CN116574226B - Bio-based acidic color fixing agent and preparation method and application thereof - Google Patents
Bio-based acidic color fixing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116574226B CN116574226B CN202310819335.5A CN202310819335A CN116574226B CN 116574226 B CN116574226 B CN 116574226B CN 202310819335 A CN202310819335 A CN 202310819335A CN 116574226 B CN116574226 B CN 116574226B
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- fixing agent
- color fixing
- acid
- ionic liquid
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- 230000002378 acidificating effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 61
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 61
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 61
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000002608 ionic liquid Substances 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 132
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- 235000019441 ethanol Nutrition 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- -1 tributyl ethyl phosphonium 2-hydroxypyridine Chemical compound 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 claims description 15
- 150000001450 anions Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 230000001105 regulatory effect Effects 0.000 claims description 10
- ADCUEPOHPCPMCE-UHFFFAOYSA-N 4-cyanobenzoic acid Chemical compound OC(=O)C1=CC=C(C#N)C=C1 ADCUEPOHPCPMCE-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000005349 anion exchange Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001778 nylon Polymers 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XOTZDSWJKMKAMT-UHFFFAOYSA-M tributyl(ethyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CC)(CCCC)CCCC XOTZDSWJKMKAMT-UHFFFAOYSA-M 0.000 claims description 6
- PYVOHVLEZJMINC-UHFFFAOYSA-N trihexyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC PYVOHVLEZJMINC-UHFFFAOYSA-N 0.000 claims description 6
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- RJELOMHXBLDMDB-UHFFFAOYSA-M trihexyl(tetradecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[P+](CCCCCC)(CCCCCC)CCCCCC RJELOMHXBLDMDB-UHFFFAOYSA-M 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000006277 sulfonation reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000980 acid dye Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 231100000481 chemical toxicant Toxicity 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 229920006052 Chinlon® Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 241000490567 Pinctada Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011090 industrial biotechnology method and process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 229940061610 sulfonated phenol Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- HOMONHWYLOPSLL-UHFFFAOYSA-N tributyl(ethyl)phosphanium Chemical compound CCCC[P+](CC)(CCCC)CCCC HOMONHWYLOPSLL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/18—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenols substituted by carboxylic or sulfonic acid groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
- B01J31/0291—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- 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
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/20—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by addition of sulfurous acid or salts thereof to compounds having carbon-to-carbon multiple bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of new materials, and particularly relates to a bio-based acidic color fixing agent, a preparation method and application thereof. The preparation method of the bio-based acidic color fixing agent provided by the invention comprises the following preparation steps: mixing the ionic liquid with water, and then introducing SO 2 Adding gas into the bio-based cardanol to react to obtain bio-based cardanol sulfonic acid; and then, water, a catalyst and the obtained bio-based cardanol sulfonic acid react with bio-based aldehyde to obtain the bio-based acidic color fixing agent. The preparation method of the ionic liquid catalyzed synthesis bio-based acid color fixing agent changes the problem that the traditional double bond addition sulfonation requires high temperature and high pressure conditions to be promised, simplifies the addition sulfonation condition, and reduces the equipment investment and the safety risk; and the obtained bio-based acidic color fixing agent has better color fixing performance.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a bio-based acidic color fixing agent, a preparation method and application thereof.
Background
The use of fossil raw materials (coal, oil, natural gas) re-releases hundreds of millions of years of solidified carbon into the atmosphere, accumulating to form a greenhouse effect. Climate change and corresponding greenhouse gas emission reduction requirements mean that humans must change thinking, and a more perfect solution is to replace fossil raw materials with biobased products. Plants absorb carbon dioxide from the air by photosynthesis, and if we use this carbon from plants or microbial biomass in the manufacture, carbon dioxide can be removed from the environment while ensuring that natural biochar circulation is not disturbed. Petroleum is not completely replaced, but only a part of petroleum is replaced, so that carbon footprint can be reduced very effectively. According to the planning of the United states 'biomass technology roadmap', the 2030 biological-based chemicals replace 25% of organic chemicals and 20% of petroleum fuels; according to the European Union 'industrial biotechnology perspective planning', the biological base raw material in 2030 replaces 6 to 12 percent of chemical raw material and 30 to 60 percent of fine chemicals are manufactured by biological base; the future production value of modern biological manufacturing industry is over 1 trillion yuan, and the proportion of the bio-based products in the total chemical product yield reaches 25 percent. The bio-based material is a strategic emerging industry in China and is incorporated in the new material field of China manufacturing 2025, the development is rapid in recent years, the key technology is continuously broken through, the product types are rapidly increased, the product economy is enhanced, the product is becoming a hotspot of industrial investment, and the strong development potential is shown. Corresponding national standards are formulated in China, GB/T39514-2020 definition, term and identification of biobased materials are formulated, and the definition, term and identification of biobased materials are standardized, so that the definition, term and identification of biobased materials are important components of a biobased material standard system, and the development of biobased materials is greatly promoted. With the advancement of three major economic policies, the global carbon emission reduction process begins to accelerate. Individuals and industries are looking for ways to reduce their environmental footprint, and the demand for bio-based chemicals will grow enormously in the next few years. The new materials industry is growing in the share of biobased products and processing aids.
At present, nylon fabric is usually dyed by adopting acid dye, and the acid dye has the advantages of complete chromatography, convenient use and the like, but because the acid dye is provided with water-soluble groups, the wet treatment fastness of the dyed fabric is relatively poor, and in order to improve the wet treatment fastness of the nylon fabric after the acid dye is dyed, the color fixing treatment is often needed to be carried out on the fabric.
For example, chinese patent application CN 102850500A discloses an acid-reactive type chinlon fixing agent, which is prepared by the following method: the condensation reaction of one kind of phenol matter and two kinds of aromatic sulfonic acid compounds with formaldehyde under the action of composite catalyst: then adding epichlorohydrin and a modifier into the reaction system to carry out modification: finally, the pH value of the modified multipolymer aromatic sulfonic acid formaldehyde condensate is regulated to 2.0-4.0 by strong acid or concentrated acid, and the acid-resistant reaction type nylon color fixing agent is obtained. Chinese patent application CN 107841896A discloses a method for preparing an acid dye fixing agent, comprising the following steps: sulfonating a part of phenols with concentrated sulfuric acid to obtain phenols with sulfonic groups, condensing another part of phenols with formaldehyde under the conditions of organic solvent and acid catalysis to obtain a precondensate, mixing the products together, and performing polycondensation reaction to obtain the viscous color fixing agent. The 3-step method is adopted to synthesize the acid dye fixing agent, part of phenols is firstly subjected to sulfonation reaction with concentrated sulfuric acid, and then the product is subjected to condensation reaction with another part of sulfonated phenol and formaldehyde in an organic solvent to control the sulfonation degree and water solubility of the final product, so that the fixing effect of the final product is regulated. The fixing agent of the acid dye is mainly formaldehyde polymer of sulfonate of phenol formaldehyde polymer or bisphenol sulfonate, and has a trend of gradually forbidden in recent years because phenol, bisphenol and the like are toxic chemicals. Meanwhile, the carbon emission problem caused by the production of the acid fixing agent based on petrochemical raw materials is generally used in the prior art, so that the development of a green acid fixing agent is urgent, and the bio-based acid fixing agent is provided.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a bio-based acidic color fixing agent, a preparation method and application thereof. The preparation method of the ionic liquid catalyzed synthesis bio-based acid color fixing agent changes the problem that the traditional double bond addition sulfonation requires high temperature and high pressure condition promise to be realized, avoids using toxic chemicals, simplifies addition sulfonation conditions, and reduces equipment investment and safety risks; and the obtained bio-based acidic color fixing agent has better color fixing performance.
The technical scheme of the invention is as follows:
the preparation method of the bio-based acidic color fixing agent comprises the following preparation steps:
mixing the ionic liquid with water, and then introducing SO 2 Adding gas into the bio-based cardanol to react to obtain bio-based cardanol sulfonic acid; and then, water, a catalyst and the obtained bio-based cardanol sulfonic acid react with bio-based aldehyde to obtain the bio-based acidic color fixing agent.
Further, the preparation method of the bio-based acidic color fixing agent comprises the following steps:
step 1: synthesizing bio-based cardanol sulfonic acid:
mixing the ionic liquid with water, and then introducing SO 2 Adding gas into the bio-based cardanol, stirring, heating to 60-70 ℃, preserving heat for reaction, and cooling to room temperature to obtain bio-based cardanol sulfonic acid; preferably, adding water and an organic solvent, stirring, standing, discharging a lower ionic liquid aqueous solution, reserving an upper oil layer, removing the organic solvent, and extracting and separating the obtained bio-based cardanol sulfonic acid; in this step, water is added to enable the ionic liquid to be better dissolved in water, and meanwhile, an organic solvent (such as toluene) is adopted to extract the synthesized bio-based cardanol sulfonic acid, so that the extraction efficiency can be effectively improved.
Step 2: synthesizing a bio-based acid color fixing agent:
mixing water and a catalyst, and stirring for dissolution; adding the bio-based cardanol sulfonic acid obtained in the step 1, regulating the pH value, then introducing nitrogen to replace oxygen, heating to 85-100 ℃, dropwise adding bio-based aldehyde, carrying out reaction after dropwise adding, cooling to room temperature, and adding water to regulate the solid content to obtain the bio-based acidic color fixing agent; the solids content is preferably 40%.
Further, the heat preservation time in the step 1 is 1.5-3 hours; the heat preservation time in the step 2 is 4-8 hours; the solid content in the step 2 is 35-45%.
Further, the ionic liquid is tributylethyl phosphonium 2-hydroxypyridine, tetramethyl guanidine 2-hydroxypyridine or trihexyltetradecylphosphonium 4-cyanobenzoic acid.
Further, the synthesis method of the ionic liquid tributyl ethyl phosphonium 2-hydroxypyridine comprises the following steps:
absolute ethanol and tributylethyl phosphonium bromide [ P ] 4442 ][Br]Mixing, stirring and dissolving at room temperature to obtain tributyl ethyl phosphonium bromide [ P ] 4442 ][Br]Is a solution of (a) in ethanol; then will [ P ] 4442 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column for anion exchange to obtain [ P ] 4442 ][OH]Is a solution of (a) in ethanol; preferably, then, by means of a metering pump, a flow rate of 100-120 m/min is controlled (too slow a flow rate would affect the production efficiency, too fast a flow rate would decrease the adsorption efficiency) [ P ] 4442 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column to perform anion exchange, and exchanging anions Br-into OH-, thereby obtaining [ P ] 4442 ][OH]Is a solution of (a) in ethanol;
then [ P ] 4442 ][OH]Ethanol solution and 2-hydroxypyridine in a molar ratio of 1:1, mixing and stirring at room temperature for reaction; after the reaction is finished, vacuumizing to-75 kpa, heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping the mixture for 4 hours under the conditions of 55 ℃ and-75 kpa vacuum degree to obtain the ionic liquid tributyl ethyl phosphonium 2-hydroxypyridine [ P ] 4442 ][2-PyO]；
The synthesis method of the ionic liquid trihexyl tetradecylphosphonium 4-cyanobenzoic acid comprises the following steps:
absolute ethyl alcohol and trihexyltetradecylphosphonium bromide [ P ] 66614 ][Br]Mixing, stirring at room temperature to dissolve to obtain [ P ] 66614 ][Br]Is a solution of (a) in ethanol; then will [ P ] 66614 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column for anion exchange to obtain [ P ] 66614 ][OH]Is a solution of (a) in ethanol; preferably, by means of a metering pump, a flow rate of 100-120 mW/min is controlled (too slow a flow rate will affect the production efficiency, too fast a flow rate will decrease the adsorption efficiency) [ P ] 66614 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column to perform anion exchange, and exchanging anions Br-into OH-, thereby obtaining [ P ] 66614 ][OH]Ethanol of (C)A solution;
then [ P ] 66614 ][OH]Ethanol solution of (C) and 4-cyanobenzoic acid [4-CN-PhCOOH ]]According to the mole ratio of 1:1, mixing and stirring at room temperature for reaction; after the reaction is finished, vacuumizing to-75 kpa, heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping the mixture for 4 hours under the conditions of 55 ℃ and-75 kpa vacuum degree to obtain the ionic liquid trihexyltetradecylphosphonium 4-cyanobenzoic acid [ P ] 66614 ][4-CN-PhCOO]；
The synthesis method of the ionic liquid tetramethylguanidine 2-hydroxypyridine comprises the following steps:
tetramethylguanidine [ TMG ] and 2-hydroxypyridine [2-PyO ] are mixed according to a molar ratio of 1:1, mixing, preserving the heat at 40 ℃ for reaction, vacuumizing, and dehydrating to obtain the ionic liquid tetramethylguanidine 2-hydroxypyridine [ TMG ] [2-PyO ].
The ionic liquid provided by the invention has the characteristics of adjustable structure, negligible vapor pressure, low melting point, excellent thermal stability and the like, and can be applied to the efficient synthesis process of the bio-based acid color fixing agent, so that the obtained bio-based acid color fixing agent has better color fixing performance on polyamide fabric acid or neutral dye.
Further, in the step 1, the ionic liquid and SO 2 The weight ratio of the gas to the bio-based cardanol is 20-50:2.1-5.5:10-40.
Further, in the step 1, the ionic liquid and SO 2 The weight ratio of the gas to the bio-based cardanol is 50:2.1:10.
further, the step 1 further comprises extracting the synthesized bio-based cardanol sulfonic acid with an organic solvent; the organic solvent is preferably toluene;
the alkaline catalyst in the step 1 is any one of sodium hydroxide, sodium carbonate, barium hydroxide, ammonia water and glycol amine;
the pH value in the step 2 is 8.3-8.8. Because the phenolic aldehyde condensation reaction speed is low, the side reaction speed of phenolic aldehyde addition is high, the gelation is easy to occur, the reaction product is complex, and the fixation effect is poor.
Further, the weight ratio of the catalyst to the water in the step 2 is 12.8:150.
further, the bio-based aldehyde in the step 2 is bio-based formaldehyde or bio-based furfural;
the weight ratio of the bio-based formaldehyde to the bio-based cardanol is 8-15:60-120;
the weight ratio of the bio-based furfural to the bio-based cardanol is 20-45:80-150.
Still further, the weight ratio of the bio-based formaldehyde to the bio-based cardanol is 10:100; the weight ratio of the bio-based furfural to the bio-based cardanol is 32:100.
the invention also provides the bio-based acid color fixing agent obtained by the preparation method of the bio-based acid color fixing agent and application of the bio-based acid color fixing agent in the dyeing preparation process of nylon fabric.
The bio-based cardanol is cashew nut shell oil extracted based on wastes produced by the food processing industry, and is a natural, non-food chain and annually renewable bio-based material. According to the invention, the bio-based cardanol is used for replacing phenol and bisphenol, and is sulfonated to synthesize the acid color fixing agent with bio-based aldehydes, and the acid color fixing agent has good color fixing performance on polyamide fabric acid or neutral dye. Meanwhile, the traditional double bond addition sulfonation can be realized only by high temperature and high pressure, and the invention prepares the catalyst with high-efficiency load SO by new process 2 The characteristics of the method, the ionic liquid with ring opening catalytic performance is induced by double bonds, ring opening addition is carried out on double bonds on a long alkyl chain of the bio-based cardanol, and a sulfonate is obtained under mild synthesis conditions, so that the bio-based cardanol sulfonic acid can be obtained by carrying out addition reaction without high temperature and high pressure, the addition sulfonation conditions are simplified, and the equipment investment and the safety risk are reduced.
The invention firstly loads SO with bio-based cardanol 2 The ionic liquid of (2) is mixed, then the ionic liquid with strong ionic charge characteristic is utilized to induce the unsaturated double bond on the catalytic bio-based cardanol to open the ring, and the SO loaded on the ionic liquid is carried at the moment 2 Ring-opening addition is carried out on unsaturated double bonds on the bio-based cardanol at 60-70 ℃ to obtain bio-based cardanol sulfonate; then condensing with formaldehyde to obtain salt of sulfonated bio-based cardanol polymer, and diluting with waterThe solid content is prepared, and finally the bio-based acidic color fixing agent with good color fixing effect and easily obtained raw materials is obtained.
Compared with the prior art, the bio-based acidic color fixing agent, the preparation method and the application thereof have the following advantages:
(1) The invention utilizes the high-efficiency load SO of the newly-prepared ionic liquid 2 The characteristics of the method, the catalytic performance of the method on double bond induced ring opening, the ring opening addition of double bonds on a long alkyl chain of the bio-based cardanol, and the preparation of the sulfonate, namely the bio-based cardanol sulfonic acid, under mild synthesis conditions are changed, the problem that the traditional double bond addition sulfonation needs to be realized under high temperature and high pressure conditions is solved, the addition sulfonation conditions are simplified, the conversion rate is improved, and the equipment investment and the safety risk are reduced.
(2) According to the invention, the synthesized bio-based cardanol sulfonic acid is condensed with formaldehyde to obtain the salt of the sulfonated bio-based cardanol polymer, and water is added for dilution to control the solid content, so that the bio-based acidic color fixing agent with easily obtained raw materials is finally obtained. Experiments prove that the acid color fixing agent has better color fixing performance on polyamide fabric acid or neutral dye.
(3) The bio-based product of the invention can effectively help CO 2 Emission reduction: they can help reduce significant amounts of CO compared to materials synthesized from fossil materials 2 Discharge amount. The acid color fixing agent is prepared from natural, non-food-chain and annually renewable bio-based materials, the bio-based carbon content is 100%, and compared with the traditional petrochemical raw material-based acid color fixing agent, the carbon content is 0% -10%, the carbon emission can be reduced by more than 90%, and the acid color fixing agent contributes to the global greenhouse gas emission reduction plan.
Drawings
FIG. 1 is a photograph of a residual color fixing liquid obtained in example 1 of the present invention after color fixing with a bio-based acid fixing agent (number: HNR 03) and an ecological environment-friendly acid fixing agent MESITOL EP 2047;
Detailed Description
The invention is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or improvements can be made by those skilled in the art in light of the basic idea of the invention, but are within the scope of the invention as long as they do not depart from the basic idea of the invention.
In the following examples and comparative examples, the reagents not specifically described were conventional reagents, and were purchased from conventional reagent manufacturers and sales companies, and the information of some raw material manufacturers and the like was as follows:
biobased cardanol suppliers: NX-2024 of the chemical industry of Kadli (Pinctada) Co., ltd;
biobased formaldehyde suppliers: POMECO-B of Seranis celanese; biological-based furfural suppliers are limited liability company of northern furfural groups in China;
tributylethyl phosphonium bromide suppliers: qingdao Alrick New Material technologies Co., ltd;
trihexyltetradecylphosphonium bromide suppliers: guangzhou merck, inc.;
tetramethyl guanidine suppliers: hubei Xinrun chemical Co., ltd;
2-hydroxypyridine suppliers: beijing carboline technologies Co., ltd;
4-cyanobenzoic acid suppliers: dalianqi Kai pharmaceutical sciences Co., ltd.
Example 1A biobased acid fixing agent
Step 1: synthesizing an ionic liquid:
adding 900kg absolute ethyl alcohol into a reaction kettle, and adding tributyl ethyl phosphonium bromide [ P ] 4442 ][Br](supplier: qingdao Alternatives New Material science Co., ltd.) 100kg, and stirring at room temperature to dissolve to obtain [ P ] 4442 ][Br]Is a solution of (a) in ethanol; then, by a metering pump, the flow rate is controlled to be 120 m/min (too slow flow rate can affect the production efficiency, too fast flow rate can reduce the adsorption efficiency) and the flow rate is controlled to be 120 m/min 4442 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column to perform anion exchange, and exchanging anions Br-into OH-, thereby obtaining [ P ] 4442 ][OH]Is a solution of (a) in ethanol. Determination of [ P ] by titration detection 4442 ][OH]Concentration (by detecting [ P ] 4442 ][OH]Concentration in order to calculate the amount of 2-hydroxypyridine that needs to be added); handle [ P ] 4442 ][OH]Adding ethanol solution into a reaction kettle according to a mole ratio of 1:1 adding 2-hydroxypyridine, stirring at room temperature, and reacting for 12 hours. After the reaction is finished, vacuumizing to 75kpa, slowly heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping the mixture for 4 hours under the conditions of 55 ℃ and 75kpa vacuum degree to obtain the ionic liquid tributyl ethyl phosphonium 2-hydroxypyridine [ P ] 4442 ][2-PyO]。
Step 2: synthesizing bio-based cardanol sulfonic acid:
500kg of tributyl ethyl phosphonium 2-hydroxypyridine and 5.5kg of deionized water are added into a clean enamel reactor to obtain SO in a steel cylinder 2 Regulating pressure to 1bar by a pressure reducing valve, regulating flow rate by a gas flowmeter, and controlling the metered SO to be introduced by a gas diffuser within 1 hour 2 (mw=64) 21kg, adding 100kg of biobased cardanol (mw=304), stirring, gradually heating to 60 ℃, preserving heat for about 2 hours, and cooling with boiled water to room temperature; 1000kg deionized water and 500kg toluene are added, stirred for 1 hour, and the mixture is stood still, and the lower layer ionic liquid aqueous solution (after the subsequent reduced pressure distillation and dehydration of the aqueous solution, the ionic liquid is obtained again for recycling) is discharged, the upper layer oil layer is reserved, and the toluene solvent is removed by reduced pressure distillation, so that the bio-based cardanol sulfonic acid is obtained.
Step 3: synthesizing a bio-based acid color fixing agent:
adding 150kg of deionized water and 12.8kg of sodium hydroxide into a reaction kettle, stirring and dissolving, adding 120kg of bio-based cardanol sulfonic acid obtained in the step 2, and adjusting the pH value to 8.3 by using 30% sodium hydroxide; introducing nitrogen, replacing oxygen for 15 minutes, gradually heating to 85 ℃, and dropwise adding bio-based furfural (the weight ratio of the bio-based furfural to the bio-based cardanol is 32:100), wherein the dropwise adding is completed; preserving heat for about 4-8 hours, cooling to room temperature, adding deionized water to adjust the solid content, and detecting the solid content to about 40% to obtain the bio-based acidic color fixing agent.
Example 2
Step 1: synthesizing an ionic liquid:
the synthesis method of the ionic liquid tetramethylguanidine 2-hydroxypyridine comprises the following steps: the molar ratio of the reaction kettle to the catalyst is 1:1, adding tetramethyl guanidine [ TMG ] and 2-hydroxypyridine [2-PyO ], carrying out heat preservation reaction at 40 ℃ for 12 hours, vacuumizing, and dehydrating for 4 hours to obtain the ionic liquid tetramethyl guanidine 2-hydroxypyridine [ TMG ] [2-PyO ].
Step 2: synthesizing bio-based cardanol sulfonic acid:
adding 500kg of tetramethyl guanidine 2-hydroxypyridine and 5.5kg of deionized water into a clean enamel reactor, and adding SO in a steel bottle 2 Regulating pressure to 1bar by a pressure reducing valve, regulating flow rate by a gas flowmeter, and controlling the metered SO to be introduced by a gas diffuser within 1 hour 2 (mw=64) 21kg, adding 100kg of biobased cardanol (mw=304), starting stirring, gradually heating to 70 ℃, preserving heat for about 2 hours, cooling to room temperature by boiled cooling water, adding 1000kg of deionized water and 500kg of toluene, stirring for 1 hour, standing, discharging a lower layer of ionic liquid aqueous solution (the ionic liquid aqueous solution is recycled after subsequent reduced pressure distillation and dehydration), retaining an upper layer of oil layer, and removing toluene solvent by reduced pressure distillation to obtain the biobased cardanol sulfonic acid.
Step 3: synthesizing a bio-based acid color fixing agent:
adding 150kg of deionized water and 12.8kg of sodium carbonate into a reaction kettle, stirring and dissolving, adding 120kg of bio-based cardanol sulfonic acid obtained in the step 2, and adjusting the pH value to 8.8 by using 30% sodium hydroxide; introducing nitrogen, replacing oxygen for 15 minutes, gradually heating to 100 ℃, dropwise adding bio-based formaldehyde (the weight ratio of the bio-based formaldehyde to the bio-based cardanol is 10:100), after the dropwise adding is finished, preserving the heat for about 8 hours, cooling to room temperature, adding deionized water to control the solid content, and detecting the solid content to about 40%, thereby obtaining the bio-based acidic color fixing agent.
Example 3
Step 1: synthesizing an ionic liquid:
the synthesis method of the ionic liquid trihexyl tetradecylphosphonium 4-cyanobenzoic acid comprises the following steps: adding 900kg of absolute ethyl alcohol into a reaction kettle, and adding trihexyl tetradecyl phosphonium bromide [ P ] 66614 ][Br](supplier: merck Co., guangzhou) 100kg, and dissolved by stirring at room temperature to give [ P ] 66614 ][Br]Is a solution of (a) in ethanol; then, the flow rate is controlled to be 100 m/min by a metering pump (too slow flow rate can affect the production efficiency, and flowToo fast will cause a decrease in adsorption efficiency) will [ P 66614 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column to perform anion exchange, and exchanging anions Br-into OH-, thereby obtaining [ P ] 66614 ][OH]Is a solution of (a) in ethanol. Determination of [ P ] by titration detection 66614 ][OH]Concentration (about 0.15mol/L, specifically looking at titration results, each time there is a certain fluctuation in concentration); handle [ P ] 66614 ][OH]Adding ethanol solution into a reaction kettle according to a mole ratio of 1:1 addition of 4-cyanobenzoic acid [4-CN-PhCOOH ]]The reaction was stirred at room temperature for 12 hours. After the reaction is finished, vacuumizing to 75kpa, slowly heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping for 4 hours under the conditions of 55 ℃ and 75kpa vacuum degree to obtain the ionic liquid trihexyltetradecylphosphonium 4-cyanobenzoic acid [ P ] 66614 ][4-CN-PhCOO]。
Step 2: synthesizing bio-based cardanol sulfonic acid:
500kg of trihexyltetradecylphosphonium 4-cyanobenzoic acid and 5.5kg of deionized water are added into a clean enamel reactor, and SO in a steel cylinder is added 2 Regulating pressure to 1bar by a pressure reducing valve, regulating flow rate by a gas flowmeter, and controlling the metered SO to be introduced by a gas diffuser within 1 hour 2 (mw=64) 21kg, adding 100kg of biobased cardanol (mw=304), stirring, gradually heating to 65 ℃, preserving heat for about 2 hours, and cooling with boiled water to room temperature; 1000kg deionized water and 500kg toluene are added, stirred for 1 hour, and the mixture is stood still, and the lower layer ionic liquid aqueous solution (after the subsequent reduced pressure distillation and dehydration of the aqueous solution, the ionic liquid is obtained again for recycling) is discharged, the upper layer oil layer is reserved, and the toluene solvent is removed by reduced pressure distillation, so that the bio-based cardanol sulfonic acid is obtained.
Step 3: synthesizing a bio-based acid color fixing agent:
adding 150kg of deionized water and 12.8kg of barium hydroxide into a reaction kettle, stirring and dissolving, adding 120kg of bio-based cardanol sulfonic acid obtained in the step 2, and adjusting the pH value to 8.5 by using 30% sodium hydroxide; introducing nitrogen, replacing oxygen for 15 minutes, gradually heating to 90 ℃, and dropwise adding bio-based furfural (the weight ratio of the bio-based furfural to the bio-based cardanol is 32:100), wherein the dropwise adding is completed; preserving heat for about 4-8 hours, cooling to room temperature, adding deionized water to control the solid content, and detecting the solid content to about 40% to obtain the bio-based acidic color fixing agent.
Example 4
Example 4 differs from example 3 in that example 4 uses ammonia as the basic catalyst.
Example 5
Example 5 differs from example 3 in that example 5 uses ethylene glycol amine as the basic catalyst.
Comparative example 1
Compared with example 1, the difference of comparative example 1 is that the synthesis step of the bio-based cardanol sulfonic acid is a conventional concentrated sulfuric acid sulfonation process: adding 100 parts of bio-based cardanol into a clean enamel reaction kettle, starting stirring, introducing nitrogen, replacing oxygen for 15 minutes, gradually heating to 110 ℃, starting to dropwise add 20 parts of concentrated sulfuric acid, continuously controlling the temperature to 120 ℃, preserving the heat for about 2 hours, and cooling to room temperature to obtain the bio-based cardanol sulfonic acid. Other parameters and operations were the same as in example 1.
The strong oxidizing and dehydrating properties of concentrated sulfuric acid result in a dark product color, which in use results in a greater fabric color. In addition, the concentrated sulfuric acid sulfonation process has a plurality of side reactions, the product is complex, and the color fixing effect is poor.
Comparative example 2
Comparative example 2 is different from example 1 in that the reaction process pH was controlled to 9.3 in step S3, and other parameters and operations were the same as example 1.
The pH value is higher, the phenolic aldehyde condensation reaction speed is low, the phenolic aldehyde addition side reaction speed is high, the gelation is easy to occur, the reaction product is complex, and the fixation test cannot be carried out.
Comparative example 3
Comparative example 3 differs from example 3 in that trihexyltetradecylphosphonium benzoate [ P 66614 ][PhCOO]Ion liquid replacing trihexyl tetradecylphosphonium 4-cyanobenzoic acid [ P 66614 ][4-CN-PhCOO]. Comparative example 3 since the anion has no cyano group, for SO 2 50% weaker adsorption and catalytic power) thus results inInsufficient sulfonation proportion affects the color fixing performance and poor water solubility of subsequent products.
Test example one, color fixing Performance test
1. Test materials: the biobased acid fixing agent obtained in example 1 (number: HNR 03), the biobased acid fixing agent obtained in example 1, the ecological environment-friendly acid fixing agent MESITOL EP 2047 (Tanatex chemical, tuona chemical, germany), the biobased acid fixing agent obtained in comparative example 1 and comparative example 3.
2. The test method comprises the following steps:
a fabric: blue nylon cloth and red nylon cloth.
(1) The color fixation process comprises the following steps:
the dosage of the acid color fixing agent is as follows: 3% o.w.f, bath ratio 1:15 Treating at 75 deg.c for 20 min, dewatering, stoving at 170 deg.c and testing the soaping fastness and perspiration fastness.
(2) The fastness testing method comprises the following steps:
fastness to soaping: taking a color-fixed cloth sample of 5cm multiplied by 10cm, sewing a piece of multi-fiber cloth with the same volume on the front surface, putting the piece of multi-fiber cloth into 100ml of working solution of 4g/L washing powder, and treating the piece of multi-fiber cloth at 60 ℃ for 30 minutes.
Perspiration fastness: the test is carried out according to the national standard GB/T3922-2013 test method.
3. Test results:
the test results of the color fixing process are shown in Table 1, the color fixing residual liquid obtained after the color fixing of the bio-based acid color fixing agent (number: HNR 03) and the ecological environment-friendly acid color fixing agent MESITOL EP 2047 obtained in the embodiment 1 of the invention is shown in FIG. 1, wherein a1 and b1 are respectively blue color fixing residual liquid and red color fixing residual liquid obtained after the color fixing of the ecological environment-friendly acid color fixing agent MESITOL EP 2047; wherein a2 and b2 are blue and red fixation residual liquids after fixation by the bio-based acidic fixation agent (number: HNR 03) obtained in the embodiment 1 of the present invention.
TABLE 1 hydrophilia/color change after fixation
The results of the soaping fastness test of the bio-based acid fixing agent (number: HNR 03) and the ecological environment-friendly acid fixing agent MESITOL EP 2047 obtained in the embodiment 1 of the invention are shown in Table 2.
TABLE 2 fastness test results
(1) As shown in table 1: color change size: comparative example 1 > MESITOL EP 2047 > comparative example 3 > comparative example 1 > example 1 (acid fixing agent HNR 03). Compared with MESITOL EP 2047, a product of Tuona chemistry, germany, example 1 (biobased acid fixing agent HNR 03) is slightly less hydrophilic and has smaller color change. The cardanol sulfonic acid prepared by the conventional concentrated sulfuric acid sulfonation process in comparative example 1 has low conversion rate and complex byproducts, so that the obtained bio-based acidic color fixing agent has a color fixing effect which is not as good as that of a product synthesized by ionic liquid catalysis, and the product has dark color due to the strong oxidation of the concentrated sulfuric acid, so that the application of the product to medium-light-colored fabrics is not facilitated. Comparative example 3 since the anion has no cyano group, for SO 2 50% weaker in adsorption and catalytic ability) thus results in insufficient sulfonation ratio, affecting the subsequent product fixation properties and poor water solubility.
(2) As shown in Table 2, the washing fastness of the bio-based acidic color fixing agent HNR03 obtained in the embodiment 1 of the invention is more than 4.5 (according to the national standard GB/T3921-2008), and is superior to the German Tuo Na like product; the biobased acidic color fixing agent HNR03 obtained in the embodiment 1 of the invention has perspiration fastness more than grade 4 (according to the national standard GB/T3922-2013), and is superior to the German Tuo Na like products.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (9)
1. The preparation method of the bio-based acidic color fixing agent is characterized by comprising the following preparation steps:
step 1: synthesizing bio-based cardanol sulfonic acid:
mixing the ionic liquid with water, and then introducing SO 2 Adding gas into the bio-based cardanol, stirring, heating to 60-70 ℃, preserving heat for reaction, and cooling to room temperature to obtain bio-based cardanol sulfonic acid;
step 2: synthesizing a bio-based acid color fixing agent:
mixing water and a catalyst, and stirring for dissolution; adding the bio-based cardanol sulfonic acid obtained in the step 1, regulating the pH value, then introducing nitrogen to replace oxygen, heating to 85-100 ℃, dropwise adding bio-based aldehyde, carrying out reaction after dropwise adding, cooling to room temperature, and adding water to regulate the solid content to obtain the bio-based acidic color fixing agent;
the ionic liquid is tributyl ethyl phosphonium 2-hydroxypyridine, tetramethyl guanidine 2-hydroxypyridine or trihexyl tetradecylphosphonium 4-cyanobenzoic acid;
the pH value in the step 2 is 8.3-8.8.
2. The method for preparing a bio-based acidic fixing agent according to claim 1, wherein the heat-preserving time in the step 1 is 1.5 to 3 hours; the heat preservation time in the step 2 is 4-8 hours; the solid content of the bio-based cardanol sulfonic acid in the step 2 is 35-45%.
3. The method for preparing the bio-based acidic color fixing agent according to claim 1, wherein the ionic liquid tributyl ethyl phosphonium 2-hydroxypyridine is synthesized by the following steps:
absolute ethanol and tributylethyl phosphonium bromide [ P ] 4442 ][Br]Mixing, stirring and dissolving at room temperature to obtain tributyl ethyl phosphonium bromide [ P ] 4442 ][Br]Is a solution of (a) in ethanol; then will [ P ] 4442 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column for anion exchange to obtain [ P ] 4442 ][OH]Is a solution of (a) in ethanol;
then [ P ] 4442 ][OH]Ethanol solution and 2-hydroxypyridineAccording to the mole ratio of 1:1, mixing and stirring at room temperature for reaction; after the reaction is finished, vacuumizing to-75 kpa, heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping the mixture for 4 hours under the conditions of 55 ℃ and-75 kpa vacuum degree to obtain the ionic liquid tributyl ethyl phosphonium 2-hydroxypyridine [ P ] 4442 ][2-PyO]；
The synthesis method of the ionic liquid trihexyl tetradecylphosphonium 4-cyanobenzoic acid comprises the following steps:
absolute ethyl alcohol and trihexyltetradecylphosphonium bromide [ P ] 66614 ][Br]Mixing, stirring at room temperature to dissolve to obtain [ P ] 66614 ][Br]Is a solution of (a) in ethanol; then will [ P ] 66614 ][Br]Pumping the ethanol solution into an ethanol strong-alkaline anion resin exchange column for anion exchange to obtain [ P ] 66614 ][OH]Is a solution of (a) in ethanol;
then [ P ] 66614 ][OH]Ethanol solution of (C) and 4-cyanobenzoic acid [4-CN-PhCOOH ]]According to the mole ratio of 1:1, mixing and stirring at room temperature for reaction; after the reaction is finished, vacuumizing to-75 kpa, heating to 55 ℃, removing ethanol and water generated by the reaction, and keeping the mixture for 4 hours under the conditions of 55 ℃ and-75 kpa vacuum degree to obtain the ionic liquid trihexyltetradecylphosphonium 4-cyanobenzoic acid [ P ] 66614 ][4-CN-PhCOO]；
The synthesis method of the ionic liquid tetramethylguanidine 2-hydroxypyridine comprises the following steps:
tetramethylguanidine [ TMG ] and 2-hydroxypyridine [2-PyO ] are mixed according to a molar ratio of 1:1, mixing, preserving the heat at 40 ℃ for reaction, vacuumizing, and dehydrating to obtain the ionic liquid tetramethylguanidine 2-hydroxypyridine [ TMG ] [2-PyO ].
4. The method for preparing bio-based acidic color fixing agent according to claim 1, wherein in the step 1, ionic liquid and SO 2 The weight ratio of the gas to the bio-based cardanol is 20-50:2.1-5.5:10-40.
5. The method for preparing a bio-based acidic fixing agent according to claim 1, wherein the step 1 further comprises extracting the synthesized bio-based cardanol sulfonic acid with an organic solvent;
the catalyst in the step 2 is any one of sodium hydroxide, sodium carbonate, barium hydroxide, ammonia water and glycol amine.
6. The method for preparing the bio-based acidic color fixing agent according to claim 1, wherein the weight ratio of the catalyst to the water in the step 2 is 12.8:150.
7. the method for preparing a bio-based acidic color fixing agent according to claim 1, wherein the bio-based aldehyde in the step 2 is bio-based formaldehyde or bio-based furfural;
the weight ratio of the bio-based formaldehyde to the bio-based cardanol is 8-15:60-120;
the weight ratio of the bio-based furfural to the bio-based cardanol is 20-45:80-150.
8. A biobased acid fixing agent obtained by the process for producing a biobased acid fixing agent according to any one of claims 1 to 7.
9. Use of the bio-based acidic fixing agent according to claim 8 in a process for dyeing preparation of nylon fabric.
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