi) with gluconolactone (Sigma- Aldrich, St. Louis Mo.) was diluted to 50% copolymer in 2-propanol. 5Og of this solution was loaded into a nitrogen purged, single-necked 100 mL round bottomed flask equipped with a condenser and magnetic stirrer. Ig of maleic anhydride (Sigma-Aldrich, St. Louis Mo.) was added with stirring. The reaction was maintained at reflux for three hours. The resultant product
was straw colored and slightly hazy. A waxy solid material was recovered after the solvent was removed using a rotary evaporator. (Bϋchi Labortechnik AG, Flawil, Switerland). An FT-IR spectrum was obtained using a Nicolet Nexus 670 FTIR. A carbonyl peak was observed at 1715 cm"1.
Claims
1. An ionically-modifϊed saccharide siloxane copolymer, wherein the saccharide- siloxane copolymer that reacts with an ionic monomer or oligomer to form the ionically- modified copolymer, comprises a saccharide component and an organosiloxane component which are linked by a linking group, and has the following formula:
R2 aR1 (3-a)Si0-[( SiR2R1O)m-( SiR^O)n VSiRVa) R2 a wherein each R1 can be the same or different and comprises hydrogen, Ci-C12 alkyl, an organic radical, or R3 -Q,
Q comprises an epoxy, cycloepoxy, primary or secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or mercapto functionality, m and n are integers from 0 to 10,000 and may be the same or different, each a is independently 0, 1, 2, or 3, y is an integer such that the copolymer has a molecular weight less than 1 million,
R2 has the formula Z-(G1)b-(G2)c, and there is at least one R2 per copolymer, wherein G1 is a saccharide component comprising 5 to 12 carbons, b+c is 1-10, b or c can be O,
G2 is a saccharide component comprising 5 to 12 carbons additionally substituted with organic or organosilicon radicals,
Z is the linking group and is independently selected from the group consisting of:
- R3-NHC(O)-R4- ;
- R3-NHC(O)O- R4- ;
- R3-NH-C(O)-NH-R4- ; - R3-C(O)-O-R4-;
- R3-O-R4- ;
- R3-CH(OH)-CH2-O-R4 - ;
- R3-S-R4 ;
- R3-CH(OH)-CH2-NH-R4- ; 
R3 and R4 are divalent spacer groups comprising (R5)r(R6)s(R7)t, where at least one of r, s and t must be 1, and
R5 and R7 are either C1-Cj2 alkyl or ((Ci-Ci2)O)p where p is any integer 1-50 and each (Ci-Ci2)O may be the same or different,
R6 is -N(R8)-, where R8 is H or Ci-Ci2 alkyl, or is Z-X where Z is previously defined or R3,
X is a carboxylic acid, phosphate, sulfate, sulfonate or quaternary ammonium radical, and at least one of R3 and R4 must be present in the linking group and may be the same or different, and wherein the saccharide-siloxane copolymer is a reaction product of a functionalized organosiloxane polymer and at least one hydroxy-functional saccharide such that the organosiloxane component is covalently linked via the linking group, Z, to the saccharide component.
2. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the hydroxy-functional saccharide comprises an aldonic acid or an oligoaldonic acid.
3. The ionically-modified saccharide siloxane copolymer according to claim 2, wherein the aldonic acid or the oligoaldonic acid comprise a lactone.
4. The ionically-modified saccharide siloxane copolymer according to claim 2, wherein the aldonic acid comprises gluconic acid.
5. The ionically-modified saccharide siloxane copolymer according to claim 2, wherein the oligoaldonic acid comprises lactobionic acid.
6. The ionically-modified saccharide siloxane copolymer according to claim 3, wherein and the lactone comprises aldonolactone.
7. The ionically-modified saccharide siloxane copolymer according to claim 6, wherein the aldonolactone comprises gluconolactone (GL) or lactobionolactone (LBL).
8. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the organosiloxane polymer comprises a polydimethylsiloxane.
9. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the linking group, Z, comprises an amide, an amino, a urethane, a urea, an ester, an ether, a thioether, or an acetal functional linking group.
10. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the linking group comprises an amino functional linking group.
11. The ionically-modified saccharide siloxane copolymer according to claim 9, wherein the amino functional linking group comprises an aminopropyl or aminoethylaminoisobutyl functional group.
12. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the saccharide-siloxane copolymer comprises the reaction product of an ammo- functional organosiloxane and an aldonolactone.
13. The ionically-modified saccharide siloxane copolymer according to claim 12, wherein the aldonolactone comprises GL or LBL.
14. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the ionic monomer or oligomer is covalently bound to the linking group, Z, or Q.
15. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the ionic monomer or oligomer comprises an ionic component and a reactive component which forms a bond with the saccharide-siloxane copolymer.
16. The ionically-modified saccharide siloxane copolymer according to claim 15, wherein the reactive component is selected from the group consisting of a β-halogenated alkyl, a 3-chloro-2-hydroxypropyl radical, 2,3-epoxypropyl group, anhydride, acrylate and methacrylate.
17. The ionically-modified saccharide siloxane copolymer according to claim 15, wherein the ionic component is selected from the group consisting of alkylammonium halide, sulfate, sulfonate, phosphate, carboxylic acid and the salts thereof.
18. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the ionic-modified saccharide siloxane copolymer comprises a cationic saccharide-siloxane having cationic character.
19. The ionically-modified saccharide siloxane copolymer according to claim 18, wherein the cationic character is provided by a quaternary ammonium compound comprising a substituent group.
20. The ionically-modified saccharide siloxane copolymer according to claim 19, wherein the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
21. The ionically-modified saccharide siloxane copolymer according to claim 19, wherein the cationic character is provided by a tertiary ammonium compound comprising a substituent group, the substituent group selected from the group consisting of an epoxide, halohydrin, anhydride and an acrylate functionality, and wherein the tertiary ammonium compound is subsequently converted to a quaternary ammonium compound by alkylation.
22. The ionically-modified saccharide siloxane copolymer according to claim 19, wherein the quaternary ammonium compound has the following structural formula:
-CH(R3)CH(OH)YN+(R4)(R5)(R6)XΓ, wherein Y is a divalent hydrocarbon group; R3 is a monovalent hydrocarbon group or hydrogen; R4, R5 and R6 are independently monovalent hydrocarbon groups; and X" is a counter ion.
23. The ionically-modified saccharide siloxane copolymer according to claim 15, wherein the ionic component is selected from the group consisting of alkylammonium halide, sulfate, sulfonate, phosphate, carboxylic acid and the salts thereof.
24. The ionically-modified saccharide siloxane copolymer according to claim 1, wherein the ionic-modified saccharide siloxane copolymer comprises a anionic saccharide-siloxane having anionic character.
25. The ionically-modified saccharide siloxane copolymer according to claim 24, wherein the anionic character is provided by a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group.
26. The ionically-modified saccharide siloxane copolymer according to claim 25, wherein the substituent group comprises at least one of epoxide, halohydrin, anhydride or acrylate functionality.
27. The ionically-modified saccharide siloxane copolymer according to claim 24, wherein the anionic character is provided by a carboxylate comprising a cyclic anhydride wherein a ring opening yields a carboxylic acid group and an amide bond to the linking group of the saccharide-siloxane copolymer.
28. The ionically modified saccharide siloxane copolymer according to claim 1, comprising the reaction product of a molecule comprising a reactive component wherein the reactive component reacts with the linking group Z of the saccharide siloxane copolymer to impart ionic functionality and cationic or anionic character.
29. The ionically-modified saccharide siloxane copolymer according to claim 28, wherein the molecule reacted to impart cationic character comprises 3-chloro-2- hydroxypropyltrimethylammonium chloride (chlorohydrin), 2,3- epoxypropyltrimethylammonium chloride (glycidyltrimetiiylammonium chloride); 2- (acryloyloxy)ethyl]trimethylammonium chloride; chlorostyrene; and 3-chloro-2- hydorxypropyl-alkyl-dimethylammonium chloride, wherein the alkyl is selected from dodecyl-, cocoalkyl, or stearyl, wherein the reaction product comprises a quaternary ammonium group comprising a methyl group substituted by a long-chain alkyl group.
30. The ionically-modified saccharide siloxane copolymer according to claim 28 wherein the molecule reacted to impart anionic character comprises 3-sulfopropyl acrylate potassium salt, chloroacetic acid, 2-carboxyethyl acrylate, poly(2-carboxyethyl) acrylate, maleic anhydride, substituted maleic anhydride, poly(ethylene-co-butyl acrylate-co-maleic anhydride), poly(methyl vinyl ether-alt-maleic anhydride), dichloromaleic anhydride, dimethylmaleic anhydride, diphenylmaleic anhydride, glutaric anhydride, substituted glutaric anhydride, hexafluoroglutaric anhydride, phthalic anhydride and derivatives, 4- sulfo-l,8-naphthalic anhydride potassium salt, 4-amino-l,8-naphthalic anhydride, dimethylphthalic anhydride, succinic anhydride and its derivatives, (2-dodecen-l- yl)succinic anhydride, phenylsuccinic anhydride, 2-sulfobenzoic acid cyclic anhydride, itaconic anhydride, phosphoric acid, tetraphosphoric acid and phosphoric anhydride.
31. The ionically-modified saccharide siloxane copolymer according to claim 19, wherein a cationic precursor molecule is reacted with an amine or hydroxyl on the linking group Z to yield a tertiary amine functional group which is converted to a quaternary ammonium group by reaction with a suitable alkylating agent.
32. The ionically-modified saccharide siloxane copolymer according to claim 31, wherein the cationic precursor molecule comprises 2-(diethylamino)ethyl acrylate, 2- dimethylaminoethyl chloride, 2-diethylaminoefhyl chloride, or N-(2,3-epoxyρropyl) diethylamine.
33. The ionically-modified saccharide siloxane copolymer according to claim 31. wherein a suitable alkylating agent comprises methyl chloride, dimethyl sulfate, diethyl sulfate, or benzyl chloride.
34. The ionically-modified saccharide siloxane copolymer according to claim 32, wherein the cationic precursor molecule comprises 2-(diethylamino)ethyl acrylate, and the linking group Z comprises a secondary amine, and the alkylating agent comprises benzyl chloride.
35. A dispersion comprising the ionic saccharide-siloxane copolymer according to claim 1, wherein the ionic saccharide copolymer is first solubilized by being dissolved in a solvent or solvent blend and then formed into the dispersion.
36. The dispersion according to claim 35 comprising a solution or an emulsion.
37. The dispersion according to claim 36 comprising a solution, wherein the solvent is substantially aqueous or substantially non-aqueous.
38. The dispersion according to claim 37, wherein the solvent is substantially nonaqueous and volatile or non-volatile.
39. The dispersion according to claim 38, wherein the substantially nonaqueous solvent comprises a volatile hydrocarbon or a silicone or mixtures thereof.
40. The dispersion according to claim 39, wherein the substantially nonaqueous solvent comprises a silicone.
41. The dispersion according to claim 35, wherein the solvent comprises polydimethylsiloxane, hydrocarbon, alcohols, cyclic siloxane, hydrocarbon-alcohol mixtures, water, or combinations thereof.
42. The dispersion according to claim 35, wherein the solvent blend comprises a mixture of paraffin and an alcohol.
43. The dispersion according to claim 42, wherein the alcohol comprises isopropyl alcohol.
44. The dispersion according to claim 36 comprising an emulsion.
45. The dispersion according to claim 44, wherein the emulsion comprises an oil in water emulsion comprising an internal phase comprising the ionic saccharide-siloxane and a continuous phase comprising water, wherein dispersion of the internal phase is maintained by at least one amphipathic surfactant.
46. A method for preparing an emulsion of the ionic saccharide-siloxane copolymer according to claim 1, the method comprising either 1) emulsifying preformed saccharide- siloxane fluids or polymers, or 2) polymerizing saccharide-siloxane monomers into higher molecular weight fluids and polymers in each individual emulsion particle.
47. The method according to claim 46, wherein emulsifying comprises simple agitation, application of high shear, a polymer emulsifϊcation, inversion, or some combination thereof.
48. A method for preparing a thick-phase emulsion of the ionic saccharide-siloxane copolymer according to claim 1, the method comprising: (a) solubilizing the saccharide- siloxane copolymer in a solvent or solvent blend to a desired viscosity; (b) blending in a surfactant; (c) adding water in increments with shear until a thick phase emulsion forms; and (d) diluting with water to desired concentration, with shear.
49. A method for preparing an emulsion of ionic saccharide siloxane copolymer according to claim 1, comprising: (a) adding water to a mixing vessel configured with an impeller; (b) blending at least one surfactant with the water; (c) adding a saccharide- siloxane copolymer phase to the water to make a rough emulsion; and (d) conveying the rough emulsion through a high shear device until a desired particle size is achieved.
50. The dispersion according to claim 44, wherein the emulsion comprises at least one nonionic surfactant.
51. The dispersion according to claim 44, wherein the emulsion comprises at least one cationic surfactant and at least one nonionic surfactant.
52. A method for making a composition comprising the ionic saccharide-siloxane copolymer according to claim 1, the method comprising: reacting a quaternary ammonium compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with the saccharide- siloxane copolymer.
53. A method for making a composition comprising the ionic saccharide-siloxane copolymer according to claim 1, the method comprising: reacting a carboxylate, phosphate, sulfate or sulfonate compound comprising a substituent group, the substituent group comprising at least one of epoxide, halohydrin, anhydride or acrylate functionality, with the saccharide-siloxane copolymer.
54. A method for making a composition comprising the ionic saccharide-siloxane copolymer according to claim 1, the method comprising: reacting a cyclic anhydride compound comprising carboxylate character, wherein a ring opening yields a carboxylic acid group and an amide bond, with the linker group, Z.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/915,077 US7834087B2 (en) | 2005-05-23 | 2006-05-23 | Anionic and cationic saccharide-siloxane copolymers |
| CN2006800251126A CN101218283B (en) | 2005-05-23 | 2006-05-23 | Anionic and cationic saccharide-siloxane copolymers |
| JP2008513717A JP4981038B2 (en) | 2005-05-23 | 2006-05-23 | Anionic and cationic saccharide-siloxane compositions |
| EP06771205.9A EP1883667B1 (en) | 2005-05-23 | 2006-05-23 | Anionic and cationic saccharide-siloxane copolymers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68371805P | 2005-05-23 | 2005-05-23 | |
| US60/683,718 | 2005-05-23 |
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| PCT/US2006/020292 WO2006127924A2 (en) | 2005-05-23 | 2006-05-23 | Anionic and cationic saccharide-siloxane copolymers |
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| US (1) | US7834087B2 (en) |
| EP (1) | EP1883667B1 (en) |
| JP (1) | JP4981038B2 (en) |
| KR (1) | KR101261255B1 (en) |
| CN (1) | CN101218283B (en) |
| WO (1) | WO2006127924A2 (en) |
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| WO2012027145A1 (en) * | 2010-08-23 | 2012-03-01 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
| WO2012027144A1 (en) * | 2010-08-23 | 2012-03-01 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
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| JP6126132B2 (en) | 2012-01-18 | 2017-05-10 | ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ | Method for making saccharide siloxane copolymer |
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| WO2011019539A2 (en) | 2009-08-13 | 2011-02-17 | Dow Corning Corporation | Granulated dry cleanser for the care of keratinous substrates |
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| US20130149259A1 (en) * | 2010-08-23 | 2013-06-13 | Dow Corning Corporation | Saccharide siloxane copolymers and methods for their preparation and use |
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| WO2012027144A1 (en) * | 2010-08-23 | 2012-03-01 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
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| WO2012027145A1 (en) * | 2010-08-23 | 2012-03-01 | Dow Corning Corporation | Emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use |
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| US9192564B2 (en) | 2010-08-23 | 2015-11-24 | Dow Corning Corporation | Saccharide siloxane copolymers and methods for their preparation and use |
| US8853372B2 (en) | 2010-08-23 | 2014-10-07 | Dow Corning Corporation | Saccharide siloxanes stable in aqueous environments and methods for the preparation and use of such saccharide siloxanes |
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| US8974775B2 (en) | 2012-01-04 | 2015-03-10 | Momentive Performance Materials Inc. | Silicone ionomer composition |
| WO2013103496A3 (en) * | 2012-01-04 | 2013-12-12 | Momentive Performance Materials Inc. | Ionic silicones and compositions containg the same |
| EP3805328A1 (en) * | 2012-01-04 | 2021-04-14 | Momentive Performance Materials Inc. | Silicone ionomer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| US7834087B2 (en) | 2010-11-16 |
| WO2006127924A3 (en) | 2007-01-04 |
| CN101218283B (en) | 2011-05-18 |
| CN101218283A (en) | 2008-07-09 |
| EP1883667B1 (en) | 2013-09-04 |
| EP1883667A2 (en) | 2008-02-06 |
| JP2008542474A (en) | 2008-11-27 |
| KR20080015021A (en) | 2008-02-15 |
| US20080200612A1 (en) | 2008-08-21 |
| KR101261255B1 (en) | 2013-05-07 |
| JP4981038B2 (en) | 2012-07-18 |
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