CN116041229A - Castor oil-based sulfonate anionic surfactant and preparation method thereof - Google Patents
Castor oil-based sulfonate anionic surfactant and preparation method thereof Download PDFInfo
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- CN116041229A CN116041229A CN202310144726.1A CN202310144726A CN116041229A CN 116041229 A CN116041229 A CN 116041229A CN 202310144726 A CN202310144726 A CN 202310144726A CN 116041229 A CN116041229 A CN 116041229A
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- Prior art keywords
- castor oil
- anionic surfactant
- sulfonate anionic
- ricinoleic
- sulfonate
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 113
- 239000004359 castor oil Substances 0.000 title claims abstract description 104
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 104
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 104
- 239000003945 anionic surfactant Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 229960003656 ricinoleic acid Drugs 0.000 claims abstract description 68
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 82
- 239000003054 catalyst Substances 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- 229910052799 carbon Inorganic materials 0.000 claims description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 38
- 229940066675 ricinoleate Drugs 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- -1 alkyl ricinoleate Chemical compound 0.000 claims description 28
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- 238000006277 sulfonation reaction Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 150000004032 porphyrins Chemical class 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 46
- 239000004094 surface-active agent Substances 0.000 abstract description 37
- 239000007864 aqueous solution Substances 0.000 abstract description 17
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000008367 deionised water Substances 0.000 description 45
- 229910021641 deionized water Inorganic materials 0.000 description 45
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 43
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 24
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 24
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 20
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 18
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 description 17
- XKGDWZQXVZSXAO-UHFFFAOYSA-N ricinoleic acid methyl ester Natural products CCCCCCC(O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-UHFFFAOYSA-N 0.000 description 17
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 16
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 14
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XKGDWZQXVZSXAO-SFHVURJKSA-N Ricinolsaeure-methylester Natural products CCCCCC[C@H](O)CC=CCCCCCCCC(=O)OC XKGDWZQXVZSXAO-SFHVURJKSA-N 0.000 description 12
- 238000007259 addition reaction Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- AZXVZUBIFYQWJK-KWRJMZDGSA-N ethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC AZXVZUBIFYQWJK-KWRJMZDGSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000005187 foaming Methods 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 229910017053 inorganic salt Inorganic materials 0.000 description 12
- 239000000693 micelle Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000003068 static effect Effects 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 10
- 150000002191 fatty alcohols Chemical class 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000004949 mass spectrometry Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 8
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- HGWAKQDTQVDVRP-OKULMJQMSA-N butyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCCCC HGWAKQDTQVDVRP-OKULMJQMSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- IIGNZLVHOZEOPV-UHFFFAOYSA-N 3-Methoxybenzyl alcohol Chemical compound COC1=CC=CC(CO)=C1 IIGNZLVHOZEOPV-UHFFFAOYSA-N 0.000 description 3
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- XQCHMGAOAWZUPI-UHFFFAOYSA-M sodium;butane-1-sulfonate Chemical compound [Na+].CCCCS([O-])(=O)=O XQCHMGAOAWZUPI-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/06—Esters of higher fatty acids with hydroxyalkylated sulfonic acids or salts thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a castor oil-based sulfonate anionic surfactant and a preparation method thereof. The castor oil-based sulfonate anionic surfactant is prepared from castor oil or castor oil alkyl ester serving as a raw material and contains a sulfonic acid group and a hydroxyl hydrophilic group. The castor oil-based sulfonate anionic surfactant is prepared from castor oil or ricinoleic acid alkyl ester serving as a raw material, and is prepared from renewable biomass resources; meanwhile, the castor oil-based sulfonate anionic surfactant disclosed by the invention is a surfactant with excellent performance, can effectively reduce the surface tension of an aqueous solution, and has the advantages of good solubility, low foam and fine foam.
Description
Technical Field
The invention relates to the technical field of surfactants, in particular to a castor oil-based sulfonate anionic surfactant and a preparation method thereof.
Background
The surfactant is an important fine chemical, is closely related to daily life and industrial production of people, and is known as industrial monosodium glutamate. Most of the commonly used surfactants are synthesized artificially and are synthesized by petrochemical raw materials, and the petrochemical raw materials are non-renewable resources and do not meet the requirements of green chemistry. Therefore, how to develop green, sustainable surfactants using renewable biomass resources is an urgent issue to be addressed at present.
Disclosure of Invention
The invention aims to provide a castor oil-based sulfonate anionic surfactant and a preparation method thereof, which can take natural renewable grease as a raw material and can efficiently reduce the surface tension of an aqueous solution.
In order to achieve the above object, the embodiments of the present invention provide a ricinoleic sulfonate anionic surfactant prepared from castor oil or an alkyl ricinoleate as a raw material and containing both a sulfonic acid group and a hydroxy hydrophilic group.
In one or more embodiments of the present invention, any one of the following structural formulas:
wherein R is C 1 ～C 12 Saturated hydrocarbon radicals, R 1 、R 2 Is selected from any one of H and sulfonic acid groups respectively, and R 1 、R 2 Are not identical.
In one or more embodiments of the present invention, any one of the following structural formulas:
wherein X is K, na, NH 4 Any one of R is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
The embodiment of the invention also provides a preparation method of the castor oil-based sulfonate anionic surfactant, which comprises the following steps:
the mixed reaction system containing solid carbon-based base catalyst, solvent, bisulphite, castor oil or ricinoleic acid alkyl ester is subjected to double bond addition sulfonation reaction to obtain the ricinoleic sulfonate anionic surfactant,
The alkyl ricinoleate has the following structural formula:
r is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
In one or more embodiments of the present invention, the double bond addition sulfonation reaction is carried out at a temperature of 30 to 80 ℃ for a time of 10 to 100 hours.
In one or more embodiments of the present invention, the solid carbon-based base catalyst is prepared by calcining an organic compound precursor containing elemental carbon and elemental nitrogen.
In one or more embodiments of the present invention, the organic compound precursor containing carbon and nitrogen is any one of porphyrin, dopamine, melamine, dicyandiamide, and urea.
In one or more embodiments of the present invention, the solid carbon-based base catalyst is 2% to 30% of the mass of castor oil or alkyl ricinoleate;
the mol ratio of the castor oil or the ricinoleic acid alkyl ester to the bisulphite is 1 (1-6);
the mass ratio of the castor oil or the ricinoleic acid alkyl ester to the low-carbon alcohol is 1 (2-5).
In one or more embodiments of the present invention, the solvent is a combination of a lower alcohol and water in a mass ratio of 1 (1 to 5).
In one or more embodiments of the present invention, the lower alcohol is any one of ethanol, isopropanol, n-butanol, t-butanol, and tert-amyl alcohol.
Compared with the prior art, the castor oil-based sulfonate anionic surfactant is prepared from castor oil or castor oil alkyl ester serving as a raw material, and the green sustainable surfactant is prepared from renewable biomass resources; meanwhile, the castor oil-based sulfonate anionic surfactant disclosed by the invention is a surfactant with excellent performance, can effectively reduce the surface tension of an aqueous solution, and has the advantages of good solubility, low foam and fine foam.
Drawings
FIG. 1 is an XRD pattern of a solid carbon-based base catalyst according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a ricinoleic sulfonate anionic surfactant according to one embodiment of the present invention;
FIG. 3 is a surface tension diagram of a ricinoleic sulfonate anionic surfactant at various concentrations in accordance with an embodiment of the present invention;
FIG. 4 is a foam microcosmic pattern of a ricinoleic sulfonate anionic surfactant at a concentration of 1.0g/L in accordance with an embodiment of the present invention;
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
According to the castor oil-based sulfonate anionic surfactant, castor oil-based sulfonate anionic surfactant is prepared from castor oil or ricinoleic acid alkyl ester serving as a raw material and contains sulfonic acid groups and hydroxyl hydrophilic groups.
It can be understood that the castor oil-based sulfonate anionic surfactant and castor oil alkyl ester derivatives are used as raw materials, the condition of catalytic sulfonation reaction is regulated and controlled by selecting proper bisulphite as a sulfonating agent, hydroxyl is reserved, only the addition sulfonation reaction of carbon-carbon double bonds is carried out to graft hydrophilic group sulfonic acid groups, and the castor oil-based sulfonate sodium salt anionic surfactant containing two hydrophilic groups of hydroxyl and sulfonic acid groups is obtained and is a novel anionic surfactant different from the existing sulfonated castor oil.
Preferably, the bisulphite may be sodium bisulphite, potassium bisulphite and ammonium bisulphite.
In one embodiment, the castor oil-based sulfonate anionic surfactant has any one of the following structural formulas:
wherein R is C 1 ～C 12 Saturated hydrocarbon radicals, R 1 、R 2 Is selected from any one of H and sulfonic acid groups respectively, and R 1 、R 2 Are not identical.
Specifically, the castor oil-based sulfonate anionic surfactant has any one of the following structural formulas:
wherein X is K, na, NH 4 Any one of R is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
When castor oil is used as raw material to prepare the castor oil-based sulfonate anionic surfactant, the sulfonic acid group can be selectively added to carbon at two ends of unsaturated double bond, thus obtaining the products with the following two structural formulas
When the ricinoleic acid alkyl ester is used as a raw material to prepare the ricinoleic sulfonate anionic surfactant, the sulfonic acid group can be selectively added to carbon at two ends of unsaturated double bond, thus obtaining the products with the following two structural formulas
The embodiment of the invention also provides a preparation method of the castor oil-based sulfonate anionic surfactant, which comprises the following steps:
carrying out double bond addition sulfonation reaction on a mixed reaction system containing a solid carbon-based base catalyst, a solvent, bisulphite, castor oil or ricinoleic acid alkyl ester to obtain a ricinoleic sulfonate anionic surfactant;
the alkyl ricinoleate has the following structural formula:
r is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
Specifically, the temperature of the double bond addition sulfonation reaction is 30-80 ℃ and the time is 10-100 h.
Wherein, the preparation process of the ricinoleic acid alkyl ester can be as follows:
with ricinoleic acid and C 1 ～C 12 Fatty alcohol is used as a raw material, organic acid p-toluenesulfonic acid is used as a catalyst, and the dosage of the p-toluenesulfonic acid catalyst is 2-10% of the mass of ricinoleic acid, and the ricinoleic acid is as follows: the mol ratio of fatty alcohol is 1:3-6, the reaction temperature is controlled at 50-90 ℃, and the reaction time is 3-9 h; after the reaction is finished, extracting, washing, drying and distilling under reduced pressure to obtain the ricinoleic acid alkyl ester compound.
In one embodiment, the solid carbon-based base catalyst can be prepared by roasting an organic compound precursor containing carbon and nitrogen elements.
Specifically, the roasting temperature of the solid carbon-based base catalyst is 400-700 ℃ and the roasting time is 2-8 h. The product obtained by roasting is fully ground to obtain the solid carbon-based base catalyst.
Specifically, the organic compound precursor containing carbon and nitrogen elements is any one of porphyrin, dopamine, melamine, dicyandiamide and urea.
In the mixed reaction system, the mass of the solid carbon-based base catalyst is 2-30% of the mass of castor oil or ricinoleic acid alkyl ester; the mol ratio of castor oil or ricinoleic acid alkyl ester to bisulphite is 1 (1-6); the mass ratio of the castor oil or the ricinoleic acid alkyl ester to the low-carbon alcohol is 1 (2-5).
In a specific embodiment, the solvent is a combination of low carbon alcohol and water, and the mass ratio of the low carbon alcohol to the water is 1 (1-5).
Wherein the lower alcohol is any one of ethanol, isopropanol, n-butanol, tert-butanol and tert-amyl alcohol.
The castor oil-based sulfonate anionic surfactant and the preparation method thereof according to the present invention will be described in detail with reference to specific examples.
Example 1
1) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of melamine, roasting in a muffle furnace at 650 ℃ for 4 hours, and grinding to obtain the required catalyst. Figure 1 is an XRD pattern of the catalyst.
2) Double bond addition sulfonation reaction:
9.334g (0.01 mol) of castor oil are added to a 100mL beaker, and 28.002g of isopropanol are then added according to castor oil: lower alcohol=1:3 (mass ratio) and stirred well to mix them well. Another 250mL three-necked flask was taken, 4.162g (0.04 mol) of sodium bisulphite was added to the flask at a mass ratio of castor oil to sodium bisulphite=1:4 (molar ratio), 28.002g of deionized water was added thereto at a mass ratio of deionized water to isopropyl alcohol of 1:1 to sufficiently dissolve the sodium bisulphite, and 0.467g of a carbon-based base catalyst (5% mass fraction to castor oil) was added thereto. The mixed solution of castor oil and isopropanol was poured into a three-necked flask and stirred at 40 ℃ for 20h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove isopropanol, adding deionized water and petroleum ether to extract and remove unreacted castor oil, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the castor oil-based sulfonate anionic surfactant with the product yield of 95.6% after the steps of distilling under reduced pressure and drying and removing water.
Wherein fig. 2 shows an infrared spectrum of the ricinoleic sulfonate anionic surfactant prepared in example 1, as seen from the figure: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm -1 The stretching vibration peak of-CH=CH-in castor oil is not shown in the figure, which indicates that the double bond has addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product, namely the castor oil-based sulfonate anionic surfactant.
Wherein fig. 3 shows the surface tension diagrams of the ricinoleic sulfonate anionic surfactant prepared in example 1 at different concentrations. 1.0g of the castor oil-based sulfonate anionic surfactant prepared in example 1 was weighed out to prepare an aqueous surfactant solution having a concentration of 1 g/L. The apparatus used for the test was a KRUSS K100C surface tension tester, germany, which was based on the platinum plate method (Wilhelmy Plate method) technique by using a platinum plate in contact with the surface of an aqueous solution containing a surfactant at a certain concentration, and controlling the test temperature to 25.+ -. 0.5 ℃ using a circulating water bath from Ulaibo technology Co. When the instrument starts to test, the surface tension of pure water is firstly measured, under the condition of keeping the volume of the measured solution constant, the constant volume of surfactant solution is continuously injected into the test container, and the solution with the corresponding volume is accurately extracted, so that the concentration of the surfactant solution is continuously changed from dilute to concentrated, and the surface tension of the solution under different concentrations can be correspondingly obtained, At the end of the test, a surface tension versus concentration curve (as shown in FIG. 2) can be obtained. From FIG. 2, it can be determined that the Critical Micelle Concentration (CMC) of the surfactant is 4.50mmol/L and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 1 was shown to have typical surfactant properties at 43.45mN/m, and to be effective in reducing the surface tension of aqueous solutions.
Wherein FIG. 4 shows a foam microcosmic morphology of the castor oil-based sodium sulfonate anionic surfactant prepared in example 1 at a concentration of 1.0 g/L. 1.0g of the castor oil-based sodium sulfonate anionic surfactant prepared in example 1 was weighed out to prepare an aqueous surfactant solution with a concentration of 1 g/L. The apparatus used for the test was a KRUSS DFA100 dynamic foam analyzer, germany, with a test temperature of 25.+ -. 0.5 ℃.50 mL of the formulated solution was placed in a 250mm cylindrical glass column and run at 6000r/min for 30s with mechanical stirring to generate foam with a total run time of 1200s. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid methyl ester sodium sulfonate anionic surfactant prepared in the embodiment 1 is less, and the foam is finer and more stable.
Example 2
1) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of dicyandiamide, roasting in a muffle furnace at 550 ℃ for 5 hours, and grinding to obtain the required catalyst.
2) Double bond addition sulfonation reaction:
9.334g (0.01 mol) of castor oil are added to a 100mL beaker, and 46.670g of n-butanol are added according to castor oil to lower alcohol=1:5 (mass ratio), and are thoroughly stirred to be uniformly mixed. Another 250mL three-necked flask was taken, 6.008g (0.05 mol) of potassium hydrogen sulfite was added to the flask at a mass ratio of castor oil to potassium hydrogen sulfite=1:5 (molar ratio), 93.340g of deionized water was added thereto at a mass ratio of deionized water to n-butanol of 1:2 to sufficiently dissolve potassium hydrogen sulfite, and 1.400g of a carbon-based base catalyst (15% mass fraction to castor oil) was further added. The mixed solution of castor oil and n-butanol was poured into a three-necked flask and stirred at 40℃for 20h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove n-butyl alcohol, adding deionized water and petroleum ether to extract and remove unreacted castor oil, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the castor oil-based sulfonate anionic surfactant with the product yield of 90.23% after the steps of distilling under reduced pressure and drying and removing water.
Using the detection method described in example 1, it can be seen from the infrared spectrogram of the prepared castor oil-based sulfonate anionic surfactant: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product, namely the castor oil-based sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 2.89mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 2 was shown to have typical surfactant properties at 35.48mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid ethyl ester sulfonate sodium salt anionic surfactant prepared in the example 2 is 110mL, and the foam is fine and stable.
Example 3
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid and 16.020g (0.50 mol) of methanol are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, wherein the mol ratio of ricinoleic acid to fatty alcohol is 1:5, the mol ratio of p-toluenesulfonic acid is 0.951g of catalyst which is 2.0% of the mass of ricinoleic acid, the mixture is stirred and heated to 60 ℃ under the nitrogen atmosphere, the mixture is cooled to room temperature after being reacted for 7 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, and the product purity is 96.8% by gas chromatography, the yield is 94.3%, and the molecular weight of the product is 312.49 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of melamine, roasting in a muffle furnace at 550 ℃ for 4 hours, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: methyl ricinoleate 10.937g (0.035 mol) was added to a 100mL beaker, and then 54.686g of isopropyl alcohol was added in a castor oil: lower alcohol=1:5 (mass ratio), and stirred well to mix well. Another 250mL three-necked flask was taken, 14.568g (0.140 mol) of sodium bisulfite was added to the flask in a mass ratio of 1:4 (molar ratio) of methyl castor oil to sodium bisulfite, 54.686g of deionized water was added thereto in a mass ratio of 1:1 (mass ratio) of deionized water to isopropyl alcohol to fully dissolve sodium bisulfite, and 1.094g of a carbon-based base catalyst (10% mass fraction to methyl ricinoleate) was added. The mixed solution of castor oil and isopropanol was poured into a three-necked flask and stirred at 40 ℃ for 20h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove isopropanol, adding deionized water and petroleum ether to extract and remove unreacted methyl ricinoleate, adding ethanol into a water phase, stirring for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and distilling under reduced pressure and drying to remove water to obtain the methyl ricinoleate sulfonate anionic surfactant, wherein the product yield is 75.68%.
The IR (KBr) of the product methyl ricinoleate sulfonate obtained in this example was obtained by the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm -1 The telescopic vibration peak of-CH=CH-in methyl ricinoleate is not shown in the infrared spectrum of the product, which indicates that the double bond has addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. From the above, the synthesized product was the target grateThe oleum Sesami sulfonate, i.e. the ricinoleic acid methyl ester sulfonate anionic surfactant of the invention. The Critical Micelle Concentration (CMC) of the surfactant was determined by a static surface tensiometer to be 12.33mmol/L and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 3 was shown to have typical surfactant properties at 34.55mN/m, which effectively reduces the surface tension of the aqueous solution. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid methyl ester sodium sulfonate anionic surfactant prepared in the example 2 is 50mL, and the foam is fine and stable.
Example 4
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid and 23.035g (0.50 mol) of ethanol are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, 5.0% of the mass of ricinoleic acid is added into the three-neck round bottom flask according to the ratio of ricinoleic acid to fatty alcohol=1:5 (mol ratio), 1.493g of p-toluenesulfonic acid serving as a catalyst is added into the three-neck round bottom flask according to the mass of ricinoleic acid, the three-neck round bottom flask is stirred and heated to 80 ℃ under the atmosphere of nitrogen, the three-neck round bottom flask is cooled to room temperature after being reacted for 9 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, and the purity of the product is 93.9% by gas chromatography, the yield is 92.0% and the molecular weight of the product is 326.52 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of urea, roasting in a muffle furnace at 600 ℃ for 5 hours, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 11.428g (0.035 mol) of ethyl ricinoleate was added to a 100mL beaker, and 52.553g of isopropyl alcohol was then added in a castor oil: lower alcohol=1:5 (mass ratio) and stirred well to mix well. Another 250mL three-necked flask was taken according to methyl castor oil: sodium bisulphite=1:4 (molar ratio) sodium bisulphite 14.568g (0.140 mol) was added to the flask, 52.553g of deionized water was added thereto in a mass ratio of deionized water to isopropyl alcohol of 1:1 to fully dissolve sodium bisulphite, and 2.286g of a carbon-based base catalyst (20% mass fraction to ethyl ricinoleate) was further added. The mixed solution of castor oil and isopropanol was poured into a three-necked flask and stirred at 40 ℃ for 20h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove isopropanol, then adding deionized water and petroleum ether to extract and remove unreacted ethyl ricinoleate, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the ethyl ricinoleate sulfonate anionic surfactant with the product yield of 76.53 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product ethyl ricinoleate sulfonate obtained in this example was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm -1 The telescopic vibration peak of-CH=CH-in ethyl ricinoleate is not shown in the infrared spectrum of the product, which indicates that the double bond has addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is known that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic ethyl sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 2.89mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 4 was shown to have typical surfactant properties at 35.48mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid ethyl ester sulfonate sodium salt anionic surfactant prepared in the example 4 is 110mL, and the foam is fine and stable.
Example 5
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 37.061g (0.50 mol) of n-butyl alcohol and 10.0% of catalyst p-toluenesulfonic acid are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, wherein the mol ratio of ricinoleic acid to fatty alcohol is 1:5, the catalyst p-toluenesulfonic acid is 2.985g, the mixture is stirred and heated to 90 ℃ under the nitrogen atmosphere, the mixture is cooled to room temperature after being reacted for 8 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, the product purity is 90.81% by gas chromatography, the yield is 91.34%, and the molecular weight of the product is 354.57 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of dicyandiamide, roasting in a muffle furnace at 650 ℃ for 3 hours, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 12.410g (0.035 mol) of butyl ricinoleate was added to a 100mL beaker, and 52.553g of t-butanol was then added according to castor oil: lower alcohol=1:5 (mass ratio) and stirred well to mix well. Another 250mL three-necked flask was taken, 21.853g (0.210 mol) of sodium bisulfite was added to the flask in a mass ratio of 1:6 (molar ratio) of methyl castor oil to sodium bisulfite, 52.553g of deionized water was added thereto in a mass ratio of 1:1 (mass ratio) of deionized water to t-butanol to fully dissolve sodium bisulfite, and 1.862g of a carbon-based base catalyst (15% mass fraction to butyl ricinoleate) was added. The mixed solution of butyl ricinoleate and tertiary butanol is poured into a three-necked flask and stirred for 10 hours at 40 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove tert-butyl alcohol, adding deionized water and petroleum ether to extract and remove unreacted butyl ricinoleate, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the butyl ricinoleate sulfonate anionic surfactant with the product yield of 78.99 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product butyl ricinoleate sulfonate obtained in this example was obtained by the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Special of sulfonate saltCharacterization of the stretching vibration peak. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic butyl sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 1.95mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 5 was shown to have typical surfactant properties at 33.05mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid butyl sulfonate sodium salt anionic surfactant prepared in the example 5 is 120mL, and the foam is fine and stable.
Example 6
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 55.901g (0.30 mol) of dodecanol and 2.0% of catalyst p-toluenesulfonic acid by weight of ricinoleic acid are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, the temperature is raised to 90 ℃ in a stirring manner under the nitrogen atmosphere, the reaction is cooled to room temperature after the reaction is carried out for 6 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, the methyl oleate is obtained, the purity of the product is 89.92% by gas chromatography, the yield is 95.12%, and the molecular weight of the product is 466.79 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of urea, roasting in a muffle furnace at 550 ℃ for 5h, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 14.004g (0.03 mol) of dodecanol ricinoleate is added to a 100mL beaker, and 42.011g of termyl alcohol is added according to the proportion of dodecanol ricinoleate to be lower alcohol=1:3 (mass ratio), and the mixture is fully stirred to be uniformly mixed. Another 250mL three-necked flask was taken, 3.1218g (0.03 mol) of sodium bisulfite was added to the flask according to a mass ratio of castor oil methyl ester to sodium bisulfite=1:1, 84.022g of deionized water was added thereto according to a mass ratio of deionized water to tertiaryamyl alcohol of 1:2 to sufficiently dissolve sodium bisulfite, and 3.501g of a carbon-based base catalyst (25% mass fraction to dodecanol ricinoleate) was added. The mixed solution of the dodecanol ricinoleate and the termyl alcohol is poured into a three-neck flask and stirred for 12 hours at 50 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove termyl alcohol, adding deionized water and petroleum ether to extract and remove unreacted ricinoleic acid dodecanol ester, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the ricinoleic acid dodecanol ester sulfonate anionic surfactant with the product yield of 77.01 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product dodecanol ricinoleate sulfonate obtained in this example was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic acid dodecyl sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 1.51mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 6 was shown to have typical surfactant properties at 30.57mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid dodecyl alcohol sulfonate sodium salt anionic surfactant prepared in the example 6 is 167mL, and the foam is fine and stable.
Example 7
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 78.138g (0.30 mol) of n-octanol and 6 mol of p-toluenesulfonic acid serving as a catalyst are added according to the proportion of ricinoleic acid to fatty alcohol=1:6 (mol ratio), 1.791g of p-toluenesulfonic acid serving as a catalyst is added according to the proportion of 6.0% of the mass of ricinoleic acid, the mixture is stirred and heated to 80 ℃ under the atmosphere of nitrogen, the mixture is cooled to room temperature after being reacted for 5 hours, and the obtained reaction solution is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure to obtain the octanol ricinoleate, wherein the purity of the product is 92.13%, the yield is 93.11% by gas chromatography, and the molecular weight of the product is 410.72 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of dopamine, roasting in a muffle furnace at 550 ℃ for 7h, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 12.322g (0.03 mol) of octanol ricinoleate is added to a 100mL beaker, and 42.011g of ethanol is added according to the ratio of octanol ricinoleate to lower alcohol=1:3 (mass ratio), and the mixture is thoroughly stirred to be uniformly mixed. Another three-necked flask was taken, to which was added 3.602g (0.03 mol) of potassium hydrogen sulfite (1:1 molar ratio) as castor oil octanol ester, 84.022g of deionized water was added thereto to sufficiently dissolve potassium hydrogen sulfite at a mass ratio of deionized water to ethanol of 1:2, and 3.697g of a carbon-based base catalyst (30% mass fraction to octanol ricinoleate) was further added. The mixed solution of the octyl ricinoleate and the ethanol is poured into a three-neck flask and stirred for 12 hours at 50 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove ethanol, adding deionized water and petroleum ether to extract and remove unreacted octyl ricinoleate, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and distilling under reduced pressure and drying to remove water to obtain the octyl ricinoleate sulfonate anionic surfactant, wherein the product yield is 82.01%.
The IR (KBr) of the product ricinoleic acid octanol sulfonate obtained in this example was obtained by the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 Stretching vibration peak at-ch=ch-, indicating double bond initiationCarrying out addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic octanol sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined by a static surface tensiometer to be 1.72mmol/L and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 7 was shown to have typical surfactant properties at 31.39mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid octanol sodium sulfonate anionic surfactant prepared in example 7 is 146mL, and the foam is fine and stable.
Example 8
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, namely, fatty alcohol=1:3 (mol ratio) of ricinoleic acid, 30.653g (0.30 mol) of hexanol and 1.492g of p-toluenesulfonic acid serving as a catalyst are added according to the mass of 5.0% of ricinoleic acid, the mixture is stirred and heated to 80 ℃ under the atmosphere of nitrogen, the mixture is cooled to room temperature after being reacted for 5 hours, the obtained reaction solution is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, so that hexyl ricinoleate is obtained, the purity of the product is 90.21% by gas chromatography, the yield is 89.73%, and the molecular weight of the product is 382.72 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of porphyrin, roasting in a muffle furnace at 500 ℃ for 5 hours, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 12.322g (0.03 mol) of hexanol ricinoleate is added to a 100mL beaker, and 42.011g of ethanol is added according to the ratio of hexanol ricinoleate to lower alcohol=1:3 (mass ratio), and the mixture is thoroughly stirred to be uniformly mixed. A250 mL three-necked flask was further prepared, to which 3.602g (0.03 mol) of potassium hydrogen sulfite was added at a mass ratio of 1:1 (mol%) of ricinoleic acid hexanol ester to potassium hydrogen sulfite, 126.003g of deionized water was added at a mass ratio of 1:3 (mol%) of deionized water to ethanol to sufficiently dissolve potassium hydrogen sulfite, and 3.697g of a carbon-based base catalyst (30% mass fraction to ricinoleic acid hexanol ester) was further added. The mixed solution of the hexanol ricinoleate and the ethanol is poured into a three-necked flask and stirred for 12 hours at 50 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove ethanol, adding deionized water and petroleum ether to extract and remove unreacted ricinoleic acid hexanol ester, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and distilling under reduced pressure and drying to remove water to obtain the ricinoleic acid hexanol ester sulfonate anionic surfactant with the product yield of 89.21%.
The IR (KBr) of the product of this example, hexanol ricinoleate sulfonate was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic hexanol sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 1.81mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 8 was found to have typical surfactant properties and to be effective in reducing the surface tension of aqueous solutions at 32.73 mN/m. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid octanol sodium sulfonate anionic surfactant prepared in example 8 is 157mL, and the foam is fine and stable.
Example 9
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 40.075g (0.50 mol) of amyl alcohol and 5.0% of catalyst p-toluenesulfonic acid are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, wherein the weight of ricinoleic acid is 1:5 (mol ratio), the catalyst p-toluenesulfonic acid is 1.492g according to the weight of ricinoleic acid, the mixture is stirred and heated to 60 ℃ under the nitrogen atmosphere, the mixture is cooled to room temperature after reacting for 5 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, and the product purity is 96.12% by gas chromatography, the yield is 90.24%, and the molecular weight of the product is 368.72 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of porphyrin, roasting in a muffle furnace at 600 ℃ for 6h, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 11.062g (0.03 mol) of amyl ricinoleate is added to a 100mL beaker, and 33.185g of ethanol is then added according to the ratio of lower alcohol to lower alcohol=1:3 (mass ratio) of the amyl ricinoleate, and the mixture is thoroughly stirred to be uniformly mixed. A250 mL three-necked flask was further prepared, 18.009g (0.15 mol) of potassium hydrogen sulfite was added to the flask in a mass ratio of 1:5 (mol%) of ricinoleic acid hexanol ester to potassium hydrogen sulfite, 33.185g of deionized water was added thereto in a mass ratio of 1:1 to sufficiently dissolve potassium hydrogen sulfite, and 1.659g of a carbon-based base catalyst (15% mass fraction to amyl ricinoleate) was further added thereto. The mixed solution of amyl ricinoleate and ethanol is poured into a three-neck flask and stirred for 12 hours at 60 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove ethanol, adding deionized water and petroleum ether to extract and remove unreacted ricinoleic acid hexanol ester, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the ricinoleic acid hexanol ester sulfonate anionic surfactant with the product yield of 92.54 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product of this example, hexanol ricinoleate sulfonate was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic hexanol sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined by a static surface tensiometer to be 1.85mmol/L and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 9 was shown to have typical surfactant properties at 32.98mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid octanol sodium sulfonate anionic surfactant prepared in example 9 is 164mL, and the foam is fine and stable.
Example 10
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 94.968g (0.60 mol) of decanol are added according to the ratio of ricinoleic acid to fatty alcohol=1:6 (mol ratio), 2.089g of p-toluenesulfonic acid serving as a catalyst is added according to the mass of 7.0% of ricinoleic acid, the mixture is stirred and heated to 65 ℃ under the atmosphere of nitrogen, the mixture is cooled to room temperature after being reacted for 4 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, the product purity is 93.13% by gas chromatography, the yield is 97.12%, and the molecular weight of the product is 438.74 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of porphyrin, roasting in a muffle furnace at 600 ℃ for 6h, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: decyl ricinoleate 13.162g (0.03 mol) is added to a 100mL beaker, and then 65.810g of t-butanol is added according to the ratio of hexanol ricinoleate to lower alcohol=1:5 (mass ratio), and the mixture is thoroughly stirred to be uniformly mixed. Another 250mL three-necked flask was taken, and 3.1218g (0.03 mol) of sodium bisulfite was added to the flask at a mass ratio of 1:1 (molar ratio) of castor oil decyl ester to sodium bisulfite, 131.62g of deionized water was added thereto at a mass ratio of 1:2 (mass ratio) of deionized water to t-butanol to fully dissolve the sodium bisulfite, and 1.316g of a carbon-based base catalyst (10% mass fraction to the castor oil decyl ester) was added. The mixed solution of the ricinoleic acid hexanol ester and the tertiary butanol alcohol is poured into a three-necked flask and stirred for 10 hours at 40 ℃. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove tert-butyl alcohol, adding deionized water and petroleum ether to extract and remove unreacted decyl ricinoleate, adding ethanol into a water phase, stirring for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the decyl ricinoleate sulfonate anionic surfactant with the product yield of 87.91 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product of this example, hexanol ricinoleate sulfonate was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm did not appear -1 A stretching vibration peak at-ch=ch-, indicating that an addition reaction of double bonds occurs; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic hexanol sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 1.74mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 10 was shown to have typical surfactant properties at 32.73mN/m, which effectively reduces the surface tension of the aqueous solution. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid octanol sodium sulfonate anionic surfactant prepared in example 10 is 177mL, and the foam is fine and stable.
Example 11
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid, 18.428g (0.40 mol) of ethanol are added according to the proportion of ricinoleic acid to fatty alcohol=1:4 (mol ratio), 0.895g of p-toluenesulfonic acid serving as a catalyst is added according to 3.0% of the mass of ricinoleic acid, the mixture is stirred and heated to 75 ℃ under the atmosphere of nitrogen, the mixture is cooled to room temperature after being reacted for 6 hours, the obtained reaction solution is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure to obtain methyl oleate, the purity of the product is 96.57% by gas chromatography, the yield is 94.56%, and the molecular weight of the product is 326.52 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of melamine, roasting in a muffle furnace at 550 ℃ for 6h, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: 11.428g (0.035 mol) of ethyl ricinoleate was added to a 100mL beaker, and 45.712g of isopropyl alcohol was then added in a castor oil: lower alcohol=1:4 (mass ratio) and stirred well to mix well. Another 250mL three-necked flask was taken, 16.808g (0.140 mol) of potassium hydrogen sulfite was added to the flask in a mass ratio of 1:4 (molar ratio) of methyl castor oil to potassium hydrogen sulfite, 45.712g of deionized water was added thereto in a mass ratio of 1:1 (mass ratio) of deionized water to n-butanol to sufficiently dissolve sodium hydrogen sulfite, and 1.714g of a carbon-based base catalyst (15% mass fraction to ethyl ricinoleate) was further added. The mixed solution of castor oil and isopropanol was poured into a three-necked flask and stirred at 50 ℃ for 24h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove isopropanol, adding deionized water and petroleum ether to extract and remove unreacted ethyl ricinoleate, adding ethanol into a water phase to stir for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the ethyl ricinoleate sulfonate anionic surfactant with the product yield of 87.93 percent after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product ethyl ricinoleate sulfonate obtained in this example was obtained using the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 at-COORStretching the vibration peak; 3008cm -1 The telescopic vibration peak of-CH=CH-in ethyl ricinoleate is not shown in the infrared spectrum of the product, which indicates that the double bond has addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is known that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic ethyl sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined to be 2.89mmol/L by a static surface tensiometer and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 4 was shown to have typical surfactant properties at 35.48mN/m, and to be effective in reducing the surface tension of aqueous solutions. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid ethyl ester sulfonate sodium salt anionic surfactant prepared in the example 4 is 110mL, and the foam is fine and stable.
Example 12
1) Esterification reaction: 29.846g (0.10 mol) of ricinoleic acid and 6.408g (0.20 mol) of methanol are added into a three-neck round bottom flask provided with a magnetic stirrer, a condenser and a nitrogen gas guide pipe, 3.0% of the mass of ricinoleic acid is added into the three-neck round bottom flask according to the ratio of ricinoleic acid to fatty alcohol=1:2 (mol ratio), 0.895g of p-toluenesulfonic acid serving as a catalyst is added into the three-neck round bottom flask according to the mass of ricinoleic acid, the three-neck round bottom flask is stirred and heated to 70 ℃ under the atmosphere of nitrogen, the three-neck round bottom flask is cooled to room temperature after being reacted for 10 hours, the obtained reaction liquid is extracted by ethyl acetate, washed by deionized water, dried by anhydrous sodium sulfate and distilled under reduced pressure, and the purity of the product is 98.37% by gas chromatography, the yield is 96.34% and the molecular weight of the product is 312.49 by mass spectrometry.
2) Preparation of solid carbon-based base catalyst: accurately weighing 5.0g of urea, roasting in a muffle furnace at 550 ℃ for 4 hours, and grinding to obtain the required catalyst.
3) Double bond addition sulfonation reaction: methyl ricinoleate 10.937g (0.035 mol) was added to a 100mL beaker, and then 32.811g of n-butanol was added according to castor oil: lower alcohol=1:3 (mass ratio), and the mixture was thoroughly stirred to be mixed uniformly. Another 250mL three-necked flask was taken, 14.568g (0.140 mol) of sodium bisulfite was added to the flask in a mass ratio of 1:4 (molar ratio) of methyl castor oil to sodium bisulfite, 32.811g of deionized water was added thereto in a mass ratio of 1:1 (mass ratio) of deionized water to n-butanol to fully dissolve sodium bisulfite, and 1.641g of a carbon-based base catalyst (15% mass fraction to methyl ricinoleate) was added. The mixed solution of castor oil and isopropanol was poured into a three-necked flask and stirred at 35 ℃ for 24h. After the reaction is finished, filtering to remove a solid carbon-based catalyst, distilling under reduced pressure to remove n-butyl alcohol, adding deionized water and petroleum ether to extract and remove unreacted methyl ricinoleate, adding ethanol into a water phase, stirring for 0.5h, sealing and standing overnight, removing precipitated inorganic salt by suction filtration, and obtaining the methyl ricinoleate sulfonate anionic surfactant with the product yield of 79.72% after the steps of distilling under reduced pressure and drying and removing water.
The IR (KBr) of the product methyl ricinoleate sulfonate obtained in this example was obtained by the detection method as described in example 1: wave number 3403cm -1 The stretching vibration peak of-OH; wave numbers 2928 and 2855cm -1 at-CH 3 and-CH 2 -a stretching vibration peak; 1741cm -1 The telescopic vibration peak of-COOR; 3008cm -1 The telescopic vibration peak of-CH=CH-in methyl ricinoleate is not shown in the infrared spectrum of the product, which indicates that the double bond has addition reaction; and at wave numbers 1168 and 1041cm -1 Characteristic stretching vibration peaks of sulfonate appear. It is clear that the synthesized product is the target product ricinoleic sulfonate, namely the ricinoleic acid methyl ester sulfonate anionic surfactant. The Critical Micelle Concentration (CMC) of the surfactant was determined by a static surface tensiometer to be 12.33mmol/L and the corresponding surface tension (. Gamma.) at that concentration CMC ) The castor oil-based sulfonate anionic surfactant prepared in example 12 was shown to have typical surfactant properties at 34.55mN/m, which effectively reduces the surface tension of the aqueous solution. Through analysis of the microscopic morphology of the foam by a dynamic foam analyzer, the initial foaming amount of the ricinoleic acid methyl ester sodium sulfonate anionic surfactant prepared in example 12 is 50mL, and the foam is fine and stable.
In summary, the castor oil-based sulfonate anionic surfactant and the preparation method thereof have the beneficial effects that:
1) Castor oil or ricinoleic acid alkyl ester is used as a raw material, and a solid carbon-based base catalyst is used for catalyzing double bond addition sulfonation reaction to synthesize the ricinoleic sodium sulfonate anionic surfactant, so that the resource utilization of castor oil is realized.
2) The solid carbon-based base catalyst has good catalytic activity on the reaction of synthesizing sodium ricinoleate sulfonate by double bond addition sulfonation of sodium bisulphite, an initiator or a cocatalyst is not needed, and the conversion rate of raw material castor oil or ricinoleic acid alkyl ester can reach more than 75%. Meanwhile, the catalyst has the advantages of simple preparation process, recycling and no corrosion to equipment.
3) The castor oil-based sulfonate anionic surfactant product is derived from natural renewable grease, can effectively reduce the surface tension of aqueous solution, and has the advantages of good solubility, low foam, fine foam and excellent surfactant performance.
4) The preparation method of the anionic surfactant is simple and convenient to operate and easy to implement industrially.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The castor oil-based sulfonate anionic surfactant is characterized by being prepared from castor oil or castor oil alkyl ester serving as a raw material and simultaneously containing sulfonic acid groups and hydroxyl hydrophilic groups.
2. The ricinoleic sulfonate anionic surfactant of claim 1, having any of the following structural formulas:
wherein R is C 1 ～C 12 Saturated hydrocarbon radicals, R 1 、R 2 Is selected from any one of H and sulfonic acid groups respectively, and R 1 、R 2 Are not identical.
3. The ricinoleic sulfonate anionic surfactant of claim 2, having any of the following structural formulas:
wherein X is K, na, NH 4 Any one of R is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
4. A method for preparing a castor oil-based sulfonate anionic surfactant, comprising the steps of:
subjecting a mixed reaction system comprising a solid carbon-based base catalyst, a solvent, a bisulphite, castor oil or an alkyl ricinoleate to double bond addition sulfonation reaction to obtain the castor oil-based sulfonate anionic surfactant according to any one of claims 1 to 3,
the alkyl ricinoleate has the following structural formula:
R is C 1 ～C 12 Is a saturated hydrocarbon group of (2).
5. The method for preparing a ricinoleic sulfonate anionic surfactant according to claim 4, wherein the temperature of the double bond addition sulfonation reaction is 30-80 ℃ and the time is 10-100 h.
6. The method for preparing the castor oil-based sulfonate anionic surfactant according to claim 4, wherein the solid carbon-based base catalyst is prepared by roasting an organic compound precursor containing carbon and nitrogen.
7. The method for preparing the ricinoleic sulfonate anionic surfactant of claim 6, wherein the organic compound precursor containing carbon and nitrogen is any one of porphyrin, dopamine, melamine, dicyandiamide and urea.
8. The method for preparing a ricinoleic sulfonate anionic surfactant of claim 4, wherein the mass of the solid carbon-based base catalyst is 2% -30% of the mass of castor oil or ricinoleic acid alkyl ester;
the mol ratio of the castor oil or the ricinoleic acid alkyl ester to the bisulphite is 1 (1-6);
the mass ratio of the castor oil or the ricinoleic acid alkyl ester to the low-carbon alcohol is 1 (2-5).
9. The method for preparing a ricinoleic sulfonate anionic surfactant of claim 4, wherein the solvent is a combination of lower alcohols and water, the mass ratio of lower alcohols to water being 1: (1-5).
10. The method for preparing the ricinoleic sulfonate anionic surfactant of claim 9, wherein the lower alcohol is any one of ethanol, isopropanol, n-butanol, t-butanol, tertbutanol.
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| CN106588706A (en) * | 2016-11-11 | 2017-04-26 | 中国日用化学工业研究院 | Method for synthesizing methyl ricinoleate ethoxylate sulfonate |
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| CN106588706A (en) * | 2016-11-11 | 2017-04-26 | 中国日用化学工业研究院 | Method for synthesizing methyl ricinoleate ethoxylate sulfonate |
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| PROF. DR. R. N . M U K H E R J E A AND A . G U P T CI: "Hydroxy Sulfonated Fatty Acid Esters as Surface Active Agents V: Surfactants Containing More Than One Hydrophilic Group", FETTE . SEIFEN ANSTRICHMITTEL, pages 579 - 582 * |
| 张遵;王旭峰;韩琳;王新德;: "磺化蓖麻油酸的合成", 应用化工, no. 02, pages 144 - 147 * |
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