EP2531547A1 - Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof - Google Patents
Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereofInfo
- Publication number
- EP2531547A1 EP2531547A1 EP10798357A EP10798357A EP2531547A1 EP 2531547 A1 EP2531547 A1 EP 2531547A1 EP 10798357 A EP10798357 A EP 10798357A EP 10798357 A EP10798357 A EP 10798357A EP 2531547 A1 EP2531547 A1 EP 2531547A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ammonium
- radicals
- group
- ammonia
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- -1 siloxanes Chemical class 0.000 title claims abstract description 57
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 21
- 125000001453 quaternary ammonium group Chemical group 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 238000007142 ring opening reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000002318 adhesion promoter Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 3
- 238000005804 alkylation reaction Methods 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 150000003868 ammonium compounds Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- KWIPUXXIFQQMKN-UHFFFAOYSA-N 2-azaniumyl-3-(4-cyanophenyl)propanoate Chemical compound OC(=O)C(N)CC1=CC=C(C#N)C=C1 KWIPUXXIFQQMKN-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004251 Ammonium lactate Substances 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 229940090948 ammonium benzoate Drugs 0.000 claims description 2
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229940059265 ammonium lactate Drugs 0.000 claims description 2
- 235000019286 ammonium lactate Nutrition 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 2
- QYTOONVFPBUIJG-UHFFFAOYSA-N azane;cyanic acid Chemical compound [NH4+].[O-]C#N QYTOONVFPBUIJG-UHFFFAOYSA-N 0.000 claims description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 2
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 claims description 2
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000005871 repellent Substances 0.000 claims description 2
- 230000002940 repellent Effects 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000009988 textile finishing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- 230000003750 conditioning effect Effects 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 150000002118 epoxides Chemical group 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 150000003335 secondary amines Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 9
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000006459 hydrosilylation reaction Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 150000003512 tertiary amines Chemical class 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000011089 carbon dioxide Nutrition 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FSCNUJMKSQHQSY-UHFFFAOYSA-N Gein Chemical compound COC1=CC(CC=C)=CC=C1OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)CO2)O)O1 FSCNUJMKSQHQSY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000003438 dodecyl 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 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001421 myristyl 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])[H] 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012038 nucleophile Substances 0.000 description 2
- 125000000913 palmityl 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])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical compound NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 description 1
- RUVWDGDZMPTZOS-UHFFFAOYSA-N 3-cyclohex-2-en-1-yloxycyclohexene Chemical compound C1CCC=CC1OC1C=CCCC1 RUVWDGDZMPTZOS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 125000003580 L-valyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(C([H])([H])[H])(C([H])([H])[H])[H] 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Chemical class 0.000 description 1
- 239000002879 Lewis base Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical class [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical class [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- CVEGDJIFCXGXJU-UHFFFAOYSA-N chloro(3-chloropropyl)silane Chemical compound ClCCC[SiH2]Cl CVEGDJIFCXGXJU-UHFFFAOYSA-N 0.000 description 1
- BGPCFXZWLWDDDU-UHFFFAOYSA-N chloro(propyl)silane Chemical compound CCC[SiH2]Cl BGPCFXZWLWDDDU-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 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 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
Definitions
- Novel organomodified siloxanes with primary amino functions novel organomodified siloxanes with quaternary ammonium functions and the process for their preparation
- the invention relates to novel organomodified siloxanes having primary amino functions and to novel organomodified siloxanes having quaternary ammonium functions and to the process for their preparation.
- Aminoalkyl-functional alkoxysilanes are used as adhesion promoters in coatings or adhesives and sealants. They are prepared by the platinum (0) -catalyzed hydrosilylation of allyl chloride, as described by way of example in DE 10104966 A1. Due to side reactions arise propene, chloropropane and propylchlorosilane, so that a distillative purification of the product is required.
- the haloalkyl of the thus obtained 3-Chlorpropylchlorsilane can be further functionalized according to EP 1273612 A1 manifold, for example by reaction with ammonia, hydrogen sulfide, alkali metal or ammonium sulfides, -rhodaniden, or methacrylates.
- the functional chlorosilanes can be converted into the corresponding alkoxysilanes.
- the method often require high amounts of catalyst and lead due to rearrangements of the double bonds and limited addition selectivities to product mixtures consisting of the branched alpha and beta as well as the linear gamma isomer of aminopropylsilane.
- the silane mixtures must be purified by distillation before further use. Due to the comparatively high amounts of catalyst and the yield losses owing to the side reactions and the required distillative purification, the hydrosilylation of allylamine is associated with high costs.
- Aminopropylalkoxysilanes can be converted to polysiloxanes by means of hydrolysis and condensation reactions. Due to the basic amino function, preference is given to using alkaline catalysts, such as, for example, KOH, ammonium hydroxide or carboxylate.
- alkaline catalysts such as, for example, KOH, ammonium hydroxide or carboxylate.
- EP 1580215 A1 and the documents cited therein are hereby incorporated by reference.
- This synthesis route has limitations. In the synthesis of aminofunctional polysiloxanes with high functionality density, the price of the expensive specialty silane increasingly increases the cost of the material and at the same time the yield is reduced by the amount of alcohol liberated during the hydrolysis. In the case of base-catalyzed equilibration reactions of polysiloxanes with amino groups, it is furthermore possible for silazanes to occur as by-products.
- EP 1008614 A2 claims linear polydimethylsiloxanes whose chain ends are each SiC-linked with an allyl polyether and an alkanolamine or alkanolalkylamine are.
- the preparation is carried out from a linear, epoxy- and polyether-functional polydimethylsiloxane by titanium-catalyzed epoxide ring opening, for example with diethanolamine at 80 ° C.
- Polysiloxanes with primary amino functions are not preparable and unreacted by the described procedure.
- US 2008/0314518 A1 describes the reaction of amino-functional silanes or ethylenediamine in situ with glycidoxypropyltriethoxysilane for the preparation of an aqueous two-component adhesion promoter.
- the crosslinking required for good adhesion is ensured because an amino function reacts with more than one of the excess epoxy rings added.
- the prior art discloses siloxanes having no more than two amino functions and poorer synthetic groups.
- Aminofunctional siloxanes and in particular their charged derivatives which are accessible to quaternary nitrogen compounds by reaction of the amino function with various acids or else by their alkylation, have pronounced electrostatic affinity towards surfaces and consequently ensure good substantivity of the compounds.
- the substantivity of the aminosiloxane as its ability to electrostatically anchor on substrates goes hand in hand with its density of functionality, ie. with the number of uncharged or even charge-carrying nitrogen functions based on the molecular weight.
- the goal of providing aminosiloxanes of arbitrary substantivity is to state that the prior art lacks selective and inexpensive synthetic approaches to siloxanes containing more than one or two primary amino functions per siloxane chain.
- the epoxide ring opening with ammonia does not remain at the stage of the primary amine.
- the formed primary and secondary amines are stronger nucleophiles and compete with the ammonia for reaction with the epoxide ring.
- the amino-functional polysiloxanes described in EP 1 00861 4 A2 are of low molecular weight and have only one terminal amino function per chain.
- the EP 1 956038 A1 also describes only linear terminal amino-functional intermediates. Subsequent reactions of the primary amines formed in the first case lead to chain extension and not to cross-linking control.
- An object of the present invention is to selectively and inexpensively produce siloxanes having primary amino functions and other organomodifications.
- the aim is to ensure a high yield of primary amino acids while avoiding the formation of secondary amines.
- Another object of the present invention is to develop a low cost process for producing high chemoselectivity siloxanes for the formation of primary amino groups.
- An object of the invention is therefore a process for the preparation of siloxanes carrying selectively primary amino groups by reacting laterally epoxy-modified siloxanes with gaseous, dissolved or in situ generated ammonia.
- Another object of the present invention is to modify siloxanes not only at the chain ends but also laterally with primary amino functions to achieve higher functionality densities.
- the invention relates to siloxanes of the general formula 1
- a 0 to 32; preferably 1 to 22, in particular 2;
- a1 0 to 10, preferably 1 to 5, in particular 2;
- a2 0 to 32; preferably 1 to 22, in particular 2;
- a3 0 to 10; preferably 1 to 5, in particular 2;
- b 0 to 600, preferably 10 to 500, in particular 20 to 400
- b1 0 to 50, preferably 0.1 to 20, in particular 2 to 10;
- b2 0 to 50, preferably 0.1 to 20, in particular 1 to 10;
- b3 0 to 50, preferably 1 to 20, in particular 2 to 10;
- b1 + 0 and / or b2 + 0 and / or b3 ⁇ 0 and / or a2 ⁇ 0 and / or a3 is 0 and it is preferred that at least two of the factors a2, a3, b1 , b2, and b3 ⁇ 0. independently of one another identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms or else aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or phenyl, in particular methyl; independently of one another identical or different organic radicals which carry a primary amino function, preferably radicals which, in addition to the amino function, carry a hydroxyl group, in particular selected from the group
- x 0 to 100 preferably> 0, in particular 1 to 50
- y is 0 to 100, preferably> 0, in particular 1 to 50,
- R ' is independently of one another an optionally substituted, for example, alkyl, aryl or haloalkyl or haloaryl substituted, alkyl or aryl group having 1 to 12 carbon atoms, wherein within a radical R 4 and / or of a molecule of the formula I with each other Substituents R 'may be present, and
- R IV a given substitute, eg. B. halogen-substituted, saturated or unsaturated hydrocarbon radical having from 1 to 50, preferably from 3 to 30, carbon atoms, in particular a decyl, dodecyl, tetradecyl or hexadecyl radical, independently of one another, identical or different linear, cyclic or branched, optionally olefinic unsaturated or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, which are with the, Heteroatoms O, N, S, P containing groups or halogen atoms may be substituted and preferably no primary or secondary amine functions, preferably alkanol radicals, carboxylic acid radicals or carboxylic acid ester radicals, in particular hydrocarbon radicals having 5 to 30 carbon atoms such as a dodecenyl, tetradecyl, hexadecyl - or octadecyl and
- R 5 independently of one another are identical or different radicals R 1 , R 2 , R 3 or R 4 , preferably R 1 , in particular methyl, phenyl, dodecyl or hexadecyl.
- the various monomer units of the structural units indicated in the formulas can be constructed in blocks with any number of blocks and any sequence or statistical distribution.
- the indices used in the formulas are to be regarded as statistical averages.
- the invention further ionic adducts of the amino-functional siloxanes of the invention with protic reactants H + A ".
- the adduct is in the form -NH 3 + A" before.
- the anions A " are identical or different counterions to the positive charges on the protonated, primary amino groups selected from inorganic or organic anions of the acids H + A " , and their derivatives.
- Preferred anions are, for example, chloride, sulfate and hydrogen sulfates, carbonate and bicarbonate, phosphate and hydrogen phosphates, acetate and homologous carboxylates with linear or branched, saturated or olefinically unsaturated alkyl chains, aromatic carboxylates, carboxylates formed from amino acids, citrates, malonates, fumarates, maleates, substituted ones and unsubstituted succinates and carboxylates formed from L-hydroxycarboxylic acids, such as lactate.
- the aminosiloxanes and their ionic adducts according to the invention can be present in dissociation equilibria.
- the invention furthermore relates to the quaternary ammonium compounds of the formula 2 deriving from the alkylation of the primary amine function
- radicals R 1 , R 3 , R 4 and R 5 likewise fulfill the abovementioned definition, and
- R 8 independently of one another, identical or different organic radicals carry the ammonium functions;
- suitable radicals R 8 are preferably identical or different radicals selected from the group
- OR 9 are independently identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or ethyl;
- the compounds of the formula 1 according to the invention are reacted with the alkylating reagents.
- the alkylating reagents for this purpose, in particular known to those skilled Alkyl miching reagentien such.
- the invention furthermore relates to preparations in the form of solutions, emulsions, dispersions and / or mixtures comprising the compounds of the formulas 1 or 2 according to the invention. These preparations may contain further additives and Aggregates include, for example, but not limited to selected from the group of fillers, emulsifiers, dyes, pigments.
- the invention further relates to the use of the aminofunctional siloxanes of the formulas 1 or 2 according to the invention as emulsifiers for cosmetic preparations, compatibilizers for plastic blends, release agents, water repellents, dispersants for color pigments and fillers, additives for textile finishing (plasticizers), conditioners for hair, primers for Surface coating / adhesion promoter, additive for corrosion protection formulations, PU foam stabilizer, defoamer and / or wetting agent.
- Another object of the invention is the process for the preparation of the aminosiloxanes of the formula 1 according to the invention.
- the compounds of the formula I according to the invention are prepared from epoxy-functional compounds of the formula 3
- radicals R 1 , R 3 , R 4 and R 5 likewise fulfill the abovementioned definition
- R 10 are independently identical or different organic epoxy radicals.
- Suitable epoxy radicals R 10 are for example preferably identical or different radicals selected from the group
- the epoxy-functional siloxanes which can carry further substituents are prepared as described in the prior art-for example in EP 0415208 A2-by means of transition metal-catalyzed hydrosilylation. Subsequently, the ring-opening reaction is carried out with introduction of ammonia, with or without use of solvents, at atmospheric pressure or in an autoclave at overpressure.
- the ammonia can also be generated in situ from compounds which split off ammonia, for example when the temperature increases.
- a variety of common solvents is suitable for the preparation according to the invention of the amino-functional siloxanes.
- the solvent is selected according to its solubility for starting material and product.
- the solvent should behave substantially inert to both the ammonia and the epoxy-functional precursor under the chosen reaction conditions.
- aromatic hydrocarbons but also ethers or alcohols are suitable.
- Toluene, xylene, methanol, ethanol, propanol and its isomers, in particular 2-propanol, are preferably used.
- higher reaction temperatures of up to 150 ° C preferably 60 ° C to 130 ° C can be set because the reaction gas remains in the closed system.
- the pressure build-up in the closed autoclave during heating in the range of 1 to 50 bar, preferably 5 to 20 bar.
- a closed pressure reactor is filled with ammonia gas via a gassing device, a predetermined pressure of 1 to 50 bar, preferably 5 to 20 bar, can be set during the filling.
- the reaction times may in this case be 1 to 10 hours, preferably 1 to 5 hours.
- a particular advantage of the process at pressures of greater than 1 bar and at temperatures above 50 ° C. is that shorter reaction times of less than 12 hours can be achieved in comparison with the prior art.
- the higher local concentration of ammonia in the dissolved phase also has a positive influence on the selectivity, since the ratio of ammonia to the primary amine formed, ie the reagents competing for the ring opening, is increased in favor of the ammonia.
- Preferred process pressures are in the range of 2 to 50 bar, in particular 5 to 20 bar.
- reaction is carried out without pressure, then a minimum temperature of 50 ° C, preferably of 60 ° C, required for a rapid reaction with acceptable selectivity.
- pressureless reaction it may be advantageous to accelerate the epoxy ring opening by means of suitable catalysts.
- suitable catalysts it is possible to use heterogeneous or homogeneous catalysts from the range of acids, Lewis acids or bases as well as metal salts or complexes, or transition metal salts or complexes.
- the reaction can be carried out in a one-pot process or else continuously. After completion of the reaction, the product is distilled to remove residual ammonia and optionally also the solvent used.
- a pH adjustment can be carried out by means of solid or dissolved buffer systems. If a pH value adjustment with solid salts is carried out, this is followed by a fi ltration step. It is not necessary to carry out a filtration in the case of the starting of the roducts.
- Ammonia can be used as a reagent not only molecular gaseous or in the form of a saturated solution, but can also be used in chemically bound form.
- amine and / or ammonium compounds which liberate ammonia at elevated temperatures with decomposition or else in ammonia in solution, for example ammonium halides, ammonium carbonate and / or or -hydrogencarbonate, ammonium sulfate and / or hydrogen sulfate, ammonium sulfamate, ammonium phosphate, hydrogen peroxide and / or dihydrogen phosphate, ammonium cyanate, ammonium carboxylates such as ammonium acetate, ammonium hydrogen oxalate and / or oxalate, ammonium hydrogen citrate, ammonium benzoate , Ammonium formate, ammonium carbamate, ammonium lac
- ammonia can be generated in situ from hydroxylamine, hydroxylamine-O-sulfonic acid or amidosulfonic acid or urotropin (hexamethylenetetramine) by decomposition under the chosen reaction conditions.
- carboxylic acid amides or carbamates can be formed by subsequent reactions on the amine function formed and / or carboxylic acid esters or corresponding sulfuric acid esters or phosphoric acid esters on the hydroxyl function formed.
- compounds such as, for example, organomodified polysiloxanes, which may have multiple monomer units in multiple, may be randomly distributed (random oligomer) or ordered (block oligomer) in these compounds. Information on the number of units in such compounds is to be understood as statistical averages, averaged over all corresponding compounds.
- the gas volumetrically determined conversion is quantitative after 2 hours. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, liquid product having an epoxide content of 0.32 wt .-% epoxy-oxygen.
- a gel bes, liquid product with an amine content of 0.2 wt .-% of primary amine nitrogen (theor., 0.27%, 74% yield), ⁇ 0.01% by weight of secondary amine nitrogen and 0.14% by weight of tertiary amine nitrogen (theor. 0.16% by weight of methylimidazole).
- a slightly cloudy, yellowish product having a viscosity of 3209 mPa * s at 25 ° C. and an amine content of 0.35% by weight is obtained.
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- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention relates to a method for producing siloxanes selectively carrying primary amino groups by reacting them with ammonia, and to compounds produced in this way.
Description
Neuartige organomodifizierte Siloxane mit primären Aminofunktionen, neuartige organomodifizierte Siloxane mit quaternären Ammoniumfunktionen und das Verfahren zu deren Herstellung Novel organomodified siloxanes with primary amino functions, novel organomodified siloxanes with quaternary ammonium functions and the process for their preparation
Die Erfindung betrifft neuartige organomodifizierte Siloxane mit primären Aminofunktionen sowie neuartige organomodifizierte Siloxane mit quaternären Ammoniumfunktionen und das Verfahren zu deren Herstellung. The invention relates to novel organomodified siloxanes having primary amino functions and to novel organomodified siloxanes having quaternary ammonium functions and to the process for their preparation.
Die Herstellung sowohl von Silanen als auch von organomodifizierten Polysiloxanen mit primären Aminofunktionen ist im Stand der Technik anhand verschiedener Syntheserouten beschrieben. The preparation of both silanes and organomodified polysiloxanes with primary amino functions has been described in the prior art by means of various synthetic routes.
Aminoalkylfunktionelle Alkoxysilane finden Einsatz als Haftvermittler in Beschichtungen oder Kleb- und Dichtstoffen. Sie werden hergestellt durch die Platin(0)-katalysierte Hydrosilylierung von Allylchlorid, wie es in der DE 10104966 A1 beispielhaft beschrieben ist. Aufgrund von Nebenreaktionen entstehen Propen, Chlorpropan und Propylchlorsilan, so dass eine destillative Aufreinigung des Produkts erforderlich ist. Die Halogenalkylfunktion der so erhaltenen 3-Chlorpropylchlorsilane kann gemäß der EP 1273612 A1 vielfältig weiter funktionalisiert werden, beispielsweise durch Umsetzung mit Ammoniak, Schwefelwasserstoff, Alkalimetall- bzw. Ammoniumsulfiden, -rhodaniden, oder auch -methacrylaten. Mittels einer Alkoholyse können die funktionellen Chlorsilane in die entsprechenden Alkoxysilane umgewandelt werden. Aminoalkyl-functional alkoxysilanes are used as adhesion promoters in coatings or adhesives and sealants. They are prepared by the platinum (0) -catalyzed hydrosilylation of allyl chloride, as described by way of example in DE 10104966 A1. Due to side reactions arise propene, chloropropane and propylchlorosilane, so that a distillative purification of the product is required. The haloalkyl of the thus obtained 3-Chlorpropylchlorsilane can be further functionalized according to EP 1273612 A1 manifold, for example by reaction with ammonia, hydrogen sulfide, alkali metal or ammonium sulfides, -rhodaniden, or methacrylates. By means of alcoholysis, the functional chlorosilanes can be converted into the corresponding alkoxysilanes.
Zur effizienteren Herstellung von aminoalkylfunktionellen Alkoxysilanen ist im Stand der Technik statt der dreistufigen Chlorsilanroute die direkte Hydrosilylierung von Allylamin mit Ethoxyhydrogensilanen beschrieben. Dieser Syntheseweg gestaltet sich jedoch schwierig, aufgrund der starken Inhibierung des Übergangsmetallkatalysators durch das komplexierende Allylamin. Eine Reihe von Patentanmeldungen belegt die Versuche, mit Hilfe von speziellen Ruthenium- oder Rhodiumkatalysatoren sowie von Stickstoff- und Phosphorverbindungen als Cokatalysatoren ein wirtschaftliches Hydrosilylierverfahren zu finden, so beispielsweise die US 4481364, US 4867501, US 4921988, US 4927953 oder US 5001246. Die Verfahren benötigen häufig hohe Katalysatormengen und führen aufgrund von Umlagerungen der Doppelbindungen und limitierten Anlagerungsselektivitäten zu Produktgemischen bestehend aus dem
verzweigten alpha und beta- sowie dem linearen gamma-lsomer des Aminopropylsilans. Die Silangemische müssen vor der Weiterverwendung destillativ aufgereinigt werden. Aufgrund der vergleichsweise hohen Katalysatormengen und der den Nebenreaktionen geschuldeten Ausbeuteverluste sowie der erforderlichen destillativen Aufreinigung ist die Hydrosilylierung von Allylamin mit hohen Kosten verbunden. For the more efficient preparation of aminoalkyl-functional alkoxysilanes, the direct hydrosilylation of allylamine with ethoxyhydrosilanes is described in the prior art instead of the three-stage chlorosilane route. However, this synthetic route is difficult because of the strong inhibition of the transition metal catalyst by the complexing allylamine. A number of patent applications prove the attempts, with the help of special ruthenium or rhodium catalysts and nitrogen and phosphorus compounds as cocatalysts to find an economical hydrosilylation, such as US 4481364, US 4867501, US 4921988, US 4927953 or US 5001246. The method often require high amounts of catalyst and lead due to rearrangements of the double bonds and limited addition selectivities to product mixtures consisting of the branched alpha and beta as well as the linear gamma isomer of aminopropylsilane. The silane mixtures must be purified by distillation before further use. Due to the comparatively high amounts of catalyst and the yield losses owing to the side reactions and the required distillative purification, the hydrosilylation of allylamine is associated with high costs.
Aminopropylalkoxysilane können mittels Hydrolyse- und Kondensationsreaktionen zu Polysiloxanen umgewandelt werden. Aufgrund der basischen Aminofunktion werden bevorzugt alkalische Katalysatoren wie beispielsweise KOH, Ammoniumhydroxid oder -carboxylat eingesetzt. Die EP 1580215 A1 und die darin zitierten Schriften seien hiermit als Referenz eingeführt. Diese Syntheseroute hat Grenzen. Bei der Synthese von aminofunktionellen Polysiloxanen mit hoher Funktionalitätsdichte treibt der Preis des teuren Spezialsilans zunehmend die Stoffkosten in die Höhe und es reduziert sich im gleichen Zug die Ausbeute um die Menge des bei der Hydrolyse freigesetzten Alkohols. Bei basisch katalysierten Äquilibrierreaktionen von Polysiloxanen mit Aminogruppen können weiterhin Silazane als Nebenprodukte auftreten. Aminopropylalkoxysilanes can be converted to polysiloxanes by means of hydrolysis and condensation reactions. Due to the basic amino function, preference is given to using alkaline catalysts, such as, for example, KOH, ammonium hydroxide or carboxylate. EP 1580215 A1 and the documents cited therein are hereby incorporated by reference. This synthesis route has limitations. In the synthesis of aminofunctional polysiloxanes with high functionality density, the price of the expensive specialty silane increasingly increases the cost of the material and at the same time the yield is reduced by the amount of alcohol liberated during the hydrolysis. In the case of base-catalyzed equilibration reactions of polysiloxanes with amino groups, it is furthermore possible for silazanes to occur as by-products.
Zur Erhöhung der Regioselektivität und Vermeidun g von Silazanbildung bei der Hydrosilylierung von ungesättigten Aminen mit Wasserstoffsiloxanen bedient man sich laut der D E 4436077 A1 der Schutzgruppentechnik, die zwei zusätzliche Syntheseschritte bedingt. Gute Selektivitäten bei der Hydrosilylierung von Allylamin mit Tetramethyldisiloxan beschreibt die US 5026890 A1 unter Verwendung des Karstedt- Katalysators. Dennoch werden von diesem Platin(0)-Divinyltetramethyl-disiloxan- Komplex vergleichsweise hohe Mengen von mindestens 40 ppm Platin benötigt. To increase the regioselectivity and avoidance of silazane formation in the hydrosilylation of unsaturated amines with hydrogen siloxanes, the protective group technique according to D E 4436077 A1 is used, which requires two additional synthesis steps. Good selectivities in the hydrosilylation of allylamine with tetramethyldisiloxane are described in US Pat. No. 5,026,890 A1 using the Karstedt catalyst. Nevertheless, this platinum (0) -divinyltetramethyl-disiloxane complex requires comparatively high amounts of at least 40 ppm of platinum.
Zur Herstellung von methacrylamidfunktionellen Alkylsilanen beschreibt die US 2005017691 1 A1 die Umsetzung von epoxyfunktionellen Alkylsilanen mit methanolischer Ammoniaklösung bei 0°C bis 25°C über 1 bis 3 Tage. Eine anschließende Derivatisierung mit Methacrylsäurec h I o r i d f ü h rt z u d e n Zielverbindu ngen . Die EP 1 956038 A1 offenbart ein ähnliches Verfahren zur Herstellung von endständig methacrylamidfunktionellen linearen Polydimethylsiloxanen . Gem ischt su bstitu ierte Polysi loxane m it zusätzl ichen funktionellen Gruppen werden nicht genannt. For the preparation of methacrylamide-functional alkylsilanes, US 2005017691 1 A1 describes the reaction of epoxy-functional alkylsilanes with methanolic ammonia solution at 0 ° C to 25 ° C for 1 to 3 days. Subsequent derivatization with methacrylic acid leads to target compounds. EP 1 956038 A1 discloses a similar process for the preparation of terminal methacrylamide-functional linear polydimethylsiloxanes. Mixtures of substituted polysi loxanes with additional functional groups are not mentioned.
Die EP 1008614 A2 beansprucht lineare Polydimethylsiloxane, deren Kettenenden mit je einem Allylpolyether und einem Alkanolamin oder Alkanolalkylamin SiC-verknüpft
sind. Die Herstellung erfolgt aus einem linearen, epoxy- und polyetherfunktionellen Polydimethylsiloxan durch titankatalysierte Epoxidringöffnung zum Beispiel mit Diethanolamin bei 80°C. Polysiloxane mit primären Aminofunktionen sind nach dem besch riebenen Verfah ren nicht herstell bar u nd werden weder genan nt noch beansprucht. EP 1008614 A2 claims linear polydimethylsiloxanes whose chain ends are each SiC-linked with an allyl polyether and an alkanolamine or alkanolalkylamine are. The preparation is carried out from a linear, epoxy- and polyether-functional polydimethylsiloxane by titanium-catalyzed epoxide ring opening, for example with diethanolamine at 80 ° C. Polysiloxanes with primary amino functions are not preparable and unreacted by the described procedure.
Die US 2008/0314518 A1 beschreibt die Reaktion von aminofunktionellen Silanen oder auch Ethylendiamin in situ mit Glycidoxypropyltriethoxysilan zur Herstellung eines wässrigen Zweikomponenten-Haftvermittlers. Die für eine gute Haftung erforderliche Vernetzung wird gewährleistet, da eine Aminofunktion mit mehr als einem der im Überschuß zugegebenen Epoxidringe reagiert. US 2008/0314518 A1 describes the reaction of amino-functional silanes or ethylenediamine in situ with glycidoxypropyltriethoxysilane for the preparation of an aqueous two-component adhesion promoter. The crosslinking required for good adhesion is ensured because an amino function reacts with more than one of the excess epoxy rings added.
Der Stand der Technik offenbart Siloxane mit nicht mehr als zwei Aminofunktionen und h ä ufi g oh n e we ite re fu n ktionelle Gruppen. Aminofunktionelle Siloxane und insbesondere deren geladene Derivate, die durch Reaktion der Aminofunktion mit d iversen Sä u ren oder aber auch durch deren Alkylierung zu quaternären Stickstoffverbindungen zugänglich sind, besitzen eine ausgeprägte elektrostatische Affinität gegenüber Oberflächen und sorgen in Folge für eine gute Substantivität der Verbindungen. Die Substantivität des Aminosiloxans als dessen Fähigkeit sich auf Untergründen elektrostatisch zu verankern geht einher mit dessen Funktionalitätsdichte, d .h. mit der Anzahl an ungeladenen oder aber auch Ladungstragenden Stickstofffunktionen bezogen auf das Molekulargewicht. Dem Zielgedanken verschrieben, Aminosiloxane mit frei wählbarer Substantivität bereitzustellen, ist zu konstatieren , dass es dem bisherigen Stand der Technik an selektiven und kostengünstigen synthetischen Zugängen zu Siloxanen mangelt, die mehr als nur eine oder zwei primäre Aminofunktionen pro Siloxankette enthalten. The prior art discloses siloxanes having no more than two amino functions and poorer synthetic groups. Aminofunctional siloxanes and in particular their charged derivatives, which are accessible to quaternary nitrogen compounds by reaction of the amino function with various acids or else by their alkylation, have pronounced electrostatic affinity towards surfaces and consequently ensure good substantivity of the compounds. The substantivity of the aminosiloxane as its ability to electrostatically anchor on substrates goes hand in hand with its density of functionality, ie. with the number of uncharged or even charge-carrying nitrogen functions based on the molecular weight. The goal of providing aminosiloxanes of arbitrary substantivity is to state that the prior art lacks selective and inexpensive synthetic approaches to siloxanes containing more than one or two primary amino functions per siloxane chain.
Wie aus der Herstellung von Alkanolaminen bekannt ist, bleibt die Epoxidringöffnung mit Ammoniak nicht auf der Stufe des primären Amins stehen. Die gebildeten primären und sekundären Amine sind stärkere Nucleophile und konkurrieren mit dem Ammoniak um die Reaktion mit dem Epoxidring. (Literatur: Ullmann's Encyclopedia of Industrial Chemistry, Release 2006, 7th Edition , Wiley VCH) Die i n d er E P 1 00861 4 A2 beschriebenen aminofunktionellen Polysiloxane sind niedermolekular und weisen nur eine endständige Aminofunktion pro Kette auf. Di e E P 1 956038 A1 beschreibt ebenfalls nur lineare endständig aminofunktionelle Zwischenstufen. Folgereaktionen der gebildeten primären Amine führen im ersten Fall zu Kettenverlängerung und nicht z u e i n e r Ve rgelung durch Quervernetzung. Sobald das Siloxan seitständige
Substituenten aufweist und insbesondere dann, wenn mehr als zwei Aminofunktionen an das Siloxan geknüpft werden sollen, führt eine Weiterreaktion der primären und sekundären Amine zu vergleichsweise starken Viskositätszunahmen. D a s Vergelungsrisiko steigt mit zunehmender Molmasse des Produkts, sowie damit einhergehend mit zunehmender Produktviskosität. Zudem sind sekundäre Amine toxikologisch bedenklich, da sie mit Nitriten oder Stickoxiden aus der Luft kanzerogene Nitrosamine bilden. As is known from the preparation of alkanolamines, the epoxide ring opening with ammonia does not remain at the stage of the primary amine. The formed primary and secondary amines are stronger nucleophiles and compete with the ammonia for reaction with the epoxide ring. (References: Ullmann's Encyclopedia of Industrial Chemistry, Release 2006, 7 th Edition, Wiley VCH) The amino-functional polysiloxanes described in EP 1 00861 4 A2 are of low molecular weight and have only one terminal amino function per chain. The EP 1 956038 A1 also describes only linear terminal amino-functional intermediates. Subsequent reactions of the primary amines formed in the first case lead to chain extension and not to cross-linking control. Once the siloxane is sideways Having substituents and in particular when more than two amino functions to be attached to the siloxane, a further reaction of the primary and secondary amines leads to relatively high viscosity increases. The risk of gelation increases with increasing molecular weight of the product, and with increasing product viscosity. In addition, secondary amines are of toxicological concern since they form carcinogenic nitrosamines with nitrites or nitrogen oxides from the air.
Eine Aufgabe der vorliegenden Erfindung besteht darin, Siloxane mit primären Aminofunktionen und weiteren Organomodifikationen selektiv und kostengünstig herzustellen. Ziel ist ei ne hohe Ausbeute an pri mären Am i nofu n ktionen bei gleichzeitiger Vermeidung der Bildung von sekundären Aminen zu gewährleisten. An object of the present invention is to selectively and inexpensively produce siloxanes having primary amino functions and other organomodifications. The aim is to ensure a high yield of primary amino acids while avoiding the formation of secondary amines.
Ein Nachteil der in EP 1956038 A1 und US 2005017691 1 A beschriebenen Verfahren zur Umsetzung von epoxyfunktionellen Verbindungen mit Ammoniak sind die langen Reaktionszeiten von mindestens 12 Stunden bis hin zu 3 Tagen . Je länger die Reaktion dauert und je niedriger die Lokalkonzentration von Ammoniak ist, desto bevorzugter reagieren die gebildeten primären Amine in Folgereaktionen mit den restl i ch en E poxyfu n kti on e n a b u n d es kom mt zu r Verge l u n g . Di e l a n gen Reaktionszeiten resultieren unvermeidlich aus den gewählten Verfahrensparametern von Druck und Temperatur. A disadvantage of the processes described in EP 1956038 A1 and US Pat. No. 2005017691 1 for reacting epoxy-functional compounds with ammonia are the long reaction times of at least 12 hours up to 3 days. The longer the reaction lasts and the lower the local concentration of ammonia, the more preferentially the formed primary amines react in subsequent reactions with the remaining epoxy-acids on the surface of the ammonia. Di eral reaction times inevitably result from the chosen process parameters of pressure and temperature.
Eine weitere Aufgabe der vorliegenden Erfindung besteht weiterhin darin, ein kostengünstiges Verfahren zur Herstellung von Siloxanen mit hoher Chemoselektivität für die Bildung primärer Aminogruppen zu entwickeln. Another object of the present invention is to develop a low cost process for producing high chemoselectivity siloxanes for the formation of primary amino groups.
Beschreibung der Erfindung: Description of the invention:
Überraschenderweise wurde gefunden, dass die Umsetzung von seitständig epoxymodifizierten Siloxanen mit Ammoniak selektiv primäre Aminogruppen tragende Siloxane hervorbringt, ohne dass Vernetzu ngen über sekundäre oder tertiäre Aminbildung erfolgen. Surprisingly, it has been found that the reaction of laterally epoxy-modified siloxanes with ammonia selectively produces primary amino-bearing siloxanes, without crosslinking occurring via secondary or tertiary amine formation.
Ein Gegenstand der Erfindung ist daher ein Verfahren zur Herstellung von selektiv primäre Aminogruppen tragenden Siloxanen durch Umsetzung von seitständig epoxymodifizierten Siloxanen mit gasförmigem, gelöstem oder in situ erzeugtem Ammoniak.
Dies ist für den Fachmann überraschend und nicht vorhersehbar, da alkylsubstituierte Amine stärkere Nucleophile sind und somit Weiterreaktionen des gewünschten Produkts mit anderen Epoxidringen zu sekundären Aminen gegenüber der Primärreaktion begünstigen. Dies gilt insbesondere für den Fall einer hohen Funktionalitätsdichte und somit einer hohen Konzentration von Epoxidgruppen im System. An object of the invention is therefore a process for the preparation of siloxanes carrying selectively primary amino groups by reacting laterally epoxy-modified siloxanes with gaseous, dissolved or in situ generated ammonia. This is surprising and unpredictable to the person skilled in the art, since alkyl-substituted amines are stronger nucleophiles and thus favor further reactions of the desired product with other epoxide rings to form secondary amines over the primary reaction. This is especially true in the case of a high density of functionality and thus a high concentration of epoxide groups in the system.
Eine weitere Aufgabe der vorliegenden Erfindung besteht darin, Siloxane nicht nur an den Kettenenden, sondern auch seitenständig mit primären Aminofunktionen zu modifizieren, um höhere Funktionalitätsdichten zu erzielen. Another object of the present invention is to modify siloxanes not only at the chain ends but also laterally with primary amino functions to achieve higher functionality densities.
Gegenstand der Erfindung sind Siloxane der allgemeinen Formel 1 The invention relates to siloxanes of the general formula 1
MA M'ai M"A2 M'"A3 DB D'M D"B2 D'"B3 TC QD M A M'ai M " A2 M '" A3 D B D M D " B2 D'" B3 T C Q D
(Formel 1 ) wobei (Formula 1) where
a = 0 bis 32; bevorzugt 1 bis 22, insbesondere 2; a = 0 to 32; preferably 1 to 22, in particular 2;
a1 = 0 bis 10, bevorzugt 1 bis 5, insbesondere 2; a1 = 0 to 10, preferably 1 to 5, in particular 2;
a2 = 0 bis 32; bevorzugt 1 bis 22, insbesondere 2; a2 = 0 to 32; preferably 1 to 22, in particular 2;
a3 = 0 bis 10; bevorzugt 1 bis 5, insbesondere 2; a3 = 0 to 10; preferably 1 to 5, in particular 2;
b = 0 bis 600, bevorzugt 10 bis 500, insbesondere 20 bis 400 b = 0 to 600, preferably 10 to 500, in particular 20 to 400
b1 = 0 bis 50, bevorzugt 0,1 bis 20, insbesondere 2 bis 10; b1 = 0 to 50, preferably 0.1 to 20, in particular 2 to 10;
b2 = 0 bis 50, bevorzugt 0,1 bis 20, insbesondere 1 bis 10; b2 = 0 to 50, preferably 0.1 to 20, in particular 1 to 10;
b3 = 0 bis 50, bevorzugt 1 bis 20, insbesondere 2 bis 10; b3 = 0 to 50, preferably 1 to 20, in particular 2 to 10;
c = 0 bis 20, bevorzugt 0 bis 10, insbesondere 0;
d = 0 bis 20, bevorzugt 0 bis 10, insbesondere 0; mit der Maßgabe, dass c = 0 to 20, preferably 0 to 10, in particular 0; d = 0 to 20, preferably 0 to 10, in particular 0; with the proviso that
im Fall von a1 = 2 gilt, dass b1 + 0 und/oder b2 + 0 und/oder b3 Φ 0 und/oder a2 Φ 0 und/oder a3 0 ist und bevorzugt gilt, dass mindestens zwei der Faktoren a2, a3, b1 , b2, und b3 Φ 0 sind. unabhängig voneinander gleiche oder verschiedene lineare oder verzweigte Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen oder auch aromatische Kohlenwasserstoff reste mit 6 bis 30 Kohlenstoffatomen bevorzugt Methyl oder Phenyl, insbesondere Methyl; unabhängig voneinander gleiche oder verschiedene organische Reste, die eine primäre Aminofunktion tragen, bevorzugt Reste, die zusätzlich zu der Aminofunktion eine Hydroxylgruppe tragen, insbesondere ausgewählt aus der Gruppe in the case of a1 = 2 it holds that b1 + 0 and / or b2 + 0 and / or b3 Φ 0 and / or a2 Φ 0 and / or a3 is 0 and it is preferred that at least two of the factors a2, a3, b1 , b2, and b3 Φ 0. independently of one another identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms or else aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or phenyl, in particular methyl; independently of one another identical or different organic radicals which carry a primary amino function, preferably radicals which, in addition to the amino function, carry a hydroxyl group, in particular selected from the group
OH OH
i CH2OH i CH 2 OH
-(CH2)3-0-CH2-C— CH2 NH2 — (CH2)3-0 -CH2-C— NH2 - (CH2) 3-0-CH2-C- CH2 NH2 - (CH 2) 3 -CH 2 -0 -C-NH 2
H H
(1a) (1b) (1a) (1b)
OH CH2OH i OH CH 2 OH i
-(CH2)m-0-CH2-C— CH2-N H2 ■(CH2)m- 0-CH2-C-NH2 - (CH 2) m -0-CH 2 -C- CH 2 -NH 2 ■ (CH 2) m - 0-CH 2 -C-NH 2
H H H H
(1c) (1d) (1c) (1d)
o o oo
II II II II
-CH2— CH-C-O— R7-CH— CH2-NH2 -CH2— CH-C -O— R7-CH"NH2 I I -CH 2 -CH-CO-R 7 -CH-CH 2 -NH 2 -CH 2 -CH-C-O-R 7 -CH " NH 2 II
R6 OH R CH2 R6 OH R CH 2
I I
OH OH
(1 i) (1j)
gleiche oder verschiedene Reste aus der Gruppe Wasserstoff oder Alkyl mit 1 bis 6 C-Atomen, bevorzugt Methylreste, gleiche oder verschiedene zweiwertige Kohlenwasserstoffreste, die gegebenenfalls Etherfunktionen enthalten und die gegebenenfal ls Polyoxyalkylenreste darstellen, bevorzugt Methylen reste und (1i) (1j) identical or different radicals from the group consisting of hydrogen or alkyl having 1 to 6 carbon atoms, preferably methyl radicals, identical or different divalent hydrocarbon radicals which optionally contain ether functions and which represent if necessary polyoxyalkylene radicals, preferably methylene radicals and
eine ganze Zahl von 2 bis 18 an integer from 2 to 18
gleiche oder verschiedene Reste aus der Gruppe identical or different radicals from the group
-CH2-CH2-CH2-0-(CH2-CH20-)x-(CH2-CH(R')0-)y-R" -CH 2 -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x - (CH 2 -CH (R ') 0-) y -R "
-CH2-CH2-0-(CH2-CH20-)x-(CH2-CH(R')0-)y-R" -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x - (CH 2 -CH (R ') O-) y -R "
-CH2-CH2-(0)X-RIV -CH 2 -CH 2 - (0) X -R IV
-CH2-CH2-CH2-0-CH2-CH(OH)-CH2OH -CH 2 -CH 2 -CH 2 -O-CH 2 -CH (OH) -CH 2 OH
oder or
-CH2-CH2-CH2-0-CH2-C(CH2OH)2-CH2-CH3, worin -CH 2 -CH 2 -CH 2 -O-CH 2 -C (CH 2 OH) 2 -CH 2 -CH 3 , wherein
x 0 bis 100, vorzugsweise > 0, insbesondere 1 bis 50, x 0 to 100, preferably> 0, in particular 1 to 50,
x' 0 oder 1 , x'0 or 1,
y 0 bis 100, vorzugsweise > 0, insbesondere 1 bis 50, y is 0 to 100, preferably> 0, in particular 1 to 50,
R' unabhängig von einander eine gegebenenfalls substituierte, beispielsweise mit Alkylresten, Arylresten oder Halogenalkyl- oder Halogenarylresten substituierte, Alkyl- oder Arylgruppe mit 1 bis 12 C-Atomen ist, wobei innerhalb eines Restes R4 und/oder eines Moleküls der Formel I untereinander verschiedene Substituenten R' vorliegen können, und R 'is independently of one another an optionally substituted, for example, alkyl, aryl or haloalkyl or haloaryl substituted, alkyl or aryl group having 1 to 12 carbon atoms, wherein within a radical R 4 and / or of a molecule of the formula I with each other Substituents R 'may be present, and
R" unabhängig voneinander ein Wasserstoffrest oder eine Alkylgruppe mit 1 bis 4 C-Atomen, eine Gruppe -C(0)-R"' mit R'" = Alkylrest, eine Gruppe - CH2-0-R', eine Alkylarylgruppe, wie z. B. eine Benzylgruppe, die Gruppe - C(0)NH-R' bedeutet, R "independently of one another are a hydrogen radical or an alkyl group having 1 to 4 C atoms, a group -C (O) -R"'withR'"= alkyl radical, a group - CH 2 -O-R ', an alkylaryl group, such as for example, a benzyl group which means - C (O) NH-R ',
RIV ein gegebenenfal ls su bstitu ierter, z. B . mit Halogenen substituierter, gesättigter oder ungesättigter Koh lenwasserstoffrest m it 1 bis 50 , vorzugsweise 3 bis 30 Kohlenstoff-Atomen, insbesondere ein Decyl-, Dodecyl-, Tetradecyl- oder Hexadecylrest ist, unabhängig voneinander gleiche oder verschiedene lineare, cyclische oder verzweigte, gegebenenfalls olefinisch ungesättigte oder aromatische Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen, die mit den, die
Heteroatome O, N, S, P enthaltenden Gruppen oder Halogenatomen substituiert sein können und die bevorzugt keine primären oder sekundären Aminfunktionen enthalten, bevorzugt Alkanolreste, Carbonsäurereste oder Carbonsäureesterreste, insbesondere Koh lenwasserstoffreste mit 5 bis 30 Kohlenstoffatomen wie beispielsweise ein Dodecenyl-, Tetradecyl-, Hexadecyl- oder Octadecylrest und R IV a given substitute, eg. B. halogen-substituted, saturated or unsaturated hydrocarbon radical having from 1 to 50, preferably from 3 to 30, carbon atoms, in particular a decyl, dodecyl, tetradecyl or hexadecyl radical, independently of one another, identical or different linear, cyclic or branched, optionally olefinic unsaturated or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms, which are with the, Heteroatoms O, N, S, P containing groups or halogen atoms may be substituted and preferably no primary or secondary amine functions, preferably alkanol radicals, carboxylic acid radicals or carboxylic acid ester radicals, in particular hydrocarbon radicals having 5 to 30 carbon atoms such as a dodecenyl, tetradecyl, hexadecyl - or octadecyl and
R5 = unabhängig voneinander gleiche oder verschiedene Reste R1, R2, R3 oder R4, bevorzugt R1, insbesondere Methyl, Phenyl, Dodecyl oder Hexadecyl ist. R 5 = independently of one another are identical or different radicals R 1 , R 2 , R 3 or R 4 , preferably R 1 , in particular methyl, phenyl, dodecyl or hexadecyl.
Die verschiedenen Monomereinheiten der in den Formeln angegebenen Bausteine (Siloxanketten bzw. Polyoxyalkylenkette) können untereinander blockweise aufgebaut sein mit einer beliebigen Anzahl an Blöcken und einer beliebigen Sequenz oder einer statistischen Verteilung unterliegen. Die in den Formeln verwendeten Indices sind als statistische Mittelwerte zu betrachten. The various monomer units of the structural units indicated in the formulas (siloxane chains or polyoxyalkylene chain) can be constructed in blocks with any number of blocks and any sequence or statistical distribution. The indices used in the formulas are to be regarded as statistical averages.
Gegenstand der Erfindung sind weiterhin ionische Addukte der erfindungsgemäßen aminofunktionellen Siloxane mit protischen Reaktanden H+A". Das Addukt liegt in der Form -NH3 +A" vor. Die Anionen A" sind gleiche oder verschiedene Gegenionen zu den positiven Ladungen an den protonierten, primären Aminogruppen, ausgewählt aus anorganischen oder organischen Anionen der Säuren H+A", sowie deren Derivate. Bevorzugte Anionen sind beispielsweise Chlorid, Sulfat und Hydrogensulfate, Carbonat und Hydrogencarbonat, Phosphat und Hydrogenphosphate, Acetat und homologe Carboxylate mit linearen oder verzweigten, gesättigten oder olefinisch ungesättigten Alkylketten, aromatische Carboxylate, aus Aminosäuren gebildete Carboxylate, Citrate, Malonate, Fumarate, Maleate, substituierte und unsubstituierte Succinate und aus L- Hydroxycarbonsäuren gebildete Carboxylate, wie beispielsweise Lactat. Die erfindungsgmäßen Aminosiloxane und ihre ionischen Addukte können je nach Stabilität des gebildeten Addukts in Dissoziationsgleichgewichten vorliegen. The invention further ionic adducts of the amino-functional siloxanes of the invention with protic reactants H + A ". The adduct is in the form -NH 3 + A" before. The anions A " are identical or different counterions to the positive charges on the protonated, primary amino groups selected from inorganic or organic anions of the acids H + A " , and their derivatives. Preferred anions are, for example, chloride, sulfate and hydrogen sulfates, carbonate and bicarbonate, phosphate and hydrogen phosphates, acetate and homologous carboxylates with linear or branched, saturated or olefinically unsaturated alkyl chains, aromatic carboxylates, carboxylates formed from amino acids, citrates, malonates, fumarates, maleates, substituted ones and unsubstituted succinates and carboxylates formed from L-hydroxycarboxylic acids, such as lactate. Depending on the stability of the adduct formed, the aminosiloxanes and their ionic adducts according to the invention can be present in dissociation equilibria.
Gegenstand der Erfindung sind darüber hinaus die sich aus der Alkylierung der primären Aminfunktion ableitenden quaternären Ammoniumverbindungen der Formel 2 The invention furthermore relates to the quaternary ammonium compounds of the formula 2 deriving from the alkylation of the primary amine function
Ma M""ai M"a2 M'"a3 Db D""b1 D"b2 D'"b3 Tc Qd M a M "" a i M " a2 M '" a3 D b D "" b1 D " b2 D'" b3 T c Q d
(Formel 2)
wobei (Formula 2) in which
a, a1 , a2, a3, b, b1 , b2, b3, c und d die oben genannte Bedeutung haben, die Reste R1, R3, R4 und R5 ebenfalls die oben genannte Definition erfüllen und a, a1, a2, a3, b, b1, b2, b3, c and d have the abovementioned meaning, the radicals R 1 , R 3 , R 4 and R 5 likewise fulfill the abovementioned definition, and
R8 unabhängig voneinander gleiche oder verschiedene organische Reste die Ammoniumfunktionen tragen; geeignete Reste R8 sind zum Beispiel vorzugsweise gleiche oder verschiedene Reste ausgewählt aus der Gruppe
R 8 independently of one another, identical or different organic radicals carry the ammonium functions; For example, suitable radicals R 8 are preferably identical or different radicals selected from the group
OR" OR "
i CH OR9 i CH OR 9
(CH2)3-0-CH2-C— CH2 NR9 (CH2)3-0-CH2-C— NR9 (CH 2 ) 3 -O-CH 2 -C-CH 2 NR 9 (CH 2 ) 3 -O-CH 2 -C -NR 9
H H
(2a) (2b) (2a) (2b)
ORa CH2ORa OR a CH 2 OR a
(CH2)M-0-CH2-C— CH2-NR9 (CH2)M-0 -CH2-C-NR9 ; (CH 2) m -0-CH 2 -C- CH 2 -NR 9 (CH 2) m -CH 2 -C -0-NR 9;
H H
(2c) (2d) (2c) (2d)
O O II II O II II
CH2— CH-C-O— R7-CH— CH2-NR9 -CH2— CH -C-O— R7 -CH-NR9 3 +A" l 1 n I CH 2 -CH-CO-R 7 -CH- CH 2 -NR 9 -CH 2 -CH-CO-R 7 -CH-NR 9 3 + A " l 1 n I
R ?6c OR9 R6 CH2 R? 6 c OR 9 R 6 CH 2
I „ I "
(2i) (2j) OR9 unabhängig voneinander gleiche oder verschiedene lineare oder verzweigte Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen oder aromatische Kohlenwasserstoff reste mit 6 bis 30 Kohlenstoffatomen, bevorzugt Methyl oder Ethyl; (2i) (2j) OR 9 are independently identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms, preferably methyl or ethyl;
Zur Herstellung der erfindungsgemäßen Verbindungen mit quaternären Ammoniumfunktionen setzt man die erfindungsgemäßen Verbindungen der Formel 1 mit dem Alkylierungsreagentien um. Hierzu können insbesondere dem Fachmann bekannte Alkylierungsreagentien wie z. B . Alkylhalogen ide oder Dial kylsu lfate eingesetzt werden. Gegenstand der Erfindung sind weiterhin Zubereitungen in Form von Lösungen, Emulsionen, Dispersionen und/oder Gemischen enthaltend die erfindungsgemäßen Verbindungen der Formeln 1 oder 2. Diese Zubereitungen können weitere Additive und
Zuschlagstoffe enthalten, beispielsweise, aber nicht beschränkt ausgewählt aus der Gruppe der Füllstoffe, Emulgatoren, Farbstoffe, Pigmente. To prepare the compounds according to the invention having quaternary ammonium functions, the compounds of the formula 1 according to the invention are reacted with the alkylating reagents. For this purpose, in particular known to those skilled Alkylierungsreagentien such. B. Alkyl halides ide or dial kylsu lfate be used. The invention furthermore relates to preparations in the form of solutions, emulsions, dispersions and / or mixtures comprising the compounds of the formulas 1 or 2 according to the invention. These preparations may contain further additives and Aggregates include, for example, but not limited to selected from the group of fillers, emulsifiers, dyes, pigments.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der erfindungsgemäßen aminofunktionellen Siloxane der Formeln 1 oder 2 als Emulgator für kosmetische Zubereitungen, Compatibilizer für Kunststoffblends, Trennmittel, Hydrophobierungsmittel, Dispergiermittel für Farbpigmente und Füllstoffe, Additive zur Textilausrüstung (Weichmacher), Konditioniermittel für Haare, Primer für Oberflächenbeschichtung / Haftvermittler, Additiv für Korrosionsschutzformulierungen, PU-Schaumstabilisator, Entschäumer und/oder als Netzmittel. The invention further relates to the use of the aminofunctional siloxanes of the formulas 1 or 2 according to the invention as emulsifiers for cosmetic preparations, compatibilizers for plastic blends, release agents, water repellents, dispersants for color pigments and fillers, additives for textile finishing (plasticizers), conditioners for hair, primers for Surface coating / adhesion promoter, additive for corrosion protection formulations, PU foam stabilizer, defoamer and / or wetting agent.
Ein weiterer Gegenstand der Erfindung ist das Verfahren zur Herstellung der erfindungsgemäßen Aminosiloxane der Formel 1 . Herstellungsverfahren der erfindungsgemäßen Siloxane: Another object of the invention is the process for the preparation of the aminosiloxanes of the formula 1 according to the invention. Production process of the siloxanes according to the invention:
Die erfindungsgemäßen Verbi nd u ngen nach Formel I werden hergestellt aus epoxyfunktionellen Verbindungen der Formel 3 The compounds of the formula I according to the invention are prepared from epoxy-functional compounds of the formula 3
Ma M a1 M"a2 M'"a3 Db D'""bi D"b2 D"'b3 Tc Qd M a M M a1 'a2 M'"a3 D b D '""biD" b2 D "' b3 T c Q d
(Formel 3) wobei (Formula 3) where
a, a1 , a2, a3, b, b1 , b2, b3, c und d die oben genannte Bedeutung haben, die Reste R1, R3, R4 und R5 ebenfalls die oben genannte Definition erfüllen und
R10 unabhängig voneinander gleiche oder verschiedene organische Epoxy-Reste sind. a, a1, a2, a3, b, b1, b2, b3, c and d have the abovementioned meaning, the radicals R 1 , R 3 , R 4 and R 5 likewise fulfill the abovementioned definition, and R 10 are independently identical or different organic epoxy radicals.
Geeignete Epoxy-Reste R10 sind zum Beispiel vorzugsweise gleiche oder verschiedene Reste ausgewählt aus der Gruppe
Suitable epoxy radicals R 10 are for example preferably identical or different radicals selected from the group
(3a) (3b)
(3a) (3b)
(3d) (3d)
Die epoxyfunktionellen Siloxane, die noch weitere Substituenten tragen können, werden wie im Stand der Technik - beispielsweise in der EP 0415208 A2 - beschrieben mittels Übergangsmetall-katalysierter Hydrosilylierung hergestellt. Anschließend wird die Ringöffnungsreaktion unter Einleiten von Ammoniak, mit oder ohne Verwendung von Lösungsmitteln, bei Normaldruck oder im Autoklaven bei Überdruck durchgeführt. Das Ammoniak kann auch in situ aus Verbindungen erzeugt werden, die beispielsweise bei Temperaturerhöhung Ammoniak abspalten. The epoxy-functional siloxanes which can carry further substituents are prepared as described in the prior art-for example in EP 0415208 A2-by means of transition metal-catalyzed hydrosilylation. Subsequently, the ring-opening reaction is carried out with introduction of ammonia, with or without use of solvents, at atmospheric pressure or in an autoclave at overpressure. The ammonia can also be generated in situ from compounds which split off ammonia, for example when the temperature increases.
Eine Vielzahl der gängigen Lösungsmittel ist für die erfindungsgemäße Herstellung der aminofunktionellen Siloxane geeignet. Je nach Polarität des epoxyfunktionellen Vorprodukts wählt man das Lösungsmittel entsprechend seines Lösungsvermögens für Edukt und Produkt. Das Lösungsmittel sollte sich unter den gewählten Reaktionsbedingungen gegenüber Ammoniak sowohl als auch gegenüber dem epoxyfunktionellen Vorprodukt weitgehend inert verhalten. So eignen sich beispielsweise aromatische Kohlenwasserstoffe, aber auch Ether oder Alkohole. Bevorzugt eingesetzt werden Toluol, Xylol, Methanol, Ethanol, Propanol und seine Isomere, insbesondere 2-Propanol.
Beim Einsatz von Autoklaven können höhere Reaktionstemperaturen von bis zu 150°C, vorzugsweise 60°C bis 130°C eingestellt werden, da das Reaktionsgas im geschlossenen System verbleibt. Wenn der Autoklav geöffnet und drucklos, beispielsweise mit gesättigter ammoniakalischer Lösung, befüllt wird, kann der Druckaufbau im geschlossenen Autoklaven während des Aufheizens im Bereich von 1 bis 50 bar, vorzugsweise 5 bis 20 bar liegen. Sofern ein geschlossener Druckreaktor über eine Begasungsvorrichtung mit Ammoniakgas befüllt wird, kann bei der Befüllung ein vorgebener Druck von 1 bis 50 bar, vorzugsweise von 5 bis 20 bar eingestellt werden. Die Reaktionszeiten können in diesem Fall 1 bis 10 Stunden betragen, vorzugsweise 1 bis 5 Stunden. A variety of common solvents is suitable for the preparation according to the invention of the amino-functional siloxanes. Depending on the polarity of the epoxy-functional precursor, the solvent is selected according to its solubility for starting material and product. The solvent should behave substantially inert to both the ammonia and the epoxy-functional precursor under the chosen reaction conditions. For example, aromatic hydrocarbons, but also ethers or alcohols are suitable. Toluene, xylene, methanol, ethanol, propanol and its isomers, in particular 2-propanol, are preferably used. When using autoclave higher reaction temperatures of up to 150 ° C, preferably 60 ° C to 130 ° C can be set because the reaction gas remains in the closed system. When the autoclave is opened and pressureless, for example, filled with saturated ammoniacal solution, the pressure build-up in the closed autoclave during heating in the range of 1 to 50 bar, preferably 5 to 20 bar. If a closed pressure reactor is filled with ammonia gas via a gassing device, a predetermined pressure of 1 to 50 bar, preferably 5 to 20 bar, can be set during the filling. The reaction times may in this case be 1 to 10 hours, preferably 1 to 5 hours.
Ein besonderer Vorteil des Verfahrens bei Drücken von größer 1 bar und bei Temperaturen ab 50°C besteht darin, dass im Vergleich zum Stand der Technik kürzere Reaktionszeiten von unter 12 Stunden realisiert werden können. Die höhere Lokalkonzentration von Ammoniak in der gelösten Phase beeinflusst zudem die Selektivität positiv, da das Verhältnis von Ammoniak zu dem gebildeten primären Amin, also der um die Ringöffnung konkurrierenden Reagenzien, zu Gunsten des Ammoniaks erhöht wird. Bevorzugte Verfahrensdrücke liegen im Bereich von 2 bis 50 bar, insbesondere 5 bis 20 bar. A particular advantage of the process at pressures of greater than 1 bar and at temperatures above 50 ° C. is that shorter reaction times of less than 12 hours can be achieved in comparison with the prior art. The higher local concentration of ammonia in the dissolved phase also has a positive influence on the selectivity, since the ratio of ammonia to the primary amine formed, ie the reagents competing for the ring opening, is increased in favor of the ammonia. Preferred process pressures are in the range of 2 to 50 bar, in particular 5 to 20 bar.
Ein weiterer Vorteil der höheren Reaktionstemperatur zeigt sich bei der Umsetzung höhermolekularer Epoxysiloxane. Die Viskosität der Ausgangsverbindungen ist bei höheren Temperaturen reduziert, was die Durchmischung und den Stofftransport erleichtert und somit ebenfalls eine zügige Reaktion bewirkt. Da im drucklosen Verfahren die höhere Reaktionstemperatur ebenfalls eine schnellere Ausgasung des Ammoniaks bewirkt, kann es vorteilhaft sein, im kleinen Maßstab mit einer Gasfritte zu arbeiten und im Produktionsmaßstab mit einem Blasensäulenreaktor. Another advantage of the higher reaction temperature is evident in the reaction of higher molecular weight epoxysiloxanes. The viscosity of the starting compounds is reduced at higher temperatures, which facilitates the mixing and the mass transfer and thus also causes a rapid reaction. Since in the pressureless process, the higher reaction temperature also causes a faster outgassing of ammonia, it may be advantageous to work on a small scale with a gas frit and on a production scale with a bubble column reactor.
Wird die Reaktion drucklos durchgeführt, so ist eine Mindesttemperatur von 50°C, bevorzugt von 60°C, erforderlich für eine zügige Reaktion mit akzeptabler Selektivität. Für die drucklose Reaktionsführung kann es vorteilhaft sein die Epoxyringöffnung mittels geeigneter Katalysatoren zu beschleunigen. Es können heterogene oder homogene Katalysatoren aus dem Bereich der Säuren, Lewis-Säuren oder Basen sowie auch Metallsalze oder -komplexe, bzw. Übergangsmetallsalze oder -komplexe eingesetzt werden.
Die Reaktion kann im Eintopfverfahren oder auch kontinuierlich durchgeführt werden. Nach beendeter Reaktion wird das Produkt destilliert, um restlichen Ammoniak und gegebenenfalls auch das verwendete Lösungsmittel zu entfernen. Eine pH-Wert- Einstellung kann mittels fester oder gelöster Puffersysteme erfolgen. Sofern eine pH- Wert-Einstellung mit festen Salzen vorgenommen wird, folgt i m An sch l uss ei n F i ltration ssch ritt. I m Fa l l von a uftreten d en P rod u kttrü bu n gen m u ss n i cht notwendigerweise eine Filtration erfolgen. If the reaction is carried out without pressure, then a minimum temperature of 50 ° C, preferably of 60 ° C, required for a rapid reaction with acceptable selectivity. For the pressureless reaction, it may be advantageous to accelerate the epoxy ring opening by means of suitable catalysts. It is possible to use heterogeneous or homogeneous catalysts from the range of acids, Lewis acids or bases as well as metal salts or complexes, or transition metal salts or complexes. The reaction can be carried out in a one-pot process or else continuously. After completion of the reaction, the product is distilled to remove residual ammonia and optionally also the solvent used. A pH adjustment can be carried out by means of solid or dissolved buffer systems. If a pH value adjustment with solid salts is carried out, this is followed by a fi ltration step. It is not necessary to carry out a filtration in the case of the starting of the roducts.
Ammoniak kann als Reagens nicht nur molekular gasförmig oder in Form einer gesättigten Lösung eingesetzt werden, sondern kann auch in chemisch gebundener Form eingesetzt werden. So können beispielsweise neben gasförmigem Ammoniak oder wässrigen oder alkoholischen Ammoniak-Lösungen auch Amin und/oder Ammoniumverbindungen verwendet werden, die bei höheren Temperaturen unter Zersetzung od er a u ch bei H yd rol yse i n Lös u n g Ammoniak freisetzen, wie beispielsweise Ammoniumhalogenide, Ammoniumcarbonat und/oder -hydrogencar- bonat, Ammoniumsulfat und/oder -hydrogensulfat, Ammoniumsulfamat, Ammoniumphosphat, -hyd roge n ph os ph at u n d/oder -dihydrogenphosphat, Ammoniumcyanat, Ammoniumcarboxylate wie beispielsweise Ammoniumacetat, Ammoniumhydrogenoxalat und/oder -oxalat, Ammoniumhydrogencitrat, Ammonium- benzoat, Ammoniumformiat, Ammoniumcarbamat, Ammoniumlactat, Ammoniumtartrat oder Ammoniumsuccinat. Weiterhin kann Ammoniak aus Hydroxylamin, Hydroxylamin- O-sulfonsäure oder Amidosulfonsäure oder Urotropin (Hexamethylentetramin) durch Zersetzung unter den gewählten Reaktionsbedingungen in situ generiert werden. Je nach verwendeter Amin- oder Ammoniumverbindung können durch Folgereaktionen an der gebildeten Aminfunktion Carbonsäureamide oder Carbamate entstehen und/oder an der gebildeten Hydroxylfunktion Carbonsäureester bzw. entsprechende Schwefelsäureester oder Phosphorsäureester. Ammonia can be used as a reagent not only molecular gaseous or in the form of a saturated solution, but can also be used in chemically bound form. For example, in addition to gaseous ammonia or aqueous or alcoholic ammonia solutions, it is also possible to use amine and / or ammonium compounds which liberate ammonia at elevated temperatures with decomposition or else in ammonia in solution, for example ammonium halides, ammonium carbonate and / or or -hydrogencarbonate, ammonium sulfate and / or hydrogen sulfate, ammonium sulfamate, ammonium phosphate, hydrogen peroxide and / or dihydrogen phosphate, ammonium cyanate, ammonium carboxylates such as ammonium acetate, ammonium hydrogen oxalate and / or oxalate, ammonium hydrogen citrate, ammonium benzoate , Ammonium formate, ammonium carbamate, ammonium lactate, ammonium tartrate or ammonium succinate. Furthermore, ammonia can be generated in situ from hydroxylamine, hydroxylamine-O-sulfonic acid or amidosulfonic acid or urotropin (hexamethylenetetramine) by decomposition under the chosen reaction conditions. Depending on the amine or ammonium compound used, carboxylic acid amides or carbamates can be formed by subsequent reactions on the amine function formed and / or carboxylic acid esters or corresponding sulfuric acid esters or phosphoric acid esters on the hydroxyl function formed.
Ausführungsbeispiele: EXAMPLES
I n den nachfolgend aufgeführten Beispielen wird die vorliegende Erfindung zur Verdeutlichung der Erfindung beschrieben, ohne dass d ie Erfi n d u ng , deren Anwendungsbreite sich aus der gesamten Beschreibung und den Ansprüchen ergibt, auf die in den Beispielen genannten Ausführungsformen beschränkt sein soll. Sind nachfolgend Bereiche, allgemeine Formeln oder Verbindungsklassen angegeben, so sollen diese nicht nur die entsprechenden Bereiche oder Gruppen von Verbindungen umfassen, die explizit erwähnt sind, sondern auch alle Teilbereiche und Teilgruppen
von Verbindungen, die durch Herausnahme von einzelnen Werten (Bereichen) oder Verbindungen erhalten werden können. Werden im Rahmen der vorliegenden Beschreibung Dokumente zitiert, so soll deren Inhalt vollständig zum Offenbarungsgehalt der vorliegenden Erfindung gehören. Werden im Rahmen der vorliegenden Erfindung Verbindungen , wie z.B. organomodifizierte Polysiloxane, beschrieben, die verschiedene Monomereinheiten mehrfach aufweisen können, so können diese statistisch verteilt (statistisches Oligomer) oder geordnet (Blockoligomer) in diesen Verbindungen vorkommen. Angaben zu Anzahl von Einheiten in solchen Verbindungen sind als statistische Mittelwerte, gemittelt über alle entsprechenden Verbindungen, zu verstehen. In the examples given below, the present invention is described to illustrate the invention, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples. If sections, general formulas or compound classes are given below, these should not only include the corresponding regions or groups of compounds that are explicitly mentioned, but also all subregions and subgroups of connections that can be obtained by removing individual values (ranges) or connections. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention. If, in the context of the present invention, compounds, such as, for example, organomodified polysiloxanes, which may have multiple monomer units in multiple, may be randomly distributed (random oligomer) or ordered (block oligomer) in these compounds. Information on the number of units in such compounds is to be understood as statistical averages, averaged over all corresponding compounds.
Beispiel 1 (erfindungsgemäß) Example 1 (according to the invention)
In einem 500-ml-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler und Innenthermometer werden 83,7 g eines Allylpolyethylenglykols mit einem mittleren Molekulargewicht von 409 g/mol mit 7,21 g Allylglycidylether (>99% Reinheit, Sigma Aldrich) und 1 59, 1 g eines Poly(methylhydrogen)dimethylsiloxan-Copolymeren mit einem Wasserstoffanteil von 1 ,27 val/kg unter Rühren auf 50° C erhitzt. 5 ppm Platin in Form eines gemäß EP 1520870 modifizierten Platin(0)-Katalysators werden mit einer S pritze h i nzu gegeben u n d d ie Rea ktionstem peratu r auf 70° C erhöht. Der gasvolumetrisch bestimmte Umsatz ist nach 2 Stunden quantitativ. Nach Destillation am Rotationsverdampfer bei 10 bis 20 mbar und 140°C erhält man ein klares, flüssiges Produkt mit einem Epoxid-Gehalt von 0,32 Gew.-% Epoxid-Sauerstoff. In a 500 ml four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer, 83.7 g of an allyl polyethylene glycol having an average molecular weight of 409 g / mol with 7.21 g of allyl glycidyl ether (> 99% pure, Sigma Aldrich) and 1 59 , 1 g of a poly (methylhydrogen) dimethylsiloxane copolymer with a hydrogen content of 1.27 val / kg with stirring to 50 ° C heated. 5 ppm of platinum in the form of a platinum (0) catalyst modified according to EP 1520870 are added with a syringe and the reaction temperature is raised to 70 ° C. The gas volumetrically determined conversion is quantitative after 2 hours. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, liquid product having an epoxide content of 0.32 wt .-% epoxy-oxygen.
In einem 500-ml-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler mit Blasenzähler und Innenthermometer werden in eine Lösung aus 100 g Ethanol und 1 ,0 g 1 -Methylimidazol (99%, Sigma Aldrich) Ammoniak eingeleitet und bei 50°C unter Rühren über einen Tropftrichter 100 g des epoxyfunktionellen Polyethersiloxans über einen Zeitraum von 1 ,5 Stunden zugetropft. Nach beendeter Zudosage wird weitere 4 Stunden bei 50°C Ammoniak eingeleitet. Nach Destillation am Rotationsverdampfer bei 70°C und 1 0 bis 20 mbar erhält man ein gel bes , flüssiges Prod ukt mit einem Amingehalt von 0,2 Gew.-% primären Aminstickstoffs (theor. 0,27%, 74% Ausbeute), <0,01 Gew.-% sekundären Aminstickstoffs und 0,14 Gew.-% tertiären Aminstickstoffs (theor. 0,16 Gew.-% aus Methylimidazol). In a 500 ml four-necked flask with attached KPG stirrer, reflux condenser with bubble counter and internal thermometer ammonia are introduced into a solution of 100 g of ethanol and 1, 0 g of 1-methylimidazole (99%, Sigma Aldrich) and stirred at 50 ° C. About a dropping funnel 100 g of the epoxy-functional polyether siloxane added dropwise over a period of 1, 5 hours. After completion of the addition of ammonia is introduced at 50 ° C for a further 4 hours. After distillation on a rotary evaporator at 70 ° C. and from 10 to 20 mbar, a gel bes, liquid product with an amine content of 0.2 wt .-% of primary amine nitrogen (theor., 0.27%, 74% yield), < 0.01% by weight of secondary amine nitrogen and 0.14% by weight of tertiary amine nitrogen (theor. 0.16% by weight of methylimidazole).
Beispiel 2 (erfindungsgemäß) Example 2 (according to the invention)
In einem 500-ml-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler und Innenthermometer werden 97,5 g 1 -Hexadecen (Reinheit 93%, Chevron Philipps Chemical Company) mit 25,5 g Allylglycidylether (>99% Reinheit, Sigma Aldrich) und
150,0 g eines Poly(methylhydrogen)dimethylsiloxan-Copolymeren mit einem Wasserstoffanteil von 3,51 val/kg unter Rühren auf 70 C erhitzt. 5 ppm Platin in Form eines gemäß EP 1520870 modifizierten Platin(0)-Katalysators werden mit einer Spritze hinzugegeben und bei 70°C gerührt. Der gasvolumetrisch bestimmte Umsatz beträgt nach 4,5 Stunden 80%. Es werden weitere 5 ppm Platinkatalysator zugegeben, bis nach 10,5 Stunden 99,5% Umsatz erreicht sind. Nach Destillation am Rotationsverdampfer bei 10 bis 20 mbar und 140°C erhält man ein klares, flüssiges Produkt mit einem Epoxid-Gehalt von 1 ,12 Gew.-% Epoxid-Sauerstoff. In a 500 ml four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer, 97.5 g of 1-hexadecene (purity 93%, Chevron Philipps Chemical Company) with 25.5 g of allyl glycidyl ether (> 99% pure, Sigma Aldrich) and 150.0 g of a poly (methylhydrogen) dimethylsiloxane copolymer with a hydrogen content of 3.51 eq / kg with stirring to 70 C heated. 5 ppm of platinum in the form of a modified according to EP 1520870 platinum (0) catalyst are added with a syringe and stirred at 70 ° C. The gas volumetrically determined conversion is 80% after 4.5 hours. A further 5 ppm of platinum catalyst are added until 99.5% conversion is achieved after 10.5 hours. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, liquid product having an epoxide content of 1, 12 wt .-% epoxy-oxygen.
In einem 330-ml-Stahlautoklaven mit Magnetrührfisch und Manometer werden 100 g des Epoxysiloxans in 200 g 2-Propanol gelöst. Mittels eines Trockeneis/Ethanol- Kältebads, wird der Autoklav samt Inhalt bis auf -70°C gekühlt und die Lösung mit Ammoniak durch 30-minütiges Einleiten gesättigt. Der Autoklav wird verschlossen und unter Rühren auf 120°C (externe Ölbadtemperatur) geheizt, wobei der Druck auf bis zu 10 bar ansteigt. Nach 4 Stunden Reaktionszeit wird der Autoklav belüftet und das Lösu ngsm ittel am Rotationsverdam pfer bei 80 bis 90° C u nd 1 0 bis 20 m bar abdestilliert. Man erhält ein klares, gelbliches Produkt mit einem Amingehalt von 0,79 Gew.-% primären Aminstickstoffs (theor. 0,97%, 81 % Ausbeute), <0,01 Gew.-% sekundären Aminstickstoffs und <= 0,01 Gew.-% tertiären Aminstickstoffs. Beispiel 3 (erfindungsgemäß) In a 330 ml steel autoclave with magnetic stirring bar and pressure gauge, 100 g of the epoxysiloxane are dissolved in 200 g of 2-propanol. By means of a dry ice / ethanol cold bath, the autoclave and its contents are cooled down to -70 ° C and the solution is saturated with ammonia by introducing 30 minutes. The autoclave is closed and heated with stirring to 120 ° C (external oil bath temperature), the pressure rises to up to 10 bar. After a reaction time of 4 hours, the autoclave is vented and the solvent is distilled off on a rotary evaporator at 80 ° to 90 ° C. and from 10 to 20 mbar. A clear, yellowish product having an amine content of 0.79% by weight of primary amine nitrogen (theoretical 0.97%, 81% yield), <0.01% by weight of secondary amine nitrogen and <= 0.01% by weight is obtained .-% tertiary amine nitrogen. Example 3 (according to the invention)
In einem 2L-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler und Innenthermometer werden 243,2 g eines an der terminalen Hydroxygruppe durch Acetylierung endverkappten Allylpolyoxyalkylenglykols mit einem mittleren Molekulargewicht von 874 g/mol und einer gewichtsanteiligen Zusammensetzung von 80% Propylenoxid u nd 20% Ethylen oxid , 759 ,4 g e i n e s a n d e r t e r minalen Hydroxygruppe durch Acetylierung endverkappten Allylpolyoxyalkylenglykols mit einem m ittl eren Molekulargewicht von 4094 g/mol und einer gewichtsanteiligen Zusammensetzung von 58% Propylenoxid und 42% Ethylenoxid, 49,0 g Allylglycidylether (>99% Reinheit, Sigma Aldrich) und 300,0 g eines Poly(methyl- hydrogen)dimethylsiloxan-Copolymeren mit einem Wasserstoffanteil von 2,29 val/kg unter Rühren auf 50 C erhitzt. 5 ppm Platin in Form eines gemäß EP 1520870 modifizierten Platin(0)-Katalysators werden mit einer Spritze hinzugegeben und bei 70°C gerührt. Der gasvolumetrisch bestimmte Umsatz beträgt nach 2,5 Stunden 100%. Nach Destillation am Rotationsverdampfer bei 10 bis 20 mbar und 140°C erhält man ein klares, flüssiges Produkt mit einer Viskosität von 2555 mPa*s bei 25°C und einem Epoxid-Gehalt von 0,44 Gew.-% Epoxid-Sauerstoff.
In einem 330-ml-Stahlautoklaven mit Begasungsrührer und Manometer werden 100 g des polyether- und epoxyfunktionellen Siloxans in 200 g 2-Propanol gelöst. Mittels eines Trockeneis/Ethanol-Kältebads, wird der Autoklav samt Inhalt bis auf -70°C gekühlt und die Lösung mit Ammoniak durch 30-minütiges Einleiten gesättigt. Der Autoklav wird verschlossen und unter Rühren auf 80°C (externe Ölbadtemperatur) geheizt, wobei der Druck auf bis auf 16 bar ansteigt. Nach 4 Stunden Reaktionszeit bei 80°C wird der Autoklav belüftet und das Lösungsmittel am Rotationsverdampfer bei 70°C und 10 bis 20 mbar abdestilliert. Man erhält ein leicht trübes, gelbliches Produkt mit einer Viskosität von 3309 mPa*s bei 25°C und einem Amingehalt von 0,34 Gew.-% primären Aminstickstoffs (theor. 0,38%, 90% Ausbeute), <0,01 Gew.-% sekundären Aminstickstoffs und <= 0,01 Gew.-% tertiären Aminstickstoffs. In a 2L four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer are 243.2 g of an endblocked at the terminal hydroxy group by acetylation Allylpolyoxyalkylenglykols having an average molecular weight of 874 g / mol and a weight composition of 80% propylene oxide and 20% ethylene oxide, 759, 4 g of a saturated hydroxyl group by acetylation of end-capped allylpolyoxyalkylene glycol having an average molecular weight of 4094 g / mol and a composition by weight of 58% of propylene oxide and 42% of ethylene oxide, 49.0 g of allylglycidyl ether (> 99% purity, Sigma Aldrich) and 300.0 g of a poly (methyl hydrogen) dimethylsiloxane copolymer with a hydrogen content of 2.29 eq / kg heated to 50 C with stirring. 5 ppm of platinum in the form of a modified according to EP 1520870 platinum (0) catalyst are added with a syringe and stirred at 70 ° C. The gas volumetric sales determined after 2.5 hours 100%. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, liquid product having a viscosity of 2555 mPa * s at 25 ° C and an epoxide content of 0.44 wt .-% epoxy-oxygen. In a 330 ml steel autoclave with gassing stirrer and pressure gauge, 100 g of the polyether- and epoxy-functional siloxane are dissolved in 200 g of 2-propanol. By means of a dry ice / ethanol cold bath, the autoclave and its contents are cooled to -70 ° C and the solution is saturated with ammonia by introducing 30 minutes. The autoclave is closed and heated with stirring to 80 ° C (external oil bath temperature), wherein the pressure rises to 16 bar. After 4 hours of reaction time at 80 ° C, the autoclave is vented and the solvent distilled off on a rotary evaporator at 70 ° C and 10 to 20 mbar. A slightly cloudy, yellowish product having a viscosity of 3309 mPa * s at 25 ° C. and an amine content of 0.34% by weight of primary amine nitrogen (theoretical 0.38%, 90% yield), <0.01 is obtained % By weight of secondary amine nitrogen and <= 0.01% by weight of tertiary amine nitrogen.
Beispiel 4 (erfindungsgemäß) Example 4 (according to the invention)
In einem 2L-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler und Innenthermometer werden 227,6 g eines Allylpolyoxyalkylenglykolmethylethers mit einem mittleren Molekulargewicht von 818 g/mol und einer gewichtsanteiligen Zusammensetzung von 80% Propylenoxid und 20% Ethylenoxid, 713,4 g eines eines Allylpolyoxyalkylenglykolmethylethers mit einem mittleren Molekulargewicht von 3846 g/mol und einer gewichtsanteiligen Zusammensetzung von 58% Propylenoxid und 42% Ethylenoxid, 49,0 g Allylglycidylether (>99% Reinheit, Sigma Aldrich) und 300,0 g eines Poly(methylhydrogen)dimethylsiloxan-Copolymeren mit einem Wasserstoffanteil von 2,29 val/kg unter Rühren auf 50 C erhitzt. 5 ppm Platin in Form eines gemäß EP 1520870 modifizierten Platin(0)-Katalysators werden mit einer Spritze hinzugegeben und bei 70°C gerührt. Der gasvolumetrisch bestimmte Umsatz beträgt nach 2,5 Stunden 100%. Nach Destillation am Rotationsverdampfer bei 10 bis 20 mbar und 140°C erhält man ein klares, flüssiges Produkt mit einer Viskosität von 2954 mPa*s bei 25°C und einem Epoxid-Gehalt von 0,42 Gew.-% Epoxid-Sauerstoff. In a 2L four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer are 227.6 g of a Allylpolyoxyalkylenglykolmethylethers having an average molecular weight of 818 g / mol and a weight composition of 80% propylene oxide and 20% ethylene oxide, 713.4 g of a Allylpolyoxyalkylenglykolmethylethers with an average molecular weight of 3846 g / mol and a composition by weight of 58% propylene oxide and 42% ethylene oxide, 49.0 g allyl glycidyl ether (> 99% purity, Sigma Aldrich) and 300.0 g of a poly (methylhydrogen) dimethylsiloxane copolymer with a hydrogen content of 2.29 eq / kg heated to 50 C with stirring. 5 ppm of platinum in the form of a modified according to EP 1520870 platinum (0) catalyst are added with a syringe and stirred at 70 ° C. The gas volumetric sales determined after 2.5 hours 100%. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, liquid product having a viscosity of 2954 mPa * s at 25 ° C and an epoxide content of 0.42 wt .-% epoxide oxygen.
In einem 330-ml-Stahlautoklaven mit Begasungsrührer und Manometer werden 100 g des polyether- und epoxyfunktionellen Siloxans in 200 g 2-Propanol gelöst. Mittels eines Trockeneis/Ethanol-Kältebads, wird der Autoklav samt Inhalt bis auf -70°C gekühlt und die Lösung mit Ammoniak durch 30-minütiges Einleiten gesättigt. Der Autoklav wird verschlossen und unter Rühren auf 80°C (externe Ölbadtemperatur) geheizt, wobei der Druck auf bis auf 10 bar ansteigt. Nach 6 Stunden Reaktionszeit bei 80°C wird der Autoklav belüftet und das Lösungsmittel am Rotationsverdampfer bei 70°C und 10 bis 20 mbar abdestilliert. Man erhält ein leicht trübes, gelbliches Produkt mit einer Viskosität von 3209 mPa*s bei 25°C und einem Amingehalt von 0,35 Gew.-%
primären Aminstickstoffs (theor. 0,36%, 97% Ausbeute), <0,01 Gew.-% sekundären Aminstickstoffs und <= 0,01 Gew.-% tertiären Aminstickstoffs. In a 330 ml steel autoclave with gassing stirrer and pressure gauge, 100 g of the polyether- and epoxy-functional siloxane are dissolved in 200 g of 2-propanol. By means of a dry ice / ethanol cold bath, the autoclave and its contents are cooled to -70 ° C and the solution is saturated with ammonia by introducing 30 minutes. The autoclave is closed and heated with stirring to 80 ° C (external oil bath temperature), wherein the pressure rises up to 10 bar. After 6 hours of reaction time at 80 ° C, the autoclave is vented and the solvent distilled off on a rotary evaporator at 70 ° C and 10 to 20 mbar. A slightly cloudy, yellowish product having a viscosity of 3209 mPa * s at 25 ° C. and an amine content of 0.35% by weight is obtained. primary amine nitrogen (theor. 0.36%, 97% yield), <0.01% by weight of secondary amine nitrogen and <= 0.01% by weight of tertiary amine nitrogen.
Beispiel 5 (erfindungsgemäß) Example 5 (according to the invention)
In einem 330-ml-Stahlautoklaven mit Begasungsrührer und Manometer werden 100 g e i n es Poly(methyl(2-cyclohexenyloxid)ethyl)dimethylsiloxan-Copolymeren mit einer Viskosität von 160 mPa*s bei 25°C und einem Epoxid-Gehalt von 1 ,9 Gew% Epoxid- Sauerstoff in 200 g 2-Propanol gelöst. Mittels eines Trockeneis/Ethanol-Kältebads, wird der Autoklav samt Inhalt bis auf -70°C gekühlt und die Lösung mit Ammoniak durch 30- minütiges Einleiten gesättigt. Der Autoklav wird verschlossen und unter Rühren auf 80°C (externe Ölbadtemperatur) geheizt, wobei der Druck auf bis auf 10 bar ansteigt. Nach 6 Stunden Reaktionszeit bei 80°C wird der Autoklav belüftet und das Lösungsmittel am Rotationsverdampfer bei 70°C und 10 bis 20 mbar abdestilliert. Man erhält ein leicht trübes, gelbliches Produkt mit einer Viskosität von 182 mPa*s bei 25°C und einem Amingehalt von 1 ,30 Gew.-% primären Aminstickstoffs (theor. 1 ,63%, 80% Ausbeute), <0,01 Gew.-% sekundären Aminstickstoffs und 0,03 Gew.-% tertiären Aminstickstoffs.
In a 330 ml steel autoclave with gassing stirrer and pressure gauge are 100 gein it poly (methyl (2-cyclohexenyloxide) ethyl) dimethylsiloxane copolymers having a viscosity of 160 mPa * s at 25 ° C and an epoxide content of 1, 9 wt % Epoxy oxygen dissolved in 200 g 2-propanol. By means of a dry ice / ethanol cooling bath, the autoclave and its contents are cooled to -70 ° C and the solution is saturated with ammonia by introducing 30 minutes. The autoclave is closed and heated with stirring to 80 ° C (external oil bath temperature), wherein the pressure rises up to 10 bar. After 6 hours of reaction time at 80 ° C, the autoclave is vented and the solvent distilled off on a rotary evaporator at 70 ° C and 10 to 20 mbar. A slightly cloudy, yellowish product having a viscosity of 182 mPa * s at 25 ° C. and an amine content of 1.30% by weight of primary amine nitrogen (theor. 1, 63%, 80% yield), <0.01 is obtained Wt% secondary amine nitrogen and 0.03 wt% tertiary amine nitrogen.
Beispiel 6 (erfindungsgemäß) Example 6 (according to the invention)
In einem 2L-Vierhalskolben mit angeschlossenem KPG-Rührer, Rückflusskühler und I nnenthermometer werden 1 7,4 g Methyl-10-Undecenoat (96% Reinheit, Sigma Aldrich), 10,0 g Allylglycidylether (>99% Reinheit, Sigma Aldrich) und 200,0 g eines Poly(methylhydrogen)dimethylsiloxan-Copolymeren mit einem Wasserstoffanteil von 0,7 val/kg unter Rühren auf 70 C erhitzt. 5 ppm Platin in Form eines gemäß EP 1520870 modifizierten Platin(0)-Katalysators werden mit einer Spritze hinzugegeben und bei 70°C gerührt. Der gasvolumetrisch bestimmte Umsatz beträgt nach 2,5 Stunden 24,7%. Es werden weitere 5 ppm Pt zugegeben und zwei Stunden weitergerührt, was den Umsatz auf 45,6% erhöht. Weitere 10 ppm Pt werden zugegeben und bei erhöhter Reaktionstemperatur von 100°C weiter gerührt. Nach weiteren zwei Stunden beträgt der Umsatz 80,0% und nach insgesamt 10,5 Stunden 97,1 %. Nach Destillation am Rotationsverdampfer bei 10 bis 20 mbar und 140°C erhält man ein klares, leicht bräunliches, flüssiges Produkt mit einer Viskosität von 189,6 mPa*s bei 25°C und einem Epoxid-Gehalt von 0,49 Gew.-% Epoxid-Sauerstoff. In a 2L four-necked flask with attached KPG stirrer, reflux condenser and internal thermometer are added 1 7.4 g of methyl 10-undecenoate (96% pure, Sigma Aldrich), 10.0 g of allylglycidyl ether (> 99% pure, Sigma Aldrich) and 200.0 g of a poly (methylhydrogen) dimethylsiloxane copolymer with a hydrogen content of 0.7 eq / kg with stirring to 70 C heated. 5 ppm of platinum in the form of a modified according to EP 1520870 platinum (0) catalyst are added with a syringe and stirred at 70 ° C. The gas volumetric sales determined after 2.5 hours 24.7%. A further 5 ppm of Pt are added and stirring is continued for two hours, which increases the conversion to 45.6%. Another 10 ppm Pt are added and stirring at elevated reaction temperature of 100 ° C on. After a further two hours, the conversion is 80.0% and after a total of 10.5 hours 97.1%. After distillation on a rotary evaporator at 10 to 20 mbar and 140 ° C to obtain a clear, slightly brownish, liquid product having a viscosity of 189.6 mPa * s at 25 ° C and an epoxide content of 0.49 wt .-% epoxide oxygen.
In einem 330-ml-Stahlautoklaven mit Begasungsrührer und Manometer werden 100 g des carbonsäureester- und epoxyfunktionellen Siloxans in 200 g 2-Propanol gelöst. Mittels eines Trockeneis/Ethanol-Kältebads, wird der Autoklav samt Inhalt bis auf -70°C gekühlt und die Lösung mit Ammoniak durch 30-minütiges Einleiten gesättigt. Der Autoklav wird verschlossen und unter Rühren auf 80°C (externe Ölbadtemperatur) geheizt, wobei der Druck auf bis auf 8 bar ansteigt. Nach 6 Stunden Reaktionszeit bei 80°C wird der Autoklav belüftet und das Lösungsmittel am Rotationsverdampfer bei 70°C und 10 bis 20 mbar abdestilliert. Man erhält ein leicht trübes, bräunliches Produkt mit einer Viskosität von 227,1 mPa*s bei 25°C und einem Amingehalt von 0,48 Gew.-% primären Aminstickstoffs (theor. 0,43%), <0,01 Gew.-% sekundären Aminstickstoffs und 0,04 Gew.-% tertiären Aminstickstoffs.
In a 330 ml steel autoclave with gassing stirrer and pressure gauge, 100 g of the carboxylic ester and epoxy functional siloxane are dissolved in 200 g of 2-propanol. By means of a dry ice / ethanol cold bath, the autoclave and its contents are cooled to -70 ° C and the solution is saturated with ammonia by introducing 30 minutes. The autoclave is closed and heated with stirring to 80 ° C (external oil bath temperature), the pressure rises to up to 8 bar. After 6 hours of reaction time at 80 ° C, the autoclave is vented and the solvent distilled off on a rotary evaporator at 70 ° C and 10 to 20 mbar. A slightly cloudy, brownish product having a viscosity of 227.1 mPa * s at 25 ° C. and an amine content of 0.48% by weight of primary amine nitrogen (theory 0.43%), <0.01% by weight is obtained. % amine secondary nitrogen and 0.04 wt% tertiary amine nitrogen.
Claims
Patentansprüche: claims:
1 . Aminofunktionelle Siloxane der allgemeinen Formel 1 und deren quaternare Ammoniumderivate 1 . Aminofunctional siloxanes of the general formula 1 and their quaternary ammonium derivatives
MA M'ai M"A2 M'"A3 DB D'M D"B2 D'"B3 TC QD M A M'ai M " A2 M '" A3 D B D M D " B2 D'" B3 T C Q D
(Formel 1 ) wobei (Formula 1) where
a = 0 bis 32; a = 0 to 32;
a1 = 0 bis 10; a1 = 0 to 10;
a2 = 0 bis 32; a2 = 0 to 32;
a3 = 0 bis 10; a3 = 0 to 10;
b = 0 bis 600; b = 0 to 600;
b1 = 0 bis 50; b1 = 0 to 50;
b2 = 0 bis 50; b2 = 0 to 50;
b3 = 0 bis 50; b3 = 0 to 50;
c = 0 bis 20; c = 0 to 20;
d = 0 bis 20; mit der Maßgabe, dass d = 0 to 20; with the proviso that
im Fall von a1 = 2 gilt, dass b1 Φ 0 und/oder b2 Φ 0 und/oder b3 Φ 0 und/oder a2 Φ 0 und/oder a3 + 0 ist, in the case of a1 = 2, it holds that b1 Φ 0 and / or b2 Φ 0 and / or b3 Φ 0 and / or a2 Φ 0 and / or a3 + 0,
R1 unabhängig voneinander gleiche oder verschiedene lineare oder verzweigte Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen, oder auch aromatische Kohlenwasserstoffreste mit 6 bis 30 Kohlenstoffatomen,
R2 unabhängig voneinander gleiche oder verschiedene organische Reste, die eine primäre Aminofunktion tragen, R 1 independently of one another are identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms, or else aromatic hydrocarbon radicals having 6 to 30 carbon atoms, R 2 independently of one another are identical or different organic radicals which carry a primary amino function,
R3 gleiche oder verschiedene Reste aus der Gruppe R 3 identical or different radicals from the group
-CH2-CH2-CH2-0-(CH2-CH20-)x-(CH2-CH(R')0-)y-R" -CH 2 -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x - (CH 2 -CH (R ') 0-) y -R "
-CH2-CH2-0-(CH2-CH20-)x-(CH2-CH(R')0-)y-R" -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x - (CH 2 -CH (R ') O-) y -R "
-CH2-CH2-(0)X-RIV -CH 2 -CH 2 - (0) X -R IV
-CH2-CH2-CH2-0-CH2-CH(OH)-CH2OH -CH 2 -CH 2 -CH 2 -O-CH 2 -CH (OH) -CH 2 OH
oder or
-CH2-CH2-CH2-0-CH2-C(CH2OH)2-CH2-CH3, worin -CH 2 -CH 2 -CH 2 -O-CH 2 -C (CH 2 OH) 2 -CH 2 -CH 3 , wherein
x 0 bis 100, x 0 to 100,
x' 0 oder 1 , x'0 or 1,
y 0 bis 100, y 0 to 100,
R' unabhängig voneinander eine lineare oder substituierte Alkyl- oder Arylgruppe mit 1 bis 12 C-Atomen ist, wobei innerhalb eines Restes R4 und/oder eines Moleküls der Formel 1 untereinander verschiedene Substituenten R' vorliegen können, und R 'independently of one another is a linear or substituted alkyl or aryl group having 1 to 12 C atoms, wherein within a radical R 4 and / or a molecule of the formula 1 different substituents R' can be present among each other, and
R" unabhängig voneinander ein Wasserstoffrest oder eine Alkylgruppe mit 1 bis 4 C-Atomen, eine Gruppe -C(0)-R"' mit R'" = Alkylrest, eine Gruppe - CH2-0-R', eine Alkylarylgruppe, die Gruppe -C(0)NH-R', R "is independently a hydrogen radical or an alkyl group having 1 to 4 C atoms, a group -C (O) -R"'withR'"= alkyl radical, a group - CH 2 -O-R ', an alkylaryl group, the Group -C (0) NH-R ',
RIV ein gegebenenfalls substituierter Kohlenwasserstoffrest mit 1 b i s 50 Kohlenstoffatomen-Atomen ist, R IV is an optionally substituted hydrocarbon radical having 1 to 50 carbon atoms,
R4 unabhängig voneinander gleiche oder verschiedene lineare, cyclische oder verzweigte, gesättigte oder unges ätti g te o d e r a ro m a ti s c h e Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen, die mit den, die Heteroatome O, N, S, P enthaltenden Gruppen oder Halogenatomen substituiert sein können und die bevorzugt keine primären oder sekundären Aminfunktionen enthalten, und R 4 independently of one another denote identical or different linear, cyclic or branched, saturated or unsatured or ataromatic hydrocarbon radicals having 1 to 30 carbon atoms which are substituted by the groups or halogen atoms containing the heteroatoms O, N, S, P and which preferably contain no primary or secondary amine functions, and
R5 unabhängig voneinander gleiche oder verschiedene Reste R1, R2, R3 oder R4 ist. R 5 are independently identical or different radicals R 1 , R 2 , R 3 or R 4 .
Verbindungen nach Anspruch 1 in denen R2 gleich einem Rest ist, der zusätzlich zu Aminofunktion eine Hydroxylgruppe trägt, ausgewählt aus der Gruppe
OH Compounds according to claim 1, in which R 2 is a radical which, in addition to the amino function, carries a hydroxyl group selected from the group OH
I CHpOH I CHpOH
"(CH2)3-0-CH2-C— CH2- -NH2 -(CH2)3-0 -CH2-C— NH2 "(CH2) 3-0-CH2-C- CH2- -NH 2 - (CH 2) 3 -CH 2 -0 -C-NH 2
(1a) (1 b) (1a) (1b)
OH CH2OH i OH CH 2 OH i
-(CH2)m-0-CH2-C— CH2-N H2 ■(CH2)m- 0-CH2-C-NH2 - (CH 2) m -0-CH 2 -C- CH 2 -NH 2 ■ (CH 2) m - 0-CH 2 -C-NH 2
H H H H
(1c) (1d) (1c) (1d)
O O I I II O I I II
-CH2— CH-C-O— R7-CH— CH2-NH2 CH2— CH-C -O— R7-CH I I 1 I I-CH 2 -CH-CO-R 7 -CH-CH 2 -NH 2 CH 2 -CH-C-O-R 7 -CH II 1 II
R 56° OH R6 CH2 R 56 ° OH R 6 CH 2
I I
OH OH
(1 i) (1j) wobei (1 i) (1 j) where
R6 gleiche oder verschiedene Reste aus der Gruppe Wasserstoff oder Alkyl mit 1 bis 6 C-Atomen ist, R 6 is identical or different radicals from the group consisting of hydrogen or alkyl having 1 to 6 C atoms,
R7 gleiche oder versch iedene zweiwertige Koh lenwasserstoffreste, die gegebenenfalls Etherfunktionen enthalten und die gegebenenfalls Polyoxyalkylenreste darstellen, und R 7 are identical or different divalent hydrocarbon radicals which optionally contain ether functions and which optionally represent polyoxyalkylene radicals, and
m eine ganze Zahl von 2 bis 18 m is an integer from 2 to 18
ist. is.
3. Verbindungen gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das aminofunktionelle Siloxane der Formel 1 mit protischen Reaktanden H+A" zu einem ionischen Addukt der Form -NH3 +A" umgesetzt wird, wobei A" einem anorganischen oder organischen Anion entspricht.
3. Compounds according to any one of claims 1 or 2, characterized in that the amino-functional siloxanes of formula 1 with protic reactants H + A " to an ionic adduct of the form -NH 3 + A " is reacted, wherein A " an inorganic or organic Anion corresponds.
4. Verbindungen gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, d a ss d a s a m inofunktionelle Siloxan der Formel 1 durch Alkylierung zu quaternären Ammoniumverbindungen der Formel 2 umgesetzt wird 4. Compounds according to any one of claims 1 or 2, characterized in that d a ss d a s a m inofunctional siloxane of formula 1 is converted by alkylation to quaternary ammonium compounds of formula 2
Ma M""ai M"a2 M'"a3 Db D""bi D"b2 D'"b3 Tc Qd M a M "" ai M " a2 M '" a3 D b D "" b i D " b2 D'" b3 T c Q d
(Formel 2) wobei (Formula 2) where
a, a1 , a2, a3, b, b1 , b2, b3, c und d und die Reste R1, R3, R4 und R5 die in Anspruch 1 genannte Bedeutung haben, a, a1, a2, a3, b, b1, b2, b3, c and d and the radicals R 1 , R 3 , R 4 and R 5 have the meaning given in claim 1,
R8 unabhängig voneinander gleiche oder verschiedene organische Reste die Ammoniumfunktionen tragen R 8 are independently identical or different organic radicals carry the ammonium functions
sind. are.
5. Verbindungen gemäß Anspruch 4, dadurch gekennzeichnet, dass R8 gleiche oder verschiedene Reste ausgewählt aus der Gruppe
5. Compounds according to claim 4, characterized in that R 8 identical or different radicals selected from the group
(CH2)3-0-CH2-
(CH 2 ) 3 -O-CH 2 -
(2a) (2b) (2a) (2b)
OR9 CH2OR OR 9 CH 2 OR
(CH2)m-0-CH2-C— CH2-NR9 (CH2)m-0 -CH2-C-NR (CH 2) m -0-CH 2 -C- CH 2 -NR 9 (CH 2) m -CH 2 -0 -C-NR
rl rl
(2c) (2d) (2c) (2d)
o o o o
II II II II
-CH2— CH-C-O— o R7'--rCuH—— CH2-NRVA- -CH2— CH -C-O— R7-CH"NR9 -CH 2 - CH-CO- o R7 '- rCuH-- CH 2 -NRVA- CH 2 - CH-CO- R 7 -CH " NR 9
I I
R ?6ö O UR9" R° CH2 R? 6ö O UR 9 "R ° CH 2
I „ I "
(2i) (2j) OR9 und (2i) (2j) OR 9 and
R9 unabhängig voneinander gleiche oder verschiedene lineare oder verzweigte Kohlenwasserstoff reste mit 1 bis 30 Kohlenstoffatomen oder aromatische Kohlenwasserstoffreste mit 6 bis 30 Kohlenstoffatomen R 9 are independently identical or different linear or branched hydrocarbon radicals having 1 to 30 carbon atoms or aromatic hydrocarbon radicals having 6 to 30 carbon atoms
sind. are.
6. Verfahren zur Herstellung von selektiv primäre Aminogruppen tragenden Siloxanen, dadurch gekennzeichnet, dass seitständig epoxymodifizierte Siloxane mit gasförmigem, gelöstem oder in situ erzeugtem Ammoniak umgesetzt werden. 6. A process for the preparation of siloxanes selectively carrying primary amino groups, characterized in that partially epoxy-modified siloxanes are reacted with gaseous, dissolved or generated in situ ammonia.
7. Verfahren nach Anspruch 6 zur Herstellung der aminofunktionellen Siloxane der Formeln 1 und/oder 2, dadurch gekennzeichnet, dass 7. The method according to claim 6 for the preparation of the amino-functional siloxanes of the formulas 1 and / or 2, characterized in that
(a) epoxyfunktionelle Verbindungen der Formel 3 (a) epoxy-functional compounds of the formula 3
Ma M'""a1 M"a2 M'"a3 Db D'""bi D"b2 D'"b3 Tc Qd M a M '"" a1 M " a2 M'" a3 D b D '"" b i D " b2 D'" b3 T c Q d
(Formel 3)
wobei (Formula 3) in which
D" = (R3R1 Si 02/2) D "= (R 3 R 1 Si 0 2/2 )
D'" = (R4R1 Si 02/2) D '''= (R 4 R 1 Si 0 2/2 )
T (R5 Si 03/2) T (R 5 Si 0 3/2 )
Q = (Si 04/2), wobei a, a1 , a2, a3, b, b1 , b2, b3, c und d sowie die Reste R1, R3, R4 und R5 dieQ = (Si 0 4/2 ), where a, a1, a2, a3, b, b1, b2, b3, c and d and the radicals R 1 , R 3 , R 4 and R 5 are the
Bedeutung wie unter Anspruch 2 und 5 genannt besitzen Meaning as mentioned in claim 2 and 5 possess
und and
R10 unabhängig voneinander gleiche oder verschiedene organische Epoxy- Reste sind R 10 are independently identical or different organic epoxy radicals
mit With
(b) mit Ammoniak, optional gelöst in einem Lösungsmittel oder optional statt mit Ammoniak mit einer Ammoniumverbindung, die Ammoniak freisetzen kann (b) with ammonia, optionally dissolved in a solvent or optionally instead of ammonia with an ammonium compound capable of releasing ammonia
(c) optional in Anwesenheit eines Ringöffnungskatalysators (c) optionally in the presence of a ring-opening catalyst
(d) optional unter Druck bei einer Mindesttemperatur von 50°C bis 150°C umgesetzt werden. (d) optionally reacted under pressure at a minimum temperature of 50 ° C to 150 ° C.
Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, dass als Verbindungen der Formel 3 solche verwendet werden bei denen R10 unabhängig voneinander gleiche oder verschiedene organische Epoxy-Reste ausgewählt aus der Gruppe
Process according to Claim 7, characterized in that the compounds of the formula 3 used are those in which R 10 independently of one another are identical or different organic epoxy radicals selected from the group
(3a) (3b)
(3a) (3b)
(3d) (3d)
sind. are.
9. Verfahren nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass als Ammoniak liefernde Verbindung gasförmiges Ammoniak oder wässrige oder alkoholische Ammoniak-Lösungen, Ammoniumhalogenide, Ammoniumcarbonat und/oder -hydrogencarbonat, Ammoniumsulfat und/oder -hydrogensulfat, Ammoniumsulfamat, Ammoniumphosphat, -hydrogenphosphat und/oder - dihydrogenphosphat, Ammoniumcyanat, Ammoniumcarboxylate,9. The method according to any one of claims 7 or 8, characterized in that as ammonia-supplying compound gaseous ammonia or aqueous or alcoholic ammonia solutions, ammonium halides, ammonium carbonate and / or bicarbonate, ammonium sulfate and / or hydrogen sulfate, ammonium sulfamate, ammonium phosphate, hydrogen phosphate and / or dihydrogen phosphate, ammonium cyanate, ammonium carboxylates,
Ammoniumacetat, Ammoniumhydrogenoxalat und/oder -Oxalat, Ammoniumhydrogencitrat, Ammoniumbenzoat, Ammoniumformiat, Ammoniumcarbamat, Ammoniumlactat, Ammoniumtartrat oder Ammoniumsuccinat, Hydroxylamin, Hydroxylamin-O-sulfonsäure oder Amidosulfonsäure oder Urotropin oder deren Gemische verwendet werden. Ammonium acetate, ammonium hydrogen oxalate and / or oxalate, ammonium hydrogen citrate, ammonium benzoate, ammonium formate, ammonium carbamate, ammonium lactate, ammonium tartrate or ammonium succinate, hydroxylamine, hydroxylamine-O-sulfonic acid or amidosulfonic acid or urotropin or mixtures thereof.
10. Verfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass gasförmiges Ammoniak drucklos durch die Reaktionsmischung geleitet wird. 10. The method according to any one of claims 7 to 9, characterized in that gaseous ammonia is passed through the reaction mixture without pressure.
11. Verfahren gemäß einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, dass die Reaktion bei Drücken über 1 bar, bevorzugt 2 bis 50 bar, insbesondere bevorzugt 5 bis 20 bar durchgeführt wird. 11. The method according to any one of claims 7 or 8, characterized in that the reaction at pressures above 1 bar, preferably 2 to 50 bar, particularly preferably 5 to 20 bar is performed.
12. Verwendung der aminofunktionellen Siloxane der Formeln 1 oder 2 als Emulgator für kosmetische Zubereitungen, als Compatibilizer für Kunststoffblends, Trennmittel, Hydrophobierungsmittel, Dispergiermittel für Farbpigmente und Füllstoffe, Additive zur Textilausrüstung (Weichmacher), Konditioniermittel für
Haare, Primer für Oberflächenbeschichtung/ Haftvermittler, Additiv für Korrosionsschutzformulierungen, PU-Schaumstabilisator, Entschäumer und/oder als Netzmittel. 12. Use of the amino-functional siloxanes of the formulas 1 or 2 as emulsifier for cosmetic preparations, as Compatibilizer for plastic blends, release agents, water repellents, dispersants for color pigments and fillers, additives for textile finishing (plasticizers), conditioning agents for Hair, primer for surface coating / adhesion promoter, additive for corrosion protection formulations, PU foam stabilizer, defoamer and / or wetting agent.
13. Zubereitungen in Form von Lösungen, Emulsionen, Dispersionen und/oder Gemischen enthaltend die erfindungsgemäßen Verbindung der Formeln 1 oder 2. 13. Preparations in the form of solutions, emulsions, dispersions and / or mixtures containing the compound of the formula 1 or 2 according to the invention.
Diese Zubereitungen können weitere Additive und Zuschlagstoffe enthalten, ausgewählt aus der Gruppe der Füllstoffe, Emulgatoren, Farbstoffe, Pigmente.
These preparations may contain other additives and additives selected from the group of fillers, emulsifiers, dyes, pigments.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102010001531A DE102010001531A1 (en) | 2010-02-03 | 2010-02-03 | Novel organomodified siloxanes with primary amino functions, novel organomodified siloxanes with quaternary ammonium functions and the process for their preparation |
| PCT/EP2010/070855 WO2011095261A1 (en) | 2010-02-03 | 2010-12-29 | Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof |
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| EP2531547A1 true EP2531547A1 (en) | 2012-12-12 |
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| EP10798357A Withdrawn EP2531547A1 (en) | 2010-02-03 | 2010-12-29 | Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof |
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| US (2) | US20120282210A1 (en) |
| EP (1) | EP2531547A1 (en) |
| JP (1) | JP2013518945A (en) |
| CN (1) | CN102741326B (en) |
| BR (1) | BR112012019049A2 (en) |
| CA (1) | CA2788748A1 (en) |
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| DE102009003274A1 (en) | 2009-05-20 | 2010-11-25 | Evonik Goldschmidt Gmbh | Compositions containing polyether-polysiloxane copolymers |
| DE102009034607A1 (en) | 2009-07-24 | 2011-01-27 | Evonik Goldschmidt Gmbh | Novel silicone polyether copolymers and processes for their preparation |
| DE102009028636A1 (en) | 2009-08-19 | 2011-02-24 | Evonik Goldschmidt Gmbh | Novel urethane-containing silylated prepolymers and process for their preparation |
| DE102009028640A1 (en) | 2009-08-19 | 2011-02-24 | Evonik Goldschmidt Gmbh | Curable composition containing urethane-containing silylated polymers and their use in sealants and adhesives, binders and / or surface modifiers |
| DE102010000993A1 (en) * | 2010-01-19 | 2011-07-21 | Evonik Goldschmidt GmbH, 45127 | Novel polysiloxanes with quaternary ammonium groups, process for their preparation and their use in cleansing and conditioning formulations |
| DE102010001350A1 (en) | 2010-01-29 | 2011-08-04 | Evonik Goldschmidt GmbH, 45127 | Novel linear polydimethylsiloxane-polyether copolymers having amino and / or quaternary ammonium groups and their use |
| DE102010001528A1 (en) | 2010-02-03 | 2011-08-04 | Evonik Goldschmidt GmbH, 45127 | New particles and composite particles, their uses and a new process for their preparation from alkoxysilyl-bearing alkoxylation products |
| DE102010002180A1 (en) | 2010-02-22 | 2011-08-25 | Evonik Goldschmidt GmbH, 45127 | Nitrogen-containing silicon-organic graft copolymers |
| DE102010002178A1 (en) | 2010-02-22 | 2011-08-25 | Evonik Goldschmidt GmbH, 45127 | Process for the preparation of amine-amide-functional siloxanes |
| DE102010029723A1 (en) | 2010-06-07 | 2011-12-08 | Evonik Goldschmidt Gmbh | Process for the preparation of organic silicon compounds |
| DE102010031087A1 (en) | 2010-07-08 | 2012-01-12 | Evonik Goldschmidt Gmbh | Novel polyester-modified organopolysiloxanes |
| DE102010062156A1 (en) | 2010-10-25 | 2012-04-26 | Evonik Goldschmidt Gmbh | Polysiloxanes with nitrogen-containing groups |
| DE102011003148A1 (en) | 2011-01-26 | 2012-07-26 | Evonik Goldschmidt Gmbh | Use of silicone polyether block copolymers with high molecular weight non-endcapped polyether radicals as stabilizers for the preparation of low density polyurethane foams |
| DE102011003150A1 (en) | 2011-01-26 | 2012-07-26 | Evonik Goldschmidt Gmbh | Silicone polyether block copolymers with high molecular weight polyether radicals and their use as stabilizers for the production of polyurethane foams |
-
2010
- 2010-02-03 DE DE102010001531A patent/DE102010001531A1/en not_active Withdrawn
- 2010-12-29 JP JP2012551525A patent/JP2013518945A/en active Pending
- 2010-12-29 EP EP10798357A patent/EP2531547A1/en not_active Withdrawn
- 2010-12-29 BR BR112012019049A patent/BR112012019049A2/en not_active IP Right Cessation
- 2010-12-29 US US13/521,351 patent/US20120282210A1/en not_active Abandoned
- 2010-12-29 WO PCT/EP2010/070855 patent/WO2011095261A1/en active Application Filing
- 2010-12-29 CN CN201080062991.6A patent/CN102741326B/en not_active Expired - Fee Related
- 2010-12-29 CA CA2788748A patent/CA2788748A1/en not_active Abandoned
-
2014
- 2014-11-20 US US14/548,724 patent/US9695202B2/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| None * |
| See also references of WO2011095261A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102741326B (en) | 2015-07-15 |
| US20150080593A1 (en) | 2015-03-19 |
| JP2013518945A (en) | 2013-05-23 |
| CN102741326A (en) | 2012-10-17 |
| US20120282210A1 (en) | 2012-11-08 |
| BR112012019049A2 (en) | 2016-09-13 |
| CA2788748A1 (en) | 2011-08-11 |
| US9695202B2 (en) | 2017-07-04 |
| DE102010001531A1 (en) | 2011-08-04 |
| WO2011095261A1 (en) | 2011-08-11 |
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