CN116143672B - Water-soluble antioxidant and preparation method and application thereof - Google Patents
Water-soluble antioxidant and preparation method and application thereof Download PDFInfo
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- CN116143672B CN116143672B CN202310177785.9A CN202310177785A CN116143672B CN 116143672 B CN116143672 B CN 116143672B CN 202310177785 A CN202310177785 A CN 202310177785A CN 116143672 B CN116143672 B CN 116143672B
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- China
- Prior art keywords
- sulfate
- water
- alkyl
- reaction
- antioxidant
- Prior art date
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 85
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 22
- 150000008051 alkyl sulfates Chemical class 0.000 claims abstract description 21
- 239000013067 intermediate product Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- -1 alkyl sulphate Chemical compound 0.000 claims description 45
- 238000007254 oxidation reaction Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000008346 aqueous phase Substances 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 10
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 7
- 229910001511 metal iodide Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 6
- WEDIIKBPDQQQJU-UHFFFAOYSA-N butane-1-sulfonyl chloride Chemical compound CCCCS(Cl)(=O)=O WEDIIKBPDQQQJU-UHFFFAOYSA-N 0.000 claims description 5
- FRYHCSODNHYDPU-UHFFFAOYSA-N ethanesulfonyl chloride Chemical compound CCS(Cl)(=O)=O FRYHCSODNHYDPU-UHFFFAOYSA-N 0.000 claims description 5
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- 239000000811 xylitol Substances 0.000 claims description 4
- 235000010447 xylitol Nutrition 0.000 claims description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
- 229960002675 xylitol Drugs 0.000 claims description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims description 4
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- NQLNHTOCFWUYQE-UHFFFAOYSA-N 2-methylpropane-1-sulfonyl chloride Chemical compound CC(C)CS(Cl)(=O)=O NQLNHTOCFWUYQE-UHFFFAOYSA-N 0.000 claims description 2
- WFBUQJSXXDVYFZ-UHFFFAOYSA-N 2-methylpropane-2-sulfonyl chloride Chemical compound CC(C)(C)S(Cl)(=O)=O WFBUQJSXXDVYFZ-UHFFFAOYSA-N 0.000 claims description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 2
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 2
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 claims description 2
- SSTZWBSEDRHYPU-UHFFFAOYSA-L barium(2+);diperiodate Chemical compound [Ba+2].[O-]I(=O)(=O)=O.[O-]I(=O)(=O)=O SSTZWBSEDRHYPU-UHFFFAOYSA-L 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- VXLUZERCXISKBW-UHFFFAOYSA-M potassium;perbromate Chemical compound [K+].[O-]Br(=O)(=O)=O VXLUZERCXISKBW-UHFFFAOYSA-M 0.000 claims description 2
- KPBSJEBFALFJTO-UHFFFAOYSA-N propane-1-sulfonyl chloride Chemical compound CCCS(Cl)(=O)=O KPBSJEBFALFJTO-UHFFFAOYSA-N 0.000 claims description 2
- DRINJBFRTLBHNF-UHFFFAOYSA-N propane-2-sulfonyl chloride Chemical compound CC(C)S(Cl)(=O)=O DRINJBFRTLBHNF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- CLURAKRVQIPBCC-UHFFFAOYSA-M sodium;perbromate Chemical compound [Na+].[O-]Br(=O)(=O)=O CLURAKRVQIPBCC-UHFFFAOYSA-M 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000004383 yellowing Methods 0.000 abstract description 25
- 239000000839 emulsion Substances 0.000 abstract description 24
- 239000003795 chemical substances by application Substances 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 239000002250 absorbent Substances 0.000 abstract description 14
- 229920000058 polyacrylate Polymers 0.000 abstract description 6
- 239000012467 final product Substances 0.000 abstract description 5
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 235000006708 antioxidants Nutrition 0.000 description 78
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 66
- 239000000243 solution Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 46
- 239000012071 phase Substances 0.000 description 29
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 230000002745 absorbent Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- ZIRHAFGGEBQZKX-UHFFFAOYSA-N pentyl hydrogen sulfate Chemical compound CCCCCOS(O)(=O)=O ZIRHAFGGEBQZKX-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 210000001124 body fluid Anatomy 0.000 description 5
- 239000010839 body fluid Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KFBRKUDVGCEQDY-UHFFFAOYSA-M potassium;pentyl sulfate Chemical compound [K+].CCCCCOS([O-])(=O)=O KFBRKUDVGCEQDY-UHFFFAOYSA-M 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- REYZKXJFXCQWEE-UHFFFAOYSA-N 3-sulfooxypropane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCOS(O)(=O)=O REYZKXJFXCQWEE-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YZFOXXKKTAGTID-UHFFFAOYSA-M potassium;propan-2-one;iodide Chemical compound [K+].[I-].CC(C)=O YZFOXXKKTAGTID-UHFFFAOYSA-M 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229930182817 methionine Natural products 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- MZQCFPABNHFYAT-UHFFFAOYSA-M sodium;propan-2-one;iodide Chemical compound [Na+].[I-].CC(C)=O MZQCFPABNHFYAT-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- HVCNQTCZNBPWBV-UHFFFAOYSA-N 2-hydroxy-2-sulfinoacetic acid Chemical compound OC(=O)C(O)S(O)=O HVCNQTCZNBPWBV-UHFFFAOYSA-N 0.000 description 1
- CEFDWZDNAJAKGO-UHFFFAOYSA-N 2-hydroxy-2-sulfoacetic acid Chemical class OC(=O)C(O)S(O)(=O)=O CEFDWZDNAJAKGO-UHFFFAOYSA-N 0.000 description 1
- MMEPTDVZHAENFV-UHFFFAOYSA-N CS(Cl)(=O)=O.CCOC(C)=O Chemical compound CS(Cl)(=O)=O.CCOC(C)=O MMEPTDVZHAENFV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical class [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- IMLUMMDFXRZWGY-UHFFFAOYSA-L disodium 2-hydroxy-2-sulfoacetate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)S(O)(=O)=O.[O-]C(=O)C(O)S(O)(=O)=O IMLUMMDFXRZWGY-UHFFFAOYSA-L 0.000 description 1
- SXZDVQTZCUPESP-UHFFFAOYSA-N ethyl acetate;propane-1,2,3-triol Chemical compound CCOC(C)=O.OCC(O)CO SXZDVQTZCUPESP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- 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
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
-
- 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
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/10—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated being further substituted by singly-bound oxygen atoms
Abstract
The invention discloses a water-soluble antioxidant which is alkyl sulfate with the following general formula (I),
Description
Technical Field
The invention relates to an antioxidant and a preparation method and application thereof, in particular to an alkyl sulfate antioxidant and a preparation method thereof and application thereof as an anti-yellowing agent in water-absorbent resin materials.
Background
Oxygen free radicals such as superoxide air anions and singlet oxygen are the most important causes of oxidation reaction. Most industrial products suffer from problems of discoloration, yellowing, hard bottoming, cracking, loss of glossiness and the like due to oxidation reaction, thereby affecting the service life. The use of antioxidants is the easiest and most reasonable of the many ways to inhibit and slow down oxidation reactions. Antioxidants are a class of substances that help to trap and neutralize oxygen radicals and, when present in only small amounts in a polymer system, retard or inhibit the progress of the oxidation process of the polymer, thereby preventing the aging of the polymer and extending its useful life.
Antioxidants can be classified into water-soluble antioxidants and oil-soluble antioxidants. Common water-soluble antioxidants are inorganic salts such as sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium metabisulfite, and the like. Such antioxidants are unstable during long-term storage, are prone to deterioration, and often have some unpleasant odors. Thus, such antioxidants may also have certain limitations in terms of use due to stability problems.
Chinese patent document CN109251361A discloses a water-soluble anti-yellowing agent for super absorbent resin, which is prepared by compounding common water-soluble antioxidants, and is used for inhibiting yellowing of acrylic super absorbent resin in the storage process by compounding sodium bisulphite, sodium sulfite, sodium nitrite, methionine and the like. However, sodium bisulphite, sodium sulfite and sodium nitrite in the water-soluble antioxidants are easily weathered into sodium sulfate and sodium nitrate when exposed to air, and the properties are unstable.
Chinese patent document CN112724461a discloses an anti-yellowing agent for a super absorbent resin, which is a water-soluble anti-yellowing agent having a chelate structure, and which is used only for anti-yellowing of a super absorbent resin.
Therefore, there is a need in the art for a water-soluble antioxidant that has good antioxidant effect and is widely used.
Disclosure of Invention
In a first aspect of the present invention, there is provided a water soluble antioxidant which is an alkyl sulfate having the general formula (I),
wherein,
r is a linear or branched alkyl group having n carbon atoms,
n=2, 3,4 or 5, m=1, 2,3,4 or 5, and m.ltoreq.n,
m is an alkali metal element, an alkaline earth metal element or zinc.
In some embodiments of the first aspect of the invention, the straight or branched alkyl group having n carbon atoms is selected from: ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and n-hexyl.
In some embodiments of the first aspect of the invention, the antioxidant has the following structural formula:
in a second aspect of the present invention, there is provided a method of preparing a water-soluble antioxidant comprising:
(1) Performing chlorosulfonation reaction on alkyl alcohol with the following general formula (II) and sulfonyl chloride reagent in an organic solvent reaction system to form chlorosulfonation intermediate products;
wherein R is a linear or branched alkyl radical having n carbon atoms, n=2, 3,4 or 5, m=1, 2,3,4 or 5 and m.ltoreq.n,
(2) Adding a heterogeneous solution formed by an organic solvent and water into the reaction system in the step (1), so as to form a heterogeneous system;
(3) Adding an oxidant into the heterogeneous system to enable the chlorosulfonated intermediate product to undergo an oxidation reaction, removing an aqueous phase after the oxidation reaction is completed, and retaining an organic phase in which oxidation reaction products are dissolved;
(4) Adding metal iodide into the organic phase of the step (3), and carrying out substitution reaction with the oxidation reaction product formed in the step (3) to generate alkyl sulfate;
wherein the metal iodide is selected from the group consisting of: alkali metal iodides, alkaline earth metal iodides or zinc iodide.
In some embodiments of the second aspect of the invention, the method of the invention further comprises: in step (4) water is added to the organic phase such that the alkyl sulphate formed is extracted into the aqueous phase, followed by separation of the aqueous phase and addition of an alcohol solvent to the aqueous phase to precipitate the alkyl sulphate from the aqueous phase. In a further embodiment of the second aspect of the invention, the volume of water added in the organic solvent phase is equal to or 1.5 times the volume of the organic solvent phase, and stirring is performed for 0.5 to 1 hour after adding water to the organic solvent phase, followed by standing for 2 to 4 hours, so that the alkyl sulfate formed is extracted into the aqueous phase, and then the organic phase is removed, and the aqueous phase is separated. In a further embodiment of the second aspect of the invention, the volume of the alcohol solvent added to the separated aqueous phase is equal to or 1.5 times the volume of the aqueous phase. In a further embodiment of the second aspect of the invention, the alkyl sulfate precipitated from the aqueous phase may be washed with an alcohol solvent and subsequently dried in vacuo at 40 to 60 ℃ for 8 to 10 hours. In a further embodiment of the second aspect of the invention, the alcoholic solvent is selected from methanol and ethanol.
In some embodiments of the second aspect of the present invention, the heterogeneous solution of step (2) comprises water, dichloromethane and acetonitrile, and in further embodiments of the second aspect of the present invention, the volume ratio of acetonitrile, dichloromethane and deionized water in the heterogeneous solution is from 1:1:1 to 1.5.
In some embodiments of the second aspect of the present invention, in step (1), the molar ratio of the sulfonyl chloride reagent to hydroxyl groups in the alkyl alcohol of formula (II) is from 1:1 to 1:1.2; the molar amount of the oxidizing agent added in step (2) is 0.95 to 1.05 times the molar amount of the sulfonyl chloride reagent added in step (1); the molar amount of the metal iodide added in step (3) is 0.95 to 1.05 times the molar amount of the sulfonyl chloride reagent added in step (1).
In a further embodiment of the second aspect of the present invention, the chlorosulfonation reaction of step (1) is carried out at a temperature of 0-4 ℃; the oxidation reaction of step (2) is carried out at 20-30 ℃.
In some embodiments of the second aspect of the invention, the sulfonyl chloride reagent is selected from the group consisting of: methylsulfonyl chloride, ethylsulfonyl chloride, propylsulfonyl chloride, isopropylsulfonyl chloride, butylsulfonyl chloride, isobutylsulfonyl chloride and tert-butylsulfonyl chloride.
In some embodiments of the second aspect of the invention, the oxidizing agent is selected from the group consisting of: sodium perchlorate, potassium perchlorate, magnesium perchlorate, sodium perbromate, potassium perbromate, sodium periodate, potassium periodate and barium periodate.
In some embodiments of the second aspect of the invention, the alkali metal is selected from: sodium and potassium; the alkaline earth metal is selected from: magnesium and calcium.
In a third aspect of the present invention there is provided a water soluble antioxidant prepared according to the method of the second aspect of the present invention.
In a fourth aspect of the present invention, there is provided an anti-yellowing agent for a water-absorbent resin and/or polyacrylate emulsion, comprising the water-soluble antioxidant according to the first or third aspect of the present invention.
In some embodiments of the fourth aspect of the present invention, the water absorbent resin is a polyacrylic material selected from polyacrylic acid, sodium polyacrylate, or polyacrylate.
In a fifth aspect of the present invention, there is provided the use of the water-soluble antioxidant according to the first or third aspect of the present invention as an anti-yellowing agent for a water-absorbent resin.
In some embodiments of the fifth aspect of the present invention, the water-absorbent resin is a polyacrylic material selected from polyacrylic acid, sodium polyacrylate, or polyacrylate.
In a sixth aspect of the invention there is provided the use of the water-soluble antioxidant of the first or third aspect of the invention as an antioxidant for polyacrylate emulsions.
Compared with the prior art, the invention has the following beneficial effects:
(1) The water-soluble antioxidant has good water solubility and higher solubility than the prior anti-yellowing agents.
(2) The antioxidant of the present invention has a good antioxidant effect under high temperature and high humidity conditions, for example, the super absorbent resin (SAP) having the antioxidant of the present invention sprayed on the surface can exhibit a good antioxidant effect under high humidity conditions of 70 ℃ and 90%, and the antioxidant of the present invention added to the PA emulsion also exhibits a good antioxidant effect at high temperature of 120 ℃, whereby the water-soluble antioxidant of the present invention can inhibit or slow down yellowing of the super absorbent resin and the PA emulsion, and can be used as an anti-yellowing agent in both the super absorbent resin and the PA emulsion.
(3) In the method for preparing the water-soluble antioxidant, the heterogeneous reaction system is adopted to enable the reaction products to be separated more conveniently, and the purity is improved. Specifically, after chlorosulfonation of an alkyl alcohol of the general formula (II) with a sulfonyl chloride reagent, the synthesis process is carried out in a heterogeneous system by adding a heterogeneous solution formed of an organic solvent and water, in which a chlorosulfonation intermediate product is subjected to an oxidation reaction, and the resulting oxidation reaction product is present in an organic phase, so that the oxidation reaction product can be purified by removing the aqueous phase. Further, after the oxidation reaction is completed, the metal iodide is added into the organic phase in which the oxidation reaction product is reserved, the corresponding alkyl sulfate can be generated through substitution reaction, and finally the generated alkyl sulfate is dissolved in the water phase, so that the final product can be extracted into the water phase by adding water into the organic phase, the organic phase can be removed, and the final product can be separated, and the separation of the final product is simpler. And, the solubility of the final product in an alcohol solution is small, which can be easily precipitated from an aqueous solution by adding an alcohol solution after the completion of the final reaction, and impurities can be easily removed to obtain a high-purity product.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of an antioxidant prepared according to example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of an antioxidant prepared according to example 2 of the present invention.
FIG. 3 is a nuclear magnetic resonance spectrum of an antioxidant prepared according to example 3 of the present invention.
FIG. 4 is a nuclear magnetic resonance spectrum of an antioxidant prepared according to example 4 of the present invention.
FIG. 5 is a nuclear magnetic resonance spectrum of an antioxidant prepared according to example 5 of the present invention.
Detailed Description
The various aspects of the present invention will now be described in detail with reference to the following examples, which are intended to illustrate the invention and are not intended to limit the scope and spirit of the invention.
Exemplary water-soluble antioxidants of the present invention, as well as methods of making and using the same, are described in further detail below by way of illustration.
In examples 1 to 5, the preparation and characterization of the exemplary water-soluble antioxidants of the present invention will be specifically described, respectively, and in examples 1 to 5, m in the following general formula (I) and the carbon number (n) of the alkyl group (R) and the structure of the alkyl group are different, but have good water solubility and antioxidant effects.
In example 6, the water solubility of the antioxidants prepared in examples 1-5 was evaluated and compared with the water solubility of antioxidants of the prior art.
In examples 7 and 8, the application effect of the antioxidant prepared in examples 1 to 5 as an anti-yellowing agent for water-absorbent resins was evaluated and compared with the anti-yellowing agent of the prior art accordingly.
Example 1
This example illustrates the preparation of a potassium pentylsulfate antioxidant (having the structural formula below) and its characterization of purity and nuclear magnetic resonance spectrum.
The preparation method of the antioxidant comprises the following steps:
step (1): 8.8g of pentanol was added to 40mL of ethyl acetate, dispersed with stirring, and the ethyl acetate solution of pentanol was cooled to 4 ℃. 15.7g of butyl sulfonyl chloride is dispersed in 20mL of ethyl acetate, then ethyl acetate solution of butyl sulfonyl chloride is dripped into ethyl acetate solution of amyl alcohol to carry out chlorosulfonation reaction, the temperature is controlled to be 4 ℃, the dripping time is 1.5h, and after dripping is finished, the reaction is carried out for 1.5h at the temperature of 4 ℃ to form an intermediate product I. The reaction equation of step 1 is shown below:
step (2): 25mL of acetonitrile, 25mL of dichloromethane and 30mL of deionized water are prepared into a heterogeneous mixed solution, and after the reaction in the step (1) is completed, the heterogeneous mixed solution is added into the reaction system in the step (1) to form a heterogeneous system.
Step (3): 27.6g of potassium perchlorate is added into the heterogeneous reaction system in the step (2), the oxidation reaction of the intermediate product I is carried out, the reaction is carried out at 20 ℃ with stirring for 3 hours, then the reaction is left for 3 hours, and the oxidation product I is dissolved in the organic solvent phase in the heterogeneous reaction system, so that the water phase is removed by separating liquid, and the oxidation product I can be easily separated. Anhydrous magnesium sulfate was then added to the organic phase to dry, the magnesium sulfate was removed by filtration, and the oxidation product I remaining in the organic phase was used for the subsequent reaction. The reaction equation of step 3 is shown below:
step (4): 16.6g of potassium iodide was prepared as a 25% potassium iodide acetone solution using acetone, and this solution was added to the above-mentioned organic solution from which anhydrous magnesium sulfate was removed by filtration after drying in step (3), substitution reaction was performed, stirring was performed at 20℃and the reaction was performed for 18 hours, whereby pentylsulfate was obtained. 110mL of deionized water was then added thereto, stirred at 20℃for 1 hour, left to stand for 3 hours, and potassium pentylsulfate was extracted into water, followed by separation to remove the organic phase. The reaction equation of step 4 is shown below:
step (5): 110mL of methanol was added to the aqueous phase solution, and the mixture was stirred at 20℃for 0.5h, and since the solubility of the obtained pentylsulfate in the alcoholic solution was small, the product pentylsulfate (i.e., the antioxidant of the present invention) was precipitated from the aqueous phase by adding methanol to the aqueous phase, followed by filtration and washing three times with methanol, vacuum drying at 40℃for 10h, and the dried product was directly used for the subsequent characterization and performance test without further purification. .
The purity of the product of amyl potassium sulfate was determined by liquid chromatography, the apparatus was LC-15C island body fluid phase chromatography, the mobile phase was dilute phosphoric acid aqueous solution (ph=2.7), the flow rate was 1.0mL/min, the sample injection amount was 1 μl, the detection wavelength was 212nm, and the prepared product was dissolved with the mobile phase to prepare a 1% solution. The purity of the product amyl potassium sulfate was 99.96%.
The product of potassium pentylsulfate was characterized by using a solid nuclear magnetic resonance whose nuclear magnetic resonance spectrum is shown in FIG. 1, and absorption peaks at 4.0ppm, 1.7ppm, 1.3ppm and 0.9ppm of hydrogen atoms on long-chain pentyl groups are clearly observed from FIG. 1, which indicates that potassium pentylsulfate was produced.
Example 2
This example illustrates the preparation of 2-sulfooxyethyl sodium sulfate antioxidant (having the structural formula shown below) and its purity and characterization of nuclear magnetic patterns.
The preparation method of the antioxidant comprises the following steps:
step (1): 6.2g of ethylene glycol was added to 40mL of ethyl acetate, dispersed with stirring, and the ethyl acetate solution of ethylene glycol was cooled to 2 ℃. Dispersing 25.7g of ethyl sulfonyl chloride in 40mL of ethyl acetate, then dripping ethyl acetate solution of ethyl sulfonyl chloride into the ethyl acetate solution of the ethylene glycol to carry out chlorosulfonation reaction, controlling the temperature to be 2 ℃, dripping for 2 hours, and reacting for 2 hours at the temperature of 2 ℃ after dripping is finished to obtain an intermediate product II. The reaction equation of step 1 is shown below:
step (2): 25mL of acetonitrile, 25mL of dichloromethane and 30mL of deionized water are prepared into a heterogeneous mixed solution, and the heterogeneous mixed solution is added into the reaction system of the step (1) after the reaction of the step (1) is completed, so as to form a heterogeneous system.
Step (3): 24.4g of sodium perchlorate is added into the heterogeneous reaction system in the step (2), the oxidation reaction of the intermediate product II is carried out, the reaction is stirred for 3 hours at 25 ℃, then the reaction is kept stand for 3 hours, and the oxidation product II can be easily separated by separating liquid to remove the water phase because the oxidation reaction product is dissolved in the organic solvent phase in the heterogeneous reaction system. Then anhydrous magnesium sulfate is added into the organic phase for drying, the magnesium sulfate is removed by filtration, and the oxidation product II remained in the organic phase is used for the subsequent reaction. The reaction equation of step 3 is shown below:
step (4): 29.9g of sodium iodide was prepared into a 30% sodium iodide acetone solution by using acetone, then, the solution was added to the organic solution dried by using anhydrous magnesium sulfate and removed of anhydrous magnesium sulfate in the above step (3), a substitution reaction was performed, the reaction was stirred at 25℃for 12 hours to obtain 2-sulfooxyethyl sodium sulfate, then 150mL of deionized water was added, the mixture was stirred at 25℃for 1 hour, the mixture was allowed to stand for 4 hours, and 2-sulfooxyethyl sodium sulfate was extracted into water, and the organic phase was separated and removed. The reaction equation of step 4 is shown below:
step (5): 150mL of ethanol was added to the aqueous phase solution, and the mixture was stirred at 25℃for 0.5h, and since the solubility of the sodium 2-sulfooxyethyl sulfate obtained by the reaction in the alcoholic solution was small, the product sodium 2-sulfooxyethyl sulfate (i.e., the antioxidant of the present invention) was precipitated from the water by adding ethanol to the aqueous phase, followed by filtration and washing the product with ethanol three times, vacuum-dried at 60℃for 8h, and the dried product was directly used for the subsequent characterization and performance test without further purification.
The purity of the product 2-sulfooxyethyl sodium sulfate was measured by liquid chromatography, the apparatus was LC-15C island body fluid phase chromatography, the mobile phase was dilute phosphoric acid aqueous solution (ph=2.7), the flow rate was 1.0mL/min, the sample injection amount was 1 μl, the detection wavelength was 212nm, and the prepared product was dissolved with the mobile phase to prepare a 1% solution. The purity of the product sodium 2-sulfooxyethyl sulfate was 99.94%.
The product sodium 2-sulfooxyethyl sulfate was characterized by using a solid nuclear magnetic resonance whose nuclear magnetic resonance spectrum is shown in FIG. 2, and from FIG. 2, it is apparent that only one absorption peak of the hydrogen atom on sodium 2-sulfooxyethyl sulfate at 3.6ppm was observed, which indicates that sodium 2-sulfooxyethyl sulfate of disulfoxy was produced.
Example 3
This example illustrates the preparation of a 2, 3-sulfopropyl potassium sulfate antioxidant (having the formula shown below) and its purity and nuclear magnetic profile characterization.
The preparation method of the antioxidant comprises the following steps:
step (1): 4.6g of glycerol was added to a solution of glycerol in 40mL of ethyl acetate, dispersed with stirring, and the ethyl acetate solution of glycerol was cooled to 0 ℃. 17.3g of methylsulfonyl chloride is dispersed in 60mL of ethyl acetate, then the methylsulfonyl chloride ethyl acetate solution is dripped into the glycerin ethyl acetate solution for chlorosulfonation reaction, the temperature is controlled to be 0 ℃, the dripping time is 2 hours, and after the dripping is finished, the reaction is carried out for 2 hours at the temperature of 0 ℃ to obtain an intermediate product III. The reaction equation of step 1 is shown below:
step (2): 30mL of acetonitrile, 30mL of dichloromethane and 40mL of deionized water are prepared into a heterogeneous mixed solution, and the heterogeneous mixed solution is added into the reaction system of the step (1) after the reaction of the step (1) is completed, so as to form a heterogeneous system.
Step (3): 27.3g of potassium perbromide is added into the heterogeneous reaction system of the step (2), the oxidation reaction of the intermediate product III is carried out, the reaction is stirred for 4 hours at 25 ℃, and then the reaction is kept stand for 4 hours, and the oxidation product III can be easily separated by separating liquid to remove the water phase because the oxidation reaction product is dissolved in the organic solvent phase in the heterogeneous reaction system. The organic phase was then dried over anhydrous magnesium sulfate, the magnesium sulfate was removed by filtration, and the oxidation product III remaining in the organic phase was used for the subsequent reaction. The reaction equation of step 3 is shown below:
step (4): 24.9g of potassium iodide was prepared into a 30% potassium iodide acetone solution by using acetone, and added to the organic solution dried by using anhydrous sodium sulfate and removed of anhydrous sodium sulfate in the above step (3), substitution reaction was performed, stirring was performed at 25℃for 18 hours to obtain 2, 3-sulfopropyl potassium sulfate, then 200mL of deionized water was added, stirring was performed at 25℃for 0.5 hour, standing was performed for 4 hours, 2, 3-sulfopropyl potassium sulfate was extracted into water, and the organic phase was separated and removed. The reaction equation of step 4 is shown below:
step (5): 200mL of methanol was added to the aqueous phase solution, stirred at 25℃for 0.5h, and since the solubility of the 2, 3-sulfopropyl potassium sulfate obtained by the reaction in the alcoholic solution was small, the product 2, 3-sulfopropyl potassium sulfate (i.e., the antioxidant of the present invention) was precipitated from water by adding methanol to the aqueous phase, followed by filtration and washing with methanol three times, vacuum-dried at 40℃for 10h, and the dried product was directly used for the subsequent characterization and performance test without further purification.
The purity of the product 2, 3-sulfopropyl potassium sulfate was measured by liquid chromatography, the apparatus was LC-15C island body fluid liquid chromatography, the mobile phase was dilute phosphoric acid aqueous solution (ph=2.7), the flow rate was 1.0mL/min, the sample injection amount was 1 μl, the detection wavelength was 212nm, and the prepared product was dissolved with the mobile phase to prepare a 1% solution. The purity of the product 2, 3-sulfopropyl potassium sulfate was 99.98%.
The product of potassium 2, 3-sulfopropyl sulfate was characterized by using a solid core magnet, the core magnet spectrum of which is shown in FIG. 3, and it is apparent from FIG. 3 that the hydrogen atoms on potassium 2, 3-sulfopropyl sulfate have an absorption peak at 3.7ppm and 5.2ppm, respectively, which indicates that potassium 2, 3-sulfopropyl sulfate was produced.
Example 4
This example illustrates the preparation of 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate antioxidant (having the structural formula below) and its characterization of purity and nuclear magnetic profile.
The preparation method of the antioxidant comprises the following steps:
step (1): 3.9g of pentaerythritol was added to 60mL of ethyl acetate, dispersed with stirring, and the ethyl acetate solution of pentaerythritol was cooled to 3 ℃. 11.5g of methylsulfonyl chloride is dispersed in 40mL of ethyl acetate, then the ethyl acetate solution of methylsulfonyl chloride is dripped into the ethyl acetate solution of pentaerythritol for chlorosulfonation reaction, the temperature is controlled to be 3 ℃, the dripping time is controlled to be 2 hours, and after the dripping is finished, the reaction is carried out for 2 hours at the temperature of 3 ℃ to obtain an intermediate product IV with four hydroxyl groups chlorosulfonated. The reaction equation of step 1 is shown below:
step (2): preparing a heterogeneous mixed solution by 35mL of acetonitrile, 35mL of dichloromethane and 35mL of deionized water, and adding the heterogeneous mixed solution into the reaction system of the step (1) after the reaction of the step (1) is completed to form a heterogeneous system.
Step (3): and (3) adding 23.0g of potassium periodate into the heterogeneous reaction system in the step (2) to perform oxidation reaction of the intermediate product IV, stirring at 20 ℃ to perform reaction for 4 hours, and standing for 4 hours to obtain an oxidation reaction product, wherein the oxidation reaction product is dissolved in an organic solvent phase in the heterogeneous reaction system, so that the water phase is removed through liquid separation, and the oxidation product IV can be easily separated. Anhydrous magnesium sulfate was then added to the organic phase to dry, the magnesium sulfate was removed by filtration, and the oxidation product iv remaining in the organic phase was used for the subsequent reaction. The reaction equation of step 3 is shown below:
step (4): 16.6g of potassium iodide was prepared as a 30% potassium iodide acetone solution using acetone, which was then added to the above-mentioned organic solution dried over anhydrous magnesium sulfate and removed from anhydrous magnesium sulfate in step (2), and substitution reaction was performed. Stirring and reacting for 18h at 20 ℃ to obtain the 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate. Then 200mL deionized water was added, stirred at 25 ℃ for 0.5h, left to stand for 4h, 3-sulfooxy-2, 2-disulfoxymethyl propyl potassium sulfate was extracted into water, and the organic phase was separated and removed. The reaction equation of step 4 is shown below:
step (5): 200mL of ethanol was added to the aqueous phase solution, stirred at 20℃for 1.0h, and since the solubility of the resulting 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate in the alcoholic solution was small, the product potassium 3-sulfoxy-2, 2-disulfoxymethyl propyl sulfate (i.e., the antioxidant of the present invention) was precipitated from the water by adding ethanol to the aqueous phase, followed by filtration and washing three times with ethanol, vacuum drying at 40℃for 10h, and the dried product was directly used for the subsequent characterization and performance test without further purification.
The purity of the product 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate was determined by liquid chromatography, the apparatus was LC-15C island body fluid phase chromatography, the mobile phase was dilute phosphoric acid aqueous solution (ph=2.7), the flow rate was 1.0mL/min, the sample injection amount was 1 μl, the detection wavelength was 212nm, and the prepared product was dissolved with the mobile phase to prepare a 1% solution. The purity of the product 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate was 99.95%.
The product of 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate was characterized by using a solid nuclear magnetic resonance whose nuclear magnetic resonance spectrum is shown in FIG. 4, and from FIG. 4, it is evident that only one absorption peak of the hydrogen atom on the 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate was observed at 3.8ppm, which indicates that the 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate was produced.
Example 5
This example illustrates the preparation of a sodium 2,3,4, 5-tetra-sulfoxy amyl sulfate antioxidant (its structural formula is as follows) and its purity and characterization of the nuclear magnetic profile.
The preparation method of the antioxidant comprises the following steps:
step (1): 3.8g of xylitol was added to 60mL of ethyl acetate, and the mixture was dispersed with stirring, and the ethyl acetate solution of xylitol was cooled to 0 ℃. Dispersing 19.3g of methylsulfonyl chloride in 40mL of ethyl acetate, then dripping the ethyl methylsulfonyl chloride acetate solution into the ethyl acetate solution of xylitol for chlorosulfonation reaction, controlling the temperature to be 0 ℃, dripping the solution for 2 hours, and reacting the solution at the temperature of 0 ℃ for 2 hours after dripping the solution, so as to obtain an intermediate product V with five hydroxyl groups chlorosulfonated. The reaction equation of step 1 is shown below:
step (2): 30mL of acetonitrile, 30mL of dichloromethane and 40mL of deionized water are prepared into a heterogeneous mixed solution, and the heterogeneous mixed solution is added into the reaction system of the step (1) after the reaction of the step (1) is completed, so as to form a heterogeneous system.
Step (3): 26.7g of sodium periodate is added into the heterogeneous reaction system in the step (2) to perform oxidation reaction of the intermediate product V, the mixture is stirred at 30 ℃ to perform reaction for 4 hours, then the mixture is left to stand for 4 hours to obtain an oxidation product V, and the oxidation product V can be easily separated by separating liquid to remove the water phase because the oxidation reaction product is dissolved in the organic solvent phase in the heterogeneous reaction system. Anhydrous magnesium sulfate was then added to the organic phase to dry, the magnesium sulfate was removed by filtration, and the oxidation product v remaining in the organic phase was used for the subsequent reaction. The reaction equation of step 3 is shown below:
step (4): 18.7g of sodium iodide is prepared into a 30% sodium iodide acetone solution by using acetone, the solution is added into the organic solution dried by anhydrous magnesium sulfate and removed of magnesium sulfate in the step (3) for substitution reaction, the reaction is stirred at 30 ℃ for 18 hours to obtain 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate, 250mL of deionized water is then added, the mixture is stirred at 30 ℃ for 1.0 hour, the mixture is left stand for 4 hours, and the 2,3,4, 5-tetra-sulfoamyl sodium sulfate is extracted into water, and the organic phase is removed by liquid separation. The reaction equation of step 4 is shown below:
step (5): 250mL of ethanol is added into the aqueous phase solution, the mixture is stirred for 1.0h at 30 ℃, and 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate obtained by the reaction has small solubility in the alcoholic solution, so that the product 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate (namely the antioxidant of the invention) can be precipitated from the aqueous phase by adding ethanol into the aqueous phase, then the product is filtered and washed three times by ethanol, and the dried product is dried in vacuum at 50 ℃ for 10h without further purification and is directly used for subsequent characterization and performance test.
The purity of the product 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate was determined by liquid chromatography, the apparatus was LC-15C island body fluid phase chromatography, the mobile phase was dilute phosphoric acid aqueous solution (ph=2.7), the flow rate was 1.0mL/min, the sample injection amount was 1 μl, the detection wavelength was 212nm, and the prepared product was dissolved with the mobile phase to prepare a 1% solution. The purity of the product 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate is 99.98%.
The product sodium 2,3,4, 5-tetrasulfonyloxy pentylsulfate was characterized by using a solid nuclear magnetic resonance whose nuclear magnetic resonance spectrum is shown in FIG. 5, and it is apparent from FIG. 5 that the hydrogen atom on sodium 2,3,4, 5-tetrasulfonyloxy pentylsulfate has an absorption peak at 4.9ppm and 5.1ppm, respectively, and the cleavage at 4.4ppm is divided into two single peaks at the position of hydrogen at structural formula position 1, which indicates that sodium 2,3,4, 5-tetrasulfonyloxy pentylsulfate was produced.
In order to facilitate comparison of the effect of the antioxidant of the present invention, the present invention provides three comparative examples as follows:
comparative example 1: according to the component content of the water-soluble anti-yellowing agent disclosed in chinese patent application CN109251361a, the anti-yellowing agent of comparative example 1 was prepared by grinding and mixing uniformly 1.0g of ascorbic acid, 3.5g of sodium bisulphite, 1.0g of sodium sulfite, 0.5g of sodium nitrite and 2.0g of methionine.
Comparative example 2: mixed magnesium-zinc-salts of 2-hydroxy-2-sulfoacetic acid prepared according to the method disclosed in example 3 of chinese patent application CN110088083 a.
Comparative example 3: a water-soluble antioxidant BRUGGOLITE FF6 from Brucgaemann Chemical, heilbron (Germany) comprises 50-60% by weight of disodium salt of 2-hydroxy-2-sulfinatoacetic acid, 30-35% by weight of sodium sulfite (Na 2 SO 3 ) And 10-15% by weight of disodium 2-hydroxy-2-sulfoacetate.
EXAMPLE 6 evaluation of antioxidant Water solubility
The mass of solute dissolved by a solid substance when it reaches saturation in 100g of solvent at a certain temperature is defined as the solubility of this substance in this solvent. At 25 ℃, 10g of the antioxidant of the above examples 1 to 5 and the sample of the comparative examples 1 to 3 were dissolved in 100g of deionized water respectively, continuously stirred, fully dissolved, 10g of the solution was taken again after 10g of the sample was dissolved until the solution was supersaturated, the solution was filtered, the remaining undissolved solid was dried, and the solubility of the antioxidant was calculated, and the results are shown in table 1.
TABLE 1 solubility of antioxidants of examples 1 to 5 in Water
From the solubility results of Table 1, it can be seen that the antioxidants of the present invention are superior in water solubility to comparative examples 1 to 3.
EXAMPLE 7 use of antioxidant as anti-yellowing agent in superabsorbent resin
0.02g of the antioxidant of examples 1 to 5 and the sample of comparative examples 1 to 3 were added to 0.98g of deionized water, respectively, to prepare a 2% mass fraction aqueous sample solution, 30g of a superabsorbent resin (SAP) was uniformly sprayed on the surfaces of the SAP particles, and the aqueous sample solution was placed in a constant temperature and humidity cabinet together with a blank SAP without any aqueous sample solution sprayed thereon, and left at 70℃for 4 weeks under 90% relative humidity, and the Hunter b values (a measure for showing yellowness) of the SAP were measured every other week, and b values were measured by a HunterLab Vista (VTS) spectrophotometer, and the test results are shown in Table 2.
TABLE 2 surface Hunter b values of SAP and blank SAP sprayed with antioxidants of examples 1-5 and comparative examples 1-3, respectively
As can be seen from table 2, the blank SAP without the antioxidant of the present invention sprayed on the surface thereof had a significantly increased b value after one week of standing and increased sharply with the increase of standing time, which indicates that the surface of the blank SAP was rapidly oxidized to turn yellow, in sharp contrast to the SAP sprayed with the alkyl sulfate antioxidant of the present invention having a b value of only half that of the blank sample after up to four weeks, that is, the alkyl sulfate antioxidant of the present invention exhibited an excellent antioxidant effect, significantly slowing down the oxidation of the SAP surface, and thus the surface of the SAP turned yellow significantly lower than that of the blank SAP. Meanwhile, it can also be seen from Table 2 that although comparative examples 1 to 3 also slow the increase in b value to some extent relative to the blank SAP, the effect of the antioxidant of the present invention is more excellent.
EXAMPLE 8 use of the antioxidant of the invention as an anti-yellowing agent in polyacrylate emulsions
0.05g of the antioxidants of examples 1 to 5 and comparative examples 1 to 3 were taken and added to 35g of the PA emulsion having a solids content of 30%, respectively, the PA emulsion to which the antioxidant of the present invention was added, the PA emulsion to which the control sample was added, and a blank to which no antioxidant was added were formed together at room temperature, and then subjected to a high temperature test at 120℃to test the Hunter b value of the latex film every other hour, the b value being measured by a HunterLab Vista (VTS) spectrophotometer, and the test results being shown in Table 3.
TABLE 3 b values for the PA emulsions and blank samples of examples 1 to 5 and comparative examples 1 to 3, respectively, mixed with antioxidants
As can be seen from the results of the change in the b values in table 3, the PA emulsion without the alkyl sulfate antioxidant of the present invention was rapidly oxidized to yellow after one hour at high temperature, whereas the PA emulsion with the alkyl sulfate antioxidant of the present invention showed significantly slowed down yellowing, especially in the first three hours at high temperature, the b value was much lower than that of the blank sample, indicating that the alkyl sulfate antioxidant of the present invention exerts excellent antioxidant effect, significantly slowed down the yellowing of the PA emulsion with the antioxidant added. Meanwhile, it can also be seen from table 2 that comparative examples 1 to 3 only slightly slowed down the yellowing of the PA emulsion, especially the PA emulsion with comparative example 1 added, which did not differ from the b-value change of the blank PA emulsion by a little, which suggests that comparative example 1 could not be used as an anti-yellowing agent in the PA emulsion, that the b-value of the PA emulsion with comparative examples 2 and 3 added was only slightly lower than the blank PA emulsion, which could not achieve the anti-oxidant effect of the present invention, and that after three hours the b-value was substantially the same as the blank PA emulsion, whereby it can be seen that comparative examples 2 and 3 could not be effectively used as an anti-yellowing agent in the PA emulsion. The water-soluble antioxidant of the present invention exhibits excellent anti-yellowing effect in PA emulsions, and is useful as an antioxidant in PA emulsions.
The present invention has been described in detail with reference to specific embodiments thereof, which are only illustrative, and not intended to limit the scope of the invention, and various modifications, changes, or substitutions can be made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, various equivalent modifications are intended to be included within the scope of this invention.
Claims (11)
1. A method of preparing a water-soluble antioxidant comprising:
(1) Performing chlorosulfonation reaction on alkyl alcohol with the following general formula (II) and sulfonyl chloride reagent in an organic solvent reaction system to form chlorosulfonation intermediate products;
wherein R is a linear or branched alkyl radical having n carbon atoms, n=2, 3,4 or 5, m=1, 2,3,4 or 5 and m.ltoreq.n,
the sulfonyl chloride reagent is selected from the group consisting of: methylsulfonyl chloride, ethylsulfonyl chloride, propylsulfonyl chloride, isopropylsulfonyl chloride, butylsulfonyl chloride, isobutylsulfonyl chloride and tert-butylsulfonyl chloride;
(2) Adding an organic solvent and water into the reaction system in the step (1) to form a heterogeneous solution, thereby forming a heterogeneous system;
(3) Adding an oxidant into the heterogeneous system to enable the chlorosulfonated intermediate product to undergo an oxidation reaction, removing an aqueous phase after the oxidation reaction is completed, and retaining an organic phase in which oxidation reaction products are dissolved; wherein the oxidizing agent is selected from the group consisting of: sodium perchlorate, potassium perchlorate, magnesium perchlorate, sodium perbromate, potassium perbromate, sodium periodate, potassium periodate and barium periodate;
(4) Adding metal iodide into the organic phase of the step (3), and carrying out substitution reaction with the oxidation reaction product formed in the step (3) to generate alkyl sulfate;
wherein the metal iodide is selected from the group consisting of: alkali metal iodides, alkaline earth metal iodides or zinc iodide;
the alkyl sulfate has the following structural general formula (I):
wherein,
r is a linear or branched alkyl group having n carbon atoms,
n=2, 3,4 or 5, m=1, 2,3,4 or 5, and m.ltoreq.n,
m is an alkali metal element, an alkaline earth metal element or zinc.
2. The method of claim 1, further comprising the step of: after step (4) water is added to the organic phase such that the alkyl sulphate formed is extracted into the aqueous phase, followed by separation of the aqueous phase and addition of an alcohol solvent to the aqueous phase to precipitate the alkyl sulphate from the aqueous phase.
3. The method of claim 1 or 2, wherein:
in step (1), the molar ratio of the sulfonyl chloride reagent to the alcoholic hydroxyl groups in the alkyl alcohol of formula (II) is from 1:1 to 1:1.2;
the molar amount of the oxidizing agent added in step (2) is 0.95 to 1.05 times the molar amount of the sulfonyl chloride reagent added in step (1);
the molar amount of the metal iodide added in step (3) is 0.95 to 1.05 times the molar amount of the sulfonyl chloride reagent added in step (1).
4. The method of claim 1 or 2, wherein the heterogeneous solution comprises water, methylene chloride, and acetonitrile.
5. The method of claim 1 or 2, wherein:
the straight or branched alkyl group having n carbon atoms is selected from: ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and pentyl.
6. The method of claim 1 wherein said alkyl sulfate has the formula:
7. the method of claim 1, wherein,
the alkyl alcohol is amyl alcohol;
the sulfonyl chloride reagent is butyl sulfonyl chloride;
the alkyl sulfate is amyl potassium sulfate and has the following structural formula:
8. the method of claim 1, wherein,
the alkyl alcohol is ethylene glycol;
the sulfonyl chloride reagent is ethyl sulfonyl chloride;
the alkyl sulfate is 2-sulfooxyethyl sodium sulfate and has the following structural formula:
9. the method of claim 1, wherein,
the alkyl alcohol is glycerol;
the sulfonyl chloride reagent is methylsulfonyl chloride;
the alkyl sulfate is 2, 3-sulfopropyl potassium sulfate and has the following structural formula:
10. the method of claim 1, wherein,
the alkyl alcohol is pentaerythritol;
the sulfonyl chloride reagent is methylsulfonyl chloride;
the alkyl sulfate is 3-sulfoxy-2, 2-disulfoxymethyl propyl potassium sulfate, and has the following structural formula:
11. the method of claim 1, wherein,
the alkyl alcohol is xylitol;
the sulfonyl chloride reagent is methylsulfonyl chloride;
the alkyl sulfate is 2,3,4, 5-tetra-sulfoxy amyl sodium sulfate, and has the following structural formula:
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