CN103228615B - 源自天然油复分解的季铵化脂肪胺、酰胺基胺以及它们的衍生物 - Google Patents
源自天然油复分解的季铵化脂肪胺、酰胺基胺以及它们的衍生物 Download PDFInfo
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- CN103228615B CN103228615B CN201180057056.5A CN201180057056A CN103228615B CN 103228615 B CN103228615 B CN 103228615B CN 201180057056 A CN201180057056 A CN 201180057056A CN 103228615 B CN103228615 B CN 103228615B
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- Prior art keywords
- amine
- mixture
- quaternary ammonium
- derivant
- glycine betaine
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- -1 amido amine Chemical class 0.000 title claims abstract description 136
- 241001597008 Nomeidae Species 0.000 title claims abstract description 65
- 150000001412 amines Chemical class 0.000 title abstract description 110
- 239000000203 mixture Substances 0.000 claims abstract description 350
- 229960003237 betaine Drugs 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 63
- 150000002148 esters Chemical class 0.000 claims abstract description 60
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 35
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 34
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 150000007513 acids Chemical class 0.000 claims abstract description 19
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 15
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 13
- 239000000344 soap Substances 0.000 claims abstract description 10
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 57
- 239000006260 foam Substances 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000001118 alkylidene group Chemical group 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 239000003599 detergent Substances 0.000 claims description 13
- 238000009472 formulation Methods 0.000 claims description 12
- 239000005562 Glyphosate Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 10
- 229940097068 glyphosate Drugs 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000004009 herbicide Substances 0.000 claims description 4
- 230000002363 herbicidal effect Effects 0.000 claims description 3
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000002453 shampoo Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 claims 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 claims 1
- SYJXFKPQNSDJLI-HKEUSBCWSA-N neamine Chemical compound N[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](N)C[C@@H]1N SYJXFKPQNSDJLI-HKEUSBCWSA-N 0.000 claims 1
- 230000001629 suppression Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 151
- 150000001336 alkenes Chemical class 0.000 abstract description 50
- 238000005649 metathesis reaction Methods 0.000 abstract description 33
- 238000005686 cross metathesis reaction Methods 0.000 abstract description 28
- 150000001408 amides Chemical class 0.000 abstract description 25
- 230000000474 nursing effect Effects 0.000 abstract description 23
- 150000003626 triacylglycerols Chemical group 0.000 abstract description 20
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 15
- 238000004140 cleaning Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 15
- 239000004744 fabric Substances 0.000 abstract description 13
- 150000003335 secondary amines Chemical class 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000012459 cleaning agent Substances 0.000 abstract description 9
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 137
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 128
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 120
- 229910001868 water Inorganic materials 0.000 description 101
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 93
- 238000012360 testing method Methods 0.000 description 88
- 239000000523 sample Substances 0.000 description 82
- 239000003921 oil Substances 0.000 description 78
- 235000019198 oils Nutrition 0.000 description 77
- 239000000243 solution Substances 0.000 description 77
- 239000011780 sodium chloride Substances 0.000 description 67
- 238000005160 1H NMR spectroscopy Methods 0.000 description 65
- 238000003756 stirring Methods 0.000 description 65
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000007864 aqueous solution Substances 0.000 description 55
- 235000011121 sodium hydroxide Nutrition 0.000 description 51
- 239000013543 active substance Substances 0.000 description 45
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 38
- 239000007787 solid Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 33
- KFYRJJBUHYILSO-YFKPBYRVSA-N (2s)-2-amino-3-dimethylarsanylsulfanyl-3-methylbutanoic acid Chemical compound C[As](C)SC(C)(C)[C@@H](N)C(O)=O KFYRJJBUHYILSO-YFKPBYRVSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 239000003054 catalyst Substances 0.000 description 30
- 239000004094 surface-active agent Substances 0.000 description 29
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical group COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 27
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 25
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 25
- 229940073608 benzyl chloride Drugs 0.000 description 25
- 150000004665 fatty acids Chemical class 0.000 description 24
- 235000014113 dietary fatty acids Nutrition 0.000 description 23
- 239000000194 fatty acid Substances 0.000 description 23
- 229930195729 fatty acid Natural products 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 23
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 22
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 238000002156 mixing Methods 0.000 description 22
- 239000000376 reactant Substances 0.000 description 22
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 21
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 20
- ATACSYDDCNWCLV-UHFFFAOYSA-N 2-chloroacetic acid;sodium Chemical compound [Na].OC(=O)CCl ATACSYDDCNWCLV-UHFFFAOYSA-N 0.000 description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 19
- 229920006395 saturated elastomer Polymers 0.000 description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 239000012141 concentrate Substances 0.000 description 18
- 235000008504 concentrate Nutrition 0.000 description 18
- 150000002333 glycines Chemical class 0.000 description 18
- 239000011630 iodine Substances 0.000 description 18
- 229910052740 iodine Inorganic materials 0.000 description 18
- 150000004702 methyl esters Chemical class 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 17
- 229920000742 Cotton Polymers 0.000 description 16
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 16
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 238000004448 titration Methods 0.000 description 15
- 238000005352 clarification Methods 0.000 description 14
- 125000004185 ester group Chemical group 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- DUWQEMMRMJGHSA-SNAWJCMRSA-N methyl (e)-dodec-9-enoate Chemical compound CC\C=C\CCCCCCCC(=O)OC DUWQEMMRMJGHSA-SNAWJCMRSA-N 0.000 description 12
- 235000010262 sodium metabisulphite Nutrition 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 11
- 150000002191 fatty alcohols Chemical class 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- KHAVLLBUVKBTBG-UHFFFAOYSA-M dec-9-enoate Chemical compound [O-]C(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-M 0.000 description 10
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000010926 purge Methods 0.000 description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 150000005690 diesters Chemical class 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 0 C=C*=CC1=NCCC1 Chemical compound C=C*=CC1=NCCC1 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 7
- 238000005576 amination reaction Methods 0.000 description 7
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- 239000002243 precursor Substances 0.000 description 7
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 6
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 6
- 239000013068 control sample Substances 0.000 description 6
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 6
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- 230000006872 improvement Effects 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
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- 239000002002 slurry Substances 0.000 description 6
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- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 5
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
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- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
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- 239000003446 ligand Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000009960 carding Methods 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000005456 glyceride group Chemical group 0.000 description 4
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- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
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- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 1
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- 229940117986 sulfobetaine Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/69—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a carbon skeleton substituted by nitrogen atoms, not being part of nitro or nitroso groups
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- A—HUMAN NECESSITIES
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Abstract
本发明公开了由脂肪胺生成的季铵、甜菜碱或磺基甜菜碱组合物,其中所述脂肪胺是通过还原复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物与仲胺的酰胺反应产物来制备的。本发明还公开了由脂肪酰胺基胺生成的季铵、甜菜碱或磺基甜菜碱组合物,其中所述酰胺基胺是通过复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物与氨基烷基取代的叔胺反应来制备的。有利地,季铵组合物被磺化或亚硫酸化。一方面,C10-C17单不饱和酸或十八碳烯-1,18-二酸的酯衍生物为低级烷基酯。在其它方面,酯衍生物为通过天然油的自复分解制备的改性的甘油三酯,或天然油与烯烃的交叉复分解制备的不饱和甘油三酯。季铵、甜菜碱和磺基甜菜碱组合物以及它们的磺化或亚硫酸化衍生物对于许多终端应用是有价值的,包括清洁剂、织物处理、头发护理、个人护理(液体清洁产品、护理皂、口腔护理产品)、抗微生物组合物、农业应用和油田应用。
Description
发明领域
本发明涉及源自天然原料,特别是天然油和它们的复分解产物的季铵化脂肪胺、酰胺基胺和衍生物组合物。
发明背景
“脂肪胺”一般具有6个或更多个碳,通常为6-30个碳的非极性链,以及至少一个包含或源自胺例如叔胺的极性末端基团。尽管脂肪胺具有其自身的价值,但是它们通常被采用多种烷基化试剂进行季铵化,得到脂肪胺季铵化合物、甜菜碱、磺基甜菜碱或其它具有广泛应用的季铵化衍生物。
季铵化脂肪胺已经被用在大范围的最终应用中,包括织物软化(参见第5,574,179号和第6,004,913号)、洗发和头发护理(第4,744,977号,第6,322,778号和第7,951,762号)、硬表面清洁剂(第6,268,324号和第6,821,943号美国专利)、化妆品(第6,919,074号和第7,074,395号美国专利)、口腔护理(第7,534,816号美国专利)、抗微生物洗手皂或清洁剂(第6,010,991号美国专利和公开的第2004/0071653号美国专利申请)、油田应用(第7,422,064号和第7,776,798号美国专利)以及农业应用(第2011/0015071号和第2010/0016163号公开的美国专利申请)。
季铵化脂肪胺可以通过将脂肪酯或酸与仲胺一起转化为酰胺衍生物,接着还原羰基来得到末端叔胺,然后将末端叔胺与季铵化试剂反应来制备。在优选的方法中,通过脂肪酯与氨基烷基取代的叔胺反应来避免了还原步骤。例如,N,N-二甲基-1,3-丙二胺(DMAPA)与脂肪甲基酯反应得到脂肪酰胺基胺。酰胺基胺具有容易被季铵化的末端叔胺基团。常见的季铵化试剂为硫酸二甲酯、一氯甲烷、氯苄、环氧乙烷等。
用于制备脂肪胺及其衍生物的脂肪酸或酯通常是由甘油三酯的水解或酯交换制备的,所述甘油三酯通常为动物或植物脂肪。因此,酸或酯的脂肪酸部分通常具有6-22个碳,具有饱和和内部不饱和链的混合。根据来源,脂肪酸或酯的C16至C22组分通常是占优势的。例如,豆油的甲醇分解提供了饱和的棕榈酸(C16)和硬脂酸(C18)的甲酯,和不饱和的油酸(C18单不饱和)、亚油酸(C18双不饱和)和α-亚麻酸(C18三不饱和)的甲酯。在这些酸中的不饱和基仅为或主要为顺式构型。
近来复分解催化剂的改进(参见J.C.Mol,GreenChem.4(2002)5)提供了由富C16至C 22 天然油如豆油或棕榈油来生成链长度降低的单不饱和原料的机会,所述单不饱和原料对于制备洗涤剂和表面活性剂是有价值的。豆油和棕榈油可以比例如椰子油更加经济,所述椰子油是用于制备洗涤剂的传统的起始原料。如Mol教授所说明的,复分解依赖于通过由过渡金属卡宾复合物介导的碳-碳双键的断裂和重整,将烯烃转化为新产物。不饱和脂肪酸酯的自复分解可以提供起始原料、内部不饱和的烃、和不饱和二酯的平衡混合物。例如,油酸甲酯(顺式-9-十八碳烯酸甲酯)部分转化为9-十八碳烯和9-十八碳烯-1,18-二酸二甲酯,两种产物均主要由反式异构体组成。复分解有效地使油酸甲酯的顺式双键异构化以在“未转化的”起始原料和复分解产物中得到顺式和反式异构体的平衡混合物,以反式异构体为主。
不饱和脂肪酸酯与烯烃的交叉复分解生成新的烯烃和具有降低的链长度和可能难以制备的新的不饱和酯。例如,油酸甲酯和3-己烯的交叉复分解提供了3-十二碳烯和9-十二碳烯酸甲酯(也参见第4,545,941号美国专利)。末端烯烃是特别希望的合成目标,并且ElevanceRenewableSciences,Inc.最近描述了通过内烯烃和α-烯烃在钌亚烷基催化剂的存在下的复分解反应制备末端烯烃的改进的方式(参见第2010/0145086号美国专利申请公开)。描述了涉及α-烯烃和不饱和脂肪酸酯(作为内烯烃来源)的各种交叉复分解反应。因此,例如豆油与丙烯反应接着水解得到(其中包括)1-癸烯、2-十一碳烯、9-癸烯酸、和9-十一碳烯酸。尽管具有降低的链长度和/或主要具有反式构型的不饱和基的不饱和脂肪酸酯是可得的(来自天然油和烯烃的交叉复分解),但是由这些原料制备的脂肪胺及其衍生物似乎是未知的。此外,季铵化脂肪胺及其衍生物还没有由C18不饱和二酯制备,所述C18不饱和二酯可以容易地通过天然油的自复分解制备。
总之,用于制备季铵化脂肪胺及其衍生物的脂肪酸和酯的传统来源通常主要(或仅)具有顺式异构体,并且相对缺少短链(例如,C10或C12)不饱和脂肪酸部分。复分解化学提供了生成具有更短的链和主要具有反式异构体的前体的机会,当前体转化为下游组合物(例如,在表面活性剂中)时,可以使其具有改进的性能。新的C18双官能季铵化脂肪胺及其衍生物也可能由天然油或C10不饱和酸或酯的自复分解得到。除了扩展的各种前体外,存在于前体中的不饱和基允许例如通过磺化或亚硫酸化进一步官能化。
发明概述
一方面,本发明涉及由脂肪胺生成的季铵、甜菜碱或磺基甜菜碱组合物,其中脂肪胺由复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物来制备。另一方面,本发明涉及由脂肪酰胺基胺生成的季铵、甜菜碱或磺基甜菜碱组合物,其中酰胺基胺由复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物与氨基烷基取代的叔胺如DMAPA反应来制备。本发明包括通过对季铵化脂肪胺或酰胺基胺进行磺化或亚硫酸化制备的衍生物。一方面,C10-C17单不饱和酸或十八碳烯-1,18-二酸的酯衍生物为低级烷基酯。在其他方面,酯衍生物为通过天然油自复分解制备的改性的甘油三酯、或天然油与烯烃的交叉复分解制备的不饱和甘油三酯。季铵、甜菜碱和磺基甜菜碱组合物以及它们的磺化或亚硫酸化衍生物对于许多终端应用是有价值的,包括清洁剂、织物处理、头发护理、个人护理(液体清洁产品、护理皂、口腔护理产品)、抗微生物组合物、农业应用和油田应用。
发明详述
一方面,本发明涉及由脂肪胺生成的季铵、甜菜碱或磺基甜菜碱组合物。脂肪胺由复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物制备。
用作反应物的C10-C17单不饱和酸、十八碳烯-1,18-二酸、或其酯衍生物来自天然油的复分解。传统地,这些物质,特别是短链酸及衍生物(例如,9-癸烯酸或9-十二碳烯酸)是难以获得的,除了以实验室规模的量获得,并且费用相当高之外。然而,由于最近在复分解催化剂中的发展,这些酸及其酯衍生物目前能够以合理的成本大量得到。因此,C10-C17单不饱和酸和酯通过天然油与烯烃的交叉复分解来便利地生成,所述烯烃优选α-烯烃,特别是乙烯、丙烯、1-丁烯、1-己烯、1-辛烯等。当C18二酸或二酯是希望的产物时,天然油或C10酸或酯前体(例如,9-癸烯酸甲酯)的自复分解以最佳的收率提供C18二酸或二酯。
优选地,至少一部分的C10-C17单不饱和酸具有“Δ9”的不饱和基,即,在C10-C17酸中的碳碳双键在相对于酸羰基的9位上。换言之,在酸羰基和C9和C10处的烯烃基之间优选地有七个碳。对于C11至C17酸而言,1至7个碳的烷基链分别连接于C10。优选地,不饱和基至少为1摩尔%的反式-Δ9,更优选地至少为25摩尔%的反式-Δ9,更优选地至少为50摩尔%的反式-Δ9,甚至更优选地至少为80摩尔%的反式-Δ9。不饱和基可以为大于90摩尔%,大于95摩尔%,或甚至为100%的反式-Δ9。相反地,具有Δ9不饱和基的天然来源的脂肪酸,例如油酸,通常具有~100%的顺式异构体。
虽然高比例的反式几何构形(特别是反式-Δ9的几何构形)在本发明的复分解生成的季铵化组合物中可能是希望的,但技术人员将认识到碳碳双键的构型和确切的位置将取决于反应条件、催化剂选择和其它因素。复分解反应通常伴随着异构化,这可能是希望或不希望的。参见,例如,G.Djigoué和M.Meier,Appl.Catal.A:General346(2009)158,尤其是图3。因此,技术人员可能会改变反应条件来控制异构化的程度或来改变生成的顺式和反式异构体的比例。例如,在灭活的复分解催化剂的存在下加热复分解产物可以使得技术人员诱导双键迁移以得到较低比例的具有反式-Δ9几何构形的产物。
反式异构体含量的比例升高(相对于通常全部为顺式构型的天然单不饱和酸或酯)使由其制备的脂肪胺组合物具有不同的物理性质,所述物理性质包括,例如,改变的物理形态、熔融范围、致密性、和其它重要性质。当配剂师在清洁剂、织物处理、个人护理、农业应用和其它最终用途中使用季铵化铵、甜菜碱或磺基甜菜碱时,这些差异应该允许使用季铵化组合物的制剂师具有更大的范围或扩大的选择。
适合的复分解生成的C10-C17单不饱和酸包括,例如,9-癸烯酸(9-癸烯酸(9-decenoicacid))、9-十一碳烯酸、9-十二碳烯酸(9-十二碳烯酸(9-dodecenoicacid))、9-十三碳烯酸、9-十四碳烯酸、9-十五碳烯酸、9-十六碳烯酸、9-十七碳烯酸等,及其酯衍生物。
通常,在天然油的交叉复分解或自复分解之后,通常通过蒸馏出更易挥发的烯烃来从改性的油流中分离烯烃流。然后将改性的油流与低级醇(通常是甲醇)反应以得到烷基酯的混合物和甘油。所述混合物通常包含饱和C6-C22烷基酯,主要是C16-C18烷基酯,这是在复分解反应中的主要旁观者(spectator)。其余的产物混合物取决于是否使用了交叉或自复分解。当天然油进行自复分解并且随后进行酯交换时,烷基酯混合物将包含C18不饱和二酯。当天然油与α-烯烃交叉复分解并且对产物混合物进行酯交换时,所得到的烷基酯混合物除了甘油副产物以外还包含C10不饱和烷基酯和一种或多种C11至C17不饱和烷基酯副产物。末端不饱和C10产物伴随不同的副产物,取决于使用哪一种(或多种)α-烯烃作为交叉复分解反应物。因此,1-丁烯得到C12不饱和烷基酯,1-己烯得到C14不饱和烷基酯,等等。如在以下的实例中所证明的,C10不饱和烷基酯容易从C11至C17不饱和烷基酯中分离出来,并且每种均容易通过分馏进行纯化。这些烷基酯是用于制备本发明的季铵化脂肪胺或酰胺基胺组合物的极好的起始材料。
适合用作通过自复分解或与烯烃的交叉复分解生成C10-C17单不饱和酸、十八碳烯-1,18-二酸、或它们的酯衍生物的原料的天然油是众所周知的。适合的天然油包括植物油、海藻油、动物脂肪、塔尔油(talloil)、这些油的衍生物及它们的组合。因此,适合的天然油包括,例如,豆油、棕榈油、菜籽油、椰子油、棕榈仁油、葵花油、红花油、芝麻油、玉米油、橄榄油、花生油、棉籽油、芥花籽油、蓖麻油、牛脂、猪油、家禽脂肪、鱼油等。豆油、棕榈油、菜籽油及其混合物是优选的天然油。
也可以使用基因改造的油,例如高油酸酯豆油,或基因改造的海藻油。优选的天然油具有相当程度的不饱和基,因为这向用于生成烯烃的复分解过程提供了反应位点。特别优选的是由油酸生成的具有高含量的不饱和脂肪基团的天然油。因此,特别优选的天然油包括豆油、棕榈油、海藻油和菜籽油。
改性的天然油,如部分氢化的植物油,可以用来代替天然油或与天然油组合。当天然油被部分氢化时,不饱和位点可以迁移到脂肪酸酯部分的烃骨架上的多个位置上。由于这种倾向,当改性的天然油发生自复分解或与烯烃发生交叉复分解时,与由未改性的天然油生成的产物混合物相比,反应产物将具有不同的并且通常更广泛的分布。然而,由改性的天然油生成的产品相似地转化为本发明的季铵化的脂肪胺或酰胺基胺组合物。
使用天然油作为原料,通过自复分解或与烯烃的交叉复分解生成C10-C17单不饱和酸、十八碳烯-1,18-二酸、或它们的酯衍生物的一种供选择的方案是由植物油或动物脂肪的水解得到的单不饱和脂肪酸,或者通过脂肪酸或羧酸盐的酯化,或通过天然油与醇的酯交换得到的这样的酸的酯或盐。作为起始组合物也有用的是多不饱和脂肪酸酯、酸、和羧酸盐。盐可以包括碱金属(例如,Li、Na或K);碱土金属(例如,Mg或Ca);第13-15族金属(例如,B、Al、Sn、Pb或Sb),或过渡金属、镧系金属或锕系金属。其它适合的起始组合物描述于PCT申请WO2008/048522的第7-17页,将其内容引入本文作为参考。
在交叉复分解中的其它反应物是烯烃。适合的烯烃为具有一个或多个碳碳双键的内烯烃或α-烯烃。可以使用烯烃的混合物。优选地,所述烯烃为单不饱和C2-C10α-烯烃,更优选地为单不饱和C2-C8α-烯烃。优选的烯烃也包括C4-C9内烯烃。因此,适合使用的烯烃包括,例如乙烯、丙烯、1-丁烯、顺式和反式2-丁烯、1-戊烯、异己烯、1-己烯、3-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯等,及其混合物。
通过在均质或异质的复分解催化剂的存在下将天然油和烯烃反应来完成交叉复分解。虽然当天然油发生自复分解时省略烯烃,但通常使用相同的催化剂类型。适合的均质复分解催化剂包括过渡金属卤化物或含氧卤化物(例如,WOCl4或WCl6)与烷基化助催化剂(例如,Me4Sn)的组合。优选的均质催化剂是定义明确的过渡金属的烷叉(或卡宾)复合物,所述过渡金属特别是Ru、Mo或W。这些包括第一和第二代的Grubbs催化剂、Grubbs-Hoveyda催化剂等。适合的烷叉催化剂具有一般结构:
M[X1X2L1L2(L3)n]=Cm=C(R1)R2
其中M是第8族过渡金属,L1、L2和L3是中性电子供体配体,n为0(从而L3可能不存在)或1,m为0、1或2,X1和X2是阴离子配体,R1和R2独立地选自H、烃基、取代的烃基、含杂原子的烃基、含杂原子的取代烃基、和官能团。X1、X2、L1、L2、L3、R1和R2中的任意两个或更多个可以形成环状基团,并且这些基团中的任意一个可以连接至支持物上。
第一代Grubbs催化剂属于这一类,其中m=n=0,并且如第2010/0145086号美国专利申请公开(“‘086公开”)所述对n、X1、X2、L1、L2、L3、R1和R2做出特定选择,将其与所有复分解催化剂相关的教导引入本文作为参考。
第二代Grubbs催化剂也具有上述通式,但L1是卡宾配体,其中卡宾碳的两侧为N、O、S或P原子,优选地两侧为两个N原子。通常,卡宾配体是环状基团的一部分。适合的第二代Grubbs催化剂的实例也出现在‘086公开中。
在另一类的适合的烷叉催化剂中,L1是如第一代和第二代Grubbs催化剂中那样的强配位的中性电子供体,而L2和L3是以任选地取代的杂环基团的形式的弱配位的中性电子供体配体。因此,L2和L3是吡啶、嘧啶、吡咯、喹啉、噻吩等。
在又一类的适合的烷叉催化剂中,一对取代基用于形成二齿或三齿配体,如二膦、二烷氧化物(dialkoxide)或烷基二酮。Grubbs-Hoveyda催化剂是这种类型的催化剂的亚组,其中L2和R2相连。通常地,中性氧或氮与金属配位,同时也键合于相对于卡宾碳的α-、β-或γ-碳,以提供二齿配体。适合的Grubbs-Hoveyda催化剂的实例出现在‘086公开中。
以下结构仅提供了可能使用的适合的催化剂的几个示意式:
适用于自复分解或交叉复分解反应的异质催化剂包括某些铼和钼化合物,例如J.C.Mol在GreenChem.4(2002)5的第11-12页所描述的。具体的实例是包括载于氧化铝上的Re2O7的催化剂***,通过烷基化的助催化剂如四烷基锡铅、锗或硅化合物来促进所述催化剂***。其它催化剂包括通过四烷基锡活化的载于二氧化硅的MoCl3或MoCl5。
对于自复分解或交叉复分解的适合的催化剂的其它实例而言,参见第4,545,941号美国专利,将其教导引入本文作为参考,以及参见其引用的参考文献。
用于制备本发明的季铵化组合物的脂肪胺可以通过复分解的到的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物与仲胺反应,接着将得到的脂肪胺还原来制备。它们还可以通过将复分解生成的酸或酯衍生物还原成脂肪醇,接着通过对脂肪醇进行胺化来制备。因此,脂肪胺的中间产物为复分解生成的脂肪醇或脂肪酰胺。
在一个方面中,酯衍生物为低级烷基酯,特别是甲基酯。低级烷基酯优选地通过对复分解生成的甘油三酯进行酯交换来生成。例如,将天然油与烯烃进行交叉复分解,接着通过汽提(strip)除去不饱和烃复分解产物,然后在碱性条件下将改性的油组分与低级烷醇进行酯交换提供了不饱和低级烷基酯的混合物。不饱和的低级烷基酯混合物可以“不经处理地”用于制备脂肪胺的脂肪酰胺前体,或可以在制备脂肪酰胺之前对其进行纯化以分离特定的烷基酯。
在另一个方面中,酯衍生物是在前面的段落中讨论的复分解生成的甘油三酯。与如上所述的复分解生成的甘油三酯与低级烷醇进行酯交换以产生低级烷基酯不同的是,在烯烃汽提之后,复分解生成的甘油三酯直接与氨或者伯胺或仲胺反应以制备脂肪酰胺混合物,然后对所述脂肪酰胺混合物进行还原得到本发明的脂肪胺混合物。供选择地,在烯烃汽提之后,对复分解生成的甘油三酯进行还原得到脂肪醇混合物,然后对所述脂肪醇混合物进行胺化以得到本发明的脂肪胺混合物。
技术人员将理解的是,本文的“酯衍生物”除了上述的低级烷基酯和甘油酯以外包括其它酰基等同物,如酰基氯、酸酐等。
在一种合成方法中,将复分解生成的酸或酯衍生物与氨或者伯胺或仲胺反应以得到脂肪酰胺,接着对所述脂肪酰胺进行还原得到脂肪胺。
适合的仲胺具有氢和两个连接于氮的烃基。烃基优选地为饱和或不饱和的直链、支链或环状C1-C20烷基、C6-C20芳基或C7-C20芳烷基、更优选地,两个烃基均为C1-C6烷基。适合的仲胺包括,例如,N,N-二甲胺、N,N-二乙胺、N,N,-二丙胺、二异丙胺、N,N-二丁胺、N-甲基-N-环己胺、N-甲基-N-苯胺、N-甲基-N-苄胺等,及其混合物。N,N-二甲胺是有成本效益的并且是特别优选的。
适合的仲胺包括醚胺。因此,可以使用的胺为氨或者伯胺与氧化烯的反应产物,所述氧化烯为例如0.1至20摩尔当量的氧化乙烯、氧化丙烯等。胺可以是例如M系列聚醚胺的单烷基化的衍生物(Huntsman的产品)。在使用醚胺的一些实例中,在酰胺形成之前或之后可能需要掩蔽任何羟基官能团以作为合适的衍生物,以便使该酰胺的随后的还原成为可能。
由于酸或酯衍生物的起始混合物是非传统的,因此虽然使用众所周知的工艺来制备脂肪酰胺,但产物混合物仍然是独特的。通常在有效地将起始酸、酯或其它衍生物转化为酰胺的条件下,在催化剂存在或不存在下,对反应物进行加热。反应温度通常为40℃至300℃,优选地为50℃至250℃,更优选地为50℃至200℃。
还原脂肪酰胺以得到末端胺是使用熟知的方法来实现的,所述方法包括与氢化物还原剂(硼烷、氢化铝、硼氢化物等)反应或催化氢化。适合的还原剂包括,例如硼烷、硼烷二甲基硫化物、硼氢化钠/碘、氰基硼氢化锂、氢化铝、氢化铝锂、氢化二异丁基铝等。关于另外的实例,参见R.Larock,ComprehensiveOrganicTransformations:AGuide toFunctionalGroupPreparations(1989),第432-434页和M.Smith和J.March,March’s AdvancedOrganicChemistry,第5版(2001),第1549-1550页。
在一个供选择的合成方法中,脂肪胺是通过首先还原复分解生成的酸或酯衍生物来得到脂肪醇,接着对所述脂肪醇进行胺化来制备的。使用金属氢化物试剂(硼氢化钠、氢化铝锂等)、催化氢化、或其它熟知的用于生成脂肪醇的技术将复分解生成的酸或酯衍生物还原成脂肪醇(参见,例如第2,865,968号、第3,193,586号、第5,124,491号、第6,683,224号和第7,208,643号美国专利,将其教导引入本文作为参考)。然后在胺化催化剂的存在下,通过在单一步骤中将脂肪醇与氨或者伯胺或仲胺反应来优选地进行胺化。合适的胺化催化剂是熟知的。包含铜、镍和/或碱土金属化合物的催化剂是常见的。用于胺化的适合的催化剂和工艺参见第5,696,294号、第4,994,622号、第4,594,455号、第4,409,399号和第3,497,555号美国专利,将其教导并入本文作为参考。
在本发明的一个优选的方面中,脂肪胺为脂肪酰胺基胺,所述脂肪酰胺基胺是通过将复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸、或它们的酯衍生物与氨基烷基取代的叔胺反应制备的。这提供了具有叔胺官能团的产物,而无需使用强还原剂将脂肪酰胺还原成脂肪胺。适合的氨基烷基取代的叔胺在一个末端具有伯氨基,在分子的另一端具有亚烷基和叔胺基。亚烷基优选地为C2-C6直链或支链双游离基如亚乙基、亚丙基、亚丁基等。因此,适合的氨基烷基取代的叔胺包括,例如N,N-二甲基-1,2-乙二胺、N,N-二甲基-1,3-丙二胺(DMAPA)、N,N-二乙基-1,3-丙二胺、N,N-二甲基-1,4-丁二胺等。DMAPA是特别优选的。伯胺基显示出与酸或酯衍生物的良好的反应性,而末端叔胺保留在产物中并提供季铵化的位点。
如与酯或酸反应物反应的仲胺、氨或氨基烷基取代的叔胺的相对量取决于所需的化学计量,并且留给技术人员进行判断。通常,使用足够的仲胺(或氨基烷基取代的叔胺)与大部分或全部的可用的酸或酯基反应,即,优选地高于90%,更优选地高于95%的可用的酸或酯基。
脂肪胺或脂肪酰胺的叔胺基经季铵化得到季铵、甜菜碱或磺基甜菜碱组合物。适合的季铵化方法和试剂是本领域熟知的。常见的试剂包括例如卤代烷(氯代甲烷、溴代甲烷)、硫酸二烷基酯、碳酸酯或磷酸酯(硫酸二甲酯、硫酸二乙酯、碳酸二甲酯)、氯苄、乙酰氯、环氧乙烷等。通常在强碱存在下,通过脂肪胺或酰胺基胺与ω-卤代烷基羧酸或其碱金属盐(例如,一氯乙酸钠或一氯丙酸钾)反应制备甜菜碱。通过将脂肪胺或酰胺基胺与环氧氯丙烷混合,接着采用亚硫酸氢钠进行亚硫酸化可以制备磺基甜菜碱。下文列出了替代步骤,其中环氧氯丙烷首先在氢氧化钠的存在下与亚硫酸氢钠反应,将脂肪胺加入反应混合物,接着通过温热和中和得到磺基甜菜碱。在另一方法中,按照第3,280,179号美国专利通过脂肪胺或酰胺与烷烃磺内酯反应制备磺基甜菜碱。下文还提供了用于采用硫酸二甲酯作为季铵化试剂来制备季铵,用于采用一氯乙酸钠制备甜菜碱的详细步骤。美国专利第3,280,179号、第3,354,213号、第4,743,660号、第4,913,841号、第5,679,150号、第7,449,435号和第7,807,614号记载了其它季铵化反应细节,它们的教导通过引述引入本申请。
一些来自脂肪胺的季铵组合物具有以下通式:
R2(R3)N+(R1)R4X-
其中:
R1为C10H18-R5或C18H34-N+(R2)(R3)R4X-;R2和R3中的每一个独立地为取代或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C1-C6烷基;X-为卤根、碳酸氢根、硫酸氢根或烷基硫酸根;以及R5为氢或C1-C7烷基。优选地,R1为(CH2)8-CH=CHR5或(CH2)8-CH=CH-(CH2)8-N+(R2)(R3)R4X-。
一些甜菜碱或磺基甜菜碱组合物具有以下通式:
R2(R3)N+(R1)R4
其中:
R1为C10H18-R5或C18H34-N+(R2)(R3)R4;R2和R3中的每一个独立地为取代或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C2-C4亚烷基羧酸根、C2-C4亚烷基磺酸根或C2-C4羟基亚烷基磺酸根;以及R5为氢或C1-C7烷基。优选地,R1为-(CH2)8-CH=CHR5或(CH2)8-CH=CH-(CH2)8-N+(R2)(R3)R4。
一些源自脂肪酰胺基胺的季铵组合物具有以下通式:
R4(R3)(R2)N+(CH2)nNH(CO)R1X-
其中:R1为C9H16-R5或C16H30-(CO)NH(CH2)nN+(R2)(R3)R4X-;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C1-C6烷基;X-为卤根、碳酸氢根、硫酸氢根或烷基硫酸根;R5为氢或C1-C7烷基;以及n=2至8。优选地,R1为(CH2)7-CH=CH-R5或-(CH2)7-CH=CH-(CH2)7-(CO)NH(CH2)nN+(R2)(R3)R4X-。
一些酰胺基胺甜菜碱或磺基甜菜碱组合物具有以下通式:
R4(R3)(R2)N+(CH2)nNH(CO)R1
其中:
R1为C9H16-R5或-C16H30-(CO)NH(CH2)nN+(R2)(R3)R4;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C2-C4亚烷基羧酸根、C2-C4亚烷基磺酸根或C2-C4羟基亚烷基磺酸根;以及R5为氢或C1-C7烷基;以及n=2至8。优选地,R1为(CH2)7-CH=CH-R5或-(CH2)7-CH=CH-(CH2)7-(CO)NH(CH2)nN+(R2)(R3)R4。
关于化学结构的一般注释:
就如技术人员将会认识到的,根据本发明制备的产物通常是顺式和反式异构体的混合物。除非另有说明,本文所提供的所有结构图示仅显示反式异构体。技术人员将理解的是,仅为了方便而使用该约定,并且除非上下文另有规定,应理解为顺式和反式异构体的混合物。(例如,产物的“C18-”系列在以下实例中为标称100%的反式异构体,而“混合-”系列为标称80:20的反式/顺式异构体混合物。)显示的结构通常是指主要产物,该主要产物可能伴随较少比例的其它组分或位置异构体。例如,来自改性的甘油三酯的反应产物为复杂的混合物。作为另一个实例,磺化或亚硫酸化过程除了异构化的产物之外,通常得到磺内酯、烷基磺酸酯和烯基磺酸酯的混合物。因此,提供的结构表示可能的或主要的产物。电荷可能显示或不显示但要被理解,例如在氧化胺结构的情况下。平衡离子(Counterion),如在季铵化的组合物中的平衡离子通常不包括在内,但是技术人员根据上下文可以理解。
基于C10、C12、C14和C16的季铵化脂肪胺和脂肪酰胺的具体实例显示如下:
基于C18的季铵化脂肪胺和脂肪酰胺基胺的一些具体实例:
当与仲胺或氨基烷基取代的叔胺反应的酯衍生物为通过天然油的自复分解且分离除去烯烃而制备的改性甘油三酯(参见,例如下述的MTG和PMTG产物),或者通过天然油与烯烃的交叉复分解且分离除去烯烃(而制备的不饱和甘油三酯参见,例如下述的UTG和PUTG产物)时,季铵化脂肪胺或脂肪酰胺产物混合物是复杂的。正如由反应过程清晰可见的,来自DMAPA的季铵化的MTG和PMTG产物包括不饱和的C18季铵化的二酰胺基胺为主要组分,而UTG和PUTG产物包括C10不饱和的季铵化的酰胺基胺和一种或多种C11至C17不饱和的季铵化的酰胺基胺组分。(例如,如图所示,以1-丁烯作为交叉复分解反应物,得到C12不饱和酰胺基胺组分。)产物混合物的其它组分为甘油和饱和或不饱和的季铵化的DMAPA酰胺。除了复杂性之外,纯化以分离特定的物质通常是不经济的也不能期望具有好的性能。
因此,一方面,脂肪酰胺基胺被季铵化。通过氨基烷基取代的叔胺与天然油自复分解制备的改性甘油三酯反应生成脂肪酰胺基胺。天然油的自复分解生成烯烃和改性的甘油三酯的混合物,所述混合物富含C18不饱和二酯组分以及C16-C18饱和二酯。通常采用热和减压将烯烃汽提出来。当改性的甘油三酯直接与DMAPA反应时,形成复杂的混合物,其中DMAPA的伯氨基完全或部分替代了甘油中的甘油酯形成酰胺基胺官能团。通过DMAPA与MTG-0(来自豆油的改性的甘油三酯)或PMTG-0(来自棕榈油的改性的甘油三酯)反应,接着进行季铵化来制备以下代表性的酰胺基胺产物。一个实例为MTGDMAPA磺基甜菜碱(“MTG-11”):
R=C16、C18饱和+不饱和的
另一方面,通过氨基烷基取代的叔胺与天然油和烯烃的交叉复分解制备的不饱和的甘油三酯反应生成脂肪酰胺基胺。天然油和烯烃的交叉复分解生成富含C10和C12不饱和酯以及C16-C18饱和酯的烯烃和不饱和甘油三酯的混合物。通常加热或减压来将烯烃汽提出来。当不饱和甘油三酯直接与DMAPA反应时,形成复杂的混合物,其中DMAPA的伯氨基完全或部分替代了甘油中的甘油酯形成酰胺基胺官能团。通过DMAPA与UTG-0(源自豆油和1-丁烯的交叉复分解的不饱和甘油三酯)或PUTG-0(源自棕榈油和1-丁烯的交叉复分解的不饱和甘油三酯)反应,然后进行季铵化来制备以下代表性的酰胺基胺产物。一个实例是PUTGDMAPA硫酸二甲酯季铵产物(“PUTG-13”):
R=C16、C18饱和的
由低级烷基酯形成酰胺基胺的反应可以在氮气喷射或真空下进行以除去释放的醇。当甘油酯为反应物时,释放的甘油无需从产物除去。当产物残留的甘油量达到期望含量,认为反应完成。
如果需要,季铵化脂肪胺或脂肪酰胺和它们的衍生物具有可以被磺化或亚硫酸化的不饱和键。使用熟知的方法进行磺化,包括烯烃与三氧化硫反应。可以任选使用惰性溶剂进行磺化。适合的溶剂的非限制性实例包括液态SO2、烃和卤代烃。在一种商业方法中,使用降膜反应器采用三氧化硫连续磺化烯烃。可以在采用或不采用溶剂的情况下使用其它磺化剂(例如,氯磺酸、发烟硫酸),但三氧化硫一般是最经济的。磺内酯是烯烃与SO3、氯磺酸等反应的中间产物,其随后可以与苛性碱液经水解反应得到烯烃磺酸盐和羟基烷基磺酸盐的混合物。第3,169,142号、第4,148,821号美国专利和第2010/0282467号公开的美国专利申请描述了适合用于磺化烯烃的方法,它们的教导通过引述引入本申请。
采用熟知的方法,通过混合水中的烯烃(以及常见的助溶剂,如异丙醇)和至少摩尔当量的亚硫酸化试剂来完成亚硫酸化。适合的亚硫酸化试剂包括例如亚硫酸钠、硫酸氢钠、焦亚硫酸钠等。任选地,包括催化剂或引发剂,如过氧化物、铁或其它自由基引发剂。反应混合物通常甚至为15-100℃,直到反应基本完成。第2,653,970号、第4,087,457号、第4,275,013号美国专利记载了适合用于烯烃亚硫酸化的方法,它们的教导通过引述引入本申请。
季铵化的脂肪胺、脂肪酰胺以及它们的磺化或亚硫酸化的衍生物可以结合到许多组合物中,用作例如表面活性剂、乳化剂、肤感剂、成膜剂、流变改性剂、杀生物剂、生物杀灭剂增效剂、溶剂、脱模剂和护理剂。组合物在多种终端应用中是有价值的,如个人护理(液体清洁产品,护理皂、口腔护理)、家用产品(液体和粉末衣物洗涤剂、液体和片状织物柔顺剂、硬和软表面清洁剂、消毒杀菌剂和消毒剂)以及工业或实验室清洁剂。
季铵化的脂肪胺或酰胺基胺和它们的衍生物可以用在乳化聚合中,包括用于生产乳胶的过程。它们可以用作表面活性剂、润湿剂、分散剂或用作农业应用中的溶剂,用作杀虫剂中的惰性成分,或用作助剂以递送用于作物保护、家庭和花园、专业应用的杀虫剂。季铵化的脂肪胺或酰胺基胺和它们的衍生物还可以被用在油田应用中,包括油和天然气的运输、生产、增产和钻井化学物、储层一致性和增效用途以及特殊发泡剂。组合物还具有作为用于石膏、水泥墙板、混凝土添加剂和灭火泡沫生产的泡沫调节剂或分散剂的价值。组合物用作涂料和涂层的聚结剂以及用作基于聚氨酯的粘合剂。
在食品和饮料的加工中,季铵化的脂肪胺或酰胺基胺和它们的衍生物可以被用于润滑用于灌装容器的输送***。当与过氧化氢混合时,季铵化脂肪胺或酰胺基胺和它们的衍生物可以用作低泡沫消毒剂和杀菌消毒剂、减味剂以及用于清洁和保护食品或饮料加工设备的抗微生物剂。在工业、实验室和洗衣应用中,季铵化脂肪胺或酰胺基胺和它们的衍生物,或它们与过氧化氢的组合可以被用于除去污物,将织物杀菌消毒,以及被用作硬表面上的抗微生物成膜组合物。
以下实施例仅是说明本发明。本领域技术人员将认识到处在本发明的精神和权利要求范围内的许多变化。
原料合成:
9-癸烯酸甲酯(“C10-0”)和9-十二碳烯酸甲酯(“C12-0”)的制备
第2011/0113679号美国专利申请公开的步骤用来如下所述生成原料C10-0和C12-0,将其教导引入本文作为参考。
实施例1A:豆油和1-丁烯的交叉复分解。向配备有内浸管、顶置式搅拌器、内部冷却/加热线圈、温度探针、取样阀、泄压阀的洁净、干燥、带有不锈钢护套的5加仑Parr反应器中充入氩气至15psig。将豆油(SBO,2.5kg,2.9mol,Costco,Mn=864.4g/mol,85重量%不饱和基,在5加仑的容器中用氩气充气1小时)加入Parr反应器中。将反应器密封,并用氩气吹扫SBO2小时,同时冷却至10℃。2小时后,将反应器排空至10psig。将内浸管阀连接于1-丁烯气缸(Airgas,CP级,33psig顶空压力,>99重量%)并用1-丁烯重新加压至15psig。再次将反应器排空至10psig以去除残留的氩气。在350rpm和9-15℃下在18-28psig的1-丁烯中搅拌SBO,直到每SBO烯烃键有3mol的1-丁烯被转移到反应器中(~2.2kg1-丁烯,在4-5小时内)。
在Fischer-Porter压力容器中,通过将130mg催化剂溶于30g的甲苯中(每摩尔SBO的烯烃键10molppm)来制备[1,3-双-(2,4,6-三甲基苯基)-2-咪唑啉亚基]-二氯化钌(3-甲基-2-丁烯亚基)(三环己基膦)(C827,Materia)的甲苯溶液。通过用氩气将Fischer-Porter容器内部的顶部空间加压至50-60psig,通过反应器的内浸管将催化剂混合物加入反应器中。使用另外的甲苯(30g)漂洗Fischer-Porter容器和内浸管。在60℃下搅拌反应混合物2.0小时,然后冷却至环境温度,同时排空顶部空间中的气体。
在释放压力后,将反应混合物转移到含有漂白粘土(B80CG粘土,Oil-DriCorporationofAmerica的产品,2%w/wSBO,58g)和磁力搅拌棒的圆底烧瓶中。在85℃下在氩气中搅拌反应混合物。2小时后,在该段时间内将任何剩余的1-丁烯排空,将反应混合物冷却至40℃并通过玻璃料滤器(glassfrit)过滤。在60℃下使用1%w/w的NaOMe的甲醇溶液对产物混合物的等分试样进行酯交换。通过气相色谱法(GC)测得其含有:9-癸烯酸甲酯(22重量%)、9-十二碳烯酸甲酯(16重量%)、9-十八碳烯二酸二甲酯(3重量%)、和9-十八碳烯酸甲酯(3重量%)。
结果较好地与针对假设的平衡混合物计算的收率相当:9-癸烯酸甲酯(23.4重量%)、9-十二碳烯酸甲酯(17.9重量%)、9-十八碳烯二酸二甲酯(3.7重量%)、和9-十八碳烯酸甲酯(1.8重量%)。
实施例1B.一般按照实施例1A的步骤,使用1.73kgSBO和3mol1-丁烯/SBO双键。如上所述使用在甲醇中的甲醇钠对产物混合物的等分试样进行酯交换。产物(通过GC测定)为:9-癸烯酸甲酯(24重量%)、9-十二碳烯酸甲酯(18重量%)、9-十八碳烯二酸二甲酯(2重量%)、和9-十八碳烯酸甲酯(2重量%)。
实施例1C.一般按照实施例1A的步骤,使用1.75kgSBO和3mol1-丁烯/SBO双键。如上所述使用在甲醇中的甲醇钠对产物混合物的等分试样进行酯交换。产物(通过GC测定)为:9-癸烯酸甲酯(24重量%)、9-十二碳烯酸甲酯(17重量%)、9-十八碳烯二酸二甲酯(3重量%)、和9-十八碳烯酸甲酯(2重量%)。
实施例1D.一般按照实施例1A的步骤,使用2.2kgSBO和3mol1-丁烯/SBO双键。此外,用SBO代替用于转移催化剂的甲苯(60g)。如上所述使用在甲醇中的甲醇钠对产物混合物的等分试样进行酯交换。产物(通过GC测定)为:9-癸烯酸甲酯(25重量%)、9-十二碳烯酸甲酯(18重量%)、9-十八碳烯二酸二甲酯(3重量%)、和9-十八碳烯酸甲酯(1重量%)。
实施例1E.从改性的甘油三酯中分离烯烃。在配备了磁力搅拌棒、加热套和温度控制器的12L圆底烧瓶中加入来自实施例1A-1D的混合的反应产物(8.42kg)。将具有真空入口的冷凝器连接于中间的烧瓶颈,将接收烧瓶连接于冷凝器。通过真空蒸馏将挥发性烃(烯烃)从反应产物中去除。釜温:22℃-130℃;蒸馏头温度:19℃-70℃;压力2000-160μtorr。去除挥发性烃后,剩余5.34kg的非挥发性残留物。如上所述使用在甲醇中的甲醇钠对非挥发性的产物混合物的等分试样进行酯交换。产物(通过GC测定)为:9-癸烯酸甲酯(32重量%)、9-十二碳烯酸甲酯(23重量%)、9-十八碳烯二酸二甲酯(4重量%)、和9-十八碳烯酸甲酯(5重量%)。该混合物也称为“UTG-0”。(由棕榈油制备的类似产物称为“PUTG-0”)。
实施例1F.改性甘油三酯的复分解。向配备有磁力搅拌棒、冷凝器、加热套、温度探针和气体接头的12L圆底烧瓶中加入在甲醇中的甲醇钠(1%w/w,4.0L)和实施例1E中制备的非挥发性产物混合物(5.34kg)。在60℃下搅拌得到的浅黄色的异质混合物。1小时后,混合物变为均质并具有橙色(pH=11)。反应2小时后,将混合物冷却至环境温度并形成两层。使用甲醇水溶液(50%v/v,2x3L)洗涤有机相,分离,并通过用冰乙酸的甲醇溶液(1molHOAc/molNaOMe)洗涤中和至pH=6.5。产量:5.03kg。
实施例1G.甲酯原料的分离。向配备有磁力搅拌棒、填充柱和温度控制器的12L圆底烧瓶中加入在实施例1F中制备的甲酯混合物(5.03kg),并将烧瓶放置在加热套内。玻璃柱为2”x36”并且包括0.16”Pro-PakTM不锈钢鞍形架(saddle)(CannonInstrumentCo.)。将柱连接于分馏头,在所述分馏头上配备1L的预先称重的烧瓶用于收集馏分。蒸馏在真空下进行(100-120μtorr)。1:3的回流比用于分离9-癸烯酸甲酯(“C10-0”)和9-十二碳烯酸甲酯(“C12-0”)。在蒸馏过程中收集的样品、蒸馏条件和馏分组成(通过GC测定)显示在表1中。1:3的回流比是指每收集1滴就有3滴返回到蒸馏柱中。混合合适的馏分来得到9-癸烯酸甲酯(1.46kg,纯度为99.7%)和9-十二碳烯酸甲酯(0.55kg,纯度>98%)。
前体合成:
C10-25:C10DMA酰胺
向圆底烧瓶中加入甲酯原料C10-0(235g)并使用氮气对混合物进行脱气。通过注射器加入甲醇钠(5g的30%甲醇溶液)并搅拌混合物5分钟。通过液面下的内浸管缓慢加入二甲胺(67g)。加入后,将混合物加热至60℃并保持过夜。通过真空蒸馏(120℃,20mmHg)回收酰胺C10-25。收率:241.2g(96.3%)。碘值=128.9gI2/100g样品。1HNMR(CDCl3),δ(ppm)=5.8(CH2=CH-);4.9(CH2=CH-);2.8-3.0(-C(O)-N(CH3)2);2.25(-CH2-C(O)-)。酯含量(通过1HNMR测定):0.54%。
C12-25:C12DMA酰胺
向圆底烧瓶中加入甲酯原料C12-0(900g)并在60℃下用氮气对原料进行脱气。通过注射器加入甲醇钠(30g的30%的甲醇溶液)并搅拌混合物5分钟。施加真空并密封反应容器。在静态真空下通过液面下的内浸管缓慢加入二甲胺(200g)。加入后,用氮气释放剩余的真空,然后在70℃下加热混合物1小时。将混合物加热至80℃,将DMA在液体中充入2小时,然后将混合物加热至90℃保持1小时。停止充入,然后将反应冷却至75℃。施加全真空并保持0.5小时。释放真空,加入50%H2SO4(16.3g)和去离子水(200mL)以淬灭催化剂。使用去离子水(2X300mL,然后1X150mL),然后使用20%盐溶液(50mL)洗涤有机层。浓缩有机层(全真空,75℃)并真空蒸馏(釜温:140-150℃)以分离酰胺C12-25。碘值:112.8gI2/100g样品,水分%:65ppm。1HNMR(CDCl3),δ(ppm):5.35(-CH=CH-);2.8-3.0(-C(O)-N(CH3)2;2.25(-CH2-C(O)-)。
胺合成
C10-38:C10胺
在氮气下将酰胺C10-25(475g)分3小时缓慢加入搅拌下的LiAlH4的THF浆液(59.4g)中,同时将温度维持在11-15℃。将混合物温热至室温并搅拌过夜。在冰浴中冷却混合物,小心地加入水(60g),接着加入15%的NaOH水溶液(60g),然后加入另外的水(180g)。将混合物温热至室温并搅拌1小时。过滤混合物,以THF洗涤滤饼。合并并浓缩滤液。对粗产物的NMR分析表明,其含有约16%的9-癸烯-1-醇,所述9-癸烯-1-醇是在酰胺的还原过程中形成的副产物。为了分离醇,加入邻苯二甲酸酐,从而形成版酯/酸。将产物混合物加热至60℃并分批加入邻苯二甲酸酐(57.5g)。混合物的NMR分析显示醇完全消耗,然后真空蒸馏混合物以分离C10-38。胺值:298.0mgKOH/g;碘值:143.15gI2/100g样品;水分%:0.02%。1HNMR(CDCl3),δ(ppm):5.8(CH2=CH-);4.9(CH2=CH-);3.7(-CH2-N(CH3)2)。
C12-26:C12胺
一般地按照用于制备C10-38的工序,使用酰胺C12-25(620g)和LiAlH4(67.8g)。当反应完全后,使用水(68g)和15%的NaOH水溶液(68g)和水(204g)淬灭反应。在正常的过滤和浓缩步骤后,对粗产物的NMR分析显示存在约16%的9-十二烯-1-醇。加入邻苯二甲酸酐(30g)以分离醇。然后真空蒸馏混合物以得到C12-26。胺值:258.1mgKOH/g样品;碘值:120.0gI2/100g样品。1HNMR(CDCl3),δ:5.35(-CH=CH-);2.2(-CH2-N(CH3)2)。
酰胺基胺合成:
C10-17:C10DMAPA酰胺
将甲酯C10-0(500g)、DMAPA(331g)和甲醇钠/MeOH溶液(基于甲酯的量0.5重量%甲醇钠)装入圆底烧瓶。缓慢将内容物加热至140℃并保持6小时。将反应混合物进行真空分离(110℃至150℃)。冷却至室温后,分析产物C10-17。胺值:224.1mgKOH/g;碘值:102.6gI2/100g样品;可滴定的胺:99.94%。1HNMR(CDCl3),δ(ppm):5.75(CH2=CH-);4.9(CH2=CH-);3.3(-C(O)-NH-CH2-);2.15(-N(CH3)2)。
C12-17:C12DMAPA酰胺
将9-十二烯酸甲酯(“C12-0,”670g)装入圆底烧瓶。机械搅拌混合物,加入DMAPA(387g)。反应器配备Dean-Stark分离器,加入甲醇钠(30重量%溶液,11.2g)。在1.5小时内升温至130℃,收集甲醇。回收100g馏出物后,升温至140℃并保持3小时。1HNMR显示反应完成。将混合物冷却至室温过夜。然后将混合物加热至110℃,在真空下回收DMAPA。在1.5小时内将温度缓慢升至150℃,并在150℃下维持1小时。将产物酰胺基胺C12-17冷却至室温。胺值:202.1mgKOH/g;碘值:89.5gI2/100g样品;游离DMAPA:0.43%;可滴定的胺:100.3%。1HNMR(CDCl3),δ:5.4(-CH=CH-);3.3(-C(O)-NH-CH2-);2.2(-N(CH3)2)。
C10胺衍生物:
C10-42:C10胺DMS季铵化合物
在氮气下,将胺C10-38(90.1g)和异丙醇(50g)装入烧瓶,将搅拌的混合物温热至60℃。伴随空气冷却滴加硫酸二甲酯(59.23g)以维持反应温度为60-70℃。再加入硫酸二甲酯(0.4g)以确保完全转化。将混合物保持在70℃下3小时,然后保持在85℃下1小时。冷却后,分析C10-42:pH:9.15(1%,在9:1的IPA/水中);游离胺:0.057meq/g;水分:0.05重量%;IPA:24.4重量%。
C10-40:C10苄基季铵化合物
向配备冷凝器和氮气入口的烧瓶中装入C10-17(86.56g)和甲醇(30g)。将混合物温热至80℃并加入氯苄(56.37g)。将温度升至82℃达1小时。冷却后,分析C10-40:pH:8.6(1%,在9:1的IPA/水中);甲醇:17.5重量%;碘值:67.37;游离胺:0.065meq/g;叔胺:0.0169meq/g;活性烷基季铵:2.645meq/g。
C10-41:C10甜菜碱
将C10-38(114g)、水(180mL)和一氯乙酸钠(74.6g)装入烧瓶。将混合物加热至100℃,通过加入50%NaOH维持pH为7-9。6小时后,滴定显示9.7%的氯化物(理论值:10%)。冷却后,分析C10-41:水分:49.58%;NaCl=9.95%。1HNMR(D2O),δ:5.8(CH2=CH-);4.9(CH2=CH-);3.7(-CH2-N+(CH3)2);3.1(-CH2-N+(CH3)2)。
C10-43:C10胺磺基甜菜碱
将焦亚硫酸(50g)和水(197g)装入配备氮气入口的烧瓶,将混合物温热至40℃。加入氢氧化钠水溶液(0.6g的50%溶液)。搅拌混合物5分钟后,在1小时内滴加环氧氯丙烷(47.7g),反应放热至70℃。混合物在70℃下再搅拌0.5小时。加入更多的NaOH水溶液(0.6g),稍微搅拌混合物。加入胺C10-38(90g),温度升至90℃。1小时后,将温度升至95℃,在90-95℃下维持11.5小时。加入50%NaOH(水溶液)(2×1g和1×0.75g),将pH维持在8.3和8.7之间。当NaCl含量稳定在7.60%时,判断反应完全。冷却混合物得到C10-43,为澄清溶液(369.7g)。分析显示:pH:7.53(10%,直接在DI水中);NaCl:7.82重量%;水分:48.8重量%。1HNMR分析证实了预期的结构(在~4.7处为次甲基质子CH-OH的多重峰)。
C12胺衍生物:
C12-45:C12胺DMS季铵化合物
向配备氮气入口的烧瓶中装入胺C12-26(95.5g),并将内容物温热至60℃。滴加硫酸二甲酯(54.28g)。将混合物冷却,保持温度为65-70℃。在添加期间形成沉淀,并加入异丙醇(26.4g)。将混合物在70℃下搅拌3小时。再加入硫酸二甲酯(0.55g)以确保完全转化,将混合物在70℃下搅拌3小时,然后在85℃下搅拌1小时。分析产物C12-45:pH:6.36(1%,在9:1的IPA/水中);游离胺:0.040meq/g;水分:0.4重量%;IPA:11.6重量%。
C12-27:C12胺苄基季铵化合物
向配备了磁力搅拌棒、氮气入口、热电偶、冷凝器和加料漏斗的圆底烧瓶中装入胺C12-26(92.77g,0.439mol)和甲醇(30g)。将混合物温热至67℃,缓慢加入氯苄(52.77g,0.417mol)。在加入氯苄期间,加入更多甲醇(6.5g)。将反应温度缓慢升至82℃。2小时后,残留游离胺(通过1HNMR),所以加入更多氯苄(1.6g,0.0126mol)。混合物在82℃下搅拌2小时。冷却产物C12-27并分析:碘值:44.97;叔胺:0.53%;甲醇:19.3重量%;游离胺:0.043meq/g;水分:0.14重量%;活性烷基季铵化合物:2.38meq/g。1HNMR分析证实了预期的结构(在~4.9ppm处为苄基亚甲基的单峰)。
C12-40:C12甜菜碱
将胺C12-26(117.7g)、水(342.9g)和一氯乙酸钠(66g)混合并加热至100℃。通过加入50%NaOH溶液将pH维持在7-9。7.5小时后,滴定显示0.387%的游离胺。将混合物冷却并用50%H2SO4中和至pH~7。产物C12-40分析显示:水分:63.8%;NaCl:7.04%;游离胺:0.014meq/g。1HNMR(d4-MeOH),δ:5.3(-CH=CH-);3.7(-C(O)-CH2-N+(CH3)2-);3.1(-C(O)-CH2-N+(CH3)2-)。
C12-46:C12胺磺基甜菜碱
一般地,采用胺C12-26(100g)、焦亚硫酸钠(48g)、水(203.5g)、50%NaOH水溶液(两份,各0.6g)和环氧氯丙烷(45.9g)进行制备磺基甜菜碱C10-43的步骤。加入叔胺后,将反应混合物加热至90-95℃,总计10.5小时,同时加入50%NaOH(水溶液)(2.3g、1g和1g)保持pH在7.9和8.6之间并监视NaCl含量。8.5小时后,NaCl含量恰好稳定在预期的理论值之下。加入3-氯-2-羟基丙烷磺酸钠盐水合物(2.7g),将混合物在95℃下再维持2小时。NaCl含量稳定在7.24%,判定反应完成并冷却至室温。用少量50%H2SO4调节产物溶液的pH至8.1。分析产物C12-46:pH:7.53(10%,直接在去离子水中);NaCl:7.82重量%;水分:48.8重量%。一份干燥样品的1HNMR分析证实了预期的结构(在~4.7处为次甲基质子CH-OH的多重峰)。
C10酰胺基胺衍生物
C10-18:C10DMAPA季铵化合物
向配备冷凝器和氮气入口的烧瓶装入酰胺基胺C10-17(151.3g)。温热至80℃后,滴加硫酸二甲酯(68.38g)。将温度升至85℃,搅拌混合物2小时。加入异丙醇(23.45g),搅拌混合物1小时。分析产物C10-18:IPA:7.72重量%;pH:8.41(1%,在9:1的IPA/水中);碘值:56.8;叔胺:0.020meq/g;水分:1.7重量%;季铵化合物活性物质:91.2重量%。
C10-19:C10DMAPA季铵磺酸盐
将甲基季铵化合物C10-18(98.30g)和水(216.3g)装入配备搅拌棒、冷凝器和热电偶的圆底烧瓶中。在80℃下加热混合物直至均质。加入焦亚硫酸钠(Na2S2O5;23.49g,1.03当量NaHSO3),将混合物在80℃下维持过夜。1HNMR(D2O)显示~50%转化成亚硫酸化的产物。将混合物维持在80℃下达48小时,然后再分析:没有显著变化。将二氧化硫充入混合物,然后在80℃下维持过夜,但在NMR图谱上仍没有显著变化。在室温下搅拌反应物经过周末。将pH调节至6.6,混合物加热至80℃过夜。NMR分析显示烯烃的峰已经消失。pH已经降至3,用苛性钠调节至7。再加热24小时,NMR分析显示不再有变化,剩余~4-5%的烯烃。加入额外的焦亚硫酸钠(0.91g,0.04当量NaHSO3),将反应混合物加热过夜。1HNMR图谱显示完全转化为期望的季铵磺酸盐C10-19。分析显示:水分:60.1%;Na2SO4:1.93%。
C10-31:C10DMAPA苄基季铵化合物
向配备搅拌棒、回流冷凝器和热电偶的圆底烧瓶中装入酰胺基胺C10-17(250.3g)和甲醇,并加热至67℃。滴加氯苄(44g),滴加开始时不再加热。调整添加速率保持温度低于95℃。氯苄添加完后,调节温度至82℃并维持2小时。加入氢氧化钠水溶液(0.33g的50%溶液),接着加入更多的氯苄(7g),将混合物维持在82℃下2小时。1HNMR显示目标产物苄基季铵化合物。将混合物冷却至室温并用水(67g)稀释。分析得到的季铵化合物产物C10-31(239g):碘值:41.87;pH:10.96(原样);水分:27.9重量%;活性物质:65.1重量%;叔胺:0.0012meq/g;甲醇:10.0重量%。1HNMR分析证实了预期的结构(在~4.3ppm处为苄基亚甲基的单峰)。
C10-22:C10DMAPA甜菜碱
将酰胺基胺C10-17(120g)、水(222.4g)和一氯乙酸钠(57.5g)装入圆底烧瓶,将内容物加热至80℃达1小时。采用50%NaOH水溶液控制pH(10%反应物在水或异丙醇中)在8.5和10之间。温度升至100℃达5小时,包括采用冷凝器和氮气喷射。使用氯化物滴定评价反应完成。5小时后,使用盐酸调节pH至7。冷却混合物分析产物C10-22:NaCl:7.39%;游离胺:0.5%。
C10-23:C10DMAPA甜菜碱磺酸盐
向圆底烧瓶装入水(54g)和亚硫酸钠(14.3g),用NaOH水溶液将pH调节至6.6。将混合物加热至75℃,加入过氧化苯甲酸叔丁酯(36μL)。30分钟后,加入甜菜碱C10-22(123g),接着加入过氧化苯甲酸叔丁酯(0.12mL)。采用二氧化硫将均质混合物保持在pH=7。16小时后,1HNMR显示起始原料完全消耗,将甜菜碱磺酸盐产物C10-23冷却至室温。分析显示:水分:62.9%;Na2SO4:1.96%;游离NaCl:4.54%;游离亚硫酸盐:0.65%。
C10-24:C10DMAPA磺基甜菜碱
一般地,采用酰胺基胺C10-17(60g)、焦亚硫酸钠(25.6g)、水(114g),50%NaOH水溶液(两份,各0.3g)和环氧氯丙烷(24.4g)进行用于制备磺基甜菜碱C10-43的步骤。反应在75℃下持续3小时,pH(10%水稀释液)保持在8.2和8.9之间。3小时后,将混合物冷却至室温过夜。混合物再加热至75℃。1小时后,pH已经降至8.1,用50%NaOH(0.3g)升高。反应持续1小时。当NaCl含量稳定在6.55%时,判定反应完成。将混合物冷却至室温,用50%H2SO4将pH调节至6.95。分析磺基甜菜碱C10-24产物:NaCl:6.55重量%;固体:51.8%;磺基甜菜碱活性物质(通过固体NaCl):45.25%。一份干燥的产物混合物的1HNMR分析证实了预期的结构。
C12酰胺基胺衍生物
C12-18:C12DMAPA季铵化合物
向配备冷凝器和氮气入口的烧瓶中装入酰胺基胺C12-17(155.8g),将其温热至80℃。滴加硫酸二甲酯(68.38g)。反应温度升至85℃并维持1小时,然后升至95℃维持3小时。加入异丙醇(24.9g),搅拌混合物1小时。对季铵化合物产物C12-18分析显示:IPA:8.9重量%;碘值:53.95;pH:8.07(1%,在9:1的IPA/水中);水分:0.6重量%。
C12-19:C12DMAPA季铵磺酸盐
向圆底烧瓶中装入甲基季铵化合物C12-18(57.88g)和水(115g),温和地加热直至均质。加入过氧化氢(35%H2O2水溶液,4滴)。将氧气充入溶液,9小时内等份加入Na2S2O5(12.62g)。然后搅拌混合物24小时。用稀释的NaOH水溶液调节pH至5。1HNMR分析显示有70%硫酸盐和30%未反应的起始材料。产物分析表明:水分:60.1%;Na2SO4:1.34%;游离亚硫酸盐:10mg/L。
C12-41:C12DMAPA苄基季铵化合物
将酰胺基胺C12-17(104.2g)装入配备有热电偶、回流冷凝器、机械搅拌器、加料漏斗和氮气入口的反应烧瓶中。加入甲醇(28.1g),搅拌溶液加热至65℃。移去加热罩,滴加氯苄(40.99g),使反应温度自行升高。氯苄加完后,恢复加热,调节温度至80℃。反应持续3.25小时。将混合物冷却至室温过夜。反应混合物再温热至50℃达3小时。再加入氯苄(0.92g),将混合物加热至80℃达2小时。在50℃下边搅拌边加入去离子水(99g),溶液冷却至室温。分析苄基季铵化合物C12-41(266.0g):pH:9.2(1%,在9:1的IPA/水中);游离叔胺HCl:0.089重量%;游离胺:0.47重量%;水分:35.9重量%;活性物质:54.0重量%。1HNMR分析证实了预期的结构(在~4.5ppm处苄基亚甲基的单峰)。
C12-22:C12DMAPA甜菜碱
将酰胺基胺C12-17(210g)和水(400g)装入圆底烧瓶中。加入一氯乙酸钠(89g),将混合物加热至80℃。用50%NaOH水溶液维持pH在8和10之间(采用pH试纸测定10%水溶液的pH)。将温度升至100℃并维持4小时。将混合物冷却至室温过夜。加水(100g)稀释混合物,再加热至100℃达4小时。氯化物滴定显示5.55%的NaCl(预期为5.62%)。冷却产物甜菜碱C12-22并分析:水分:62.13%;NaCl:5.66%;游离胺:2.28%。1HNMR(d4-MeOH),δ:5.4(-CH=CH-);3.8(-C(O)-CH2-N+(CH3)2-);3.2(-C(O)-CH2-N+(CH3)2-)。
C12-23:C12DMAPA甜菜碱磺酸盐
将甜菜碱C12-22(284.6g)与水和亚硫酸钠混合(33mg)混合。以0.5mL/分钟将空气充入溶液。在室温下边搅拌边每小时加入各份焦亚硫酸钠(5.99g),长达4小时,得到的溶液搅拌过夜。1HNMR显示74%的转化率。再加入焦亚硫酸钠(2.39g),搅拌反应过夜。1HNMR显示77%的转化率。分析产物磺酸盐C12-23:水分:77.2%;Na2SO4:1.6%;游离亚硫酸盐:10mg/L。
C12-24:C12DMAPA磺基甜菜碱
一般地,采用酰胺基胺C12-17(105g)、焦亚硫酸钠(39.6g)、水(190g)、50%NaOH水溶液(两份各0.6g)和环氧氯丙烷(37.8g)进行用于制备磺基甜菜碱C10-24的步骤。反应在80℃下持续3.5小时,pH(10%水溶液)保持在8.2和8.6之间。3.5小时后,将混合物冷却至室温过夜。将混合物再加热至80℃。2小时后,pH为8.5,NaCl含量为6.36%。判断反应完成。将混合物冷却至室温,用50%H2SO4将pH调节至7.6。分析磺基甜菜碱产物C12-24:NaCl:6.34重量%;水分:49.7%;固体:50.4%;磺基甜菜碱活性物质(通过固体NaCl):44.0%。一部分干燥的产物混合物的1HNMR分析证实了预期的结构。
9-十六烯酸甲酯(“C16-0”)原料的制备
除了用1-辛烯代替1-丁烯与豆油进行交叉复分解之外,一般按照实施例1A的步骤进行。然后如实施例1E所述对合并的反应产物进行汽提,以从改性的油馏分中除去更易挥发的不饱和烃馏分。实施例1F的步骤用于将改性的油馏分转化为包含9-十六碳烯酸甲酯的甲酯混合物。减压分馏用于从其他甲酯中分离出所需的产物9-十六碳烯酸甲酯。
C16-10:C16DMAPA季铵化合物
向配备冷凝器和氮气入口的烧瓶中装入相应的C16酰胺基胺C16-9(105.5g,一般如在C12-17中制备的)。温热至80℃后,滴加硫酸二甲酯(39.4g)保持温度<90℃。加入后,加入IPA(20g)使产物变稀。温度降至70℃,搅拌混合物2小时。通过高氯酸滴定(PAT)分析得到的数值为0.069meq/gKOH(目标=0.065meq/gKOH),温度升高至85℃并维持3小时。将产物C16-10冷却至室温得到蜡状固体。分析显示:IPA:10.6%;pH(90/10IPA/H2O):6.7;水分:0.23%;游离叔胺:0.065meq/gKOH;季铵化合物活性物质:1.66meq/gKOH。
C16-13:C16DMAPA甜菜碱
将酰胺基胺C16-9(126.6g,一般如C12-17中制备的)、一氯乙酸钠(SMCA,44.7g)和水(237g)装入配备有机械搅拌、热电偶、温度控制器、氮气入口和冷凝器圆底烧瓶中。充分搅拌并将混合物加热至80℃,约1小时后变得澄清。按需要通过加入多份50%NaOH水溶液,将pH(采用试纸在10%水溶液中测定)维持在8和10之间。随着反应进行,混合物胶化,加入水(100g)稀释混合物。将温度升至95℃并维持4小时。1HNMR分析显示完全转化为DMAPA甜菜碱C16-13。NaCl:4.44%;水分:55.5%;游离叔胺:0.70%。
C16-14:C16DMA酰胺
将C16-0甲酯(502g、1.8mol)装入配备有机械搅拌、热电偶、真空计和蒸馏侧臂的容器中。将原料加热至50℃,施用全真空30分钟以使***干燥和脱气。用氮气回填容器,经注射器注入甲醇钠(30%甲醇溶液,20g)。搅拌混合物5分钟,然后减压至约-25"Hg。在静态真空下密封容器,开始经液面下汲取管加入二甲胺(DMA)。当容器中压力平衡时,将蒸馏侧臂连接至脱水器/起泡器,在大气压下持续负载,调节添加速率从而使漏气最小化(洗涤器中冒泡表明)。当已经装入稍微过量的DMA时,容器在氮气、60℃下搅拌3小时。1HNMR分析显示甲酯完全消耗,将混合物冷却至室温过夜。将混合物再加热至65℃,真空分离以除去过量的DMA和MeOH。当分离完成时,用氮气回填容器。逐份加入浓缩的HCl直到润湿的pH试纸显示略微酸性pH。搅拌15分钟后,水洗中和的混合物(3x200mL),按需要加入20%NaCl以促进相分离。将洗涤的产物加热至65℃,缓慢施加真空除去水。当分离完成后,用氮气回填容器,通过玻璃粉上的硅胶塞过滤经分离的产物以除去细小沉淀。产物保持浑浊,用乙酸乙酯稀释,并通过硅藻土垫再次过滤,得到澄清的黄色液体。经旋转蒸发器除去挥发物,然后在高真空下得到浅黄色油状的C16-14二甲基酰胺(509.4g;96.8%的收率)。1HNMR分析与目标结构一致,显示剩下0.8%甲酯。进一步分析显示:水分:0.04%;碘值:89.3gI2/100g样品。
C16-15:C16胺
在氮气下、3小时内将酰胺C16-14(358.8g)缓慢加入搅拌的LiAlH4的THF浆料(37.5g)中,同时保持温度为11-15℃。将混合物温热至约20℃并搅拌2小时。在冰浴中冷却混合物,小心加入水(37.5g),接着加入15%NaOH水溶液(37.5g),然后再加入水(112.5g)。将混合物温热至室温并搅拌1小时。过滤混合物,滤饼用THF清洗。合并滤液并浓缩。逐份加入邻苯二甲酸酐(20g),并将混合物进行真空蒸馏以分离C16-15。产物的1HNMR显示剩余约6.5%脂肪醇副产物,随后再用邻苯二甲酸酐处理产物,然后如上所述再蒸馏。胺值:187.8mgKOH/g;碘值:94.4gI2/100g样品;%水分:0.02%。1HNMR(CDCl3),δ(ppm):5.8(CH2=CH-);4.9(CH2=CH-);3.7(-CH2-N(CH3)2)。
C16-16:C16甜菜碱
向配备有机械搅拌器、热电偶、温度控制器、加热罩和pH探针的圆底烧瓶中,装入胺C16-15(123.2g)、水(200g)和一氯乙酸钠(64.6g)。将乳状的反应混合物加热至80℃达1小时,通过加入50%的NaOH水溶液保持pH在7和10之间。然后将反应混合物加热至95℃;再过1小时后,混合物变得澄清并开始变浓。再加入水(50g)并加入NaOH以保持pH在7和8之间。在95℃下,在总时间4小时后,使反应混合物冷却。1HNMR(干燥样品,溶解于MeOD)显示一氯乙酸钠完全消耗,75%的胺转化为季铵。将反应混合物再加热至95℃,加入更多的一氯乙酸钠(6g)。再次通过加入50%NaOH水溶液将pH维持在7和8之间。1.5小时后,1HNMR显示胺具有85%转化率,以及微量的剩余的氯乙酸盐。向浓混合物加入水(50mL)和一氯乙酸钠(7.2g)。1小时后,NMR显示胺具有92%的转化率。加入更多的一氯乙酸钠(1.9g)。1小时后,转化率为95.6%。用NaOH水溶液将pH调节至7.6,将混合物在95℃下加热4小时。在该时间点,1HNMR显示胺的转化率为98.2%。将混合物冷却至60℃,分析略带颜色浓的甜菜碱产物C16-16:水分:60.0%;游离叔胺:0.024meq/g;NaCl:7.19%。
C16-17:C16胺苄基季铵化合物
将胺C16-15(70.0g)装入配备有热电偶、回流冷凝器、机械搅拌器、加料漏斗和氮气入口的烧瓶中。一边搅拌一边加入甲醇(25.2g),溶液加热至65℃。在~45分钟内滴加氯苄(30.3g),使得内部温度升至~72℃。调整反应温度至80℃,维持4小时,然后冷却至室温,使之在氮气下静置过夜。冷却后,反应混合物凝胶化,再加入甲醇(5g)。将混合物加热至50℃。NMR分析显示没有残留氯苄,但显示有少量的游离叔胺。再加入氯苄(0.94g),在80℃下搅拌混合物4小时。1HNMR分析证实了反应完成。冷却混合物,分析苄基季铵化合物C16-17:水分:2.83%;游离叔胺:0.0015meq/g;烷基季铵化合物活性物质=2.28meq/g。
原料合成:
9-十八碳烯-1,18-二酸二甲酯(“Mix-0”或“C18-0”)的制备
将9-十二碳烯酸甲酯的八个样品(每个10.6g,参见表2)升温至50℃,并且用氩气脱气30分钟。将复分解催化剂([1,3-双-(2,4,6-三甲基苯基)-2-咪唑啉亚基]-二氯化钌(3-甲基-2-丁烯亚基)-(三环己基膦),Materia的产品)加入到9-十二碳烯酸甲酯(量显示于表2中)中并施加真空以提供<1mmHg的压力。使反应混合物在所报导的时间内进行自复分解。气相色谱分析表明所制备的9-十八碳烯-1,18-二酸二甲酯具有如表2所报导的收率。“Mix-0”为获得自反应混合物的80:20反式/顺式异构体混合物。结晶提供了全反式异构体原料,“C18-0”。
C18-26:C18DiDMAPA酰胺(100%反式)
将C18-0二甲酯(545.6g)、DMAPA(343.3)和甲醇钠溶液(基于甲酯1.1重量%NaOMe)混合,缓慢加热至150℃,并维持10.5小时。再加入DMAPA(100mL),将混合物加热至150-160℃达4小时,然后在125℃下搅拌过夜。再加入30%甲醇钠的MeOH溶液(10g),将混合物加热至155-160℃达4小时。加入更多DMAPA(50mL),并将混合物在180℃下加热2小时。将混合物冷却至110-120℃,加入浓盐酸,将内容物剧烈搅拌15分钟。移去加热罩,当温度达到90℃时,加入去离子水,磨碎产物。将浆料冷却至室温并过滤。用水清洗固体几次。分析二酰胺产物C18-26:熔点:97-101℃;胺值:230.4mgKOH/g;游离DMAPA:0.08%;水分:0.08%;可滴定的胺:98.95%。1HNMR(CDCl3),δ(ppm):5.35(-CH=CH-);3.3(-C(O)-NH-CH2-);2.2(-N(CH3)2)。
MIX-26:C18DiDMAPA酰胺(80%反式,20%顺式)
将二甲酯C18-0(824.3g)、DMAPA(519.5g)和甲醇钠溶液(基于甲酯2.4重量%NaOMe)缓慢加热至140℃,维持几个小时。最后采用液面下氮气喷射促使甲醇除去。将温度降至100℃,将内容物经真空分离。将由去离子水和(1.0L)和50%的H2SO4(11g)制备的溶液缓慢加入熔融的反应产物。冷却混合物,过滤分离糊状固体。用去离子水清洗固体,滤液经氯仿萃取(2X250mL)。浓缩氯仿萃取物,得到的黄色油状物经1HNMR鉴定为富含顺式异构体的产物。将黄色油状物再溶解于CHCl3,通过二氧化硅过滤,并与糊状固体合并。再向内容物加入CHCl3(100mL),将混合物在旋转蒸发器上在70℃下旋转蒸发直至均质。施用真空,除去CHCl3,接着加水。当在98℃下产物保持为固体时,停止蒸发。分析冷却的产物Mix-26:胺值:229.1mgKOH/g样品;游离DMAPA:0.08%;水分:0.09%;总碱度:4.08meq/g。1HNMR(CDCl3),δ(ppm)=5.3(-CH=CH-);3.25(-C(O)-NH-CH2-);2.2(-N(CH3)2)。13CNMR(CDCl3),δ(ppm)=130(反式-CH=CH-);129.5(顺式,-CH=CH-)。产物比例:79.3%反式对20.7%顺式。
C18-27:C18DiDMAPA二季铵化合物(100%反式)
将二酰胺C18-26(83.0g)和异丙醇(68.8g)装入配备有氮气入口的烧瓶中,将混合物温热至70℃。再加入IPA(49.11g)得到均质的溶液。加入硫酸二甲酯(92.0g)。空气冷却外面的烧瓶,调节添加速率保持反应温度~70℃。在70℃下,搅拌混合物3小时,然后在85℃下搅拌3小时。分析得到的二季铵化合物产物C18-27:碘值:14.52;pH:7.72(1%,在9:1的IPA/水中);IPA:28.1重量%;游离胺:0.055重量%;水分:0.48重量%;活性物质(烷基季铵化合物):73.0重量%。
MIX-27:C18DiDMAPA二季铵化合物(80:20反式/顺式)
将二酰胺Mix-26(157.3g)装入配备有冷凝器和氮气入口的烧瓶中,温热至80℃。滴加硫酸二甲酯(68.38g)。将反应温度升至85℃,反应混合物搅拌2小时。加入异丙醇(23.45g),将反应混合物搅拌1小时。分析二季铵化合物产物Mix-27:IPA:7.72重量%;pH:8.41(1%,在9:1的IPA/水中);碘值:56.76;叔胺:0.020meq/g;水分:1.7重量%;季铵化合物活性物质:91.2重量%。
C18-28:C18DiDMAPA二季铵磺酸盐(100%反式)
将二季铵化合物C18-27(216.5g)、Na2S2O5(42.75g)、水(400.5g)和过氧化苯甲酸叔丁酯(0.44g)混合,边搅拌边在75℃下加热18小时。1HNMR显示96%的转化率。对异丙醇(来自C18-27起始原料)进行汽提。分析季铵磺酸盐C18-28:水分:60.7%;Na2SO4:2.85%;游离亚硫酸盐:1.48%。
C18-31:C18二磺基甜菜碱(100%反式)
将焦亚硫酸钠(42.3g)和水(190g)装入氮气吹扫的烧瓶,将混合物温热至40℃。加入氢氧化钠水溶液(0.6g50%溶液)。稍微搅拌混合物,在1小时内滴加环氧氯丙烷(40.4g)。使混合物放热至60℃。在70℃下搅拌混合物0.5小时,并加入更多的50%NaOH(0.6g)。稍微搅拌后,加入一份二酰胺C18-26(100g)。接着的放热使混合物温热至80℃。将温度维持在80℃,搅拌混合物3.5小时。采用50%NaOH将pH维持在8.2和8.6之间。3.5小时后,混合物的NaCl含量为6.75%。将混合物冷却至室温过夜。再将混合物加热至80℃。0.5小时后,pH为8.1,采用50%NaOH(水溶液)将pH升至9.1。1小时后,NaCl含量维持在6.75%,判定反应完成。将反应混合物冷却至室温,用50%H2SO4水溶液将pH调节至7.94。磺基甜菜碱C18-31的分析显示:NaCl:6.83重量%;水分:51.0%;固体:49.0%;磺基甜菜碱活性物质(通过固体NaCl):42.2%。一份干燥的产物混合物的1HNMR分析证实了预期的结构。
MIX-31:C18二磺基甜菜碱(80:20反式/顺式)
一般地,采用二酰胺Mix-26(96g)、焦亚硫酸钠(40.7g)、水(175g)、50%NaOH水溶液(两份,各0.5g)和环氧氯丙烷(38.8g)进行制备C18-31的步骤。将温度维持在75℃,搅拌混合物3小时。用50%NaOH将pH保持在8.3和8.7之间。将混合物冷却至室温过夜。再将混合物加热至75℃。0.5小时后,pH为8.2,采用将50%NaOH(水溶液)将pH升至8.8。再在75℃下搅拌混合物4.5小时。NaCl含量为6.81%,判定反应完成。将混合物冷却至室温,用50%的H2SO4水溶液调节pH至8.0。磺基甜菜碱Mix-31的分析显示:NaCl:6.94重量%;水分:48.9%;固体:51.1%;磺基甜菜碱活性物质(通过固体NaCl):44.1%。一份干燥的产物混合物的1HNMR分析证实预期的结构。
C18-32:C18二甜菜碱(100%反式)
将二酰胺C18-26(224.0g)装入烧瓶,接着装入水(614.3g)和一氯乙酸钠(106g)。将混合物加热至100℃,通过加入50%的NaOH将pH保持在7-9。3小时后,滴定显示0.038%的游离胺和5.68%的NaCl。将混合物冷却,用50%H2SO4中和至pH~8并分析:水分:65.4%;NaCl:5.68%;游离胺:1.4meq/g。1HNMR(d4-MeOH),δ:5.25(-CH=CH-);3.7(-C(O)-CH2-N+(CH3)2-);3.05(-C(O)-CH2-N+(CH3)2-)。
MIX-32:C18二甜菜碱(80:20反式/顺式)
将二酰胺Mix-26(128.17g)装入烧瓶,接着装入水(282.0g)和一氯乙酸钠(62.8g)。将混合物加热至100℃,通过加入50%的NaOH将pH保持在7-9。几个小时后,滴定显示6.53%的游离NaCl。冷却混合物,用50%H2SO4中和至pH~8并分析:水分:59.7%;NaCl:6.68%;游离胺:0.031meq/g。
C18-33:C18二甜菜碱磺酸盐(100%反式)
将二甜菜碱C18-32(447.7g的32%活性物质)、Na2S2O5(23.45g)、水(197g)、Na2SO3(0.78g)和过氧化苯甲酸叔丁酯(0.24g)混合,并在80℃下搅拌17.5小时,同时采用定期加入NaOH将pH调节至~6。1HNMR显示70%的转化率。加入水(100mL)和另外的催化剂,持续加热5.5小时,然后过夜。1HNMR显示向磺酸盐的转化完成了82%。分析磺酸盐C18-33:水分:68.8%;Na2SO4:1.70%;NaCl:4.18%;亚硫酸盐(通过试纸):200-400mg亚硫酸盐/L。
C18-34:C18DiDMAPA单季铵化合物(100%反式)
将二胺C18-26(225.8g)装入氮气吹扫的圆底烧瓶,加热至70℃。加入异丙醇(105.26g)。然后经加料漏斗缓慢加入硫酸二甲酯(DMS)(58.8g),从而使温度维持在约70℃。DMS添加完后,将混合物维持在70℃达3小时,然后维持在85℃达1小时。游离胺(通过PAT):1.199meq/g。可用的叔胺50%季铵化的理论预期PAT值为1.196meq/g。
MIX-34:C18DiDMAPA单季铵化合物(80:20反式/顺式)
一般地,采用二胺Mix-26(241.6g)、异丙醇(98.4g)和硫酸二甲酯(60g)进行制备C18-34的步骤。DMS添加完后,将反应在70℃下保持3小时,然后在85℃下保持3小时。高氯酸滴定显示1.317meq/g的游离胺。1HNMR分析(CD3OD)基于分别位于2.25和3.11ppm的甲基信号的整合显示49%的游离胺和51%的季铵化胺。
C18-35:C18DiDMAPA季铵化合物AO(100%反式)
将单季铵胺C18-34(75%固体,192.3g)、去离子水(205.0g)和Hamp-Ex80(0.5g)装入圆底烧瓶中。将混合物加热至70℃,用柠檬酸调节pH至>8。滴加H2O2(35%,22.86g)水溶液,保持温度低于70℃。过氧化物添加完后,将混合物维持在70℃下长达20小时。1HNMR显示叔胺完全转化为氧化胺。将混合物冷却至室温。滴定显示:氧化胺:0.50meq/g;游离胺:0.042meq/g;阳离子活性物质:0.62meq/g;游离过氧化物:0.08%;以及水:55.8%。
MIX-35:C18DiDMAPA季铵化合物AO(80:20反式/顺式)
将Mix-34(186.9g)溶解在去离子水中(200g),在75℃下除去异丙醇。将浓缩物(321.6g)转移至圆底烧瓶,并加入Hamp-Ex80(0.53g)。将混合物加热至50℃,加入几片干冰直到混合物pH为8-9。然后滴加H2O2水溶液(35%,18.23g),保持温度在70℃以下。过氧化物添加完后,将混合物保持在85℃下达16小时。加入去离子水(75g)。将混合物冷却至室温。1HNMR分析与预期的季铵氧化胺Mix-35的结构一致,显示没有可检测的游离胺。其它分析显示:游离过氧化物:0.002%;水:59.2%。
C18-36:C18DiDMAPA单甜菜碱(100%反式)
将酰胺基胺C18-26(348g)和去离子水(500g)装入圆底烧瓶。将混合物加热至80℃,加入柠檬酸(2.5g)。在1小时内,向酰胺基胺溶液滴加由一氯乙酸钠(SMCA,88.5g)和去离子水(300g)制备的溶液。添加完后,将混合物加热至85℃达3小时,然后加热至95℃达0.5小时。然后将混合物冷却至室温。硝酸银滴定分析显示3.49%的NaCl。再加入SMCA(1.5g),再将混合物加热至95℃达6小时。6小时后,NaCl含量为3.53%。一份干燥的产物的1HNMR分析基于对分别位于2.28和3.22ppm的甲基信号的整合显示45.7%的游离胺和54.3%季铵化胺。
MIX-36:C18DiDMAPA单甜菜碱(80:20反式/顺式)
一般地,采用酰胺基胺Mix-26(224.5g)、去离子水(322g)、柠檬酸(1.5g)和一氯乙酸钠水溶液(57g的SMCA在200g的DI水中)进行用于制备C18-36的步骤。SMCA添加完后,将混合物加热至90℃达2小时。再加入SMCA(3.5g),将混合物维持在90℃达2小时。NaCl含量:3.82%。一份干燥样品的1HNMR分析显示44%的游离胺和56%的季铵化胺。
C18-37:C18DiDMAPA甜菜碱AO(100%反式)
将熔融的单甜菜碱C18-36(35%固体,415.2g)装入烧瓶中,并加热至70℃。在0.5小时内滴加H2O2水溶液(35%,23.6g),保持反应温度低于78℃。过氧化物添加完后,在70℃下搅拌混合物9小时。一份干燥样品的1HNMR(CD3OD)显示单甜菜碱完全转化为期望的氧化胺。证据是2.28ppm处胺的N(CH3)2峰消失,3.15ppm处出现氧化胺的N(CH3)2峰。
MIX-37:C18DiDMAPA甜菜碱AO(80:20反式/顺式)
将单甜菜碱Mix-36(35%固体,470g)装入烧瓶并加热至60℃。在0.5小时内滴加H2O2水溶液(35%,27.6g),将温度保持在70℃。添加完后,将混合物在70℃下搅拌3小时。加入少量部分干燥的单甜菜碱(Mix-36)与过量过氧化物反应。将混合物保持在70℃下达5小时。滴定显示的游离过氧化物:0.18%。一份干燥样品的1HNMR(CD3OD)显示单甜菜碱完全转化为预期的氧化胺产物。整合氧化胺和甜菜碱的N(CH3)2峰表明:甜菜碱:53.4mol%;氧化胺:46.6mol%。
C18-38:C18DiDMAPA甜菜碱季铵化合物(100%反式)
将单甜菜碱C18-36(138.9g)、异丙醇(40g)和乙醇(42.5g)装入氮气吹扫的烧瓶中。将混合物温热至70℃,滴加硫酸二甲酯(21.77g)。冷却混合物以保持温度为~70℃。将混合物在70℃下保持6小时,然后在85℃下保持2小时。使混合物冷却并浓缩。加水调节固含量至~50重量%。产物C18-38的分析表明:pH:7.59;NaCl:1.09重量%;IPA:0.49重量%;EtOH:0.78重量%;水分:48.9重量%。
MIX-38:C18DiDMAPA甜菜碱季铵化合物(80:20反式/顺式)
将单甜菜碱Mix-36(113.9g)、异丙醇(66g)和乙醇(30g)装入氮气吹扫的烧瓶中。将混合物温热至70℃,滴加硫酸二甲酯(15.65g)。冷却混合物并维持温度为~70℃。将混合物保持在70℃下达3小时。再加入硫酸二甲酯(0.96g),在70℃下持续加热3小时,然后在85℃下持续加热2小时。使混合物冷却并浓缩。加水(195g)至~40重量%的固体。甜菜碱季铵化合物产物Mix-38的分析显示:pH:8.35(1%在水中);水分:47.7重量%;NaCl:4.74重量%;硫酸钠:0.3重量%。1HNMR数据证实了预期的结构。
MIX-69:C18酯/酸(80:20反式/顺式)
如OrganicSyntheses:Col.Vol.IV(1963)635中所述,由二元酯Mix-0(用作被接收的)制备半酸/酯Mix-69。因此,将Mix-0(1kg)加入甲醇(~9L),机械搅拌混合物。在分开的容器中,将Ba(OH)2(274.4g)溶解在甲醇(~4L)中,并在2小时内逐份将溶液加入搅拌的二酯溶液中,导致形成白色沉淀。过滤分离固体,用甲醇洗涤几次,在空气中干燥。然后将固体转移至12L反应容器中,在乙酸乙酯(~3.5L)中形成浆料。逐份将HCl水溶液(32%,Aldrich,1248.6g)加入搅拌的浆料,导致固体溶解,形成澄清的溶液。用水洗涤溶液三次,移去水层并收集在分开的容器中。合并的水层用乙酸乙酯萃取一次,将有机相与洗涤的产物溶液合并。干燥(Na2SO4)、过滤并经旋转蒸发器浓缩混合物。在高真空下彻底干燥并经冷却后得到蜡状固体结晶(655g,~70%的收率)。气相色谱产物(接着衍生化)分析显示其包含94%的酸/酯和6%的二酸。定量13CNMR显示86:14的反式:顺式异构体比例。
MIX-43:C18酯/DMAPA酰胺(80:20反式/顺式)
通过与稍微过量的氯化亚砜(SOCl2)的二氯甲烷溶液反应,将混合的酸/酯Mix-69转化为酸氯化物/酯,并且通过减压下除去溶剂和过量的SOCl2分离产物。分离的产物的1HNMR分析显示基本上定量转化为酸氯化物/酯,并且使用材料无需进一步纯化。
将二氯甲烷(200mL)、DMAPA(172.1g)和吡啶(133.3g)装入配备有机械搅拌器、氮气入口和热电偶的3L反应容器中。将之前制备的酸氯化物/酯滴加到搅拌的DMAPA吡啶溶液。加入期间,如需要通过冰浴冷却将温度保持在25-40℃,在1.5小时内完成添加。形成沉淀,在室温下搅拌过夜后,混合物变成浓的浆料。用二氯甲烷(500mL)稀释混合物,并加入水(500mL)得到澄清的均质溶液。加入乙酸乙酯不能引起相分离。然而,加入饱和的NaCl溶液导致缓慢分离出较少的水相,将其排出并弃去。经旋转蒸发浓缩有机相得到粘滞的褐色油状物。1HNMR分析显示游离的吡啶,并表明DMAPA部分的末端叔胺被质子化。将物质置于丙酮中,过滤混合物除去少量的沉淀固体。用50%NaOH水溶液调节溶液的pH至~8.5(直接在物质上测定),导致固体沉淀的形成。再过滤混合物,浓缩澄清的滤液,然后在高真空下干燥。当冷却时,物质固化。1HNMR分析与目标结构一致,显示存在游离的吡啶。将产物加热至60℃,搅拌,在减压的情况下在液面下的氮气喷射5小时,然后在105℃下喷射30分钟。汽提后,产物的1HNMR分析显示没有残余的吡啶。
MIX-44:C18酯DMAPA季铵化合物(80:20反式/顺式)
将酯-酰胺基胺Mix-43(162.7g)装入配备有机械搅拌、热电偶和氮气入口的烧瓶。加入异丙醇(IPA;47.8g),将混合物加热至70℃。使用对酯/酰胺起始原料进行高氯酸滴定来计算所需的硫酸二甲酯(DMS)的量。滴加DMS(28.6g),同时采用外部冷却将反应温度维持在70℃。DMS添加完后,在70℃下搅拌混合物3小时,然后在85℃下搅拌混合物1小时。高氯酸滴定显示叔胺几乎完全消耗。冷却季铵化合物产物Mix-44得到蜡状固体。经Drager仪器分析残余的DMS为负值。
MIX-48:C18酯DMAPA甜菜碱(80:20反式/顺式)
将酯-酰胺基胺Mix-43(134.2g,0.327mol)装入配备有热电偶、氮气入口和机械搅拌的圆底烧瓶。加入水(250mL)和一氯乙酸钠(38.9g,0.334mol)。将混合物温热至70℃,大约1小时后,混合物变成澄清。在反应期间,用50%的NaOH水溶液将混合物的pH维持在~8。在70℃下持续加热5小时。1HNMR图谱与预期的结构一致,显示没有残余的叔胺。冷却产物酯-甜菜碱Mix-48并分析:水:59.9%;NaCl:4.29%。
C18-65:C18DiDMAPA苄基季铵化合物(100%反式)
将双(酰胺基胺)C18-26(100g)和甲醇(67g)装入配备有热电偶、机械搅拌、回流冷凝器和氮气入口的烧瓶。将混合物加热至67℃,滴加氯苄(44g),同时使温度升至82℃。在加热期间,用蒸馏侧臂替代回流冷凝器,从混合物回流甲醇蒸馏物直至温度达到82℃。用回流冷凝器替代侧臂,并在82℃下搅拌混合物2小时。加入氢氧化钠(50%水溶液,0.33g),接着加入更多的氯苄(9g),将混合物保持在82℃下2小时。将混合物冷却至50℃并倒入水(67g)中。搅拌5分钟后,分析双(苄基季铵化合物)溶液:甲醇:16.4%;游离叔胺:未检测到;水:26.8%;季铵化合物活性物质:58.7%。1HNMR图谱与目标结构一致。
MIX-65:C18DiDMAPA苄基季铵化合物(80:20反式/顺式)
将双(酰胺基胺)C18-26(118.4g)和甲醇(44g)装入配备有搅拌棒、回流冷凝器和热电偶的圆底烧瓶。将混合物加热至67℃,并滴加氯苄(50g)。调整添加速率以保持温度在95℃以下。加入氯苄后,调节温度至82℃并保持2小时。加入更多甲醇(21g)以降低粘度。加入氢氧化钠(50%水溶液;0.33g),接着加入更多的氯苄(11.2g),并将混合物在82℃下保持2小时。1HNMR分析与目标结构一致,显示没有残余的叔胺。将热的苄基季铵化合物加到去离子水(140g),充分搅拌,使混合物冷却。双(苄基季铵化合物)Mix-65的分析显示:MeOH:10.8%;水:39.7%;游离叔胺:0.027meq/g;季铵化合物活性物质:49.1%。
基于豆油的改性的甘油三酯(“MTG-0”)
一般地,进行实施例1A和1E的步骤,除了省略1-丁烯。
源自豆油和1-丁烯的交叉复分解的改性的甘油三酯(“UTG-0”)
不饱和的甘油三酯(富含C10和C12,还包含C16和C18饱和的)
一般地,进行实施例1A和1E的步骤从而由豆油和1-丁烯生产UTG-0。基于棕榈油的改性的甘油三酯(“PMTG-0”)
进行用于制备MTG-0的步骤,除了使用棕榈油替代豆油。
源自棕榈油和1-丁烯的交叉复分解的改性的甘油三酯(“PUTG-0”)
不饱和的甘油三酯(富含C10和C12,还包含C16和C18饱和的)
进行用于制备UTG-0的步骤,除了使用棕榈油替代豆油。
MTG-0原料衍生物
下文描述了用于由MTG-0或PUTG-0开始制备MTG和PUTG产物的详细步骤。PMTG产物与MTG产物结构类似。UTG产物与PUTG产物结构类似。
MTG-5:MTGDMAPA酰胺混合物
R=C16、C18饱和+不饱和的
将MTG-0(180g,皂化值=226.5mgKOH/g,0.73mol)装入圆底烧瓶,将内容物加热至50℃。混合物用氮气吹扫1小时并加入二甲基氨基丙胺(DMAPA,78g,0.76mol)和NaBH4(0.1g)。将混合物加热至160℃达18小时。通过短程蒸馏(135℃,30mmHg)除去过量的胺,产物冷却至室温得到酰胺基胺混合物MTG-5。胺值:172.9mgKOH/g(当量重量:324.45g/mol)。游离DMAPA:1.80%;碘值:71.9gI2/100g样品。
MTG-6:MTGDMAPA甜菜碱混合物
R=C16、C18饱和+不饱和的
将MTG-5(107.8g,0.32mol)、一氯乙酸钠(SMCA,38.4g,0.33mol)和水(237g)装入圆底烧瓶。将混合物加热至80℃保持1小时,混合物变成均质。用50%NaOH水溶液将pH维持在8.5-10之间(以在IPA和/或水中稀释至10%进行测定)。pH稳定之后,将混合物加热至100℃保持14小时。当NaCl含量稳定时,判定反应完成。将产物冷却至室温,调节pH至8.5。甜菜碱产物MTG-6是澄清的、均一的溶液。NaCl含量:5.22%;固体:39.4%;甜菜碱活性物质:34.2%。
MTG-11:MTGDMAPA磺基甜菜碱
R=C16、C18饱和+不饱和的
将焦亚硫酸钠(46.4g)和水(250g)装入氮气吹扫的烧瓶,将混合物温热至40℃。加入NaOH水溶液(0.75g的50%溶液)并稍微搅拌。在1小时内滴加环氧氯丙烷(44.3g),使得混合物温热至70℃。在70℃下搅拌混合物0.5小时,加入更多50%NaOH(0.75g)。稍加混合后,加入一份MTG-5(150g)。将混合物保持在80℃下并搅拌3小时。以常规方法将pH由8.2调节至10.3。3小时后,将混合物冷却至室温。再将混合物加热至80℃并搅拌1小时。当pH=10.35且NaCl含量=6.81%时,判定反应完成。将产物冷却至室温,并用50%H2SO4水溶液调节pH至8.60。磺基甜菜碱MTG-11的分析表明:NaCl:5.65重量%;水分:49.7%;固体:50.3%;磺基甜菜碱活性物质(通过固体NaCl):44.7%。一份干燥样品的1HNMR分析证实了预期的结构。
MTG-13:MTGDMAPADMS季铵化合物
R=C16、C18饱和+不饱和的
将MTG-5(159.9g)装入氮气吹扫的烧瓶,并将内容物温热至80℃。加入硫酸二甲酯(56.86g)。将混合物温热至95℃,但是粘度一直大,所以将温度降至70℃,并加入异丙醇(25.5g)。在70℃下搅拌反应3小时,使之冷却。季铵化合物产物MTG-13的分析表明:游离胺:0.055meq/g;水分:0.13重量%;活性季铵化合物:1.80meq/g。
MTG-14:MTGDMAPA苄基季铵化合物
R=C16、C18饱和+不饱和的
将MTG-5(118.4g)和甲醇(23g)装入配备有搅拌棒、回流冷凝器和热电偶的圆底烧瓶。将混合物加热至67℃,滴加氯苄(39.3g)。调节添加速率保持温度在95℃以下。添加后,调节温度至82℃并保持2小时。加入氢氧化钠水溶液(0.33g的50%溶液),接着加入更多氯苄(6.9g),并将混合物保持在82℃下达2小时。1HNMR显示了目标产物。将热的苄基季铵化合物加到水(140g)中,将混合物冷却至室温同时搅拌。分析苄基季铵化合物产物MTG-14(300g):pH:6.7(1%,在9:1在IPA/水中);游离胺:0.011meq/g;水分:42.9重量%;活性季铵化合物:1.06meq/g;叔胺:0.023meq/g。
PUTG-5:PUTGDMAPA酰胺混合物
R=C16、C18饱和
将熔融的PUTG-0(750g,皂化值:227.6mgKOH/g,3.04mol)装入配备有回流冷凝器、热电偶、氮气/真空抽吸和机械搅拌器的反应容器。将混合物在60℃、氮气下搅拌。加入硼氢化钠(0.4g),并搅拌混合物0.5小时。在全真空下对混合物脱气(0.5小时)。用氮气释放真空,然后加入二甲基氨基丙胺(DMAPA,325g,3.18mol)。升高温度直至DMAPA出现少量回流(~150℃)。将混合物保持在150℃直到回流减慢。然后将温度升至160℃。在160℃下持续搅拌4小时,然后在150℃下搅拌混合物过夜。将混合物冷却至100℃,并使用低真空和干冰冷阱除去过量的DMAPA。缓慢地加大真空度直到达到全真空。持续汽提1小时。用HCl滴定蜡状产物PUTG-5。酸值:160.6meq/g;当量重量:349.4g/mol。胺值:160.56mgKOH/g;%游离DMAPA:0.08%。1HNMR(CDCl3),δ:5.8(CH2=CH-);5.4(-CH=CH-);4.9(CH2=CH-);3.2(-C(O)-NH-CH2-);2.15(-N(CH3)2)。
PUTG-6:PUTGDMAPA甜菜碱混合物
R=C16、C18饱和
将熔融的PUTG-5(200g,0.57mol)装入反应容器,温热至50℃,并进行机械搅拌同时用氮气冲刷容器0.5小时。将由一氯乙酸钠(SMCA,0.58mol,68g)和水(498g)制备的溶液加到熔融的胺,温度升至70℃。最初浑浊的混合物变得澄清和均质。在整个反应中,如需要,通过加入50%NaOH水溶液将pH维持在8.5-10(以10%的水稀释液测定)。还定期分析混合物的NaCl以判定反应完成。4小时后,将温度升至80℃并在冷却至室温过夜前保持2小时。NaCl含量:4.21%(基于100%转化率的NaCl理论值:4.45%)。再将混合物加热至80℃。游离胺(通过滴定):0.43%。加入作为补充加料的SMCA(1.10g),在80℃下持续搅拌2小时。测定的pH:8.78;NaCl含量:4.35%。判定反应完全,并将产物PUTG-6冷却至室温。分离的固体的1HNMR分析与目标结构一致。通过加入50%H2SO4(1g)调节最终的pH为7.5,得到的产物为澄清的水溶液。固体含量:35.8%;游离胺:0.85%;NaCl:4.39%。
PUTG-11:PUTGDMAPA磺基甜菜碱
R=C16、C18饱和
一般地,采用PUTG-5(200g)、焦亚硫酸钠(61.1g)、水(330.8g)、50%NaOH水溶液(两份,各1.0g)和环氧氯丙烷(58.3g)进行用于制备MTG-11的步骤。将混合物冷却至室温后,另外加水(10g)得到蜡状凝胶,再将混合物加热至80℃保持2.5小时。此外,如果需要,采用NaOH水溶液将pH保持在8.4和9.2之间。当NaCl含量稳定在5.49%时,判定反应完成。冷却至室温后,将浓的产物温热至40℃,并加水(15g)。通过加入50%的H2SO4(水溶液)将pH调节至6.52。当冷却产物时,产物再次变成浓的凝胶,需要进一步稀释。另外加水得到约50%固体溶液。分析产物PUTG-11:NaCl:5.29重量%;水分:51.2%;固体:48.8%;磺基甜菜碱活性物质(通过固体NaCl):43.5%。一份干燥的样品的1HNMR分析证实了预期的结构。
PUTG-13:PUTGDMAPADMS季铵化合物
R=C16、C18饱和
将PUTG-5(113.3g)装入氮气吹扫的圆底烧瓶,并将内容物温热至80℃。加入硫酸二甲酯(40.23g)。将混合物温热至95℃保持1小时。粘度一直高,加入异丙醇(~20g)。搅拌混合物1小时,然后冷却至室温。对季铵化合物产物PUTG-13的分析显示:pH:7.47(1%,在9:1的2-丙醇/水中);碘值:21.55;游离胺:0.053meq/g;水分:0.29重量%。
PUTG-14:PUTGDMAPA苄基季铵化合物
R=C16、C18饱和
将PUTG-5(110g)和甲醇(21g)装入配备有搅拌棒、回流冷凝器和热电偶的圆底烧瓶。将混合物加热至67℃,并滴加氯苄(34.4g)。调节添加速率以保持温度在95℃以下。添加后,将温度调节至82℃并保持2小时。加入氢氧化钠水溶液(0.30g的50%溶液),接着加入更多的氯苄(5.5g),并在82℃下维持混合物2小时。1HNMR显示理想的产物。形成凝胶,将混合物再次温热至80℃。加水得到澄清的溶液,对其分析。分析苄基季铵化合物产物PUTG-14(248g):碘值:10.22;pH:9.15(1%,在9:1的2-丙醇/水中);NaCl:7.12重量%;水分:32.1重量%;叔胺:0.22重量%;活性物质(烷基季铵化合物):1.23meq/g。
农业草甘膦制剂:制剂稳定性
样品制备:
通过首先将草甘膦酸(486.19g,90.5%酸当量,Monsanto的产品)装入配备有搅拌器和温度探针的冰冷的1L反应容器来制备44.0%酸当量(a.e.)制剂。边搅拌边加入去离子水(337.23g)生成草甘膦酸浆料。缓慢加入氢氧化钾微粒(176.58g,86.6%KOH,Fisher),使得溶液温度不超过50℃。然后使混合物冷却至室温并混合直至得到澄清的44%a.e.的草甘膦浓缩物。通过制备10%浓缩物的去离子水溶液来测定浓缩物的pH,以pH电极测定pH。如果浓缩物的pH介于4.2和4.4之间,则直接使用浓缩物。如果pH需要调节,那么以合适的量加入草甘膦酸、KOH和水以得到正确的pH,同时保持浓缩物所需的44%a.e.水平。
稳定性测试:
将测试表面活性剂(5.0g)加入45.0g上述草甘膦浓缩物(44%a.e.),得到草甘膦制剂浓缩物~39.6%a.e.(~540g/La.e.K盐)。混合该浓缩物直到得到澄清的溶液。如果没有得到澄清的溶液,则将等份的月桂基二甲基氧化胺(LDMAO,~55-60%活性物质)加到表面活性剂以制备90:10的表面活性剂:LDMAO的共混物。然后如上所述测试稳定性。如果未能通过测试,则继续向表面活性剂添加LDMAO的步骤直至达到能得到稳定的草甘膦制剂的比例。如果不能制备稳定的制剂,表面活性剂被视为与草甘膦不相容。如果得到澄清的均质的溶液,将样品分成两部分,均置于54℃烘箱和-10℃冰箱中两周。如果没有浑浊或分离,认为制剂在该温度下稳定。
对照例的表面活性剂为C12-C14DMEA酯季铵化合物。这是通过月桂酸(C12)和肉豆蔻酸(C14)的混合物与N,N-二甲基乙醇胺(DMEA)在140℃下反应5小时,然后加热至175℃完成反应来制备的。以常规方法在80℃、40psig下用一氯甲烷的丙二醇溶液进行季铵化反应得到目标酯季铵化合物。对照例的表面活性剂在室温下为澄清的制剂,但制剂在-10℃下分离。需要以9:1至1:1的比例(对照例的表面活性剂比氧化胺)添加氧化胺得到理想的与对照在一起的稳定性。
如表4所示,在稳定性测试中,二十二份样品的性能相当于或优于类似化合物。
水溶性除草剂制剂测试
考察应用于水溶性除草剂的候选表面活性剂,其作为阴离子、非离子或阴离子非离子共混物部分的替代品,将其与用在百草枯中的已知工业标准品比较,百草枯是水溶性除草剂浓缩物制剂。进行标准的稀释测试,其中浓缩物在水中稀释以确定溶解是否完全。
对照例:将百草枯(9.13g的43.8%活性物质)加到20mL玻璃瓶。加入已知的工业百草枯助剂(2.8g),剧烈混合30秒。加入去离子水(8.07g),重新混合30秒。将标准的342ppm水(47.5mL)加入50mL奈斯勒量筒(Nesslercylinder)中,将其塞住并在30℃水浴中平衡。一旦测试水平衡,就通过移液器将百草枯制剂(2.5mL)加入量筒中。将圆筒塞住并颠倒十次。记录溶解完全或不完全。使量筒静置并在30分钟、1小时、2小时和24小时后记录分离的量(以mL计)和类型。溶解性测试结果记载在下面的表5中。
阴离子测试样品:将百草枯(4.57g的43.8%的活性物质)加到20mL玻璃瓶中。加入8至10摩尔烷基酚烷氧化物表面活性剂(0.7g)并剧烈搅拌30秒。加入测试样品(0.7g),重新混合30秒。加入去离子水(4.03g),重新混合30秒。将2.5mL百草枯制剂样品加到47.5mL的342ppm硬水中,如上所述,对对照样品进行连续测试。
非离子测试样品:将百草枯(4.57g的43.8%活性物质)加到20mL玻璃瓶。加入测试样品(0.7g)并剧烈搅拌30秒。加入直链烷基苯基磺酸钠(“NaLAS,”0.7g),并继续混合30秒。加入去离子水(4.03g),继续混合30秒。将2.5mL百草枯制剂样品加到47.5mL的342ppm硬水中,如上所述,对对照样品进行连续测试。参见表5的溶解性结果。
助剂(阴离子/非离子)测试样品:将百草枯(4.57g的43.8%的活性物质)加到20mL玻璃瓶中。加入测试样品(1.4g)并剧烈混合30秒。加入去离子水(4.03g),继续混合30秒。将2.5mL百草枯制剂样品加到47.5mL的342ppm硬水中,如上所述,对对照样品进行连续测试。乳剂溶解度标准:测试样品与对照例一样良好或优于对照,一小时后无分离。在乳液稳定性测试中,三十三个测试样品的性能等同于或优于对照例。结果记载在表5中。
农业产品:阴离子乳化剂
阴离子乳化剂样品包含相对大量的水(>20%),被制备成水包油(EW)浓缩物。对相对于包含标准表面活性剂的对照例或空白对照例进行测试。制备足够的制剂,对三种样品中的每一种进行两种硬度(34ppm和1000ppm)的测试。
样品的制备:将吡草醚(Pyraflufen)(97.8%活性物质,0.30g)与(辛酸/癸酸甲酯,7.20g)和N-甲基-2-吡咯烷酮(1.20g)混合,磁力搅拌混合物直至溶解。在分离的容器中,将8242(蓖麻油乙氧基化物,POE40,Stepan的产品,0.96g)、MT-630F(脂肪酸乙氧基化物,POE30,Stepan,0.19g)、MT-615(脂肪酸乙氧基化物,POE15,Stepan,0.17g)、Aromatic150溶剂(ExxonMobil,0.37g)以及待测阴离子样品(0.71g)混合。如果需要,在与其它表面活性剂混合之前,在烘箱中在50-60℃下将阴离子样品熔化。当吡草醚已经溶解时,加入整个表面活性剂共混物并磁力搅拌直至均质。边搅拌边缓慢加入去离子水(0.90g)并混合以防止凝胶化。注意并记录浊度变化。
对照例的样品1:进行相同的步骤,除了以(烷基苯基磺酸钙,Stepan,0.71g)替代阴离子样品。
对照例的样品2:不包括Ninate60L(或阴离子样品),Aromatic150的量升至1.08g。
乳液稳定性测试
如下所示改进ASTME1116-98(2008)。将34ppm或1000ppm的水(95mL)装入100mL平底量筒。使用Mohr移液器将EW浓缩物送入每个量筒。塞住量筒并颠倒十次,然后使之静置0.5、1和24小时,同时记录每次的类型和分离%显示稳定性。
根据以下标准记录自发性:(1)差:非常薄的乳液云,油滴大量分离;(2)一般:薄的乳液云,油滴少量分离;(3)良好:薄的乳液云达到量筒底部,无任何类型的分离;(4)优:稠密的乳液云达到量筒底部,无任何类型的分离。
表6提供了结果。以下显示的四个样品全部被评价为“良好”的阴离子表面活性剂。
抗微生物产品:杀生物剂的活性物质
采用快速筛选试验评价生物杀灭效率,所述快速筛选试验是测定在5分钟的时间内细菌的相对杀灭率%的基于ATP的方法。使用的对照例为第一代ADBACBTC835(苄基二甲基氯化铵)。测试微生物:绿脓杆菌和金黄色葡萄球菌。
在MuellerHinton肉汤培养基中制备寿命为二十四小时的测试微生物培养物并培养。考虑样品的活性物质含量,准确称量在去离子水或400ppm水中的样品以制备1000ppm溶液。将24小时的培养物稀释至10体积%以得到细胞浓度为~107cfu/mL(每mL菌落形成单位)。采用BacTiter-Glo微生物细胞活力测试试剂盒(Promega的产品)中提供的说明制备试剂,在室温下校准15分钟。将每一制剂类型分散(90μL,1000ppm)到96孔板的每一排中。将空白培养基,即MuellerHinton肉汤(10μL)培养基同样分散到三个孔(1-3)以确定基线,同时将待测微生物(10μL)同样分散到九个实验孔(4-12)。启动计时器,振摇测试板30秒。在适当时间(例如,5分钟或10分钟)的接触结束时,将等量的BacTiter-Glo试剂混合物加到每一反应混合物,从试验样品开始到基线样品结束。振摇确保充分混合后,测定和记录每一孔的相对发光单位(RLU)。5分钟接触时间后由以下公式计算每一微生物在DI或硬水中107cfu/mL的杀灭率%:
杀灭率%=[1-(孔实验的平均RLU-孔基线对照的平均RLU)]/80000
如表7A和7B所示,当作为抗微生物活性物质测试时,二十个测试组合物的性能等同或优于对照例。
硬表面清洁剂:水性去污剂
该试验测量了清洁产品将油污(greasydirtsoil)从白色乙烯基瓷砖上去除的能力。试验是自动化的,并且使用工业标准的加德纳直线式洗涤装置(GardnerStraightLineWashabilityApparatus)。摄像机和受控制的照明用于采集清洁过程的现场录像。机器使用以已知量的试验产品润湿的海绵。当机器用海绵擦拭污染的瓷砖时,录像记录结果,由所述结果可测定清洁百分比。使用以1:32的比例用水稀释的试验制剂总共进行十次擦拭并且计算1-10次中的每一次的清洁度以提供产品清洁效率的数据图。根据是否为阴离子型、两性或非离子型将试验样品用作不同对照例制剂的组分。
阴离子型试验样品:
由丙二醇正丙醚(4.0g)、丁基卡必醇(4.0g)、柠檬酸钠(4.0g)、EC-690乙氧基化醇(1.0g,Stepan的产品)、试验样品(0.29g,如果是100%活性物质)、和去离子水制备中性可稀释的多用途清洁剂(至100.0g溶液)。在用于阴离子型试验的对照样品中,用WA-ExtraPCK(十二烷基硫酸钠,Stepan,1.0g,标称30%的活性物质)代替试验样品。
非离子型和两性试验样品:
由丙二醇正丙醚(4.0g)、丁基卡必醇(4.0g)、柠檬酸钠(4.0g)、StepanolWA-ExtraPCK(十二烷基硫酸钠,1.0g)、试验样品(0.90g,如果是100%活性物质)、和去离子水制备中性可稀释的多用途清洁剂(至100.0g溶液)。在用于非离子型/两性试验的对照样品中,用Bio-SoftEC-690(乙氧基化醇,1.0g,标称90%的活性物质)代替试验样品。
污物组成:
使用颗粒介质(50mg)和油介质(5滴)污染瓷砖。颗粒介质由(以重量份计)hyperhumus(39)、石蜡油(1)、废机油(1.5)、波特兰水泥(17.7)、二氧化硅1(8)、莫拉卡黑(1.5)、氧化铁(0.3)、带状黑粘土(18)、硬脂酸(2)和油酸(2)组成。油介质由煤油(12)、Stoddard溶剂(12)、石蜡油(1),SAE-10机油(1)、Crisco(1)、橄榄油(3)、亚油酸(3)和角鲨烯(3)组成。
十三种两性的(甜菜碱、磺基甜菜碱)和五种阴离子(磺酸盐)样品的性能等同于或优于该测试中的对照例(参见表8和9)。注意将季铵磺酸盐C10-19和C12-19作为Bio-SoftEC-690的替代品来进行测试,因为它们的净总电荷为零,尽管它们作为阴离子测试样品列在表9中。
硬表面活性剂:起泡的玻璃和窗户清洁剂
对照例:将LO(月桂基氧化胺,0.70g,Stepan的产品,标称30%活性物质)和PAS-8S(2.00g,辛酰基磺酸钠,Stepan的产品,标称38%的活性物质)与异丙醇(2.50g)混合,用去离子水稀释至100mL。
测试制剂:将测试样品(0.21g,如果100%的活性物质)和Bio-TergePAS-8S(2.00g)与异丙醇(2.50g)混合,并用去离子水稀释至100mL。
方法:评价测试制剂的透明度;在低膜/低条纹测试中仅评价透明的制剂。测试测定清洁剂离开测试镜的无条纹和膜表面的能力。以可控的量将测试制剂施用到镜子并用标准的基材前后擦拭,使扩散的产品干燥。一旦干燥,由二人小组观察和评价镜子。给出“优于”、“等同”、“差于”对照例的评价。这里使用的制剂用于评价两性和非离子表面活性剂。
在测试中,八种样品C16-13、C16-16、MTG-6、MTG-11、PMTG-6、PMTG-11、PUTG-6和PUTG-11性能等同于对照例。
压缩衣物洗涤剂的冷水清洁性能
该方法评价衣物洗涤剂制剂的整体冷水(55°F)清洁性能,该制剂包含阴离子表面活性剂和非离子表面活性剂的浓缩共混物、助洗剂、C16MES和实验样品。如下述部分所述制备制剂。相对于椰油酰胺DEA,测试实验样品改善整体清洁性能的能力。
浓缩的共混物的制备:
首先将去离子水(需要总量的90%)与S-101(十二烷基苯磺酸,3.27重量%,Stepan的产品)合并,并在50℃下混合。加入氢氧化钠(50%水溶液)至pH11(需要总量的24%的约4重量%)。加入柠檬酸(50%水溶液,6.2重量%),接着加入三乙醇胺(3.45重量%)。缓慢加入EC-690(月桂醇聚醚,90%活性物质,27.8重量%,Stepan的产品)。将pH调节至7.8至8.4,使用剩余的氢氧化钠水溶液达到8.1的目标。加入二甲苯磺酸钠(40%活性物质,4.30重量%),接着加入防腐剂和剩余的去离子水(足量至100重量%)。
使用C 16 MES和共混物制备超级衣物洗涤剂:
在55-60℃下加入去离子水(足量至100重量%)。加入以上制备的浓缩的共混物(58.0重量%),同时将温度保持在50℃至60℃。缓慢加入C16MES(87%活性物质,10.34重量%)并使其溶解。然后将混合物冷却至35℃。然后缓慢加入试验样品或椰油酰胺DEA标准(5.0重量%)并混合,直到该批变成均质的。
冷水清洁评价:
将衣物洗涤剂(30g,参见A部分)加入洗衣机中,接着加入连接于枕套的污染的/染色的布样。洗涤温度:55°F。漂洗:55°F。将布样从枕套上拆下,干燥并熨烫。扫描布样以测量L*a*b*值,所述值用于计算每种类型的布样的去污指数(SRI)。最后,计算ΔSRI,它等于试验样品SRI减去预定的标准衣物洗涤制剂(或对照)的SRI。当│ΔSRI│≥1时,差别是肉眼可见的。如果ΔSRI的值大于或等于1,样品是优异的。如果ΔSRI小于或等于-1,样品是较差的。如果ΔSRI大于-1且小于1,认为样品与标准是同等的。
使用以下标准的弄脏/或玷污的织物样本:棉布上的皮脂细末(DSC)、牛脂(BT)、聚酯上的高岭土和羊毛脂(WFK30C)、棉布上的草(GC)、棉布上的蓝莓(BC)、棉布上的可可粉(EMPA112)以及棉布上的血/墨汁/牛奶(EMPA116)。每次洗涤使用每种样本的至少三个。将样本钉在枕套上洗涤,包括额外的枕套达到6磅装载量。
使用相同的步骤洗涤所有的枕套/样本,注意确保水温、洗涤时间、添加方式等在冷水洗涤过程中保持恒定。当循环结束时,从枕套取出样本,在架子上稍微加热干燥,并用干熨斗简单按压。
使用HunterXE分光光度计确定L*a*b*值来计算每一类样本的SRI,去污指数(SRI)计算如下:
ΔSRI=SRI样品-SRI标准
如表10所示,当评价冷水清洁性能时,测试样品中的两种的性能等同于或优于椰油酰胺DEA。
廉价的衣物洗涤剂增效剂
该方法评价实验样品被用作廉价衣物洗涤剂制剂中的添加剂时其增强清洁的能力,所述制剂包含中和的十二烷基苯磺酸钠、如乙氧基化的合成的C12-C15醇(7EO)的非离子表面活性剂、柠檬酸、单乙醇胺、三乙醇胺和防腐剂。以相对于LO(月桂基氧化胺,Stepan,标准增效剂)1%的固体含量测试试验样品改善整体清洁性能的能力。将衣物洗涤剂制剂(46g)装入洗衣机,接着装入与衬套相连的弄脏的/玷污的织物样本。洗涤温度:90°F。漂洗:70°F。将样本从枕套取下来,干燥并熨烫。
由氢氧化钠中和的十二烷基苯磺酸钠(NaLAS,S-101,Stepan,33.9%活性物质,41.3重量%)、N25-7(脂肪醇乙氧基化物,Stepan的产品,5.00重量%),增效剂(实验样品或AmmonyxLO,其为30%的活性物质,3.33重量%)、柠檬酸(50%水溶液,1.00重量%)、单乙醇胺(1.00重量%)、三乙醇胺(1.00重量%),以及去离子水加防腐剂(余量至100重量%)制备含有增效剂的廉价衣物洗涤剂。
通过在50℃下装入总量的90%的水,然后依次边加入边混合柠檬酸溶液、单乙醇胺、三乙醇胺、中和的磺酸、Bio-SoftN25-7和增效剂来制备制剂。用25%NaOH水溶液调节pH至9.5,然后加入防腐剂和余量的水。
使用了以下标准的污染/染色的布样:棉布上的皮脂细末(DSC);棉布/聚酯上的皮脂细末(DSCP);牛脂(BT);棉布上的粘土(CC);棉布/聚酯上的粘土(CCP);棉布上的草(GC);棉布上的红酒(RWC);棉布上的蓝莓(BC);棉布上的咖啡(COFC);棉布上的可可粉(EMPA112);棉布上的血/墨水/牛奶(EMPA116);和棉布上的化妆品(EMPA143)。每次洗涤至少使用三块每种布样。将布样订在枕套上以进行洗涤,包括额外的枕套以达到六磅的负载。
使用相同的步骤洗涤所有的枕套/样本,注意确保水温、洗涤时间、添加方式等在冷水清洗过程中保持恒定。当循环结束时,从枕套取下样本,在架子上稍微加热干燥并用干的熨斗简单按压。
使用HunterXE分光光度计确定L*a*b*值,以计算每一类型样本的SRI,如上文讨论的冷水清洁步骤中所述的计算去污指数(SRI)。
如表11中所示,当作为廉价衣物洗涤剂的增效剂进行评价时,一种测试样品的性能等同于月桂基氧化胺对照例。
气井发泡剂:批动力测试
在该步骤中,将测试表面活性剂、盐水和/或冷凝物加入柱,然后用氮气搅拌从而产生泡沫。5分钟后柱上持续的泡沫的重量%是测试样品性能的测量值。收集结果作为盐水组合物、表面活性剂浓度和溶液中存在的浓缩物百分比的函数。
以12.5%和25%总溶解的固体(TDS)来制备盐水。盐水中NaCl与CaCl2的比例为80:20。12.5%TDS的密度为1.087g/mL,25%的TDS为1.184g/mL。过滤盐水溶液除去微粒。
在上文列出的每一盐水溶液中,以每百万5000、2000、1000和500份活性物质测试表面活性剂样品。当适用时,测试溶液由盐水、表面活性剂和冷凝物组成。以下公式显示了基于活性物质含量和使用的盐水的密度需要的表面活性剂的量。
该样品的计算显示了需要多少45%的活性表面活性剂制备5000ppm的12.5%的TDS盐水中的溶液:
使用5000ppm溶液制备2000ppm溶液,将2000ppm溶液稀释制成1000ppm溶液等等。当包含冷凝物时,盐水中理想的活性物质含量应使得总测试溶液中的活性物质含量与存在的变化量的冷凝物保持恒定。例如,当制备含10%冷凝物的5000ppm溶液时,盐水/表面活性剂溶液实际上是5556ppm,使得溶液加冷凝物为~5000ppm。当测试产物以何种程度处理冷凝物时,向溶液加入10%或20%。对每一浓度水平的盐水溶液都这样做。
使用的冷凝物是低芳香性的矿物油,D-40(d=0.7636g/mL),ExxonMobil的产品。在加入盐水/表面活性剂之后,加入理想量的冷凝物。通过柱底部的玻璃粉供入氮气,使用质量流量控制器每小时供入14标准立方英尺。使用DataStudio(来自Pasco)软件和天平来测量收集的泡沫的量。在10分钟的运行过程中每秒记录重量。表12报道了每种盐水溶液在每一冷凝物含量%下5分钟后持续作为泡沫的液体的百分比。
如表12所示,当作为潜在的气井发泡剂进行评价时,八种测试样品的性能等同或优于对照例。
个人护理:清洁应用
使用粘性和机械振摇泡沫测试来评估特定表面活性剂作为用于个人护理的清洁应用中的辅助表面活性剂(secondarysurfactant)的可能的价值。
相对于对照例(椰油酰胺丙基羟基磺基甜菜碱或椰油酰胺丙基甜菜碱)评价所有实验样品的性能。
通过用12%活化的月桂基醚(1)硫酸钠(SLES-1)制备稀释的测试物质或对照(3%活性物质含量)的水溶液,然后通过BrookfieldDV-1+粘度计来测定粘度以生成粘度曲线。逐渐加入氯化钠(1-3重量%),记录粘度作为升高的NaCl浓度的函数。“良好”的结果是曲线显示粘度的确立比得上对照样品。“优异”的评价显示样品比对照基本上更快速地确立粘度。
采用机械振摇泡沫测试评价发泡性质。此后,采用25℃自来水由水溶液制备样品溶液(以0.2%总表面活性剂活性物质计算)。将一份100.0g的溶液小心地转移至500mL量筒。加入蓖麻油(2.0g)。将量筒塞住并机械颠倒十次,然后使其静置15秒。记录泡沫高度。5分钟后再记录泡沫高度。在不使用蓖麻油的情况下重复实验。在一组实验中,在实验和对照轮次中清洁基质都包含SLES-1。在第二组实验中,清洁基质包含另一种广泛使用的阴离子表面活性剂,即2-磺基月桂酸甲酯钠和2-磺基月桂酸二钠的混合物,替代SLES-1。当包含测试物质的溶液得到的泡沫高度在对照轮次的+/-25mL内记录为“良好”。结果>对照的25mL获得优的评价;结果<对照的25mL评价为差。
表13确认的十种测试物质在粘度和泡沫测试中显示良好的整体性能。
个人护理/抗微生物洗手皂:
确定泡沫增强益处的方法
泡沫量对于消费者标志着“干净”,是抗微生物洗手皂中的一种希望的特性。由于阳离子抗微生物活性物质与阴离子表面活性剂(最好的发泡剂)不相容,因此使用阳离子抗微生物活性物质实现足够的泡沫量是具有挑战性的。以下方法确定了在抗微生物的洗手皂基中能够比椰油酰胺丙基甜菜碱(活性物质/活性物质基础)提供更多的泡沫量的表面活性剂。制剂:去离子水(足量至100重量%)、椰油基葡糖苷(3.0重量%)、月桂胺氧化物(3.0重量%)、苯扎氯铵(0.1重量%)、和试验分子或椰油酰胺丙基甜菜碱(3.0重量%)。
通过按以上指定的顺序合并成分来制备溶液,使用搅拌棒搅拌或使用顶置式搅拌器温和混合或使用抹刀手动混合。如果试验分子在室温下为固态,可以加热。维持混合以确保得到均质的溶液。将pH调节至6.5+/-0.5。
在0.2%的总表面活性剂活性物质浓度(使用来自密歇根湖的自来水将2.22g溶液配制成100mL,~150ppmCa/Mg硬度)下,在有和没有2%蓖麻油的条件下使用量筒倒置试验(cylinderinversiontest)比较了试验溶液和对照例溶液的泡沫量。进行了初始和延时(5分钟)测量。
评价***:优异:在油和无油***中结果>25mL超过椰油酰胺丙基甜菜碱对照例。良好:在油和无油***中,结果在椰油酰胺丙基甜菜碱对照例的25mL内。差:在油和无油***中结果>25mL低于椰油酰胺丙基甜菜碱对照例。
与对照例相比,表14中鉴定的四种测试物质均在抗微生物洗手皂测试中显示出优异的整体性能:
与对照例相比,表15中鉴定的十七种测试物质均在抗微生物洗手皂测试中显示出优异的整体性能:
头发护理剂:评价湿梳理性的步骤:
采用一致且均一的头发类型(二次漂白的金发)制备长发(10”长,2-3g)。用15%活性十二烷基硫酸钠溶液一起洗长发。注意避免在洗发期间过度纠缠。用40℃自来水将长发漂洗干净。重复该过程来模拟两次应用洗发水。将长发分开并标记用于测试。采用注射器将测试护理剂制剂(2.0cm3)施用到每一干净、湿的长发。基础护理剂包含十六烷醇(2.0%)、羟乙基纤维素(0.7%)、十六烷基三甲基氯化铵(1.0%)和水(足量至100%)。将测试样品制成2重量%(活性物质)添加剂,加入基础护理剂。
通过手指向下运动一分钟使护理剂穿过头发起作用。以40℃的自来水将长发彻底漂洗干净。把每一长发中过量的水挤出以模拟毛巾擦干的头发。首先梳理湿状态的头发。评价样品和基础护理剂的梳理容易程度。对测试样品给出定性评价,与仅使用基础护理剂的结果对比。
对于测试的季铵化组合物而言,评价体系如下:“优异”为湿梳理性能的改善超过用作测试对照的护理剂的湿梳理性能的改善;“等同”为湿梳理性能与用作测试对照的护理剂相当;“差”为湿梳理性能比用作测试对照的护理剂差。
在该测试中,一种样品Mix-44优于基础护理剂,两种样品C16-10和PUTG-13的性能等同于对照。
油田腐蚀抑制:极化电阻方法
在温和(sweet)条件(喷射CO2)、在50℃下,在稀释的NACE盐水(3.5重量%NaCl;0.111重量%CaCl2·2H2O;0.068重量%MgCl2·6H2O)中施用极化电阻。工作电极是圆柱形的,由C1018steel制成,以3000rpm旋转。对电极为铂丝。参比为带有内盐桥的甘汞电极。在至少3小时时间内确定基线腐蚀率。一旦确定基线腐蚀率,就注射腐蚀抑制剂,收集测试期间的剩余时间的数据。理想的抑制剂浓度为0.00011-0.0010meq/g活性物质。软件细节:最初延迟在1800秒下持续,具有0.05mV/秒的稳定性;范围:-0.02至+0.02V;扫描速率:0.1mV/s;样品时间:1秒;数据收集:~24小时。最终的腐蚀率为最后5-6小时收集的数据的平均值。保护率由以下公式计算:
如表16中所示,作为腐蚀抑制剂,八种测试样品显示出等同或超过对照例的整体性能。
油田产品:石蜡分散剂
沥青烯筛选试验
在油井的酸增产过程中,将HCl、HF和腐蚀抑制剂的共混物泵送至井中,静置,然后泵出。在酸的传输过程中,在酸溶液中形成少量的氯化铁。一旦酸性共混物溶解了一定尺寸并沉积在井筒中,原油就开始流动并与井中的酸性溶液混合。原油在酸化后可以固化,而沥青烯一直与该问题相关。因此,通常在酸中加入分散剂以防止固化。
测试方法:
通过将1%FeCl3加入15%HCl溶液中来制备铁污染的酸储备溶液。将待测试的样品分散剂(0.2重量%)加入酸储备溶液(7.5mL)中。将酸/分散剂混合物和原油(2.5mL)加入到15mL小瓶中,并剧烈振摇小瓶30秒。记录初始的外观。在室温下静置1小时后,再次记录外观。将小瓶放置在烘箱(50℃)中24小时并记录其外观。将小瓶冷却至室温并再次记录外观。最后,在室温下24小时后,再次记录外观。运行含有原油和酸溶液但不含分散剂的空白对照例。也运行了含有大豆酰胺基胺三甲基氯化铵作为分散剂的对照例样品。还运行了含有测试分散剂与大豆酰胺基胺三甲基氯化铵1:1的混合物的另一种样品。
在该测试中,一种样品C18-65提供了等同于对照例的性能,而C18-27显示出优异的性能。
作为用于专业发泡剂应用的发泡剂或泡沫添加剂的性能
专业发泡剂应用包括(除了别的之外)石膏、混凝土和灭火泡沫。以下测试评价样品用作主要发泡剂的泡沫稳定性,还评价了当被用作泡沫稳定剂、增效剂和去稳定剂时样品作为添加剂的性能。
特别是针对石膏而言,其在商业生产线上的准备时间快,理想的泡沫助剂有助于控制泡沫的合并,从而在规定的时间范围内得到更大的气泡。优选地,在以下的测试中,在第一分钟结束时泡沫的稳定开始破坏。在表17中,这些组合物被确认为具有“良好”的作为石膏泡沫去稳定剂的性能,因为它们使得该平衡被有效破坏。
泡沫稳定性:排流法
通过将表面活性剂与不同硬度(342ppm硬水或1000ppmCaSO4水)的水混合制备表面活性剂溶液(0.4重量%活性物质)。小心地将表面活性剂溶液(100mL)转移至不锈钢混合杯,然后使用HamiltonBeach混合器高速(27Krpm)混合10秒。将内容物迅速倒入100mL量筒至100mL刻度,立即启动秒表。4分钟内,每15秒记录置于量筒中的液体的量。较少液体排出说明泡沫稳定性较高。
泡沫稳定性:泡沫半衰期
将如上所述制备的表面活性剂溶液样品(100g)高速混合30秒。将混合物快速倒入1000mL量筒,立即启动秒表。记录初始泡沫高度。当量筒中出现50mL液体时,记录时间和泡沫高度分别作为泡沫半衰期(以秒计)和半衰期的泡沫高度(以mL计)。
之前的实施例仅意味着举例说明。以下权利要求限定了本发明。
Claims (16)
1.季铵、甜菜碱或磺基甜菜碱组合物,其具有(i)式:
R2(R3)N+(R1)R4X-
其中:
R1为-(CH2)8-CH=CHR5或-(CH2)8-CH=CH-(CH2)8N+(R2)(R3)R4X-;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C1-C6烷基;X-为卤根、碳酸氢根、硫酸氢根或烷基硫酸根;R5为C1-C7烷基;或
式(ii)
R2(R3)N+(R1)R4
其中:
R1为-(CH2)8-CH=CHR5或-(CH2)8-CH=CH-(CH2)8N+(R2)(R3)R4;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C2-C4亚烷基羧酸根,C2-C4亚烷基磺酸根,或C2-C4羟基亚烷基磺酸根,和R5是氢或C1-C7的烷基;并且
当R5是C1-C7的烷基时,所述组合物具有至少1摩尔%的反式-Δ9的不饱和基。
2.季铵、甜菜碱或磺基甜菜碱组合物,其具有(i)式:
R4(R3)(R2)N+(CH2)nNH(CO)R1X-
其中:
R1为-(CH2)7-CH=CH-R5或-(CH2)7CH=CH-(CH2)7-(CO)NH(CH2)nN+(R2)(R3)R4X-;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C1-C6烷基;X-为卤根、碳酸氢根、硫酸氢根或烷基硫酸根;R5为氢或C1-C7烷基;以及n=2至8;或
(ii)式:
R4(R3)(R2)N+(CH2)nNH(CO)R1
其中
R1为-(CH2)7-CH=CH-R5或-(CH2)7CH=CH-(CH2)7-(CO)NH(CH2)nN+(R2)(R3)R4;R2和R3中的每一个独立地为取代的或未取代的烷基、芳基、烯基、氧化亚烷基或聚氧化亚烷基;R4为C2-C4亚烷基羧酸根,C2-C4亚烷基磺酸根,或C2-C4羟基亚烷基磺酸根,和R5是氢或C1-C7的烷基;和n=2至8;并且
当R5是C1-C7的烷基时,所述组合物具有至少1摩尔%的反式-Δ9的不饱和基。
3.通过磺化或亚硫酸化权利要求1或2所述的组合物来制备的衍生物。
4.权利要求2所述的组合物,其由脂肪酰胺基胺生成,其中所述脂肪酰胺基胺是通过复分解生成的C10-C17单不饱和酸、十八碳烯-1,18-二酸或它们的酯衍生物和氨基烷基取代的叔胺反应来制备的,其中所述氨基烷基取代的叔胺选自N,N-二甲基氨基丙胺(DMAPA)、N,N-二乙基氨基丙胺、N,N-二甲基氨基乙胺和N,N-二甲基氨基丁胺。
5.草甘膦制剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
6.水溶性除草剂组合物,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
7.抗微生物组合物,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
8.硬表面清洁剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
9.衣物洗涤剂制剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
10.洗发水或头发护理剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
11.个人清洁剂或洗手皂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
12.用于油田应用的腐蚀抑制剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
13.用于油田应用的石蜡分散剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
14.用于油田应用的气井发泡剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
15.用于石膏、混凝土或灭火应用的发泡剂、泡沫添加剂、或分散剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
16.用于农业组合物的阴离子乳化剂,其包含权利要求1或2所述的季铵、甜菜碱或磺基甜菜碱组合物,或权利要求3所述的衍生物。
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