CN114644762B - Multiple modified lignin sulfonate dye dispersant and preparation method thereof - Google Patents
Multiple modified lignin sulfonate dye dispersant and preparation method thereof Download PDFInfo
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- CN114644762B CN114644762B CN202210414749.5A CN202210414749A CN114644762B CN 114644762 B CN114644762 B CN 114644762B CN 202210414749 A CN202210414749 A CN 202210414749A CN 114644762 B CN114644762 B CN 114644762B
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- lignin
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- sulfonate
- sulfonating
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 50
- 229920001732 Lignosulfonate Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920005610 lignin Polymers 0.000 claims abstract description 84
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 50
- 230000000903 blocking effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- -1 aldehyde compound Chemical class 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 16
- 238000000502 dialysis Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 8
- ONGGURNBDHMMTE-UHFFFAOYSA-N ClCC(C[Na])O Chemical compound ClCC(C[Na])O ONGGURNBDHMMTE-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- SAWCWRKKWROPRB-UHFFFAOYSA-N 1,1-dibromohexane Chemical compound CCCCCC(Br)Br SAWCWRKKWROPRB-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATWLRNODAYAMQS-UHFFFAOYSA-N 1,1-dibromopropane Chemical compound CCC(Br)Br ATWLRNODAYAMQS-UHFFFAOYSA-N 0.000 claims description 3
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 claims description 3
- PGEVTVXEERFABN-UHFFFAOYSA-N 1,1-dichloropentane Chemical compound CCCCC(Cl)Cl PGEVTVXEERFABN-UHFFFAOYSA-N 0.000 claims description 3
- JNVXRQOSRUDXDY-UHFFFAOYSA-N 1,1-diiodoethane Chemical compound CC(I)I JNVXRQOSRUDXDY-UHFFFAOYSA-N 0.000 claims description 3
- QRYOSNCUQBSECP-UHFFFAOYSA-N 1,1-diiodohexane Chemical compound CCCCCC(I)I QRYOSNCUQBSECP-UHFFFAOYSA-N 0.000 claims description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims description 3
- AZUCPFMKPGFGTB-UHFFFAOYSA-N 2,2-diiodopropane Chemical compound CC(C)(I)I AZUCPFMKPGFGTB-UHFFFAOYSA-N 0.000 claims description 3
- NTIGNJOEVBTPJJ-UHFFFAOYSA-N 3,3-dibromopentane Chemical compound CCC(Br)(Br)CC NTIGNJOEVBTPJJ-UHFFFAOYSA-N 0.000 claims description 3
- MORAJFQPKBZENL-UHFFFAOYSA-N 3,3-diiodopentane Chemical compound CCC(I)(I)CC MORAJFQPKBZENL-UHFFFAOYSA-N 0.000 claims description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 3
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001284 azanium sulfanide Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 8
- 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 claims 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 6
- 229910052700 potassium Inorganic materials 0.000 claims 6
- 239000011591 potassium Substances 0.000 claims 6
- 229910052708 sodium Inorganic materials 0.000 claims 6
- 239000011734 sodium Substances 0.000 claims 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 55
- 239000000986 disperse dye Substances 0.000 abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 8
- 238000004043 dyeing Methods 0.000 abstract description 7
- 238000010186 staining Methods 0.000 abstract description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000000987 azo dye Substances 0.000 description 4
- DDLBHIIDBLGOTE-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid Chemical compound ClCC(O)CS(O)(=O)=O DDLBHIIDBLGOTE-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- OIQCMCUFGWKBBV-UHFFFAOYSA-N 2,3-diiodobutane Chemical compound CC(I)C(C)I OIQCMCUFGWKBBV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NFSNPELKGUOTIZ-UHFFFAOYSA-N C1C(C)O1.[K] Chemical compound C1C(C)O1.[K] NFSNPELKGUOTIZ-UHFFFAOYSA-N 0.000 description 1
- ICDUXFJWENHMAG-UHFFFAOYSA-N CC(O)C[Na] Chemical compound CC(O)C[Na] ICDUXFJWENHMAG-UHFFFAOYSA-N 0.000 description 1
- HFNPVBWQJKZODW-UHFFFAOYSA-N CC1CO1.[Na] Chemical compound CC1CO1.[Na] HFNPVBWQJKZODW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- RQZPDCLTYWTFRG-UHFFFAOYSA-M potassium 3-chloro-2-hydroxypropane-1-sulfonate Chemical compound ClCC(CS(=O)(=O)[O-])O.[K+] RQZPDCLTYWTFRG-UHFFFAOYSA-M 0.000 description 1
- JJWASFJUFNBZJD-UHFFFAOYSA-M potassium;oxiran-2-ylmethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)CC1CO1 JJWASFJUFNBZJD-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- RPCLCTYQNQJEHS-UHFFFAOYSA-M sodium;oxiran-2-ylmethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1CO1 RPCLCTYQNQJEHS-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/0086—Non common dispersing agents anionic dispersing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- D06P1/16—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 dispersed, e.g. acetate, dyestuffs
-
- 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
- D06P1/16—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 dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo 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
- 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
- D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—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 insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
-
- 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
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Coloring (AREA)
- Compounds Of Unknown Constitution (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a multiple modified lignin dye dispersant and a preparation method thereof, which take industrial alkali lignin as a raw material, take a sulfonation reagent 1 and a sulfonation reagent 2 as a sulfonation reagent system under an alkaline condition, and simultaneously introduce sulfonic acid groups at different sites, so that the content of hydrophilic group sulfonic acid groups can be greatly improved. Then selectively adding a blocking reagent to reduce the residual hydroxyl content and simultaneously increase the molecular weight. The multi-modified lignin sulfonate can be applied to dye dispersants, can be prepared into a disperse dye system with good dispersibility and excellent high-temperature stability without grinding, has extremely low staining property, has low reduction rate for diazo dye, can obviously improve the dye uptake, and can greatly reduce the production cost of the printing and dyeing industry. The multi-modified lignin dye dispersant prepared by the method is simple in method, excellent in performance, low in raw material cost and wide in source, and has potential application and popularization prospects.
Description
Technical Field
The invention relates to a multiple modified lignin-based dye dispersant and a preparation method thereof, and belongs to the technical field of dye dispersants.
Background
In general, disperse dyes have poor water solubility and are difficult to effectively diffuse into polyester fibers. The addition of the dye dispersing agent can improve the dispersibility and stability of the dye dispersing agent and remarkably improve the dyeing efficiency.
The most commonly used dispersants at present are naphthalene sulfonates and sulfonated lignin. Wherein, naphthalene sulfonate mainly comes from non-renewable petrochemical resources, has high price and high toxicity, and is unfavorable for sustainable development and environmental protection. Lignin is the second most abundant renewable biomass resource on the earth, is mainly used as industrial waste at present, and the high-value utilization rate of the lignin is only 2% by burning and recycling the heat value. Therefore, the production of lignin-based dye dispersant by using industrial lignin has wide development prospect.
The lignin dye dispersant has the advantages of low cost, rich source, reproducibility and the like, and has wide application in the world. Among the foreign dye auxiliary agents, the lignin dye dispersing agent is used up to 95%. In contrast, the lignin dispersant in China is only 30% -40% in dosage, and 50% of the lignin dispersant depends on import, because the lignin-based dye dispersant in China has the problem of poor performance. The industrial lignin for preparing dye dispersants is mainly derived from pulping and papermaking processes. Most domestic pulping and papermaking enterprises pulp by an alkaline method or a sulfate method, so the domestic dye dispersant is mainly prepared by taking alkali lignin or sulfate lignin as a raw material and carrying out single-site sulfonation modification. But is limited by the number of reaction sites, compared with lignin sulfonate obtained by a foreign sulfite pulping method, the domestic sulfonated modified alkali lignin or kraft lignin has small molecular weight, dark color and poor water solubility. The molecular structure of the lignin sulfonate is greatly different from that of lignin sulfonate prepared by a sulfite method, the dispersibility and high-temperature stability of the lignin sulfonate still have great improvement space, and the fiber pollution and the reduction rate of azo dyes are high, so that the application effect is not very ideal. Therefore, the development of the novel high-performance lignin-based dye dispersant by taking the alkali lignin as the raw material plays a vital role in the development of the printing and dyeing industry in China.
Under the background, the invention develops a multi-modified lignin-based dye dispersant with excellent performance by taking industrial alkali lignin as a raw material, taking a sulfonating agent and an aldehyde compound as a sulfonating reagent system and taking epichlorohydrin or dihaloalkane as a blocking reagent under an alkaline condition.
Disclosure of Invention
Aiming at the problems of serious fiber contamination, poor dispersion performance, poor high-temperature stability, strong reduction of the diazo dye and the like of the prior lignin-based dye dispersant, the invention develops a multi-modified lignin sulfonate dye dispersant which takes alkali lignin as a raw material and has higher stability, good dispersion performance, low reduction rate of the diazo dye and low fiber contamination and a preparation method thereof.
The invention takes industrial alkali lignin as raw material, and carries out multi-site sulfonation modification on lignin by a sulfonation reagent system under alkaline condition. Wherein sulfite, bisulfite react with lignin to realize sulfonation modification of C alpha position of lignin; the sulfonating agent and the aldehyde compound are used as a synergistic sulfonating agent to react with lignin to realize sulfomethylation modification of the ortho-position of lignin hydroxyl; 3-chloro-2-hydroxypropyl sulfonate or 2, 3-epoxypropyl sulfonate reacts with lignin to realize hydroxypropyl sulfonation modification on lignin hydroxyl. The lignin sulfonic acid group content after multi-site sulfonation can be greatly improved, and the hydrophilicity and the charge capacity of the lignin sulfonic acid group can be increased, so that the diffusion effect on dye is improved. The 3-chloro-2-hydroxypropyl sulfonate or 2, 3-epoxypropyl sulfonate is adopted as a sulfonating agent to introduce sulfonic acid groups on the phenolic hydroxyl groups and simultaneously reduce the content of the phenolic hydroxyl groups, so that a blocking agent can be omitted. And more phenolic hydroxyl groups are remained in the lignin modified by C alpha position and hydroxyl ortho-position sulfonation. The existence of phenolic hydroxyl can lead to the lignin-based dye dispersant to have higher reduction rate on the azo dye, and the lignin-based dye dispersant forms a dark quinone compound after being oxidized, so that the fiber is higher in staining property, at the moment, the addition of the blocking reagent can reduce the residual phenolic hydroxyl content, and meanwhile, the molecular weight of the modified lignin sulfonate is increased, so that the adsorption of the lignin-based dye dispersant on the dye is increased, and the dispersion effect and the high-temperature stability of the lignin-based dye dispersant are improved.
The invention aims at realizing the following technical scheme:
the multiple modified lignin sulfonate dye dispersant is characterized in that the modified lignin has the molecular structure as follows:
the preparation method of the multiple modified lignosulfonate dye dispersant comprises the following steps:
dissolving lignin in alkaline aqueous solution with pH value of 10-13, adding sulphonation reagent 1 for reaction, then adding sulphonation reagent 2, or simultaneously adding sulphonation reagent 1 and sulphonation reagent 2, regulating the reaction temperature to 90-150 ℃ and the reaction time to 2-4 h. And then selectively adding a blocking reagent according to the type of the sulfonation reagent system, and adding the blocking reagent for reaction or directly ending the reaction without adding the blocking reagent. After the reaction is finished, the multi-modified lignin is obtained after dialysis, evaporation and drying.
The sulfonating agent 2 comprises a sulfonating agent and/or an aldehyde compound.
When the sulfonating agent 1 is added first, the reaction conditions are as follows: reacting for 0.5-5 h at 90-150 ℃, treating by using a sulfonating reagent 1, and then adding a sulfonating reagent 2;
when the blocking reagent is added, the reaction conditions are as follows: the temperature is regulated to 90-120 ℃ and the reaction time is 2-5 h.
The lignin is industrial alkali lignin which is dissolved in an alkaline aqueous solution to form a solution with the mass fraction of 5-10%.
NaOH, KOH, HCl, H is adopted in the steps 2 SO 4 One or more of which adjusts the pH of the alkaline aqueous solution.
The method of multi-site sulfonation is adopted, the sulfonating agent 1 comprises one or more of sodium sulfite, sodium bisulfate, ammonium sulfite, ammonium bisulfide, potassium sulfite and potassium bisulfide, the mass ratio of the sulfonating agent to lignin is (0.1-0.5): 1, the sulfonating agent in the sulfonating agent 2 comprises one or more of 3-chloro-2-hydroxypropyl sodium sulfonate, 3-chloro-2-hydroxypropyl potassium sulfonate, 2, 3-epoxypropane sodium sulfonate and 2, 3-epoxypropane potassium sulfonate, and the mass ratio of the sulfonating agent to lignin is (0.1-1.0): 1, preferably (0.1-0.5): 1. The aldehyde compound in the sulfonating agent 2 comprises one or more of formaldehyde, acetaldehyde and glutaraldehyde, and the mass ratio of the aldehyde compound to lignin is (0.1-0.3): 1.
When one or more of sulfonating agent sodium 3-chloro-2-hydroxypropyl sulfonate, potassium 3-chloro-2-hydroxypropyl sulfonate, sodium 2, 3-epoxypropane sulfonate and potassium 2, 3-epoxypropane sulfonate are added, the blocking agent may not be added, otherwise, the blocking agent is added.
The sealing reagent comprises one or more of epichlorohydrin, dichlorohexane, dibromohexane, diiodohexane, dichloropentane, dibromopentane, diiodopentane, dichlorobutane, dibromobutane, diiodobutane, dichloropropane, dibromopropane, diiodopropane, dibromoethane, dichloroethane and diiodoethane, and the mass ratio of the sealing reagent to lignin is (0.3-0.5): 1.
The alkaline aqueous solution is NaOH, KOH, NH 4 One or more of OH solution, and lignin in the water of the alkaline aqueous solution has a mass concentration of 1% -20%.
The molecular weight cut-off of the dialysis bag used in the dialysis is 300-1500.
The chemical reaction involved in the preparation method is as follows:
all medicines related to the invention except lignin are calculated by pure content.
Compared with the prior art, the invention has the following advantages and effects:
1. according to the invention, hydrophilic sulfonic acid groups are simultaneously introduced into multiple sites such as Calpha, hydroxyl ortho-position and hydroxyl, so that the content of the sulfonic acid groups can be remarkably improved, and the electrostatic repulsive force of the lignin is improved, and therefore, the dispersibility and high-temperature stability of the lignin to disperse dyes can be improved.
2. The invention adopts the blocking reagent to reduce the content of residual phenolic hydroxyl, and particularly when halogenated alkane is used as the blocking reagent, no new reducing and chromophoric groups are introduced, so that the reducibility of azo dyes and the staining property of fibers can be greatly reduced. Meanwhile, the molecular weight of the modified disperse dye is increased after the modification, and the adsorption performance of the modified disperse dye on the disperse dye is improved, so that the disperse dye dispersing effect and the high-temperature stability of the modified disperse dye are improved.
3. The multi-modified lignin-based dye dispersant can prepare a disperse dye system with excellent dispersibility and excellent high-temperature stability without grinding, has the advantages of extremely low contamination to fibers, low reduction rate of diazo dye and the like, and can greatly reduce the production cost of the printing and dyeing industry.
4. The multi-modified lignin dye dispersant prepared by the method is simple in method, excellent in performance, low in raw material cost and wide in source, and has potential application and popularization prospects.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention as claimed is not limited to the examples.
Example 1
50 g of alkali lignin is added into 500mL of water, naOH is added to adjust the pH to 10 so that the lignin is dissolved, 5 g of sodium sulfite is added, 5 g of formaldehyde is added after the reaction is carried out for 2 hours at 150 ℃, the temperature is adjusted to 90 ℃, the reaction is carried out for 2.5 hours, and 20 g of dibromohexane is added for 2 hours. After cooling to room temperature, the product was purified by dialysis against a dialysis bag having a molecular weight of 1000. And then carrying out reduced pressure rotary evaporation on the dialyzed solution to remove most of water, and finally carrying out freeze drying on the rotary evaporated viscous solution to finally obtain the powdery multiple modified lignosulfonate.
Example 2
50 g of alkali lignin is added into 500mL of water, naOH is added to adjust the pH to 10 to dissolve the lignin, 5 g of sodium sulfite is added, 25 g of 3-chloro-2-hydroxypropyl sodium sulfonate is added after the reaction is carried out for 2 hours at 150 ℃, the temperature is raised to 90 ℃ for 2.5 hours, 12 g of epichlorohydrin is added for reaction for 2 hours, and after the reaction is cooled to room temperature, a dialysis bag with the molecular weight of 1000 is used for dialysis and purification of the product. And then carrying out reduced pressure rotary evaporation on the dialyzed solution to remove most of water, and finally carrying out freeze drying on the rotary evaporated viscous solution to finally obtain the powdery multiple modified lignosulfonate.
Example 3
50 g of alkali lignin is added into 500mL of water, naOH is added to adjust the pH to 10 so as to dissolve the lignin, 5 g of sodium sulfite is added, 25 g of 3-chloro-2-hydroxypropyl sodium sulfonate is added after the reaction is carried out for 2 hours at 150 ℃, the temperature is raised to 90 ℃ and the reaction is carried out for 2.5 hours, and 20 g of 1,6 dibromohexane is added and the reaction is carried out for 2 hours, thus obtaining the modified lignin sulfonate solution product. After cooling to room temperature, the product was purified by dialysis against a dialysis bag having a molecular weight of 1000. And then carrying out reduced pressure rotary evaporation on the dialyzed solution to remove most of water, and finally carrying out freeze drying on the rotary evaporated viscous solution to finally obtain the powdery multiple modified lignosulfonate.
Example 4
50 g of alkali lignin is added into 500mL of water, naOH is added to adjust the pH value to 10 so as to dissolve the lignin, 5 g of sodium sulfite is added, after 2h of reaction at 150 ℃, 25 g of 3-chloro-2-hydroxypropyl sodium sulfonate is added, the temperature is raised to 90 ℃ and the reaction is carried out for 2.5h, thus obtaining a modified lignin sulfonate solution product. After cooling to room temperature, the product was purified by dialysis against a dialysis bag having a molecular weight of 1000. And then carrying out reduced pressure rotary evaporation on the dialyzed solution to remove most of water, and finally carrying out freeze drying on the rotary evaporated viscous solution to finally obtain the powdery multiple modified lignosulfonate.
Example 5
50 g of alkali lignin is added into 500mL of water, naOH is added to adjust the pH to 10 so as to dissolve the lignin, then 25 g of 3-chlorine 2-hydroxypropyl sodium sulfonate, 5 g of sodium sulfite and 5 g of formaldehyde are added, the temperature is raised to 120 ℃, and the reaction is carried out for 2.5h, thus obtaining a modified lignin sulfonate solution product. After cooling to room temperature, the product was purified by dialysis against a dialysis bag having a molecular weight of 1000. And then carrying out reduced pressure rotary evaporation on the dialyzed solution to remove most of water, and finally carrying out freeze drying on the rotary evaporated viscous solution to finally obtain the powdery multiple modified lignosulfonate. Description of effects of the examples:
table 1 shows the results of the sulfonation degree and the phenolic hydroxyl group content of the products of the examples of the present invention, and the results of comparison with the dispersant of unmodified lignosulfonate are used as the comparative commercial products.
TABLE 1
Table 1 illustrates:
1. comparative example commodity was offered by Shanghai Dongsheng New Material Co., ltd;
2. the phenolic hydroxyl group content of the sample is determined by an ultraviolet spectrophotometer by adopting an FC-reagent method: the absorbance of the sample is measured at 760nm after being treated by FC reagent;
3. the sulfonation degree of the sample is determined by an elemental analysis method.
As shown in Table 1, the modified lignin sulfonate products of examples 1 to 5 have significantly reduced phenolic hydroxyl groups content compared with the comparative example commodity, which is about 78% lower than the comparative example commodity, and is advantageous for reducing the reduction of azo dye and the staining property of the dispersant to fibers. Through sulfonation reaction, the sulfonic acid groups of the products of examples 1-5 are obviously increased by 1.4-1.8 times compared with the original products, and the dispersion performance and dye-uptake of the lignin dispersing agent can be effectively improved.
Table 2 shows the test data of the performance of the inventive example product applied to disperse dyes, compared with the dispersant of unmodified lignosulfonate as a comparative commodity.
TABLE 2
Table 2 illustrates:
(1) The disperse dye is commercial disperse red GC200%;
(2) The preparation method of the dye dispersion liquid comprises the following steps: according to the dispersing agent: dye = 1.5:1, respectively adding a dispersing agent and a dye according to the mass ratio, then adding water to prepare a disperse dye system with the mass concentration of 30%, and then stirring at the room temperature for 12 hours at the rotating speed of 600r/min to obtain a dye dispersion liquid;
(3) The particle size is tested by a Markov laser particle sizer;
(4) Dye high temperature treatment: preparing dye dispersion liquid into 0.5%, adjusting pH to=5.5 with acetic acid, placing into high-temperature high-pressure sample dyeing machine, and standing at 2deg.C for 2 min -1 Heating to 130deg.C, maintaining the temperature for 30min, and adding dye liquor for 4 deg.C and min -1 Cooling to 80 ℃ and taking out;
(5) Reduction rate test of dye: preparing dye dispersion liquid before and after high-temperature treatment into a solution with the mass concentration of 0.02g/L based on the dye by using acetone, and testing at the wavelength of 510nm by using an ultraviolet spectrophotometer;
(6) Dye uptake test for dye: when the dye dispersion liquid is treated at high temperature, 3g/100mL polyester fiber is added into the dye dispersion liquid, the dye dispersion liquid before and after the high temperature treatment is prepared into a solution with the mass concentration of 0.02g/L based on the dye by using acetone, and the solution is tested at the wavelength of 510nm by using an ultraviolet spectrophotometer;
(7) Stain resistance test on dye: preparing a lignin dispersing agent sample with the concentration of 2g/L, adjusting the pH value to be=5.5 by using acetic acid, adding the lignin dispersing agent sample into a dyeing cup, adding 2.0g of polyester fiber for high-temperature treatment, and measuring the K/S value of the treated polyester fiber by using a color measuring instrument after the polyester fiber is dried at normal temperature, wherein the higher the K/S value is, the more serious the pollution is.
As shown in Table 2, the average particle size of the disperse dye prepared by using the products of examples 1-5 of the invention as the dye dispersing agent is far lower than that of the comparative example commodity at normal temperature and after high temperature treatment, and the original 319.704-345.884 mu m is reduced to 0.262-22.676 mu m, which shows that the lignin dispersing agent prepared by the invention can realize the high-efficiency dispersion of the disperse dye under the condition of no grinding, and the disperse dye basically does not have the adverse phenomena of flocculation, aggregation and the like after high temperature treatment, and has excellent high temperature stability. The dye uptake of the invention in the examples 1-5 can reach more than 90%, and is improved by 20.9-28.6% compared with the dye uptake of the commodity in the comparative example. The staining property is obviously reduced by 34 times. The reduction rate is also obviously reduced from 20.8% to 3.0%. In a word, compared with the comparative commodity, the product provided by the embodiment of the invention has the advantages of excellent dispersibility, high-temperature stability and extremely low staining property, the reduction rate of disperse dye is smaller, and meanwhile, the dye uptake can be improved, so that the production cost of the printing and dyeing industry is greatly reduced.
Claims (9)
1. The multiple modified lignin sulfonate dye dispersant is characterized in that the modified lignin has the molecular structure as follows:
the preparation method of the multi-modified lignin sulfonate dye dispersant comprises the following steps:
dissolving lignin in an alkaline aqueous solution with pH of 10-13, adding a sulfonating reagent 1 for reaction, and then adding a sulfonating reagent 2, or simultaneously adding the sulfonating reagent 1 and the sulfonating reagent 2, regulating the reaction temperature to be 90-150 ℃ and the reaction time to be 2-4 hours; adding a blocking reagent, and reacting or not adding the blocking reagent; after the reaction is finished, obtaining multiple modified lignin through dialysis, evaporation and drying;
wherein the sulfonation reagent 1 comprises one or more of sodium sulfite, sodium bisulfite, ammonium sulfite, ammonium bisulfide, potassium sulfite and potassium bisulfide; the sulfonating agent 2 comprises a sulfonating agent and/or an aldehyde compound, wherein the sulfonating agent in the sulfonating agent 2 comprises one or more of 3-chloro-2-hydroxypropyl sodium sulfonate, 3-chloro-2-hydroxypropyl potassium sulfonate, 2, 3-epoxypropyl sodium sulfonate and 2, 3-epoxypropyl potassium sulfonate; the blocking reagent comprises one or more of epichlorohydrin, dichlorohexane, dibromohexane, diiodohexane, dichloropentane, dibromopentane, diiodopentane, dichloropropane, dibromopropane, diiodopropane, dibromoethane, dichloroethane and diiodoethane;
when the sulfonation reagent 1 is added first for reaction, the reaction conditions are as follows: reacting for 0.5-5 h at 90-150 ℃;
adding or not adding a blocking reagent when the added sulfonating agent is one or more of 3-chlorine-2-hydroxypropyl sodium sulfonate, 3-chlorine-2-hydroxypropyl potassium sulfonate, 2, 3-epoxypropyl sodium sulfonate and 2, 3-epoxypropyl potassium sulfonate, otherwise adding the blocking reagent;
when the blocking reagent is added, the reaction conditions are as follows: the temperature is regulated to 90-120 ℃ and the reaction time is 2-5 h.
2. A method of preparing the multiple modified lignosulfonate dye dispersant of claim 1, comprising the steps of:
dissolving lignin in an alkaline aqueous solution with pH of 10-13, adding a sulfonating reagent 1 for reaction, and then adding a sulfonating reagent 2, or simultaneously adding the sulfonating reagent 1 and the sulfonating reagent 2, regulating the reaction temperature to be 90-150 ℃ and the reaction time to be 2-4 hours; adding a blocking reagent, and reacting or not adding the blocking reagent; after the reaction is finished, obtaining multiple modified lignin through dialysis, evaporation and drying;
wherein the sulfonation reagent 1 comprises one or more of sodium sulfite, sodium bisulfite, ammonium sulfite, ammonium bisulfide, potassium sulfite and potassium bisulfide; the sulfonating agent 2 comprises a sulfonating agent and/or an aldehyde compound, wherein the sulfonating agent in the sulfonating agent 2 comprises one or more of 3-chloro-2-hydroxypropyl sodium sulfonate, 3-chloro-2-hydroxypropyl potassium sulfonate, 2, 3-epoxypropyl sodium sulfonate and 2, 3-epoxypropyl potassium sulfonate; the blocking reagent comprises one or more of epichlorohydrin, dichlorohexane, dibromohexane, diiodohexane, dichloropentane, dibromopentane, diiodopentane, dichloropropane, dibromopropane, diiodopropane, dibromoethane, dichloroethane and diiodoethane;
when the sulfonation reagent 1 is added first for reaction, the reaction conditions are as follows: reacting for 0.5-5 h at 90-150 ℃;
adding or not adding a blocking reagent when the added sulfonating agent is one or more of 3-chlorine-2-hydroxypropyl sodium sulfonate, 3-chlorine-2-hydroxypropyl potassium sulfonate, 2, 3-epoxypropyl sodium sulfonate and 2, 3-epoxypropyl potassium sulfonate, otherwise adding the blocking reagent;
when the blocking reagent is added, the reaction conditions are as follows: the temperature is regulated to 90-120 ℃ and the reaction time is 2-5 h.
3. The method for preparing the multiple modified lignin sulfonate dye dispersant according to claim 2, wherein the lignin is industrial alkali lignin, and the lignin is dissolved in an alkaline aqueous solution to form a solution with a mass fraction of 5-10%.
4. The method for preparing a multi-modified lignin-based dye dispersant according to claim 2 wherein NaOH, KOH, NH is used in the step 4 OH、HCl、H 2 SO 4 One or more of which adjusts the pH of the alkaline aqueous solution.
5. The method for preparing the multi-modified lignin-based dye dispersant according to claim 2, wherein the mass ratio of the sulfonation reagent 1 to lignin is (0.1 to 0.5): 1.
6. the method for preparing a multi-modified lignin-based dye dispersant according to claim 2 wherein the mass ratio of sulfonating agent to lignin is (0.1-1.0): 1.
7. The method for preparing the multi-modified lignin-based dye dispersant according to claim 2, wherein the aldehyde compound in the sulphonating agent 2 comprises one or more of formaldehyde, acetaldehyde and glutaraldehyde, and the mass ratio of the aldehyde compound to lignin is (0.1-0.3): 1.
8. The method for preparing a multi-modified lignin sulfonate dye dispersant according to claim 2, wherein the mass ratio of the blocking agent to lignin is (0.3-0.5): 1.
9. The method for preparing a multiple modified lignin sulfonate dye dispersant according to claim 2 wherein the aqueous alkaline solution is NaOH, KOH, NH 4 One or more of OH solution, and lignin in the water of the alkaline aqueous solution has a mass concentration of 1% -20%.
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